CN107446135A - A kind of dynamic aggregation thing with dynamic crosslinking structure - Google Patents

A kind of dynamic aggregation thing with dynamic crosslinking structure Download PDF

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CN107446135A
CN107446135A CN201610382046.3A CN201610382046A CN107446135A CN 107446135 A CN107446135 A CN 107446135A CN 201610382046 A CN201610382046 A CN 201610382046A CN 107446135 A CN107446135 A CN 107446135A
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boron
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CN107446135B (en
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不公告发明人
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Xiamen Tiance Material Technology Co ltd
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Weng Qiumei
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Abstract

The invention discloses a kind of dynamic aggregation thing with dynamic crosslinking structure, contain organic boronic estersil key on its cross linked chain synthetism frame on the polymer chain skeleton of cross-linked network and/or between polymer chain, wherein, described organic boronic estersil key is the necessary condition to form/maintain dynamic aggregation thing structure.Such dynamic aggregation thing structure-rich, performance is various, by the regulation and control to reaction materil structure, can prepare dynamic aggregation thing of different nature.Further, since strong dynamic reversibility possessed by organic boronic estersil key in polymer, makes polymer reflect the functional characteristics such as stimulating responsive, self-repairability, recuperability；Meanwhile the presence of organic boronic estersil key, polymer is played energy-absorbing effect, and toughness reinforcing can be carried out to polymeric material in specific structure.The dynamic aggregation thing can be used for making damping, buffering material, defense of resistance to impact material, self-repair material, toughness material etc..

Description

A kind of dynamic aggregation thing with dynamic crosslinking structure
Technical field
The present invention relates to intelligent polymer field, and in particular to a kind of by what dynamic reversible covalent bond was formed to there is dynamic to hand over It is coupled the dynamic aggregation thing of structure.
Background technology
Dynamic covalent chemical that dynamic chemical is combined with supramolecular chemistry and covalent chemical and the intersection to grow up Subject.Traditional molecular chemistry is concerned with stable covalent interaction, and dynamic chemical concern be then some relatively Weak noncovalent interaction and reversible covalent bonds.Among these, supramolecular chemistry be based on it is non-covalent it is intermolecular mutually Effect, for these noncovalent interactions compared with traditional covalent bond, general bond energy is weaker, larger by thermodynamic effects, is formed Supramolecular structure to a certain extent for be not a stable system, easily destroyed, it is characterized, study and Using causing many restrictions.And for dynamic covalent chemical, it has some features similar to supramolecular chemistry, suitable Reversible covalent bond " fracture " and " formation " can occur under conditions of preferably；And compared to supramolecular chemistry, because dynamic is covalent The bond energy of dynamic covalent bond in chemistry is more than intermolecular interaction so that dynamic covalent bond has certain intensity, energy Enough form relatively stable molecular structure.Dynamic covalent bond combine well the invertibity of supermolecule noncovalent interaction with The steadiness of covalent bond so that it is widely used, and is constructing functional molecular and material, exploitation chemical sensor, is adjusting Control biomolecule, control smart molecule switch and machine etc. show important function.
Dynamic aggregation thing is then that the novel polymeric system of the one kind formed is linked by dynamic chemical key.According to link dynamic The difference of the dynamic chemical key of polymer, dynamic aggregation thing can be divided into the physical dynamic aggregation based on supermolecule interaction Thing and the covalent type dynamic aggregation thing based on dynamic covalent bond.By the covalent type dynamic aggregation thing of dynamic reversible covalent bond formation, Due to special nature possessed by dynamic reversible covalent bond, it may have outstanding feature.Relative to physical dynamic aggregation thing, move State reversible covalent polymer is more stable, often also has more excellent mechanical performance；And the presence of dynamic reversible covalent bond, Also ensure that polymer can embody under appropriate conditions stimulating responsive, self-repairability, recuperability, can re-workability Etc. characteristic.
But fracture and formation of the chemical balance process in conventional dynamic polymer due to being related to covalent bond, often compare Relatively slowly, still usually need to add catalyst or extraneous offer energy to accelerate equilibrium process.In addition, some reversible covalent bonds are certainly In there is also certain defect, these are all caused to the use environment and application field of dynamic aggregation thing in actual use Limitation.For example, the reversible exchange reaction that traditional ester exchange reaction is people to be applied earliest, but the condition of ester exchange reaction Compare harsh, generally requiring could complete in the case where adding alkali, counterflow condition, while the dynamic activity of traditional ester bond is poor, so as to The application of dynamic aggregation thing to being constructed using ester exchange reaction generates limitation；Based on furans-maleimide Diels- The product of Alder cycloaddition reactions generally requires and carries out dissociation reaction under the high temperature conditions, and this reacts in organic solvent Process carries out slow；Primary amine and the imine linkage of aldehyde reaction generation, it is influenceed strongly, to cause such imine linkage usual by acid-base value Under the conditions of be difficult to stabilization；The reversible exchange reaction of transamination then needs to carry out in the presence of Special Proteins enzyme；Based on alkane The dynamic reversible key of oxygen nitrogen base, its dissociation reaction temperature often will also reach 100-130 DEG C, meanwhile, the dissociation generation of alcoxyl nitrogen base Ionization Potential of C-Centered Radicals to oxygen and sensitive, the irreversible bonding thus brought can impact to the performance of material；Contain The dynamic aggregation thing of three thioester groups then needs that dynamic exchange reaction could occur under the conditions of ultraviolet light；Dynamic is covalently Cystine linkage dynamic in key is preferable, and it can swap reaction under cryogenic, but mercaptan self stability is poor, make It can be acted on during with surrounding air and produce continuous oxidation and the mercaptans content in reversible system is constantly reduced, influence material The use of material.The presence of such situation so that possessed characteristic is difficult at typical condition in itself for dynamic reversible covalent bond Fully to be embodied, it is necessary to develop a kind of new dynamic aggregation thing so that the dynamic reversible covalent bond in system can Meet the condition that reversible reaction speed is fast, reaction condition is gentle, reversible reaction is controllable simultaneously, to solve present in prior art Above mentioned problem.
The content of the invention
The present invention is directed to above-mentioned background, there is provided one kind is based on organic boronic estersil key, in the polymerization of cross-linked network There is dynamic crosslinking knot containing organic boronic estersil key on cross linked chain synthetism frame on thing chain backbone and/or between polymer chain The dynamic aggregation thing of structure.Described dynamic aggregation thing stability is good, and dynamic reversibility is strong, it may be unnecessary to it is extra add catalyst and The external additives such as accelerator, also can there can be good move under in general temperate condition without illumination and hot conditions State invertibity, and reflect plasticity, dilatancy, self-repairability, recuperability, can re-workability and bionical mechanical property Etc. characteristic.
The present invention is achieved by following technical solution：
A kind of dynamic aggregation thing with dynamic crosslinking structure, it is on the polymer chain skeleton of cross-linked network and/or poly- Contain organic boronic estersil key on cross linked chain synthetism frame between compound chain.Wherein, described organic boronic estersil key is as dynamic The polymerization linking point of state polymer and/or crosslinking linking point and exist, be the necessary bar to form/maintain dynamic aggregation thing structure Part.
The organic boronic estersil key contained in described cross-linked network, it has following structure：
Wherein, a boric acid estersil key (B-O-Si) is at least formed between boron atom and silicon atom；In the structure at least There is a carbon atom to be connected by boron carbon key with boron atom, and at least one organic group passes through the boron carbon key connection to boron On atom；Represent the connection with polymer chain, the group that crosslinking links or other are any appropriate, boron atom and silicon atom Pass through at least one connection access cross-linked network respectively.
In embodiments of the present invention, described organic boronic estersil key is by organic boron acidic group and/or organic boric acid ester Base forms with silicone hydroxyl and/or the reaction of silicone hydroxyl precursor.
Heretofore described organic boron acidic group, it is referred to by boron atom and a hydroxyl being connected 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 passes through in the boron carbon key connection to boron atom.In the present invention, a hydroxyl in organic boron acidic group (- OH) it is a functional group.
Described 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, it 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 passes through in the boron carbon key connection to boron atom. In the present invention, an ester group (- OR) in organic boronic ester group is a functional group.
Heretofore described silicone hydroxyl, it is referred to by silicon atom and a hydroxyl institute group being connected with the silicon atom Into structural motif (Si-OH), wherein, silicone hydroxyl can be organic silicone hydroxyl (silicon atom i.e. in silicone hydroxyl at least with a carbon Atom is connected by silicon-carbon bonds, and at least one organic group is connected on silicon atom by the silicon-carbon bonds), or nothing Machine silicone hydroxyl (silicon atom i.e. in silicone hydroxyl is not connected with organic group), preferably organic silicone hydroxyl.In the present invention, silicon A hydroxyl (- OH) in hydroxyl is a functional group.
Heretofore described silicone hydroxyl presoma, it is referred to can by silicon atom and be connected with the silicon atom one Hydrolysis obtains the structural motif (Si-X) that the group of hydroxyl is formed, wherein, X is that hydrolyzable obtains the group of hydroxyl, and its is optional From halogen, cyano group, oxygen cyano group, thiocyanogen, alkoxy, amino, sulfate group, boric acid ester group, acyl group, acyloxy, acylamino-, ketone Oximido, alkoxide group.In the present invention, the group (- X) that a hydrolyzable in silicone hydroxyl presoma obtains hydroxyl is an official Can group.
Dynamic aggregation thing described in the present invention, it can be prepared by implementation below：
The first of the present invention prepares embodiment, and reaction generation organic boronic estersil key is participated in by least following components Obtain described dynamic aggregation thing：
At least one organoboron compound (I) containing organic boron acidic group and/or organic boronic ester group, at least one contains The silicon-containing compound of silicone hydroxyl and/or silicone hydroxyl presoma (II)；Wherein, organoboron compound (I) and silicon-containing compound (II) Containing two or more functional groups, and at least one organoboron compound (I) or at least one silicon-containing compound (II) contain There are three or more than three functional groups.
Second of preparation embodiment of the present invention, reaction generation organic boronic estersil key is participated in by least following components Described dynamic aggregation thing is obtained with common covalent bond：
At least one organoboron compound (I) containing organic boron acidic group and/or organic boronic ester group, at least one contains The silicon-containing compound of silicone hydroxyl and/or silicone hydroxyl presoma (II)；Wherein, organoboron compound (I) and silicon-containing compound (II) Containing one or more functional groups, and at least one organoboron compound (I) or at least one silicon-containing compound (II) contain There are one or more other reactive groups.
The third of the present invention prepares embodiment, and reaction generation organic boronic estersil key is participated in by least following components Obtain described dynamic aggregation thing：
At least one body before containing organic boron acidic group and/or organic boronic ester group and silicone hydroxyl and/or silicone hydroxyl simultaneously The compound (III) of body, or itself and at least one organoboron compound containing organic boron acidic group and/or organic boronic ester group And/or at least one silicon-containing compound (II) containing silicone hydroxyl and/or silicone hydroxyl presoma (I)；Wherein, compound (III), Organoboron compound (I), silicon-containing compound (II) contain two or more functional groups, and at least one compound (III) or at least one organoboron compound (I) or at least one silicon-containing compound (II) contain three or more than three functions Group.
The 4th kind of the present invention prepares embodiment, and reaction generation organic boronic estersil key is participated in by least following components Described dynamic aggregation thing is obtained with common covalent bond：
At least one body before containing organic boron acidic group and/or organic boronic ester group and silicone hydroxyl and/or silicone hydroxyl simultaneously The compound (III) of body, or itself and at least one organoboron compound containing organic boron acidic group and/or organic boronic ester group And/or at least one silicon-containing compound (II) containing silicone hydroxyl and/or silicone hydroxyl presoma (I)；Wherein, compound (III) Containing two or more functional groups, organoboron compound (I), silicon-containing compound (II) contain one or more functions Group, and at least one compound (III) or at least one organoboron compound (I) or at least one silicon-containing compound (II) contain One or more other reactive groups.
In above-described preparation embodiment, the organoboration of proper amount of simple function group is also selectively introduced into Silicon-containing compound (II) component of compound (I) and/or simple function group, described move can be obtained by the regulation of component formula State cross-linked structure.Mono-functional compounds can play the effects such as regulation crosslink density, dynamic, Mechanics of Machinery intensity.
In above-described preparation embodiment, the reaction of other reactive groups can also be by introducing without organic Boronate and/or organic boronic ester group, silicone hydroxyl and/or silicone hydroxyl presoma, organic boronic estersil key but containing other reaction The compound component of property group is realized together.Only the compound containing other reactive groups can be any appropriate chemical combination Thing, it can reach and other reactions in organoboron compound (I) and/or silicon-containing compound (II) and/or compound (III) Property radical reaction obtain the purpose of the dynamic aggregation thing with " the dynamic crosslinking structure ".
In above-described preparation embodiment, for preparing the compound (III) of the dynamic aggregation thing, it can be with Selected from same compound (III), not same compound (III) can also be selected from；When it is selected from same compound (III) When, before it is by intramolecular and/or intermolecular organic boron acidic group and/or organic boronic ester group and silicone hydroxyl and/or silicone hydroxyl The reaction driven between body obtains described dynamic aggregation thing.
Other described in the present invention reactive groups, refer to can spontaneously, or can initiator or light, Reaction is performed the derivatization under the conditions of heat, irradiation, catalysis etc., or carries out polymerized/cross-linked reaction, generation removes organic boronic estersil key The group of common covalent bond in addition, suitable group citing is such as：Hydroxyl, phenolic hydroxyl group, carboxyl, acyl group, amide groups, acyloxy, Amino, aldehyde radical, sulfonic group, sulfonyl, sulfydryl, alkenyl, alkynyl, cyano group, piperazine base, oximido, diazanyl, guanidine radicals, halogen, isocyanates Group, anhydride group, epoxide group, acrylate group, acrylamide group, maleimide base group, N- hydroxysuccinimidyl acyls Imine group, ENB group, azo group, azido group, heterocyclic group etc.；The preferred hydroxyl of other reactive groups, carboxylic Base, amino, sulfydryl, alkenyl, isocyanate groups, epoxide group, acrylate group, acrylamide group.
The organoboron compound (I) containing organic boron acidic group and/or organic boronic ester group described in the present invention, it can With following representation：
Wherein, A is the module containing organic boron acidic group and/or organic boronic ester group；M be modules A number, m >=1；L is Substituted radical on individual module A, or the linking group between two or more modules As；P be group L number, p >= 1。
The described modules A containing organic boron acidic group, it may be selected from following any or appoints several structures：
Wherein, K1For the group being joined directly together with boron atom, it is selected from following any structure：Hydrogen atom, hetero atom base The small molecule alkyl of group, molecular weight no more than 1000Da, molecular weight are more than 1000Da polymer chain residue；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 ring-type knot In structure, cyclic structure can be small molecule ring or macromolecular ring, and it is preferably 3~100 yuan of rings, more preferably 3~50 Yuan of rings, more preferably 3~10 yuan of 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 form 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 Group L connection；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 passes through in the boron carbon key connection to boron atom.
The described modules A containing organic boronic ester group, it may be selected from following any or appoints several structures：
Wherein, K2For the group being joined directly together with boron atom, it is selected from following any structure：Hydrogen atom, hetero atom base The small molecule alkyl of group, molecular weight no more than 1000Da, molecular weight are more than 1000Da polymer chain residue；R1、R2、R3、R4、R6 For the monovalent organic group or monovalence organosilicon radical being joined directly together with oxygen atom, it passes through carbon atom or silicon atom and oxygen atom It is joined directly together, it is selected from following any structure：Small molecule alkyl, molecular weight of the molecular weight no more than 1000Da are no more than 1000Da small molecule silylation, molecular weight are more than 1000Da polymer chain residue；R5To be joined directly together with two oxygen atoms Divalent organic group or divalence organosilicon radical, it is joined directly together by carbon atom or silicon atom with oxygen atom, its be selected from Under any structure：Divalence small molecule alkyl of the molecular weight no more than 1000Da, molecular weight are no more than 1000Da small point of divalence Sub- silylation, molecular weight are more than 1000Da diatomic polymer chain residue；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 or macromolecular ring, it is preferably 3~100 yuan of rings, more preferably 3~50 yuan of rings, more preferably 3~10 Yuan of rings；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 form organic boronic ester group, and at least one ring member nitrogen atoms are connected with group L；Ring-type 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 monocyclic knot Structure, multiring structure, spirane structure, condensed cyclic structure, caged scaffold, nested ring structure；Represent 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 key connection is in boron atom.
, can be same in a boron atom in the modules A containing organic boron acidic group and/or organic boronic ester group in the present invention When connect a hydroxyl and an ester group, can also have at least one boron hydroxyl and at least one boric acid simultaneously in same module Ester group.
In the present invention, when the modules A containing organic boron acidic group and/or organic boronic ester group is present in polymer In, and when having two or more connections, it can be connected to not cyclic or not into the polymer chain of cluster, can also connect It is connected in side base/side chain of ring-type or cluster；When an only connection, it can be connected to any position of polymer chain Put.
As m=1, p=1 or 2, L are the substituted radical on individual module A；As p=2, L may be selected from same knot Structure or a variety of different structures；Described L structures may 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 1000Da polymer chain residue.
Work as m>When 1, modules A may be selected from same structure or a variety of different structures, now p >=1, and L is two or more moulds Linking group between block A；As p >=2, L may be selected from same structure or a variety of different structures；Described L structures may be selected from It is any below or appoint it is several：Singly-bound, hetero atom linker, molecular weight are no more than 1000Da divalence or multivalence small molecule hydrocarbon Base, molecular weight are more than 1000Da divalence or multivalence polymer chain residue.
The silicon-containing compound (II) containing silicone hydroxyl and/or silicone hydroxyl precursor described in the present invention, it can be to have Machine silicon-containing compound, or be inorganic silicon-containing compound, it can following representation：
Wherein, G is the module containing silicone hydroxyl and/or silicone hydroxyl presoma；N be module G number, n >=1；J is single Substituted radical on module G, or the linking group between two or more module G；Q be group J number, q >=1.
The described module G containing silicone hydroxyl, it can be selected from following any or several structures：
Wherein, K3、K4、K5、K6、K7For the group being joined directly together with silicon atom, it is each independently selected from following any Structure：The small molecule alkyl of hydrogen atom, heteroatom group, molecular weight no more than 1000Da, molecular weight are more than 1000Da polymerization The inorganic molecules chain residue of thing chain residue, molecular weight no more than 1000Da, molecular weight are more than 1000Da inorganic macromolecular chain Residue；Wherein, the cyclic structure in C7, C8, C9 is the nonaro-maticity containing at least one silicone hydroxyl or armaticity sila ring group Group, silicon atom is placed in cyclic structure, and cyclic structure can be small molecule ring or macromolecular ring, and it is preferably 3~ 100 yuan of rings, more preferably 3~50 yuan of rings, more preferably 3~10 yuan of rings；The ring member nitrogen atoms of cyclic structure in C7, C8, C9 are each From independently being carbon atom, silicon atom or other hetero atoms, and at least one ring member nitrogen atoms are silicon atom and form silicone hydroxyl, and At least one ring member nitrogen atoms are connected with group J；The hydrogen atom on each ring member nitrogen atoms of cyclic structure in C7, C8, C9 can be by Substitution, can not also be substituted；Cyclic structure in C7, C8, C9 can be single ring architecture, multiring structure, spirane structure, condensed ring Structure, caged scaffold, nested ring structure；Represent the connection with group J.
The described module G containing silicone hydroxyl presoma, it can be selected from following any or several structures：
Wherein, K8、K9、K10、K11、K12For the group being joined directly together with silicon atom, it is each independently selected from following any Kind structure：The small molecule alkyl of hydrogen atom, heteroatom group, molecular weight no more than 1000Da, molecular weight are poly- more than 1000Da The inorganic molecules chain residue of compound chain residue, molecular weight no more than 1000Da, molecular weight are more than 1000Da inorganic macromolecular Chain residue；X1、X2、X3、X4、X5、X6、X7、X8、X9、X10、X11、X12、X13、X14For the hydrolyzable base being joined directly together with silicon atom Group, include but are not limited to halogen, cyano group, oxygen cyano group, thiocyanogen, alkoxy, amino, sulfate group, boric acid ester group, acyl group, Acyloxy, acylamino-, ketoxime base, alkoxide group, preferably halogen, alkoxy；Wherein, the cyclic structure in D7, D8, D9 is containing extremely The nonaro-maticity or armaticity sila cyclic group, silicon atom of a few silicone hydroxyl presoma are placed in cyclic structure, cyclic structure Can be small molecule ring or macromolecular ring, it is preferably 3~100 yuan of rings, more preferably 3~50 yuan of rings, more preferably 3~10 yuan of rings；The ring member nitrogen atoms of cyclic structure in D7, D8, D9 are each independently carbon atom, silicon atom or other miscellaneous originals Son, and at least one ring member nitrogen atoms are silicon atom and form silicone hydroxyl presoma, and at least one ring member nitrogen atoms and group J phases Even；The hydrogen atom on each ring member nitrogen atoms of cyclic structure in D7, D8, D9 can be substituted, and can not also be substituted；D7、D8、 Cyclic structure in D9 can be single ring architecture, multiring structure, spirane structure, condensed cyclic structure, caged scaffold, nested ring structure；Represent the connection with group J.In said structure, between suitable different group K, between different group X and group Can also cyclization between K and group X.
In the present invention, in the module G containing silicone hydroxyl and/or silicone hydroxyl precursor, it can connect simultaneously on a silicon atom At least one hydroxyl and at least one hydroxyl groups precursors are connect, there can also be at least one silicone hydroxyl and extremely in same module simultaneously A few silicone hydroxyl presoma.
In the present invention, when the module G containing silicone hydroxyl and/or silicone hydroxyl presoma is present in polymer, And when having two or more connections, it can be connected to not cyclic or not into the polymer chain of cluster, can also connect In side base/side chain of ring-type or cluster；When an only connection, it can be connected to any position of polymer chain Put.
As n=1, q=1,2 or 3, J are the substituted radical on individual module G；As q=2 or 3, J may be selected from together A kind of structure or a variety of different structures；Described J structures may 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 1000Da inorganic molecules chain residue, molecular weight are more than 1000Da inorganic macromolecular chain residue.
Work as n>When 1, module G may be selected from same structure or a variety of different structures, now q >=1, and J is two or more moulds Linking group between block G；As q >=2, J may be selected from same structure or a variety of different structures；Described J structures may be selected from It is any below or appoint it is several：Singly-bound, hetero atom linker, molecular weight are no more than 1000Da divalence or multivalence small molecule hydrocarbon Base, molecular weight more than 1000Da divalence or multivalence polymer chain residue, molecular weight no more than 1000Da divalence or multivalence without Machine small molecule chain residue, molecular weight are more than 1000Da divalence or polyvalent mineral macromolecular chain residue.
Contain organic boron acidic group and/or organic boronic ester group and silicone hydroxyl and/or silicon while described in the present invention The compound (III) of hydroxyl precursor, it can following representation：
Wherein, A is the module containing organic boron acidic group and/or organic boronic ester group, and it, which is specifically defined, refers to organic boron The definition of modules A, is repeated no more here in compound (I)；X be modules A number, x >=1；As x >=2, modules A may be selected from Same structure or a variety of different structures；G is the module containing silicone hydroxyl and/or silicone hydroxyl presoma, and it, which is specifically defined, to join The definition of module G in silicon-containing compound (II) is examined, is repeated no more here；Y be module G number, y >=1；As y >=2, module G It may be selected from same structure or a variety of different structures；T between two or more A or between two or more G or A with Linking group between G, described T structures may be selected from following any or appoint several：Singly-bound, hetero atom linker, molecular weight Divalence or multivalence small molecule alkyl, molecular weight no more than 1000Da are more than 1000Da divalence or multivalence polymer chain residue；v For group T number, v >=1；As v >=2, T may be selected from same structure or a variety of different structures.
In organoboron compound (I), silicon-containing compound (II), compound (III), except containing organic boron acidic group and/ Or outside organic boronic ester group, silicone hydroxyl and/or silicone hydroxyl presoma, it is also an option that property contain other reactive groups.
The 5th kind of the present invention prepares embodiment, at least contains at least one organic boronic silicon by one or more The compound of ester bond and at least one other reactive group (IV) is anti-by the polymerized/cross-linked between other reactive groups Described dynamic aggregation thing should be obtained；Or at least by one or more containing at least one organic boronic estersil key and The compound (IV) of at least one other reactive group is not with containing organic boronic estersil key but containing at least one other anti- The compound of answering property group obtains described dynamic aggregation thing by the polymerized/cross-linked reaction between other reactive groups.
For compound (IV), it is generally the monomer containing organic boronic estersil key, contains organic boronic estersil key Oligomer, the prepolymer containing organic boronic estersil key.
The compound (IV) containing organic boronic estersil key He other reactive groups described in the present invention, it can be with Following representation：
Wherein, E is the module containing organic boronic estersil key；U be module E number, u >=1；Y is on individual module E Substituted radical, or the linking group between the substituted radical on individual module E and two or more module E, and at least one Individual group Y is connected with the boron atom of organic boronic estersil key, at least one group Y and organic boronic estersil key silicon atom phase Even；Wherein, at least one other reactive group is contained at least one group Y, and contain in all group Y its He is more than or equal to 2 by reactive group number；R be group Y number, r >=2.
The described module E containing organic boronic estersil key, it can following representation：
Wherein, K13、K16、K20For the group being joined directly together with boron 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 1000Da polymer Chain residue；K14、K15、K17、K18、K19、K21For the group being joined directly together with silicon atom, it is each independently selected from following any Structure：The small molecule alkyl of hydrogen atom, heteroatom group, molecular weight no more than 1000Da, molecular weight are more than 1000Da polymerization The inorganic molecules chain residue of thing chain residue, molecular weight no more than 1000Da, molecular weight are more than 1000Da inorganic macromolecular chain Residue；Represent the connection with group Y.In said structure, between suitable different group K, between different group Y with And can also cyclization between group K and group Y；Group Y can be connected by Si-O keys with boron atom, can also pass through B-O keys and silicon Atom is connected.
As u=1, r=2,3,4 or 5, Y are the substituted radical on individual module E, and Y may be selected from same structure or a variety of Different structure, and the quantity of other reactive groups that contains of Y and structure must assure that can obtain described dynamic aggregation Thing；Described Y structure may be selected from following any or appoint several：Molecular weight is no more than 1000Da small molecule alkyl, molecular weight Polymer chain residue more than 1000Da.
Work as u>When 1, module E may be selected from same structure or a variety of different structures, now r >=2, and Y is on individual module E Linking group between substituted radical and two or more module E, Y may be selected from same structure or a variety of different structures, and Y The quantity and structure of other reactive groups contained, which must assure that, can obtain described dynamic aggregation thing；Described Y structure It may be selected from any of small molecule alkyl of the molecular weight no more than 1000Da, the polymer chain residue of molecular weight more than 1000Da Or the divalence or multivalence small molecule alkyl, molecular weight for appointing several and singly-bound, hetero atom linker, molecular weight to be no more than 1000Da Any of divalence or multivalence polymer chain residue more than 1000Da are appointed several.
It is connected as the group Y that the boron atom with organic boronic estersil key is connected and with the silicon atom of organic boronic estersil key When cyclic structure is formed between group Y, then compound (IV) of the organic boronic estersil key mapping in cyclic structure is can obtain, now Under suitable conditions, react, obtain using the dynamic of organic boronic estersil key and the polymerized/cross-linked of other reactive groups Obtain described dynamic crosslinking polymer.
Dynamic aggregation thing in the present invention is not limited only to be prepared using above-mentioned embodiment.In every case in embodiments As raw material prepare dynamically using organoboron compound (I), silicon-containing compound (II), compound (III), compound (IV) Polymer, no matter it is in the form of raw material, or in the form of the compound of synthesis material, also either with synthetic polymer Intermediate product form, by it can be drawn according to the guidance of the present invention, patent protection of the invention ought to be included in In the range of.
In summary, described dynamic aggregation thing can be obtained as raw material at least with following one or more of compounds：
Organoboron compound (I) containing organic boron acidic group and/or organic boronic ester group；Contain silicone hydroxyl and/or silicon hydroxyl The silicon-containing compound (II) of base precursor；Contain organic boron acidic group and/or organic boronic ester group and silicone hydroxyl and/or silicon simultaneously The compound (III) of hydroxyl precursor；Compound (IV) containing organic boronic estersil key He other reactive groups；Wherein, Organoboron compound (I), silicon-containing compound (II), compound (III) contain at least one functional group；Wherein, organoboration Compound (I), silicon-containing compound (II), compound (III) can contain, and can be free of has other reactive groups；Wherein, organic boron Compound (I) or silicon-containing compound (II) do not prepare described dynamic aggregation thing separately as raw material.
Organoboron compound (I) and/or compound (III) by organic boron acidic group and/or organic boronic ester group with it is siliceous In compound (II) and/or compound (III) silicone hydroxyl (including can by conversion obtain the silicone hydroxyl forerunner of silicone hydroxyl Body) condensation reaction or ester exchange reaction formation organic boronic estersil key are carried out, obtain dynamic aggregation thing.In addition, organic boron chemical combination Thing (I), silicon-containing compound (II), that compound (III) also may optionally utilize other reactive groups is anti-by polymerized/cross-linked Should be commonly covalently attached, so as to organic boron acidic group and/or organic boronic ester group and silicone hydroxyl and/or silicone hydroxyl precursor Together, common reaction obtains dynamic aggregation thing.
For the compound (IV) containing organic boronic estersil key, it is generally by contained its in compound (IV) Reacting to each other between his reactive group, or by other reactive groups contained in compound (IV) with other not Reacting to each other between other contained reactive groups in compound containing organic boronic estersil key, so as to be contained The dynamic aggregation thing of organic boronic estersil key.
In the preparation process of dynamic aggregation thing, some addible auxiliary agents can also be added, filler is blended to be total to With composition dynamic aggregation thing, but these additives it is not necessary to.
Described dynamic aggregation physical performance is adjustable on a large scale, can be applied to every field, has broad application prospects, Military aerospace equipment, functional paint and coating, biological medicine, bio-medical material, the energy, building, bionical, intellectual material etc. are led Domain, all embody 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 sheet material, self-repairability binding agent, The products such as toughness material, toy.
Compared with prior art, the invention has the advantages that：
(1) in the present invention dynamic aggregation thing structure-rich, performance is various.By using containing organic boron acidic group and/or The organoboron compound (I) of organic boronic ester group, the siliceous compound (II) containing silicone hydroxyl and/or silicone hydroxyl presoma, simultaneously Containing organic boron acidic group and/or organic boronic ester group and the compound of silicone hydroxyl and/or silicone hydroxyl presoma (III) and contain The compound (IV) of organic boronic estersil key carries out formula combination as reaction raw materials and prepares dynamic aggregation thing so that reaction raw materials The advantage of structure diversity finds full expression possessed by itself.In the present invention, by adjusting the official in starting compound Number, molecular structure, molecular weight can be rolled into a ball and/or the group with reactivity is introduced in starting compound, promotes the base of dynamic Group, there is the parameter such as functional group and/or adjustment raw material composition, the dynamic aggregation thing with different structure can be prepared, So that dynamic aggregation object reveals abundant different performance.The use of the organoboron compound, is advantageous in dynamic aggregation Homogeneous reaction is carried out in the preparation process of thing, improves reaction efficiency during the course of the reaction, also improve product uniformity and Hydrolytic stability.And some as the inorganic boric acid estersil key obtained by inorganic compounds of boron often due to structure is single, functional group Number is fixed, and what inorganic compounds of boron typically carried out is out-phase reaction, and obtained product easily absorbs water hydrolysis and failed, therefore nothing Method reaches corresponding effect.
(2) dynamic response of dynamic aggregation thing is strong, dynamic response mild condition.It is covalent compared to other existing dynamics System, the present invention take full advantage of organic boronic estersil key with good heat endurance and high dynamic invertibity, can be Synthesis and dynamic reversibility without catalyst, without realizing dynamic aggregation thing under conditions of high temperature, illumination or specific pH, are being carried While high preparation efficiency, the limitation of use environment is also reduced, extends the application of polymer.In addition, pass through Other conditions (such as adding auxiliary agent, adjustment reaction temperature) are optionally controlled, can be accelerated or quench under appropriate environment Dynamic of going out covalent chemical balances, and is at required state, this is in existing supramolecular chemistry and dynamic covalent systems Face is more difficult to accomplish.
(3) dynamic reversibility of organic boronic estersil key can also be by adjusting the knot of organic boronic estersil key adjacent group The structure of structure and polymer chain is regulated and controled.Compared to common covalent bond and existing common dynamic covalent bond, organic boronic silicon Ester bond preferably can occur reversible fracture as regulatable " can sacrifice key " in stress and consume big energy so that should Power focuses primarily upon to be dissipated at organic boronic estersil key, plays energy-absorbing function, and excellent increasing is played in specific structure Tough effect；Compared to existing supermolecule interaction force, the covalent bond essence of organic boronic estersil key causes again in the present invention Energy needed for fracture is higher, so as to the energy absorption characteristics and toughness of more energy that dissipate, preferably lifting material；With nothing Machine boric acid estersil key is compared, and it has the bigger regulation and control free degree again.
Embodiment
The present invention relates to a kind of dynamic aggregation thing with dynamic crosslinking structure, its polymer chain skeleton in cross-linked network Contain organic boronic estersil key on cross linked chain synthetism frame between upper and/or polymer chain.Wherein, described organic boronic estersil Key exists as polymerization linking point and/or the crosslinking linking point of dynamic aggregation thing, forms/maintain dynamic aggregation thing structure Necessary condition；For the organic boronic estersil key contained in dynamic aggregation thing once dissociating, polymeric system is decomposed into following A kind of or several units：Monomer, polymer chain fragment, straight chain polymer unit, non-cross-linked polymer unit, polymer cluster Unit etc.；Meanwhile it can be realized between dynamic aggregation thing and said units by the bonding and dissociation of organic boronic estersil key mutual Conversion and dynamic reversible.
Described dynamic aggregation thing, it can contain organic boronic estersil only on the polymer chain skeleton of cross-linked network Key, contain organic boronic estersil key on cross linked chain synthetism frame that can be only between the polymer chain of cross-linked network, can also be same When cross linked chain synthetism frame on the polymer chain skeleton of cross-linked network between polymer chain on contain organic boronic estersil key.
The organic boronic estersil key contained in described cross-linked network, it has following structure：
Wherein, a boric acid estersil key (B-O-Si) is at least formed between boron atom and silicon atom；In the structure at least There is a carbon atom to be connected by boron carbon key with boron atom, and at least one organic group passes through the boron carbon key connection to boron On atom；Represent the connection with polymer chain, the group that crosslinking links or other are any appropriate, boron atom and silicon atom Pass through at least one connection access cross-linked network respectively.
Described dynamic aggregation thing, it has cross-linked structure.Described " cross-linked structure ", refer to that dynamic aggregation thing has Three-dimensional infinite networks, it is generally by least one containing three or more than three functions that can participate in cross-linking reaction The components such as the monomer or prepolymer of group/reactive group participate in homopolymerization, copolymerization forms, or passes through polymerization linearly or nonlinearly The cross-linking reaction of thing interchain is formed.In cross-linked network, described polymer chain skeleton be present in it is any in cross-linked network Segment；Crosslinking link between polymer chain can be an atom, a singly-bound, a group, a segment, a cluster Deng, therefore the cross linked chain synthetism frame between polymer chain can also be considered as polymer chain skeleton.In the present invention, due to being crosslinked Contain organic boronic estersil key on cross linked chain synthetism frame on the polymer chain skeleton of network and/or between polymer chain, and The disintegration and reconstruction of polymer network structure, therefore dynamic aggregation can be realized by the dissociation and bonding of organic boronic estersil key Thing tool has plenty of " dynamic crosslinking structure ".
In embodiments of the present invention, described organic boronic estersil key is by organic boron acidic group and/or organic boric acid ester Base forms with silicone hydroxyl and/or the reaction of silicone hydroxyl precursor.Wherein it is possible to using any appropriate organic boron acidic group and/or have Machine boric acid ester group is combined with silicone hydroxyl and/or silicone hydroxyl precursor to form organic boronic estersil key, it is preferred to use organic boronic Base forms organic boronic estersil key with silicone hydroxyl, organic boron acidic group and silicone hydroxyl precursor, organic boronic ester group and silicone hydroxyl, Organic boronic estersil key is more preferably formed using organic boron acidic group and silicone hydroxyl, organic boronic ester group and silicone hydroxyl, more preferably Organic boronic estersil key is formed using organic boronic ester group and silicone hydroxyl.
Heretofore described organic boron acidic group, it is referred to by boron atom and a hydroxyl being connected 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 passes through in the boron carbon key connection to boron atom.In the present invention, a hydroxyl in organic boron acidic group (- OH) it is a functional group.
Described 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, it 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 passes through in the boron carbon key connection to boron atom. In the present invention, an ester group (- OR) in organic boronic ester group is a functional group.
Heretofore described silicone hydroxyl, it is referred to by silicon atom and a hydroxyl institute group being connected with the silicon atom Into structural motif (Si-OH), wherein, silicone hydroxyl can be organic silicone hydroxyl (silicon atom i.e. in silicone hydroxyl at least with a carbon Atom is connected by silicon-carbon bonds, and at least one organic group is connected on silicon atom by the silicon-carbon bonds), or nothing Machine silicone hydroxyl (silicon atom i.e. in silicone hydroxyl is not connected with organic group), preferably organic silicone hydroxyl.In the present invention, silicon A hydroxyl (- OH) in hydroxyl is a functional group.
Heretofore described silicone hydroxyl presoma, it is referred to can by silicon atom and be connected with the silicon atom one Hydrolysis obtains the structural motif (Si-X) that the group of hydroxyl is formed, wherein, X is that hydrolyzable obtains the group of hydroxyl, and its is optional From halogen, cyano group, oxygen cyano group, thiocyanogen, alkoxy, amino, sulfate group, boric acid ester group, acyl group, acyloxy, acylamino-, ketone Oximido, alkoxide group.Suitable silicone hydroxyl presoma citing is such as：Si-Cl, Si-CN, Si-CNS, Si-CNO, Si-SO4CH3, Si-OB (OCH3)2, Si-NH2, Si-N (CH3)2, Si-OCH3, Si-COCH3, Si-OCOCH3, Si-CONH2, Si-O-N=C (CH3)2, Si- ONa.In the present invention, the group (- X) that a hydrolyzable in silicone hydroxyl presoma obtains hydroxyl is a functional group.
Functional group described in the present invention, in the case where no other specialize, refer to above-described Hydroxyl in organic boron acidic group or the hydroxyl in ester group or silicone hydroxyl in organic boronic ester group or silicone hydroxyl forerunner Hydrolyzable in body obtains the group or combinations thereof of hydroxyl.
In the present invention, organic boron acidic group and organic boronic ester group may reside in identical compound, can also deposit In different compounds；Silicone hydroxyl and silicone hydroxyl precursor are generally present in different compounds, but when it can be total to There may also be in same compound when depositing；When organic boron acidic group and/or organic boronic ester group can be with silicone hydroxyl and/or silicon When hydroxyl precursor coexists, there may also be in identical compound.In the present invention, containing organic boron acidic group and/or have The machine boric acid ester group but compound for not containing silicone hydroxyl and/or silicone hydroxyl precursor is heretofore described organic boron chemical combination Thing (I), it can be big point of micromolecular compound of the molecular weight no more than 1000Da or molecular weight more than 1000Da Sub- compound；Compound containing silicone hydroxyl and/or silicone hydroxyl presoma but without organic boronate and/or organic boronic ester group As heretofore described silicon-containing compound (II), it can be the micromolecular compound that molecular weight is no more than 1000Da, It can be the macromolecular compound that molecular weight is more than 1000Da；Contain organic boronate and/or organic boronic ester group and silicon hydroxyl simultaneously The compound of base and/or silicone hydroxyl presoma is heretofore described compound (III), and it can be that molecular weight is no more than 1000Da micromolecular compound or molecular weight is more than 1000Da macromolecular compound.
The organoboron compound (I) containing organic boron acidic group and/or organic boronic ester group described in the present invention, it can With following representation：
Wherein, A is the module containing organic boron acidic group and/or organic boronic ester group；M be modules A number, m >=1；L is Substituted radical on individual module A, or the linking group between two or more modules As；P be group L number, p >= 1。
The described modules A containing organic boron acidic group, it may be selected from following any or appoints several structures：
Wherein, K1For the group being joined directly together with boron atom, it is selected from following any structure：Hydrogen atom, hetero atom base The small molecule alkyl of group, molecular weight no more than 1000Da, molecular weight are more than 1000Da polymer chain residue；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 ring-type knot In structure, cyclic structure can be small molecule ring or macromolecular ring, and it is preferably 3~100 yuan of rings, more preferably 3~50 Yuan of rings, more preferably 3~10 yuan of 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 form 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 Group L connection；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 passes through in the boron carbon key connection to boron atom.
Wherein, the cyclic structure in A4 may 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：
The described modules A containing organic boronic ester group, it may be selected from following any or appoints several structures：
Wherein, K2For the group being joined directly together with boron atom, it is selected from following any structure：Hydrogen atom, hetero atom base The small molecule alkyl of group, molecular weight no more than 1000Da, molecular weight are more than 1000Da polymer chain residue；R1、R2、R3、R4、R6 For the monovalent organic group or monovalence organosilicon radical being joined directly together with oxygen atom, it passes through carbon atom or silicon atom and oxygen atom It is joined directly together, it is selected from following any structure：Small molecule alkyl, molecular weight of the molecular weight no more than 1000Da are no more than 1000Da small molecule silylation, molecular weight are more than 1000Da polymer chain residue；R5To be joined directly together with two oxygen atoms Divalent organic group or divalence organosilicon radical, it is joined directly together by carbon atom or silicon atom with oxygen atom, its be selected from Under any structure：Divalence small molecule alkyl of the molecular weight no more than 1000Da, molecular weight are no more than 1000Da small point of divalence Sub- silylation, molecular weight are more than 1000Da diatomic polymer chain residue；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 or macromolecular ring, it is preferably 3~100 yuan of rings, more preferably 3~50 yuan of rings, more preferably 3~10 Yuan of rings；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 form organic boronic ester group, and at least one ring member nitrogen atoms are connected with group L；Ring-type 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 monocyclic knot Structure, multiring structure, spirane structure, condensed cyclic structure, caged scaffold, nested ring structure；Represent 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 key connection is in boron atom.
Wherein, the cyclic structure in B5 may 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：
, can be same in a boron atom in the modules A containing organic boron acidic group and/or organic boronic ester group in the present invention When connect a hydroxyl and an ester group, can also contain at least one boron hydroxyl and at least one boron simultaneously in same module Perester radical, citing is such as：
Compound helps to regulate and control its dissolubility, reaction rate, anti-containing organic boron acidic group and organic boronic ester group simultaneously The parameters such as degree are answered, and available for performances such as the dynamics for regulating and controlling dynamic aggregation thing.
In the present invention, when the modules A containing organic boron acidic group and/or organic boronic ester group is present in polymer In, and when having two or more connections, it can be connected to not cyclic or not into the polymer chain of cluster, can also connect It is connected in side base/side chain of ring-type or cluster；When an only connection, it can be connected to any position of polymer chain Put.
As m=1, p=1 or 2, L are the substituted radical on individual module A；As p=2, L may be selected from same knot Structure or a variety of different structures；Described L structures may 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 1000Da polymer chain residue.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, be only some more representational structures under the conditions of this, rather than the present invention is protected The restriction of scope.
Work as m>When 1, modules A may be selected from same structure or a variety of different structures, now p >=1, and L is two or more moulds Linking group between block A；As p >=2, L may be selected from same structure or a variety of different structures；Described L structures may be selected from It is any below or appoint it is several：Singly-bound, hetero atom linker, molecular weight are no more than 1000Da divalence or multivalence small molecule hydrocarbon Base, molecular weight are more than 1000Da divalence or multivalence polymer chain residue.
When L is selected from singly-bound, it may be selected from boron boron singly-bound, carbon-carbon single bond, carbon nitrogen singly-bound, nitrogen nitrogen singly-bound, boron carbon single bond, boron 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.
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, be only some more representational structures under the conditions of this, rather than the present invention is protected The restriction of scope.
When L is selected from hetero atom linker, it may be selected from following any or appoints several combinations：Ether, sulfenyl, double sulphur Base, thioether group, divalence tertiary amine groups, trivalent tertiary amine groups, divalence silicon substrate, trivalent silicon substrate, tetravalence silicon substrate, divalence phosphorus base, three valent phosphors base, Divalence boryl, trivalent boryl；Hetero atom linker is preferably ether, sulfenyl, divalence tertiary amine groups, trivalent tertiary amine groups.The conjunction of formation Suitable organoboron compound (I) structure example is as follows：
Wherein, g, h are each independently a fixed value or average value, g >=1, h >=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, be only some more representational structures under the conditions of this, rather than the present invention is protected The restriction of scope.
When L, which is selected from molecular weight, is no more than 1000Da divalence or multivalence small molecule alkyl, it typically contains 1 to 71 carbon Atom, the valence state of alkyl can be 2-144 valencys, and it can contain heteroatom group, and can be free of has heteroatom group.Generally, Described divalence or multivalence small molecule alkyl may 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 C1-71Alkyl, two to one hundred four ten tetravalence ring C3-71Alkane 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 Valency ethyl, two arrive octavalence propyl group, and two to sexavalence cyclopropane base, two arrive octavalence cyclobutyl, two to ten valency cyclopenta, two to ten divalence Cyclohexyl, two arrive sexavalence phenyl.Suitable organoboron compound (I) structure example formed is as follows：
Wherein, g, h are each independently a fixed value or average value, g >=1, h >=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, be only some more representational structures under the conditions of this, rather than the present invention is protected The restriction of scope.
When L, which is selected from molecular weight, is more than 1000Da divalence or multivalence polymer chain residue, it can be any appropriate two Valency or multivalence polymer chain residue, include but are not limited to divalence or multivalence carbochain polymer residue, divalence or multivalence heterochain gathers Compound residue, divalence 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 divalence or multivalence carbochain polymer residue, its can be any appropriate macromolecular main chain mainly by The polymer residue that carbon atom is formed, its may 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：Divalence or multivalence TPO chain residue, as divalence or multivalence Polyethylene Chain residue, Divalence or multivalence polypropylene chains residue, divalence or multivalence polyisobutene chain residue, divalence or multivalence polystyrene chain residue, divalence Or multivalence polyvinyl chloride chain residue, divalence or multivalence Vingon chain residue, divalence or multivalence polyvinyl fluoride chain residue, divalence Or multivalence polytetrafluoroethylene (PTFE) chain residue, divalence or multivalence polytrifluorochloroethylene chain residue, divalence or multivalence polyvinyl acetate chain Residue, divalence or multivalence polyvinyl alcohol chain residue, divalence or multivalence Polyvinylalkylethers chain residue, divalence or multivalence polybutadiene The poly- drop of alkene chain residue, divalence or multivalence polyisoprene chain residue, divalence or multivalence polychlorobutadiene chain residue, divalence or multivalence Bornylene chain residue etc.；Divalence or multivalence polyacrylic chain residue, such as divalence or multivalence polyacrylic acid chain residue, divalence or more Valency polyacrylamide chain residue, divalence or multivalence PMA chain residue, divalence or multivalence polymethyl methacrylate chain Residue etc.；Divalence or multivalence polypropylene nitrile chain residue, such as divalence or multivalence polyacrylonitrile chain residue.L preferred divalence or more Valency Polyethylene Chain residue, divalence or multivalence polypropylene chains residue, divalence or multivalence polystyrene chain residue, divalence or multivalence polychlorostyrene Ethylene chain residue, divalence or multivalence polybutadiene chain residue, divalence or multivalence polyisoprene chain residue, divalence or multivalence poly- third Olefin(e) acid chain residue, divalence or multivalence polyacrylamide chain residue, divalence 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。
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, be only some more representational structures under the conditions of this, rather than the present invention is protected The restriction of scope.
When L is selected from divalence or multivalence heterochain polymer residue, its can be any appropriate macromolecular main chain mainly by The polymer residue that the hetero atom such as carbon atom and nitrogen, oxygen, sulphur is formed, it may be selected from any in the following group, any insatiable hunger With form, any substituted form or any by hydridization form：Divalence or multivalence polyethers chain residue, such as divalence or Multivalence focused beam-forming residue, divalence or multivalence polyethylene oxide chain residue, divalence or multivalence PPOX chain residue, divalence or Multivalence PolyTHF chain residue, divalence or multivalence asphalt mixtures modified by epoxy resin fat chain residue, divalence or multivalence phenolic resin chain residue, divalence or Multivalence polyphenylene oxide chain residue etc.；Divalence or multivalence polyesters chain residue, such as divalence or multivalence polycaprolactone chain residue, divalence or more The poly- valerolactone chain residue of valency, divalence or multivalence polylactide chain residue, divalence or multivalence polyethylene terephthalate chain are residual Base, divalence or multivalence unsaturated polyester (UP) chain residue, divalence or multivalence alkyd resin chain residue, divalence or multivalence polycarbonate chain are residual Base etc.；Divalence or multivalence polyamine class chain residue, as divalence or multivalence polyamide chains residue, divalence or multivalence polyimides chain are residual Base, divalence or multivalence polyurethane chain residue, divalence or multivalence polyureas chain residue, divalence or multivalence Lauxite chain residue, divalence Or multivalence melamine resin chain residue etc.；Divalence or multivalence polysulfide class chain residue, such as divalence or multivalence polysulfones chain residue, divalence or more Valency polyphenylene sulfide chain residue, divalence or multivalence polysulfide rubber chain residue etc..The preferred divalence of L or multivalence focused beam-forming residue, divalence Or multivalence polyethylene oxide chain residue, divalence or multivalence PolyTHF chain residue, divalence or multivalence asphalt mixtures modified by epoxy resin fat chain residue, two Valency or multivalence polycaprolactone chain residue, divalence or multivalence polylactide chain residue, divalence or multivalence polyamide chains residue.Formed Suitable organoboron 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。
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, be only some more representational structures under the conditions of this, rather than the present invention is protected The restriction of scope.
When L is selected from divalence or element of multivalence organic polymer residue, it can be any appropriate macromolecular main chain master The polymer residue to be made up of the hetero atom such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus, its may be selected from Any in the following group, any unsaturated form, any substituted form or any by hydridization form：Divalence or Multivalence silicone-based polymers chain residue, such as divalence or multivalence poly-organosilicon alkane chain residue, divalence or multivalence polysiloxane Chain residue, divalence or multivalence poly-organosilicon borine chain residue, divalence or multivalence poly-organosilicon azane chain residue, divalence or multivalence are gathered Organic silithiane chain residue, divalence or the poly- organophosphor siloxane chain residue of multivalence, divalence or the poly- organic metal siloxane chain of multivalence Residue；Divalence or multivalence organic boron are birdsed of the same feather flock together compound chain residue, as divalence or multivalence poly- organo-borane chain residue, divalence or multivalence are gathered Organic boroxane chain residue, divalence or the poly- organic boron azane chain residue of multivalence, divalence or the poly- organic boron sulfane chain residue of multivalence, two Valency or the poly- organic boron phosphine chain residue of multivalence etc.；Divalence or multivalence organic phosphates polymer chain residue；Divalence or multivalence Organic leadP Birds of the same feather flock together compound chain residue；Divalence or multivalence organic tin polymer chain residue；Divalence or multivalence organo-arsenic are birdsed of the same feather flock together compound chain residue； Divalence or multivalence antimony organic are birdsed of the same feather flock together compound chain residue.The preferred divalence of L or multivalence poly-organosilicon alkane chain residue, divalence or multivalence are poly- to be had Organic siloxane chain residue, divalence or the poly- organo-borane chain residue of multivalence.Suitable organoboron compound (I) structure example formed It 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 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, be only some more representational structures under the conditions of this, rather than the present invention is protected The restriction of scope.
The silicon-containing compound (II) containing silicone hydroxyl and/or silicone hydroxyl precursor described in the present invention, it can be to have Machine silicon-containing compound, or be inorganic silicon-containing compound, it can following representation：
Wherein, G is the module containing silicone hydroxyl and/or silicone hydroxyl presoma；N be module G number, n >=1；J is single Substituted radical on module G, or the linking group between two or more module G；Q be group J number, q >=1.
The described module G containing silicone hydroxyl, it can be selected from following any or several structures：
Wherein, K3、K4、K5、K6、K7For the group being joined directly together with silicon atom, it is each independently selected from following any Structure：The small molecule alkyl of hydrogen atom, heteroatom group, molecular weight no more than 1000Da, molecular weight are more than 1000Da polymerization The inorganic molecules chain residue of thing chain residue, molecular weight no more than 1000Da, molecular weight are more than 1000Da inorganic macromolecular chain Residue；Wherein, the cyclic structure in C7, C8, C9 is the nonaro-maticity containing at least one silicone hydroxyl or armaticity sila ring group Group, silicon atom is placed in cyclic structure, and cyclic structure can be small molecule ring or macromolecular ring, and it is preferably 3~ 100 yuan of rings, more preferably 3~50 yuan of rings, more preferably 3~10 yuan of rings；The ring member nitrogen atoms of cyclic structure in C7, C8, C9 are each From independently being carbon atom, silicon atom or other hetero atoms, and at least one ring member nitrogen atoms are silicon atom and form silicone hydroxyl, and At least one ring member nitrogen atoms are connected with group J；The hydrogen atom on each ring member nitrogen atoms of cyclic structure in C7, C8, C9 can be by Substitution, can not also be substituted；Cyclic structure in C7, C8, C9 can be single ring architecture, multiring structure, spirane structure, condensed ring Structure, caged scaffold, nested ring structure；Represent the connection with group J.
Wherein, the cyclic structure in C7, C8, C9 may be selected from by it is any in the following group, any it is unsaturated in the form of, it is any The substituted form or any by hydridization form of kind：Sila cycloalkanes, sila cyclic hydrocarbon, cyclosiloxane, cyclosilazane, ring silicon sulphur Alkane, ring silicon phosphine, ring silicon borine, sila benzene, sila naphthalene, sila anthracene, sila are luxuriant and rich with fragrance, sila aromatic hydrocarbons；Listed cyclic structure is preferred Silacyclopentan, Silinane, sila cyclohexene, silacyclohexadiene, sila cyclonene, sila benzene, cyclotrisiloxane, Cyclotetrasiloxane, the siloxanes of ring six, the silazane of ring three, cyclotetrasilazane, the silazane of ring six.Citing is such as：
The described module G containing silicone hydroxyl presoma, it can be selected from following any or several structures：
Wherein, K8、K9、K10、K11、K12For the group being joined directly together with silicon atom, it is each independently selected from following any Kind structure：The small molecule alkyl of hydrogen atom, heteroatom group, molecular weight no more than 1000Da, molecular weight are poly- more than 1000Da The inorganic molecules chain residue of compound chain residue, molecular weight no more than 1000Da, molecular weight are more than 1000Da inorganic macromolecular Chain residue；X1、X2、X3、X4、X5、X6、X7、X8、X9、X10、X11、X12、X13、X14For the hydrolyzable base being joined directly together with silicon atom Group, include but are not limited to halogen, cyano group, oxygen cyano group, thiocyanogen, alkoxy, amino, sulfate group, boric acid ester group, acyl group, Acyloxy, acylamino-, ketoxime base, alkoxide group, preferably halogen, alkoxy；Wherein, the cyclic structure in D7, D8, D9 is containing extremely The nonaro-maticity or armaticity sila cyclic group, silicon atom of a few silicone hydroxyl presoma are placed in cyclic structure, cyclic structure Can be small molecule ring or macromolecular ring, it is preferably 3~100 yuan of rings, more preferably 3~50 yuan of rings, more preferably 3~10 yuan of rings；The ring member nitrogen atoms of cyclic structure in D7, D8, D9 are each independently carbon atom, silicon atom or other miscellaneous originals Son, and at least one ring member nitrogen atoms are silicon atom and form silicone hydroxyl presoma, and at least one ring member nitrogen atoms and group J phases Even；The hydrogen atom on each ring member nitrogen atoms of cyclic structure in D7, D8, D9 can be substituted, and can not also be substituted；D7、D8、 Cyclic structure in D9 can be single ring architecture, multiring structure, spirane structure, condensed cyclic structure, caged scaffold, nested ring structure；Represent the connection with group J.It is pointed out that in said structure, between suitable different group K, different groups Can also cyclization between X and between group K and group X.
Wherein, the cyclic structure in D7, D8, D9 may be selected from by it is any in the following group, any it is unsaturated in the form of, it is any The substituted form or any by hydridization form of kind：Sila cycloalkanes, sila cyclic hydrocarbon, cyclosiloxane, cyclosilazane, ring silicon sulphur Alkane, ring silicon phosphine, ring silicon borine, sila benzene, sila naphthalene, sila anthracene, sila are luxuriant and rich with fragrance, sila aromatic hydrocarbons；Listed cyclic structure is preferred Silacyclopentan, Silinane, sila cyclohexene, silacyclohexadiene, sila cyclonene, sila benzene, cyclotrisiloxane, Cyclotetrasiloxane, the siloxanes of ring six, the silazane of ring three, cyclotetrasilazane, the silazane of ring six.Citing is such as：
In the present invention, in the module G containing silicone hydroxyl and/or silicone hydroxyl precursor, it can connect simultaneously on a silicon atom Connect at least one hydroxyl and at least one hydroxyl groups precursors, in same module can also simultaneously containing at least one silicone hydroxyl and At least one silicone hydroxyl presoma.Citing is such as：
Compound helps to regulate and control its dissolubility, reaction rate, reaction interval containing silicone hydroxyl and silicone hydroxyl presoma simultaneously The parameters such as degree,
And the performance such as dynamic available for regulation and control dynamic aggregation thing.
In the present invention, when the module G containing silicone hydroxyl and/or silicone hydroxyl presoma is present in polymer, And when having two or more connections, it can be connected to not cyclic or not into the polymer chain of cluster, can also connect In side base/side chain of ring-type or cluster；When an only connection, it can be connected to any position of polymer chain Put.
As n=1, q=1,2 or 3, J are the substituted radical on individual module G；As q=2 or 3, J may be selected from together A kind of structure or a variety of different structures；Described J structures may 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 1000Da inorganic molecules chain residue, molecular weight are more than 1000Da inorganic macromolecular chain residue.What is formed is suitable siliceous Compound (II) structure example is as follows：
Wherein, g, h, j are each independently a fixed value or average value, g >=1, h >=1, j >=1.
The structure of the silicon-containing compound (II) of the example above is only that silicon-containing compound (II) is better described on this condition Possessed typical structure and propose, be only this under the conditions of some more representational structures, rather than to the present invention protect model The restriction enclosed.
Work as n>When 1, module G may be selected from same structure or a variety of different structures, now q >=1, and J is two or more moulds Linking group between block G；As q >=2, J may be selected from same structure or a variety of different structures；Described J structures may be selected from It is any below or appoint it is several：Singly-bound, hetero atom linker, molecular weight are no more than 1000Da divalence or multivalence small molecule hydrocarbon Base, molecular weight more than 1000Da divalence or multivalence polymer chain residue, molecular weight no more than 1000Da divalence or multivalence without Machine small molecule chain residue, molecular weight are more than 1000Da divalence or polyvalent mineral macromolecular chain residue.
When J is selected from singly-bound, it may be selected from silicon silicon singly-bound, carbon-carbon single bond, carbon nitrogen singly-bound, nitrogen nitrogen singly-bound, silicon-carbon singly-bound, silicon Nitrogen singly-bound；It is preferred that silicon silicon singly-bound, carbon-carbon single bond, silicon-carbon singly-bound.Suitable silicon-containing compound (II) structure example formed is as follows：
Wherein, g, h be each independently a fixed value or Average value, g >=1, h >=1.
The structure of the silicon-containing compound (II) of the example above is only that silicon-containing compound (II) is better described on this condition Possessed typical structure and propose, be only this under the conditions of some more representational structures, rather than to the present invention protect model The restriction enclosed.
When J is selected from hetero atom linker, it may be selected from following any or appoints several combinations：Ether, sulfenyl, double sulphur Base, thioether group, divalence tertiary amine groups, trivalent tertiary amine groups, divalence silicon substrate, trivalent silicon substrate, tetravalence silicon substrate, divalence phosphorus base, three valent phosphors base, Divalence boryl, trivalent boryl；Hetero atom linker is preferably ether, sulfenyl, divalence tertiary amine groups, trivalent tertiary amine groups.The conjunction of formation Suitable silicon-containing compound (II) structure example is as follows：
Wherein, g, h are each independently a fixed value or average value, g >=1, h >=1.
The structure of the silicon-containing compound (II) of the example above is only that silicon-containing compound (II) is better described on this condition Possessed typical structure and propose, be only this under the conditions of some more representational structures, rather than to the present invention protect model The restriction enclosed.
When J, which is selected from molecular weight, is no more than 1000Da divalence or multivalence small molecule alkyl, it typically contains 1 to 71 carbon Atom, the valence state of alkyl can be 2-144 valencys, and it can contain heteroatom group, and can be free of has heteroatom group.Generally, Described divalence or multivalence small molecule alkyl may 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 C1-71Alkyl, two to one hundred four ten tetravalence ring C3-71Alkane Base, two to sexavalence phenyl, two to octavalence benzyl, two to one hundred four ten tetravalence aryl；J preferably two arrives tetravalence methyl, two to six Valency ethyl, two arrive octavalence propyl group, and two to sexavalence cyclopropane base, two arrive octavalence cyclobutyl, two to ten valency cyclopenta, two to ten divalence Cyclohexyl, two arrive sexavalence phenyl.Suitable silicon-containing compound (II) structure example formed is as follows：
Wherein, g, h are each independently a fixed value or average value, g >=1, h >=1.
The structure of the silicon-containing compound (II) of the example above is only that silicon-containing compound (II) is better described on this condition Possessed typical structure and propose, be only this under the conditions of some more representational structures, rather than to the present invention protect model The restriction enclosed.
When J, which is selected from molecular weight, is more than 1000Da divalence or multivalence polymer chain residue, it can be any appropriate two Valency or multivalence polymer chain residue, include but are not limited to divalence or multivalence carbochain polymer residue, divalence or multivalence heterochain gathers Compound residue, divalence 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 divalence or multivalence carbochain polymer residue, its can be any appropriate macromolecular main chain mainly by The polymer residue that carbon atom is formed, its may 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：Divalence or multivalence TPO chain residue, as divalence or multivalence Polyethylene Chain residue, Divalence or multivalence polypropylene chains residue, divalence or multivalence polyisobutene chain residue, divalence or multivalence polystyrene chain residue, divalence Or multivalence polyvinyl chloride chain residue, divalence or multivalence Vingon chain residue, divalence or multivalence polyvinyl fluoride chain residue, divalence Or multivalence polytetrafluoroethylene (PTFE) chain residue, divalence or multivalence polytrifluorochloroethylene chain residue, divalence or multivalence polyvinyl acetate chain Residue, divalence or multivalence polyvinyl alcohol chain residue, divalence or multivalence Polyvinylalkylethers chain residue, divalence or multivalence polybutadiene The poly- drop of alkene chain residue, divalence or multivalence polyisoprene chain residue, divalence or multivalence polychlorobutadiene chain residue, divalence or multivalence Bornylene chain residue etc.；Divalence or multivalence polyacrylic chain residue, such as divalence or multivalence polyacrylic acid chain residue, divalence or more Valency polyacrylamide chain residue, divalence or multivalence PMA chain residue, divalence or multivalence polymethyl methacrylate chain Residue etc.；Divalence or multivalence polypropylene nitrile chain residue, such as divalence or multivalence polyacrylonitrile chain residue.J preferred divalence or more Valency Polyethylene Chain residue, divalence or multivalence polypropylene chains residue, divalence or multivalence polystyrene chain residue, divalence or multivalence polychlorostyrene Ethylene chain residue, divalence or multivalence polybutadiene chain residue, divalence or multivalence polyisoprene chain residue, divalence or multivalence poly- third Olefin(e) acid chain residue, divalence or multivalence polyacrylamide chain residue, divalence or multivalence polyacrylonitrile chain residue.What is formed suitably contains Silicon compound (II) 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。
The structure of the silicon-containing compound (II) of the example above is only that silicon-containing compound (II) is better described on this condition Possessed typical structure and propose, be only this under the conditions of some more representational structures, rather than to the present invention protect model The restriction enclosed.
When J is selected from divalence or multivalence heterochain polymer residue, its can be any appropriate macromolecular main chain mainly by The polymer residue that the hetero atom such as carbon atom and nitrogen, oxygen, sulphur is formed, it may be selected from any in the following group, any insatiable hunger With form, any substituted form or any by hydridization form：Divalence or multivalence polyethers chain residue, such as divalence or Multivalence focused beam-forming residue, divalence or multivalence polyethylene oxide chain residue, divalence or multivalence PPOX chain residue, divalence or Multivalence PolyTHF chain residue, divalence or multivalence asphalt mixtures modified by epoxy resin fat chain residue, divalence or multivalence phenolic resin chain residue, divalence or Multivalence polyphenylene oxide chain residue etc.；Divalence or multivalence polyesters chain residue, such as divalence or multivalence polycaprolactone chain residue, divalence or more The poly- valerolactone chain residue of valency, divalence or multivalence polylactide chain residue, divalence or multivalence polyethylene terephthalate chain are residual Base, divalence or multivalence unsaturated polyester (UP) chain residue, divalence or multivalence alkyd resin chain residue, divalence or multivalence polycarbonate chain are residual Base etc.；Divalence or multivalence polyamine class chain residue, as divalence or multivalence polyamide chains residue, divalence or multivalence polyimides chain are residual Base, divalence or multivalence polyurethane chain residue, divalence or multivalence polyureas chain residue, divalence or multivalence Lauxite chain residue, divalence Or multivalence melamine resin chain residue etc.；Divalence or multivalence polysulfide class chain residue, such as divalence or multivalence polysulfones chain residue, divalence or more Valency polyphenylene sulfide chain residue, divalence or multivalence polysulfide rubber chain residue etc..The preferred divalence of J or multivalence focused beam-forming residue, divalence Or multivalence polyethylene oxide chain residue, divalence or multivalence PolyTHF chain residue, divalence or multivalence asphalt mixtures modified by epoxy resin fat chain residue, two Valency or multivalence polycaprolactone chain residue, divalence or multivalence polylactide chain residue, divalence or multivalence polyamide chains residue.Formed Suitable silicon-containing compound (II) 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。
The structure of the silicon-containing compound (II) of the example above is only that silicon-containing compound (II) is better described on this condition Possessed typical structure and propose, be only this under the conditions of some more representational structures, rather than to the present invention protect model The restriction enclosed.
When J is selected from divalence or element of multivalence organic polymer residue, it can be any appropriate macromolecular main chain master The polymer residue to be made up of the hetero atom such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus, its may be selected from Any in the following group, any unsaturated form, any substituted form or any by hydridization form：Divalence or Multivalence silicone-based polymers chain residue, such as divalence or multivalence poly-organosilicon alkane chain residue, divalence or multivalence polysiloxane Chain residue, divalence or multivalence poly-organosilicon borine chain residue, divalence or multivalence poly-organosilicon azane chain residue, divalence or multivalence are gathered Organic silithiane chain residue, divalence or the poly- organophosphor siloxane chain residue of multivalence, divalence or the poly- organic metal siloxane chain of multivalence Residue；Divalence or multivalence organic boron are birdsed of the same feather flock together compound chain residue, as divalence or multivalence poly- organo-borane chain residue, divalence or multivalence are gathered Organic boroxane chain residue, divalence or the poly- organic boron azane chain residue of multivalence, divalence or the poly- organic boron sulfane chain residue of multivalence, two Valency or the poly- organic boron phosphine chain residue of multivalence etc.；Divalence or multivalence organic phosphates polymer chain residue；Divalence or multivalence Organic leadP Birds of the same feather flock together compound chain residue；Divalence or multivalence organic tin polymer chain residue；Divalence or multivalence organo-arsenic are birdsed of the same feather flock together compound chain residue； Divalence or multivalence antimony organic are birdsed of the same feather flock together compound chain residue.The preferred divalence of J or multivalence poly-organosilicon alkane chain residue, divalence or multivalence are poly- to be had Organic siloxane chain residue, divalence or the poly- organo-borane chain residue of multivalence.Suitable silicon-containing compound (II) structure example formed It 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 structure of the silicon-containing compound (II) of the example above is only that silicon-containing compound (II) is better described on this condition Possessed typical structure and propose, be only this under the conditions of some more representational structures, rather than to the present invention protect model The restriction enclosed.
When J, which is selected from molecular weight, is no more than 1000Da divalence or polyvalent mineral small molecule chain residue, it can be any Suitable molecular backbone and side chain are mainly made up of the hetero atom such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus Inorganic molecules chain residue, generally, described divalence or polyvalent mineral small molecule chain residue may be selected to appoint in the following group A kind of, any unsaturated form, any substituted form or any by hydridization form：Divalence or multivalence chain Sulphur residue, divalence or multivalence silane chain residue, divalence or multivalence silicon oxide compound chain residue, divalence or multivalence sulphur silicon compound chain Residue, divalence or multivalence sulfur-nitrogen compound chain residue, divalence or multivalence phosphazene compound chain residue, divalence or multivalence phosphorus oxygen chemical combination Thing chain residue, divalence or multivalence borine chain residue, divalence or multivalence boron-oxygen chain residue.The preferred divalence of J or multivalence chain Sulphur residue, divalence or multivalence silane chain residue, divalence or multivalence silicon oxide compound chain residue, divalence or multivalence phosphazene compound chain Residue, divalence or multivalence borine chain residue.Suitable silicon-containing compound (II) structure example formed is as follows：
Wherein, g, h are each independently a fixed value or average value, g >=1, h >=1.
The structure of the silicon-containing compound (II) of the example above is only that silicon-containing compound (II) is better described on this condition Possessed typical structure and propose, be only this under the conditions of some more representational structures, rather than to the present invention protect model The restriction enclosed.
When J, which is selected from molecular weight, is more than 1000Da divalence or polyvalent mineral macromolecular chain residue, it can be any conjunction Suitable macromolecular main chain and side chain are mainly made up of the hetero atom such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus Inorganic macromolecular chain residue.
Wherein, J may 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：Divalence or multivalence chain sulphur polymer residue, divalence or multivalence polysilane chain residue, divalence or multivalence Polysiloxane chain residue, divalence or multivalence polysulfide silicon chain residue, divalence or multivalence polysulfide nitrogen chain residue, divalence or multivalence polyphosphoric acid Chain residue, divalence or multivalence polyphosphazene chain residue, divalence or multivalence polychlorostyrene are residual for phosphonitrile chain residue, divalence or multivalence polyborane chain Base, divalence or the poly- boroxane chain residue of multivalence.The preferred divalence of J or multivalence chain sulphur polymer residue, divalence or multivalence polysilane Chain residue, divalence or multivalence polysiloxane chain residue, divalence or multivalence polyphosphazene chain residue, divalence or multivalence polyborane chain are residual Base.Suitable silicon-containing compound (II) structure example formed is as follows：
Wherein, g, h, i are each independently a fixed value or average value, preferably g >=36, h >=36, i >=36.
The structure of the silicon-containing compound (II) of the example above is only that silicon-containing compound (II) is better described on this condition Possessed typical structure and propose, be only this under the conditions of some more representational structures, rather than to the present invention protect model The restriction enclosed.
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, carbon fiber, white phosphorus, red phosphorus, five phosphorous oxides, molybdenum sulfide, silica, silicon disulfide, silicon nitride, carborundum, cunning Stone, kaolin, montmorillonite, mica, asbestos, feldspar, cement, glass, quartz, ceramics, boron oxide, nitridation sulphur, calcium silicide, silicic acid Salt, glass fibre, beryllium oxide, magnesia, mercury oxide, boron hydride, boron nitride, boron carbide, aluminium nitride, diaspore, gibbsite, Corundum, titanium dioxide.Graphite that J is modified preferably through surface, the carbon fiber being modified by surface, the dioxy being modified by surface SiClx, by surface be modified silicon nitride, by surface be modified carborundum, by surface be modified silicate, by surface Modified glass fibre, the boron nitride being modified by surface.The suitable silicon-containing compound (II) formed is generally inorganic structure, Citing is such as：Silicon nitride of the surface with silicone hydroxyl, carborundum of the surface with silicone hydroxyl, titanium dioxide of the surface with silicone hydroxyl The silicate of silicon, surface with silicone hydroxyl, surface carry the glass fibre of silicone hydroxyl.
Contain organic boron acidic group and/or organic boronic ester group and silicone hydroxyl and/or silicon while described in the present invention The compound (III) of hydroxyl precursor, it can following representation：
Wherein, A is the module containing organic boron acidic group and/or organic boronic ester group, and it, which is specifically defined, refers to organic boron The definition of modules A, is repeated no more here in compound (I), wherein, A is preferably the module containing organic boronic ester group；X is mould Block A number, x >=1；As x >=2, modules A may be selected from same structure or a variety of different structures；G be containing silicone hydroxyl and/ Or the module of silicone hydroxyl presoma, it is specifically defined the definition for referring to module G in silicon-containing compound (II), no longer superfluous here State, wherein, G is preferably the module containing silicone hydroxyl presoma；Y be module G number, y >=1；As y >=2, module G is optional From same structure or a variety of different structures；T between two or more A or between two or more G or A and G it Between linking group, described T structures may be selected from it is following any or appoint it is several：Singly-bound, hetero atom linker, molecular weight do not surpass Cross 1000Da divalence or multivalence small molecule alkyl, molecular weight are more than 1000Da divalence or multivalence polymer chain residue；V is base Group T number, v >=1；As v >=2, T may be selected from same structure or a variety of different structures.
When T is selected from singly-bound, it may be selected from carbon-carbon single bond, carbon nitrogen singly-bound, nitrogen nitrogen singly-bound, boron carbon single bond, boron nitrogen singly-bound, boron Silicon singly-bound, silicon silicon singly-bound, silicon-carbon singly-bound, silicon nitrogen singly-bound；Preferably carbon-carbon single bond, silicon silicon singly-bound, borosilicate singly-bound.What is formed is suitable Compound (III) structure example it is as follows：
Wherein, g, h are each independently a fixed value or average value, g >=1, h >=1.
The structure of the compound (III) of the example above is only that compound (III) is better described on this condition to be had Typical structure and propose, be only some more representational structures under the conditions of this, rather than the limit to the scope of the present invention It is fixed.
When T is selected from hetero atom linker, it may be selected from following any or appoints several combinations：Ether, sulfenyl, double sulphur Base, thioether group, divalence tertiary amine groups, trivalent tertiary amine groups, divalence silicon substrate, trivalent silicon substrate, tetravalence silicon substrate, divalence phosphorus base, three valent phosphors base, Divalence boryl, trivalent boryl；Hetero atom linker is preferably ether, sulfenyl, divalence tertiary amine groups, trivalent tertiary amine groups.The conjunction of formation Suitable compound (III) structure example is as follows：
Wherein, g, h are each independently a fixed value or average value, g >=1, h >=1.
The structure of the compound (III) of the example above is only that compound (III) is better described on this condition to be had Typical structure and propose, be only some more representational structures under the conditions of this, rather than the limit to the scope of the present invention It is fixed.
When T, which is selected from molecular weight, is no more than 1000Da divalence or multivalence small molecule alkyl, it typically contains 1 to 71 carbon Atom, the valence state of alkyl can be 2-144 valencys, and it can contain heteroatom group, and can be free of has heteroatom group.Generally, Described divalence or multivalence small molecule alkyl may 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 C1-71Alkyl, two to one hundred four ten tetravalence ring C3-71Alkane 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 Valency ethyl, two arrive octavalence propyl group, and two to sexavalence cyclopropane base, two arrive octavalence cyclobutyl, two to ten valency cyclopenta, two to ten divalence Cyclohexyl, two arrive sexavalence phenyl.Suitable compound (III) structure example formed is as follows：
Wherein, g, h are each independently a fixed value or average value, g >=1, h >=1.
The structure of the compound (III) of the example above is only that compound (III) is better described on this condition to be had Typical structure and propose, be only some more representational structures under the conditions of this, rather than the limit to the scope of the present invention It is fixed.
When T, which is selected from molecular weight, is more than 1000Da divalence or multivalence polymer chain residue, it can be any appropriate two Valency or multivalence polymer chain residue, include but are not limited to divalence or multivalence carbochain polymer residue, divalence or multivalence heterochain gathers Compound residue, divalence 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 divalence or multivalence carbochain polymer residue, its can be any appropriate macromolecular main chain mainly by The polymer residue that carbon atom is formed, its may 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：Divalence or multivalence TPO chain residue, as divalence or multivalence Polyethylene Chain residue, Divalence or multivalence polypropylene chains residue, divalence or multivalence polyisobutene chain residue, divalence or multivalence polystyrene chain residue, divalence Or multivalence polyvinyl chloride chain residue, divalence or multivalence Vingon chain residue, divalence or multivalence polyvinyl fluoride chain residue, divalence Or multivalence polytetrafluoroethylene (PTFE) chain residue, divalence or multivalence polytrifluorochloroethylene chain residue, divalence or multivalence polyvinyl acetate chain Residue, divalence or multivalence polyvinyl alcohol chain residue, divalence or multivalence Polyvinylalkylethers chain residue, divalence or multivalence polybutadiene The poly- drop of alkene chain residue, divalence or multivalence polyisoprene chain residue, divalence or multivalence polychlorobutadiene chain residue, divalence or multivalence Bornylene chain residue etc.；Divalence or multivalence polyacrylic chain residue, such as divalence or multivalence polyacrylic acid chain residue, divalence or more Valency polyacrylamide chain residue, divalence or multivalence PMA chain residue, divalence or multivalence polymethyl methacrylate chain Residue etc.；Divalence or multivalence polypropylene nitrile chain residue, such as divalence or multivalence polyacrylonitrile chain residue.T preferred divalence or more Valency Polyethylene Chain residue, divalence or multivalence polypropylene chains residue, divalence or multivalence polystyrene chain residue, divalence or multivalence polychlorostyrene Ethylene chain residue, divalence or multivalence polybutadiene chain residue, divalence or multivalence polyisoprene chain residue, divalence or multivalence poly- third Olefin(e) acid chain residue, divalence or multivalence polyacrylamide chain residue, divalence or multivalence polyacrylonitrile chain residue.Suitableization formed Compound (III) structure example 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。
The structure of the compound (III) of the example above is only that compound (III) is better described on this condition to be had Typical structure and propose, be only some more representational structures under the conditions of this, rather than the limit to the scope of the present invention It is fixed.
When T is selected from divalence or multivalence heterochain polymer residue, its can be any appropriate macromolecular main chain mainly by The polymer residue that the hetero atom such as carbon atom and nitrogen, oxygen, sulphur is formed, it may be selected from any in the following group, any insatiable hunger With form, any substituted form or any by hydridization form：Divalence or multivalence polyethers chain residue, such as divalence or Multivalence focused beam-forming residue, divalence or multivalence polyethylene oxide chain residue, divalence or multivalence PPOX chain residue, divalence or Multivalence PolyTHF chain residue, divalence or multivalence asphalt mixtures modified by epoxy resin fat chain residue, divalence or multivalence phenolic resin chain residue, divalence or Multivalence polyphenylene oxide chain residue etc.；Divalence or multivalence polyesters chain residue, such as divalence or multivalence polycaprolactone chain residue, divalence or more The poly- valerolactone chain residue of valency, divalence or multivalence polylactide chain residue, divalence or multivalence polyethylene terephthalate chain are residual Base, divalence or multivalence unsaturated polyester (UP) chain residue, divalence or multivalence alkyd resin chain residue, divalence or multivalence polycarbonate chain are residual Base etc.；Divalence or multivalence polyamine class chain residue, as divalence or multivalence polyamide chains residue, divalence or multivalence polyimides chain are residual Base, divalence or multivalence polyurethane chain residue, divalence or multivalence polyureas chain residue, divalence or multivalence Lauxite chain residue, divalence Or multivalence melamine resin chain residue etc.；Divalence or multivalence polysulfide class chain residue, such as divalence or multivalence polysulfones chain residue, divalence or more Valency polyphenylene sulfide chain residue, divalence or multivalence polysulfide rubber chain residue etc..The preferred divalence of T or multivalence focused beam-forming residue, divalence Or multivalence polyethylene oxide chain residue, divalence or multivalence PolyTHF chain residue, divalence or multivalence asphalt mixtures modified by epoxy resin fat chain residue, two Valency or multivalence polycaprolactone chain residue, divalence or multivalence polylactide chain residue, divalence or multivalence polyamide chains residue.Formed Suitable compound (III) structure example 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。
The structure of the compound (III) of the example above is only that compound (III) is better described on this condition to be had Typical structure and propose, be only some more representational structures under the conditions of this, rather than the limit to the scope of the present invention It is fixed.
When T is selected from divalence or element of multivalence organic polymer residue, it can be any appropriate macromolecular main chain master The polymer residue to be made up of the hetero atom such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus, its may be selected from Any in the following group, any unsaturated form, any substituted form or any by hydridization form：Divalence or Multivalence silicone-based polymers chain residue, such as divalence or multivalence poly-organosilicon alkane chain residue, divalence or multivalence polysiloxane Chain residue, divalence or multivalence poly-organosilicon borine chain residue, divalence or multivalence poly-organosilicon azane chain residue, divalence or multivalence are gathered Organic silithiane chain residue, divalence or the poly- organophosphor siloxane chain residue of multivalence, divalence or the poly- organic metal siloxane chain of multivalence Residue；Divalence or multivalence organic boron are birdsed of the same feather flock together compound chain residue, as divalence or multivalence poly- organo-borane chain residue, divalence or multivalence are gathered Organic boroxane chain residue, divalence or the poly- organic boron azane chain residue of multivalence, divalence or the poly- organic boron sulfane chain residue of multivalence, two Valency or the poly- organic boron phosphine chain residue of multivalence etc.；Divalence or multivalence organic phosphates polymer chain residue；Divalence or multivalence Organic leadP Birds of the same feather flock together compound chain residue；Divalence or multivalence organic tin polymer chain residue；Divalence or multivalence organo-arsenic are birdsed of the same feather flock together compound chain residue； Divalence or multivalence antimony organic are birdsed of the same feather flock together compound chain residue.The preferred divalence of T or multivalence poly-organosilicon alkane chain residue, divalence or multivalence are poly- to be had Organic siloxane chain residue, divalence or the poly- organo-borane chain residue of multivalence.Suitable compound (III) structure example formed is such as Under：
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 structure of the compound (III) of the example above is only that compound (III) is better described on this condition to be had Typical structure and propose, be only some more representational structures under the conditions of this, rather than the limit to the scope of the present invention It is fixed.
It should be noted that when the group L in organoboron compound (I) structure, the base in silicon-containing compound (II) structure When group T in group J, compound (III) structure is selected from the chain structure in addition to cyclic structure, group A may connect to L end End, the optional position being also connected in L；Group G may connect to J end, the optional position being also connected in J；Group A T end is may connect to G, the optional position being also connected in T.As the group L in organoboron compound (I) structure, contain When the group T in group J, compound (III) structure in silicon compound (II) structure is selected from two-dimentional or three-dimensional cluster structure, institute The cluster structure stated typically is formed by common covalent bond, the organic boron acidic group and/or organic boronic ester group in cluster structure and It is peripheral and only anti-in the progress dynamic aggregation/crosslinking of cluster periphery that silicone hydroxyl and/or silicone hydroxyl presoma are usually dispersed in cluster Should.Therefore, after the organic boronic estersil key dissociation of dynamic reversible of the dynamic aggregation thing obtained contained by it, that is, dissociate agglomerating Cluster unit.
Any one for organoboron compound (I), silicon-containing compound (II), compound (III), in its organic boron acidic group Any one hydroxyl in any one ester group, silicone hydroxyl in hydroxyl, organic boronic ester group, any one in silicone hydroxyl presoma can The group that hydrolysis obtains hydroxyl is a functional group.For organoboron compound (I), silicon-containing compound (II), it can be Simple function group, difunctional, trifunctional or polyfunctional compound, for example, being for structure
Organoboron compound (I), it is respectively simple function group, difunctional, trifunctional, four-functional group；For another example It is for structure
Silicon-containing compound (II), it is respectively simple function group, difunctional, trifunctional, four-functional group；For chemical combination Thing (III), it can be difunctional, trifunctional or polyfunctional compound, for example, being for structure
Compound (III), it is respectively difunctional, trifunctional, four-functional group, five functional groups.
In organoboron compound (I), silicon-containing compound (II), compound (III), except containing organic boron acidic group and/ Or outside organic boronic ester group, silicone hydroxyl and/or silicone hydroxyl presoma, 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 of common covalent bond of the chemical reaction generation in addition to organic boronic estersil key is carried out under the conditions of heat, irradiation, catalysis etc.；Close Suitable group citing is such as：Hydroxyl, phenolic hydroxyl group, carboxyl, acyl group, amide groups, acyloxy, amino, aldehyde radical, sulfonic group, sulfonyl, mercapto Base, alkenyl, alkynyl, cyano group, piperazine base, oximido, diazanyl, guanidine radicals, halogen, isocyanate groups, anhydride group, epoxide group, third Enoate group, acrylamide group, maleimide base group, n-hydroxysuccinimide group, ENB group, azo Group, azido group, heterocyclic group etc.；The preferred hydroxyl of other reactive groups, carboxyl, amino, sulfydryl, alkenyl, isocyanates Group, epoxide group, acrylate group, acrylamide group.As an example, the suitable structure in part is in previous example In provide.
Other described in the present invention reactive groups, it plays a part of in system, first, performing the derivatization anti- The dynamic aggregation thing of functionalization (such as hydrophobicity, fluorescence, inoxidizability functional characteristic) should be prepared, second, in described chemical combination Thing is in itself or it between other compounds or is reacted between product directly by the anti-of other described 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 increase, promotees Enter the crosslink density to form the described dynamic aggregation thing with dynamic crosslinking structure and/or increase the dynamic aggregation thing. In the present invention, the common covalent attachment 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 estersil key in dynamic aggregation thing dissociates, polymeric system can be dissociated into Smaller unit, reach purpose that is recyclable or rebuilding.It should be noted that all " other reactions occurred in the present invention Property group ", be only used for performing the derivatization and/or form common covalent attachment.
Dynamic aggregation thing described in the present invention, it can be prepared by implementation below：
The first of the present invention prepares embodiment, and reaction generation organic boronic estersil key is participated in by least following components Obtain described dynamic aggregation thing：
At least one organoboron compound (I) containing organic boron acidic group and/or organic boronic ester group, at least one contains The silicon-containing compound of silicone hydroxyl and/or silicone hydroxyl presoma (II)；Wherein, organoboron compound (I) and silicon-containing compound (II) Containing two or more functional groups, and at least one organoboron compound (I) or at least one silicon-containing compound (II) contain There are three or more than three functional groups.
Second of preparation embodiment of the present invention, reaction generation organic boronic estersil key is participated in by least following components Described dynamic aggregation thing is obtained with common covalent bond：
At least one organoboron compound (I) containing organic boron acidic group and/or organic boronic ester group, at least one contains The silicon-containing compound of silicone hydroxyl and/or silicone hydroxyl presoma (II)；Wherein, organoboron compound (I) and silicon-containing compound (II) Containing one or more functional groups, and at least one organoboron compound (I) or at least one silicon-containing compound (II) contain There are one or more other reactive groups.
The third of the present invention prepares embodiment, and reaction generation organic boronic estersil key is participated in by least following components Obtain described dynamic aggregation thing：
At least one body before containing organic boron acidic group and/or organic boronic ester group and silicone hydroxyl and/or silicone hydroxyl simultaneously The compound (III) of body, or itself and at least one organoboron compound containing organic boron acidic group and/or organic boronic ester group And/or at least one silicon-containing compound (II) containing silicone hydroxyl and/or silicone hydroxyl presoma (I)；Wherein, compound (III), Organoboron compound (I), silicon-containing compound (II) contain two or more functional groups, and at least one compound (III) or at least one organoboron compound (I) or at least one silicon-containing compound (II) contain three or more than three functions Group.
The 4th kind of the present invention prepares embodiment, and reaction generation organic boronic estersil key is participated in by least following components Described dynamic aggregation thing is obtained with common covalent bond：
At least one body before containing organic boron acidic group and/or organic boronic ester group and silicone hydroxyl and/or silicone hydroxyl simultaneously The compound (III) of body, or itself and at least one organoboron compound containing organic boron acidic group and/or organic boronic ester group And/or at least one silicon-containing compound (II) containing silicone hydroxyl and/or silicone hydroxyl presoma (I)；Wherein, compound (III) Containing two or more functional groups, organoboron compound (I), silicon-containing compound (II) contain one or more functions Group, and at least one compound (III) or at least one organoboron compound (I) or at least one silicon-containing compound (II) contain One or more other reactive groups.
In above-described preparation embodiment, the organoboration of proper amount of simple function group is also selectively introduced into Silicon-containing compound (II) component of compound (I) and/or simple function group, described move can be obtained by the regulation of component formula State cross-linked structure.Mono-functional compounds can play the effects such as regulation crosslink density, dynamic, Mechanics of Machinery intensity.
In above-described preparation embodiment, the reaction of other reactive groups can also be by introducing without organic Boronate and/or organic boronic ester group, silicone hydroxyl and/or silicone hydroxyl presoma, organic boronic estersil key but containing other reaction The compound component of property group is realized together.Only the compound containing other reactive groups can be any appropriate chemical combination Thing, it can reach and other reactions in organoboron compound (I) and/or silicon-containing compound (II) and/or compound (III) Property radical reaction is had the purpose of the dynamic aggregation thing of " dynamic crosslinking structure ".
In above-described preparation embodiment, for preparing the compound (III) of the dynamic aggregation thing, it can be with Selected from same compound (III), not same compound (III) can also be selected from；When it is selected from same compound (III) When, before it is by intramolecular and/or intermolecular organic boron acidic group and/or organic boronic ester group and silicone hydroxyl and/or silicone hydroxyl The reaction driven between body obtains described dynamic aggregation thing.
In the preparation process of dynamic aggregation thing, after the compound as raw material mutually participates in reaction, raw material components it Between can carry out polymerized/cross-linked by linking point of organic boronic estersil key or common covalent bond, obtain that there is higher molecular weight Dynamic aggregation thing.Wherein, the functional group contained in raw material components can react completely, can also partial reaction, it is not required that its In all organic boron acidic group and/or organic boronic ester group and silicone hydroxyl and/or silicone hydroxyl precursor all react to each other completely shape Into organic boronic estersil key, as long as the organic boronic estersil key formed is enough to maintain dynamic aggregation thing structure.
In the present invention, because the preparation process step that dynamic aggregation thing is prepared using above-mentioned several embodiments is simple, Operation is easy, and controllability is strong, therefore is the preferred embodiment of the present invention.
Dynamic aggregation thing described in the present invention, can also be prepared by implementation below：
The 5th kind of the present invention prepares embodiment, at least contains at least one organic boronic silicon by one or more The compound of ester bond and at least one other reactive group (IV) is anti-by the polymerized/cross-linked between other reactive groups Described dynamic aggregation thing should be obtained；Or at least by one or more containing at least one organic boronic estersil key and The compound (IV) of at least one other reactive group is not with containing organic boronic estersil key but containing at least one other anti- The compound of answering property group obtains described dynamic aggregation thing by the polymerized/cross-linked reaction between other reactive groups.
Wherein, the compound (IV) containing organic boronic estersil key He other reactive groups, its can be molecular weight not Micromolecular compound or molecular weight more than 1000Da are more than 1000Da macromolecular compound；At compound (IV) In also can contain organic boron acidic group and/or organic boronic ester group, silicone hydroxyl and/or silicone hydroxyl presoma；Organic boronic is not contained Estersil key but the compound containing other reactive groups, it can be the micromolecular compound that molecular weight is no more than 1000Da, It can also be the macromolecular compound that molecular weight is more than 1000Da.
The compound (IV) containing organic boronic estersil key He other reactive groups described in the present invention, it can be with Following representation：
Wherein, E is the module containing organic boronic estersil key；U be module E number, u >=1；Y is on individual module E Substituted radical, or the linking group between the substituted radical on individual module E and two or more module E, and at least one Individual group Y is connected with the boron atom of organic boronic estersil key, at least one group Y and organic boronic estersil key silicon atom phase Even；Wherein, at least one other reactive group is contained at least one group Y, and contain in all group Y its He is more than or equal to 2 by reactive group number；R be group Y number, r >=2.
The described module E containing organic boronic estersil key, it can following representation：
Wherein, K13、K16、K20For the group being joined directly together with boron 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 1000Da polymer Chain residue；K14、K15、K17、K18、K19、K21For the group being joined directly together with silicon atom, it is each independently selected from following any Structure：The small molecule alkyl of hydrogen atom, heteroatom group, molecular weight no more than 1000Da, molecular weight are more than 1000Da polymerization The inorganic molecules chain residue of thing chain residue, molecular weight no more than 1000Da, molecular weight are more than 1000Da inorganic macromolecular chain Residue；Represent the connection with group Y.It is pointed out that in said structure, between suitable different group K, no With can also cyclization between group Y and between group K and group Y；Group Y can be connected by Si-O keys with boron atom, also may be used It is connected by B-O keys with silicon atom.
In the present invention, the module E containing organic boronic estersil key, can be appointed by what is be previously mentioned in the present invention It is a kind of or appoint several modules As containing organic boron acidic group and/or organic boronic ester group with it is any or appoint and several contain silicone hydroxyl And/or before the module G of silicone hydroxyl presoma is by organic boron acidic group and/or organic boronic ester group and silicone hydroxyl and/or silicone hydroxyl Drive obtained by condensation reaction or the ester exchange reaction between body.
As u=1, r=2,3,4 or 5, Y are the substituted radical on individual module E, and Y may be selected from same structure or a variety of Different structure, and the quantity of other reactive groups that contains of Y and structure must assure that can obtain described dynamic aggregation Thing；Described Y structure may be selected from following any or appoint several：Molecular weight is no more than 1000Da small molecule alkyl, molecular weight Polymer chain residue more than 1000Da.
Work as u>When 1, module E may be selected from same structure or a variety of different structures, now r >=2, and Y is on individual module E Linking group between substituted radical and two or more module E, Y may be selected from same structure or a variety of different structures, and Y The quantity and structure of other reactive groups contained, which must assure that, can obtain described dynamic aggregation thing；Described Y structure It may be selected from any of small molecule alkyl of the molecular weight no more than 1000Da, the polymer chain residue of molecular weight more than 1000Da Or the divalence or multivalence small molecule alkyl, molecular weight for appointing several and singly-bound, hetero atom linker, molecular weight to be no more than 1000Da Any of divalence or multivalence polymer chain residue more than 1000Da or appoint it is several, its be specifically defined refer to group L and Group T, no longer illustrates one by one here.
It is connected as the group Y that the boron atom with organic boronic estersil key is connected and with the silicon atom of organic boronic estersil key When cyclic structure is formed between group Y, then compound (IV) of the organic boronic estersil key mapping in cyclic structure is can obtain, now Under suitable conditions, react, obtain using the dynamic of organic boronic estersil key and the polymerized/cross-linked of other reactive groups Obtain described dynamic crosslinking polymer.
For the compound (IV) containing organic boronic estersil key He other reactive groups, it generally contains organic boron Monomer, the oligomer containing organic boronic estersil key, the prepolymer containing organic boronic estersil key of sour estersil key.Compound (IV) it can be prepared by any appropriate method, including be entered by suitable organoboron compound (I) and silicon-containing compound (II) It is prepared by row.Preferably, compound (IV) can by least one organoboron compound (I) containing other reactive groups and At least one silicon-containing compound (II) containing other reactive groups carries out reaction preparation, can also be contained by least one The organoboron compound (I) of other reactive groups and at least one silicon-containing compound (II) for not containing other reactive groups Reaction preparation is carried out, at least one organoboron compound (I) and at least one for not containing other reactive groups can also be passed through Silicon-containing compound (II) of the kind containing other reactive groups carries out reaction preparation；Compound (IV) can also pass through at least one Compound (III) containing other reactive groups or its with organoboron compound (I) and/or silicon-containing compound (II) carry out it is anti- It should prepare.
Similarly, it can be any appropriate not contain organic boronic estersil key but the compound containing other reactive groups Compound, it, which can reach to obtain with other reaction-ity group reactions in compound (IV), has " the dynamic crosslinking structure " Dynamic aggregation thing purpose.
Compound containing other reactive groups during the course of the reaction, between component can other be anti-by contained Answering property group react to each other to be formed it is common covalently attached, so as to obtain the dynamic aggregation thing with " the dynamic crosslinking structure ".
In the present invention, because this embodiment has its specific for preparing dynamic aggregation thing in certain special cases Advantage, therefore be also the preferred embodiment of the present invention.
Dynamic aggregation thing in the present invention is not limited only to be prepared using above-described several embodiments, and it also may be used To be above-mentioned several embodiments or its combination with other kind of embodiment.In every case organic boron chemical combination is utilized in embodiments Thing (I), silicon-containing compound (II), compound (III), compound (IV) prepare dynamic aggregation thing as raw material, no matter its It is in the form of raw material, or in the form of the compound of synthesis material, also either with the intermediate product of synthetic polymer Form, by it can be drawn according to the guidance of the present invention, it ought to be included in the scope of patent protection of the present invention.Equally Ground, those skilled in the art reasonably can also implement to obtain institute according to the guidance of the present invention using above-mentioned several compounds The dynamic aggregation thing stated.
In summary, described dynamic aggregation thing can be obtained as raw material at least with following one or more of compounds：
Organoboron compound (I) containing organic boron acidic group and/or organic boronic ester group；Contain silicone hydroxyl and/or silicon hydroxyl The silicon-containing compound (II) of base precursor；Contain organic boron acidic group and/or organic boronic ester group and silicone hydroxyl and/or silicon simultaneously The compound (III) of hydroxyl precursor；Compound (IV) containing organic boronic estersil key He other reactive groups；Wherein, Organoboron compound (I), silicon-containing compound (II), compound (III) contain at least one functional group；Wherein, organoboration Compound (I), silicon-containing compound (II), compound (III) can contain, and can be free of has other reactive groups；Wherein, organic boron Compound (I) or silicon-containing compound (II) do not prepare described dynamic aggregation thing separately as raw material.
The heteroatom group being previously mentioned in the present invention, its can be it is any appropriate contain heteroatomic group, it can Selected from following any group：Halogen, hydroxyl, mercaptan, carboxyl, nitro, primary amine groups, silicon substrate, phosphorus base, triazole, isoxazoles, acyl Amido, imide, thioamides base, enamine base, carbonate group, thiocarbonic acid ester group, dithiocarbonic acids ester group, three thio carbon Perester radical, carbamate groups, thiocarbamate base, dithiocarbamate groups, thioester substrate, thio ester group, two sulphur For ester group, ortho acid ester group, phosphate-based, phosphorous acid ester group, hypophosphorous acid ester group, phosphonate group, phosphoryl, phosphorous acyl group, secondary phosphorus Acyl group, thiophosphoryl, thio phosphorous acyl group, thio secondary phosphoryl, phosphorus silane ester group, silane ester group, phosphoamide, thio acyl Amine, phosphamide, phosphoramidite, pyrophosphoramide, endoxan, ifosfamide, thio-phosphamide, orthosilicic acid base, metasilicic acid base, Secondary silicic acid base, boronate, metaboric acid base, rhizome of Chinese monkshood acyl group, peptide bond, acetal, cyclic ketal, mercaptal, azepine acetal, azacyclo- contracting Aldehyde, nitrogen thia acetal, ithioacetals, hemiacetal, hemimercaptol, azepine hemiacetal, ketal, thioketal, azepine ketal, nitrogen Heterocycle ketal, nitrogen thia ketal, acylhydrazone key, oxime key, sulfime ether, semicarbazones key, thiosemicarbazone key, diazanyl, hydrazides Base, thio carbohydrazide base, azo carbonyl hydrazide group, thio azo carbonyl hydrazide group, carbazic acid ester group, thiocarbazates base, Carbonohydrazides, thiocarbohydrazide, azo group, isourea base, isothiourea group, allophanate group, thioallophanate base, guanidine radicals, amidine Base, amino guanidine radicals, amido-amidinate, imido acidic group, imidic acid thioester substrate, nitroxyl, nitrosyl radical, sulfonic group, sulfonate group, Asia Sulfonate group, sulfoamido, sulfonamido, sulfonyl hydrazino, sulfonylurea group, maleimide.
The molecular weight being previously mentioned in the present invention is no more than 1000Da small molecule alkyl, and it typically contains 1 to 71 carbon Atom, it can contain heteroatom group, and can be free of has heteroatom group.Generally, described small molecule alkyl may 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：C1-71 Alkyl, ring C3-71Alkyl, phenyl, benzyl, aryl；Small molecule alkyl is preferably methyl, ethyl, propyl group, propylene, butyl, fourth Alkene, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, cyclohexyl, phenyl；More preferably methyl, ethyl, propyl group, phenyl.
The molecular weight being previously mentioned in the present invention is more than 1000Da polymer chain residue, and it can be any appropriate polymerization Thing chain residue, include 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, described carbochain polymer residue, it can be any appropriate macromolecular main chain mainly by carbon atom structure Into polymer residue, its may be selected from by it is any in the following group, any it is unsaturated in the form of, any substituted form or It is any by hydridization form：TPO chain residue, as Polyethylene Chain residue, polypropylene chains residue, polyisobutene chain residue, Polystyrene chain residue, polyvinyl chloride chain residue, Vingon chain residue, polyvinyl fluoride chain residue, polytetrafluoroethylene (PTFE) chain are residual Base, polytrifluorochloroethylene chain residue, polyvinyl acetate chain residue, polyvinyl alcohol chain residue, Polyvinylalkylethers chain residue, Polybutadiene chain residue, polyisoprene chain residue, polychlorobutadiene chain residue, polynorbornene chain residue etc.；Polyacrylic acid Class chain residue, such as polyacrylic acid chain residue, polyacrylamide chain residue, PMA chain residue, poly-methyl methacrylate Ester chain residue etc.；Polypropylene nitrile chain residue, such as polyacrylonitrile chain residue；It is preferred that Polyethylene Chain residue, polypropylene chains residue, Polystyrene chain residue, polyvinyl chloride chain residue, polybutadiene chain residue, polyisoprene chain residue, polyacrylic acid chain residue, Polyacrylamide chain residue, polyacrylonitrile chain residue；Described carbochain polymer residue, it can be by click-reaction, such as Diels-Alder reacts to be formed.
Described heterochain polymer residue, its 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 formed, its may be selected from by it is any in the following group, any it is unsaturated in the form of, it is any Substituted form or any by hydridization form：Polyethers chain residue, as focused beam-forming residue, polyethylene oxide chain residue, PPOX chain residue, PolyTHF chain residue, asphalt mixtures modified by epoxy resin fat chain residue, phenolic resin chain residue, polyphenylene oxide chain residue Deng；Polyesters chain residue, such as polycaprolactone chain residue, poly- valerolactone chain residue, polylactide chain residue, poly terephthalic acid second Diol ester chain residue, unsaturated polyester (UP) chain residue, alkyd resin chain residue, polycarbonate chain residue etc.；Polyamine class chain residue, such as Polyamide chains residue, polyimides chain residue, polyurethane chain residue, polyureas chain residue, Lauxite chain residue, melamine resin chain Residue etc.；Polysulfide class chain residue, such as polysulfones chain residue, polyphenylene sulfide chain residue, polysulfide rubber chain residue；It is preferred that focused beam-forming Residue, 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；Described heterochain polymer residue, its can by click-reaction, as Diels-Alder reactions, CuAAC reactions, thiol-ene react to be formed.
Described elemento-organic polymer residue, it can be any appropriate macromolecular main chain mainly by silicon, boron, aluminium etc. The hetero atom such as inorganic elements hetero atom and nitrogen, oxygen, sulphur, phosphorus form polymer residue, its may be selected from it is any in the following group, appoint A kind of unsaturated form, any substituted form or any by hydridization form：Silicone-based polymers chain residue, 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 is birdsed of the same feather flock together compound Chain residue, such as poly- organo-borane chain residue, gather organic boroxane chain residue, poly- organic boron azane chain residue, poly- organic boron sulfane Chain residue, poly- organic boron phosphine chain residue etc.；Organic phosphates polymer chain residue；Organic leadP is birdsed of the same feather flock together compound chain residue；Organotin Birds of the same feather flock together compound chain residue；Organo-arsenic is birdsed of the same feather flock together compound chain residue；Antimony organic is birdsed of the same feather flock together compound chain residue；It is preferred that poly-organosilicon alkane chain is residual Base, polysiloxane chain residue, poly- organo-borane chain residue.
The molecular weight being previously mentioned in the present invention is no more than 1000Da small molecule silylation, and it can be any appropriate The small molecule silylation that molecular backbone is mainly made up of the hetero atom such as silicon atom and nitrogen, oxygen, sulphur, phosphorus, generally, described is small Molecule silylation may 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 1000Da inorganic molecules chain residue, and it can be any conjunction What suitable molecular backbone and side chain were mainly made up of the hetero atom such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus Inorganic molecules chain residue, generally, described inorganic molecules chain residue may be selected from any in the following group, any Unsaturated form, any substituted form or any by hydridization form：Chain sulphur residue, 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, boron-oxygen chain residue；It is preferred that chain sulphur residue, 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 1000Da inorganic macromolecular chain residue, and it can be any appropriate Macromolecular main chain and side chain be mainly made up of the hetero atom such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus Inorganic macromolecular chain residue, its may be selected from by it is any in the following group, any it is unsaturated in the form of, any substituted form It is or any by hydridization form：Chain sulphur polymer residue, polysilane chain residue, polysiloxane chain residue, polysulfide silicon chain are residual Base, polysulfide nitrogen chain residue, polyphosphoric acid chain residue, polyphosphazene chain residue, polychlorostyrene are for phosphonitrile chain residue, polyborane chain residue, poly- boron Oxygen alkane chain residue；Also selected from any inorganic macromolecular with residue or any band being modified by surface in the following group There is 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, carbon fiber, white phosphorus, red phosphorus, five phosphorous oxides, molybdenum sulfide, silica, silicon disulfide, silicon nitride, carborundum, cunning Stone, kaolin, montmorillonite, mica, asbestos, feldspar, cement, glass, quartz, ceramics, boron oxide, nitridation sulphur, calcium silicide, silicic acid Salt, glass fibre, beryllium oxide, magnesia, mercury oxide, boron hydride, boron nitride, boron carbide, aluminium nitride, diaspore, gibbsite, Corundum, titanium dioxide；It is preferred that chain sulphur polymer residue, polysilane chain residue, polysiloxane chain residue, polyphosphazene chain residue, Polyborane chain residue, by surface be modified graphite, by surface be modified carbon fiber, by surface be modified silica, By surface be modified silicon nitride, by surface be modified carborundum, by surface be modified silicate, by surface be modified Glass fibre, the boron nitride being modified by surface.
For small molecule alkyl, polymer chain residue, small molecule silane chain residue, inorganic molecules chain residue, inorganic big The structure of strand residue is not particularly limited, and it can be straight chain shape, branch chain, more arm configuration shapes, star, comb shape, tree Branch shape, supermolecule shape, single annular, more annular, loop coil shape, condensed ring shape, bridged ring shape, the chain with cyclic structure, two and three dimensions Cluster shape；In small molecule alkyl, polymer chain residue, small molecule silane chain residue, inorganic molecules chain residue, inorganic macromolecular In chain residue, soft segment can be contained, can also contain rigid chain segment.
For the simplicity of explanation, in the description of the invention, described term is represented using conjunction "and/or" The option selected from the conjunction "and/or" foregoing description, or described option after conjunction "and/or" can be included, Or it is simultaneously selected from described these three situations of option before and after conjunction "and/or".For example, " one kind tool in specification There is the dynamic aggregation thing of dynamic crosslinking structure, its friendship on the polymer chain skeleton of cross-linked network and/or between polymer chain Connection link skeleton on contains organic boronic estersil key " in "and/or", its implication is that dynamic aggregation thing can be in cross-linked network Polymer chain skeleton on contain organic boronic estersil key, or the cross linked chain synthetism frame between the polymer chain of cross-linked network It is upper to contain organic boronic estersil key, or the cross linked chain on the polymer chain skeleton of cross-linked network between polymer chain simultaneously Contain organic boronic estersil key on synthetism frame；For another example " described organic boronic estersil key is as dynamic aggregation thing in specification Polymerization linking point and/or crosslinking linking point and exist " in "and/or", its implication is that organic boronic estersil key can be made Exist for the polymerization linking point of dynamic aggregation thing, either exist as the crosslinking linking point of dynamic aggregation thing or simultaneously Exist as polymerization linking point and the crosslinking linking point of dynamic aggregation thing；For another example " A is to contain organic boronic in specification "and/or" in the module of base and/or organic boronic ester group ", its implication are that A is the module containing organic boron acidic group, or For the module containing organic boronic ester group, or it is the module containing organic boron acidic group and organic boronic ester group simultaneously.In this hair The conjunction "and/or" occurred elsewhere in bright specification, represents such implication.
Heretofore described " organic group ", refer to the base mainly formed using carbon and protium as skeleton Group, it can be the polymer chain that small molecule group of the molecular weight no more than 1000Da or molecular weight are 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 what is mainly formed using element silicon and protium as skeleton Group, it can be that small molecule silylation of the molecular weight no more than 1000Da or molecular weight are organic more than 1000Da Silicon is birdsed of the same feather flock together compound chain residue, and suitable group citing is such as：Silylation, siloxy group, silithiane base, silazane base etc..
" common covalent bond " described in the present invention, what is referred to is traditional being total in addition to dynamic covalent bond Valence link, include but are not limited to carbon-carbon bond, carbon-oxygen bond, carbon-hydrogen link, carbon-nitrogen bond, carbon-sulfide linkage, nitrogen-hydrogen bond, nitrogen-oxygen key, Hydrogen-oxygen key, nitrogen-nitrogen key etc..
The relative molecular mass of term " molecular weight " used representative species in the present invention, for micromolecular compound, small Molecular radical and some macromolecular compounds with fixed structure, for macro-radical, its molecular weight typically have single point Property is dissipated, namely there is fixed member amount；And there is polydispersion for oligomer, high polymer, oligomer residue, high polymer residue etc. The material of property molecular weight, its molecular weight generally refer to mean molecule quantity.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 1000Da compound or group.
Term " polymerization " used in the present invention, refers to that the reactant of lower molecular weight passes through polycondensation, addition polymerization, ring-opening polymerisation Deng the process of product of the reaction formation synthesis with higher molecular weight.Among these, reactant is typically polymerizing power (i.e. Can spontaneously be polymerize, or can initiator or it is additional can effect under be polymerize) monomer, oligomer, pre-polymerization The compounds such as thing.The product for being polymerize to obtain by a kind of reactant is referred to as homopolymer.Entered by two or more reactant The product that row polymerization obtains is referred to as copolymer.It is pointed out that described in the present invention " polymerization ", it includes reactant point The linear growth process of subchain, the branched process comprising reactant molecule chain, the annulation process of reactant molecule chain is included, but simultaneously Cross-linking process not comprising reactant molecule chain；I.e. described " polymerization ", refers to the reactant in addition to cross-linking reaction process Molecule chain polymerization propagation process.
Term " crosslinking " used in the present invention, refer between reactant molecule and/or in reactant molecule by dynamic altogether Valence link to form the process with three-dimensional infinitely reticular pattern product with being connected chemically for optional common covalent bond.With common covalent When key is crosslinked, it is necessary to assure the degree of cross linking of the common covalent cross-linking of polymer is less than gel point, so that dynamic reversible Organic boronic estersil key dissociation when, polymeric system can be dissociated into smaller non-crosslinked and/or cluster unit.
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 with straight or branched structure in the present invention.In appropriate situation Under, alkyl can have the carbon number specified, for example, C1-4Alkyl, the alkyl be included in straight or branched arrangement in have 1, 2nd, the alkyl of 3 or 4 carbon atoms.The example of suitable alkyl includes but is not limited to methyl, ethyl, propyl group, normal-butyl, isobutyl Base, the tert-butyl group, 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 group, nonyl, decyl.
Term " cycloalkyl " used refers to the cyclic hydrocarbon of saturation in the present invention.Cycloalkyl ring may include the carbon number specified. For example, 3 to 8 yuan of cycloalkyl include 3,4,5,6,7 or 8 carbon atoms.The example of suitable cycloalkyl includes but is not limited to ring third Base, cyclobutyl, cyclopenta, cyclohexyl, suberyl and cyclooctyl.
Term " aryl " used means the monocyclic or more of in each ring any stabilization of at most 7 atoms in the present invention Ring carbon ring, wherein at least one ring are aromatic.The example of such aryl includes but is not limited to phenyl, xenyl, naphthyl, connection Naphthyl, tetralyl, indanyl, anthryl, dianthranide base, phenanthryl, connection phenanthryl.
Term " heteroaryl alkyl " used represents the monocyclic or more of in each ring stabilization of at most 7 atoms 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 is not limited to acridinyl, carbazyl, cinnolines base, quinoxalinyl, quinazolyl, pyrazolyl, indoles Base, BTA base, furyl, thienyl, thiophenyl, 3,4- propylidene dioxies thiophenyl, benzothienyl, benzofuran Base, benzodioxan, benzo dioxine, quinolyl, isoquinolyl, oxazolyl, isoxazolyls, imidazole radicals, pyrazinyl, Pyridazinyl, pyridine radicals, 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 being previously mentioned in the cyclic structure of the present invention, refers to comprising only a ring in cyclic structure, Citing is such as：
The multiring structure being previously mentioned, refer to that citing is such as containing two or more independent rings in cyclic structure：
The spirane structure being previously mentioned, refer in cyclic structure containing by two or more rings to each other by sharing one The cyclic structure of individual atomic building, citing is such as：
The condensed cyclic structure (it also includes two rings, virtue and ring structure) being previously mentioned, refers to containing by two in cyclic structure Individual 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, refer in cyclic structure containing by two or more rings to each other by sharing two The cyclic structure of adjacent atomic building more than individual, it has three-dimensional cage structure, and citing is such as：
The nested ring structure being previously mentioned, refer in cyclic structure containing connected or embedding to each other by two or more rings The cyclic structure formed is covered, citing is such as：
For simplicity, the carbon atom number range in group is also labeled in C lower mark in the present invention with the form of subscripts Put, represent the carbon number that the group has, such as C1-10Represent " there is 1 to 10 carbon atom ", C3-20Represent " there is 3 to 20 Individual carbon atom "." undersaturated C3-20Alkyl " refers to C3-20Compound containing unsaturated bond in alkyl." substituted C3-20Alkyl " Refer to C3-20The substituted obtained compound of the hydrogen atom of alkyl." the C of hydridization3-20Alkyl " refers to C3-20Carbon atom in alkyl is miscellaneous Atom substitutes obtained compound.When a group may be selected from C1-10During alkyl, it may be selected from any in scope shown in subscript The alkyl of carbon number, you can 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, represent to may be selected from any integer in the range of this with the subscript that range format marks, the scope Including two end points.
Can be any of which in the case of not specifying when the structure being related to has isomer Isomers.Such as alkyl, in the case of not specifying, refer to and lose the alkyl that the hydrogen atom of any position is formed.Specifically Ground, as propyl group is criticized any in propyl group, isopropyl, propylidene refers to any in 1,3- propylidene, 1,2- propylidene, isopropylidene Kind.
In the present invention " substituted ", by taking " substituted alkyl " as an example, refer to any of any position in substituted " alkyl " Individual or more than one hydrogen atom can be substituted by any substituent.In the case of being not particularly limited, substituent therein It is not particularly limited.
For a compound, a group or an atom, can be substituted simultaneously and by hydridization, such as nitrobenzophenone Substitute hydrogen atom, and for example-CH2-CH2-CH2- it is replaced by-CH2-S-CH(CH3)-。
In the present invention, for the organic boron acidic group and organic boric acid ester of composition dynamic aggregation thing organic boronic estersil key Base, due to electron deficient possessed by boron atom in group so that it is easily entered by the nucleopilic reagent containing unshared electron pair Attack and produce bonding；And for form organic boronic estersil key silicone hydroxyl (including can by conversion obtain the silicon of silicone hydroxyl Hydroxyl groups precursors), due to containing unshared electron pair on silicone hydroxyl oxygen atom, and silicone hydroxyl it is possessed highly polar in itself and High activity, it more can be quickly dehydrated during being in contact with organic boron acidic group and/or organic boronic ester group The reactions such as condensation reaction, ester exchange reaction form organic boronic estersil key, so as to form polymer.The present invention is exactly that make use of Machine boronate and organic boronic ester group and high reaction activity possessed by silicone hydroxyl are stronger possessed by organic boronic estersil key Dynamic reversibility, the dynamic aggregation thing that dynamic effect is reflected under conditions of more gently is made.Meanwhile using having Machine boronate and/or organic boronic ester group form organic boronic estersil key so that form the component choosing of organic boronic estersil key More horn of plenty is selected, it is big for the control of the structure of dynamic aggregation thing, dynamic reversibility, mechanical property, solvent resistance etc. It is big to improve, extend the application of polymer.
When by the organoboron compound (I) containing organic boron acidic group and/or organic boronic ester group with containing silicone hydroxyl and/or When the silicon-containing compound (II) of silicone hydroxyl presoma is mixed under dissolving or molten condition, in organoboron compound (I) Organic boron acidic group can carry out quick condensation reaction with the silicone hydroxyl in silicon-containing compound (II) and form organic boronic estersil key, So as to obtain dynamic aggregation thing；Organic boronic ester group in organoboron compound (I), can directly with silicon-containing compound (II) Silicone hydroxyl carry out ester exchange reaction and form organic boronic estersil key, can also first pass through hydrolyze to form after organic boron acidic group again with Silicone hydroxyl in silicon-containing compound (II) carries out condensation reaction and forms organic boronic estersil key, so as to obtain dynamic aggregation thing；Contain Silicone hydroxyl presoma in silicon compound (II), can be directly with the organic boron acidic group in organoboron compound (I) by sloughing Small molecule carry out condensation reaction, can also first pass through after hydrolyzing to form silicone hydroxyl, then with the organic boron in organoboron compound (I) Acidic group carry out condensation reaction, or with organoboron compound (I) organic boronic ester group carry out ester exchange reaction formed it is organic Boric acid estersil key, so as to obtain dynamic aggregation thing.Wherein, preferably by the organoboron compound (I) containing organic boron acidic group with Silicon-containing compound (II) containing silicone hydroxyl presoma, the organoboron compound (I) containing organic boronic ester group and contain silicon hydroxyl The silicon-containing compound (II) of base forms organic boronic estersil key and obtains dynamic aggregation thing, more preferably utilizes and contains organic boronic ester group Organoboron compound (I) with containing silicone hydroxyl silicon-containing compound (II) formed organic boronic estersil key obtain dynamic aggregation Thing.When the use organoboron compound (I) containing organic boronic ester group or the silicon-containing compound (II) containing silicone hydroxyl presoma When being reacted, generally require higher temperature and reacted, or by being condensed after one of them progress in-situ hydrolysis Reaction.In one polymerization system, it can contain simultaneously containing one or more kinds of organoboron compounds (I) and one or more Silicon compound (II).
For simultaneously containing organic boron acidic group and/or organic boronic ester group and silicone hydroxyl and/or silicone hydroxyl precursor Compound (III), it generally requires by controlling reaction condition and the suitable reaction promoter of addition, made in compound (III) Organic boron acidic group can be reacted with silicone hydroxyl presoma that is of the same race or not containing in same compound (III) formed with Machine boric acid estersil key, either enable organic boronic ester group in compound (III) and of the same race or not same compound (III) In the silicone hydroxyl presoma that contains carry out reaction and form organic boronic estersil key, or make the organic boronic in compound (III) Ester group first pass through hydrolysis obtain after organic boron acidic group again with silicone hydroxyl forerunner that is of the same race or not containing in same compound (III) Body carries out reaction and forms organic boronic estersil key, either make organic boronic ester group in compound (III) from it is of the same race or different The silicone hydroxyl precursor contained in kind compound (III) first passes through the silicone hydroxyl that hydrolysis obtains and carries out condensation reaction formation organic boron Sour estersil key, or make organic boronic ester group in compound (III) and silicone hydroxyl precursor while first hydrolyze to be condensed again Reaction forms organic boronic estersil key, so as to obtain dynamic aggregation thing.It is a kind of or more except that can contain in one polymerization system Kind compound (III) outside, can also contain containing one or more kinds of organoboron compounds (I) and/or one or more simultaneously Silicon compound (II).
For organoboron compound (I), silicon-containing compound (II), compound (III), it is forming the mistake of dynamic aggregation thing Cheng Zhong, except utilizing the organic boron acidic group and/or organic boronic ester group contained in compound and body before silicone hydroxyl and/or silicone hydroxyl Outside body is reacted, it also may optionally utilize other reactive groups and be commonly covalently attached by polymerized/cross-linked reaction, So as to which together with organic boron acidic group and/or organic boronic ester group and silicone hydroxyl and/or silicone hydroxyl precursor, common reaction obtains Dynamic aggregation thing.
For compound (IV), it is generally by the phase between other reactive groups contained in compound (IV) Mutual reactance, or by other reactive groups contained in compound (IV) with other compounds contained by other are anti- Reacting to each other between answering property group, so as to obtain the dynamic aggregation thing containing organic boronic estersil key.
The embodiment participated in for the compound containing other reactive groups, it can pass through the anti-of such as following form Dynamic aggregation thing should be obtained：Condensation reaction is carried out by the carboxyl contained in the hydroxyl and compound that contain in compound and forms ester Key, so as to obtain dynamic aggregation thing；Condensation reaction is carried out by the carboxyl contained in the amino and compound that contain in compound Amido link is formed, so as to obtain dynamic aggregation thing；By the hydroxyl that contains in the epoxide group and compound that contain in compound, Amino, sulfydryl carry out ring-opening reaction and form ehter bond, secondary amine key, thioether bond, so as to obtain dynamic aggregation thing；In initiator or additional In the presence of energy, radical polymerization is carried out by the alkene contained in compound, so as to obtain dynamic aggregation thing；In initiator or In the presence of additional energy, anion/cation polymerization is carried out by the alkene contained in compound, so as to obtain dynamic aggregation thing；It is logical Cross the epoxide group contained in compound and carry out ring-opening polymerisation formation ehter bond, so as to obtain dynamic aggregation thing；In monovalence copper catalysis Under, CuAAC reactions are carried out by the alkynyl contained in the azido group and compound that contain in compound, it is poly- so as to obtain dynamic Compound；Thiol-ene click-reactions are carried out by the alkene contained in the sulfydryl and compound that contain in compound, so as to obtain Dynamic aggregation thing；By the addition reaction between the double bond that contains in compound, so as to obtain dynamic aggregation thing etc..
For preparing the organoboron compound (I) of dynamic aggregation thing, silicon-containing compound (II), compound (III), compound (IV), other compounds for containing other reactive groups, it can be gas, liquid, crystal, powder, particle, glue, cream Shape etc..
During dynamic aggregation thing is prepared, having in the organoboron compound (I), compound (III) as raw material Machine boric acid, it can exist in the form of organic boronic or organic boric acid ester.Wherein, with compound existing for organic boronic ester-formin Raw material is relatively stable, is advantageous to transport and preserves；In addition, by using the raw material containing organic boric acid ester, can preferably adjust The parameters such as the degree of polymerization, the degree of cross linking and the dynamic in final dynamic aggregation thing are controlled, so as to regulate and control the synthesis of polymer Performance.
During dynamic aggregation thing is prepared, the silicon hydroxyl in silicon-containing compound (II), compound (III) as raw material Base, it can exist in the form of silicone hydroxyl or silicone hydroxyl presoma.Wherein, the silicon in silicon-containing compound (II), compound (III) In the presence of hydroxyl is with silicone hydroxyl precursor form, it can have a variety of sources to be hydrolyzed during silicone hydroxyl is hydrolyzed into Required water, can be artificially adding or raw material or substrate surface absorption the or water that contains in air What vapour or chemical reaction generated.Silicon-containing compound (II), compound (III) are during hydrolysis, in order to avoid silicon Hydroxyl self condenses, and can be selectively added a small amount of condensation inhibitor so that reaction system is maintained at neutral as far as possible；Can also Add appropriate nonpolar atent solvent so that the silanol of generation is dissolved in organic solvent, reduces its phase in aqueous medium Interaction；The generation of condensation reaction can also be slowed down by adjusting reaction temperature.Wherein, exist with silicone hydroxyl precursor form Compound it is relatively stable as raw material, be advantageous to transport and preserve, also can by using group activity difference it is poly- to regulate and control The building-up process and performance parameter of compound.
During the synthesis and use of silicon-containing compound (II) raw material, some condensations can be selectively added and suppressed Agent, it is usually in order that system can be maintained at neutral or close under conditions of neutral, avoids silicone hydroxyl from being condensed into siloxanes, So as to obtain the compound containing silicone hydroxyl of high yield.During silicon-containing compound (II) use, ensure as far as possible Silicon-containing compound (II) after synthetic or hydrolysis now closes current；More particularly suitable selection is closed in silicon-containing compound (II) Into or hydrolysis after, condensation reaction and then is carried out by itself and organoboron compound (I) with regard to control condition, obtains dynamic aggregation Thing.During by silicon-containing compound (II) and organoboron compound (I) reaction, ensure to react as far as possible organic Boron compound (I) is in the state of excess, and for silicon-containing compound (II) solid or liquid, use is slowly added or be added dropwise more Form be added in organoboron compound (I).
When raw material is selected from compound (III), to ensure the stability of raw material, the organic boronic in compound (III) is excellent First select to exist in the form of organic boric acid ester, the silicone hydroxyl prioritizing selection in compound (III) is with the shape of silicone hydroxyl presoma Formula is present, and in compound (III) preparation process, should try one's best and use nonpolar atent solvent as reaction dissolvent, and Preserved under cryogenic；Meanwhile be often also required to add some condensation inhibitor in the building-up process of raw material, and to the greatest extent It is current that amount ensures that compound (III) is now closed.In compound (III), organic boron acidic group and/or organic boronic ester group mole are worked as Amount generally needs the molar equivalent for being more than silicone hydroxyl and/or silicone hydroxyl precursor, and by controlling the conditions such as temperature, pH, So that silicone hydroxyl and/or silicone hydroxyl precursor fully react with organic boron acidic group and/or organic boronic ester group.
In view of compound (III), used methods are comparatively numerous and diverse during preparation and preservation, because The raw material components that this is used to prepare dynamic aggregation thing in silicon-containing compound (II) preferentially in organoboron compound (I) with being arranged in pairs or groups Selection, but one of important composition of compound (III) and dynamic aggregation raw material, it is specific with its in certain special cases Advantage, it is impossible to ignore.
When from the compound (IV) containing organic boronic estersil key to prepare dynamic aggregation thing, it can first pass through from conjunction Suitable organoboron compound (I) and silicon-containing compound (II) prepare compound (IV), then the compound prepared (IV) is passed through Suitable polymerized/cross-linked method obtains dynamic aggregation thing, also can not optionally contain the compound prepared (IV) with other The compound of organic boronic estersil key obtains dynamic aggregation thing by suitable polymerized/cross-linked method.
Wherein, described suitable polymerization, it can be anti-by the general any suitable polymerization in this area It should carry out, include but are not limited to condensation polymerization reaction, polyaddition reaction, ring-opening polymerization；Wherein, addition polymerization is anti- Raolical polymerizable, anionic polymerisation, cationic polymerization, coordination poly-merization should be included but are not limited to.
In specific implementation process, compound (IV), the compound containing other reactive groups can utilize above-mentioned appoint A kind of polymerisation process, implemented by the general any suitable polymerization technique in this area, to obtain dynamic aggregation Thing.For example, when compound (IV), the compound containing other reactive groups obtain dynamic aggregation thing in the form of condensation polymerization When, it can be implemented by polymerization techniques such as melt polymerization, polymerisation in solution, interfacial polymerizations；In another example when compound (IV), When compound containing other reactive groups obtains dynamic aggregation thing in the form of radical polymerization, it can be gathered by body The polymerization techniques such as conjunction, polymerisation in solution, suspension polymerisation, emulsion polymerization are implemented；For another example when compound (IV), contain other When the compound of reactive group obtains dynamic aggregation thing in the form of ionic polymerization, its can by polymerisation in solution, slurry polymerization, The polymerization techniques such as gas-phase polymerization are implemented.
The melt polymerization being previously mentioned in above-mentioned polymerization technique, its common implementation are by compound (IV), contained The compound of other reactive groups is under molten condition, is gathered using the condition such as initiator or light, heat, irradiation, catalysis Close, obtain the dynamic aggregation thing of molten condition；The polymerisation in solution being previously mentioned, its common implementation be by compound (IV), Compound, initiator containing other reactive groups, which are dissolved in appropriate solvent, to be polymerize to obtain dynamic aggregation thing；It is previously mentioned Interfacial polymerization, its common implementation is that compound (IV), the compound containing other reactive groups are dissolved in into two In the immiscible solvent of kind, (or interface organic phase side) is polymerize to obtain dynamic aggregation thing on the interface of solution；Institute The polymerisation in bulk mentioned, its common implementation are few by compound (IV), the compound containing other reactive groups It is polymerize to obtain dynamic aggregation thing under the conditions of amount initiator or light, heat, irradiation, catalysis etc.；The suspension polymerisation being previously mentioned, it is logical Normal implementation is that compound (IV), the compound containing other reactive groups dissolved with initiator are stirred into small liquid Drop, is suspended in aqueous medium and is polymerize to obtain dynamic aggregation thing；The emulsion polymerization being previously mentioned, its common implementation be by Compound (IV), the compound containing other reactive groups are dispersed in the water dissolved with initiator by the effect of emulsifying agent and are situated between In matter, it is polymerize to obtain dynamic aggregation thing again after forming emulsion；The slurry polymerization being previously mentioned, its common implementation be by Compound (IV), the compound containing other reactive groups are dissolved in appropriate solvent, and initiator is then deposited in the form of dispersion It is being polymerize in solvent, obtained dynamic aggregation thing is separated out in the form of precipitating；The gas-phase polymerization being previously mentioned, its is common Implementation be by compound (IV), the compound containing other reactive groups under gas phase state, using initiator or light, The conditions such as heat, irradiation, catalysis are polymerize to obtain dynamic aggregation thing.
Described suitable cross-linking method, it can be entered by the general any suitable cross-linking reaction in this area OK.
In specific implementation process, compound (IV), the compound containing other reactive groups can utilize thermal initiation to hand over Connection, photo-initiated crosslinking, radiation-induced crosslinking, plasma trigger crosslinking, microwave to trigger the physical crosslinking means such as crosslinking to be moved State polymer；Peroxide crosslinking is can also be used in compound (IV), the compound containing other reactive groups, sulfide is handed over The chemical crosslinking means such as connection, nucleopilic reagent substitution crosslinking, crosslinking copolymerization, ion complexation crosslinking obtain dynamic aggregation thing.It was crosslinked Journey can be carried out in the form of body, solution, emulsion etc..When being dissociated for the ease of the organic boronic estersil key of dynamic reversible, polymerization Objects system can resolve into following any or several units：Monomer, polymer chain fragment, straight chain polymer unit, non-friendship Linked polymer unit, polymer cluster unit etc., it is necessary to assure the degree of cross linking of chemical crosslinking is less than gel point.
In embodiments of the present invention, its in organoboron compound (I), silicon-containing compound (II), compound (III) His reactive group can also form common covalent attachment by above-mentioned polymerized/cross-linked method between compound.Organic boron chemical combination Thing (I), silicon-containing compound (II), compound (III) can also use polymerisation in solution/crosslinking process, emulsion polymerization/crosslinking process To prepare dynamic aggregation thing.Described polymerisation in solution/crosslinking process, emulsion polymerization/crosslinking process, it has and can reduce system Viscosity, it is easy to mass-and heat-transfer, the advantage be easy to temperature control, hot-spot can be avoided, the solution obtained, emulsion are easy to concentrate Or it is scattered, be advantageous to be coated, mix etc. and operate.
In each preparation embodiment of the present invention, it can be incited somebody to action by any appropriate material hybrid mode known in the art For the raw material necessarily matched by being mixed with dynamic aggregation thing, it can be interval, semicontinuous or continuous processing form mixing； Similarly, interval also may be selected, semicontinuous or continuous processing form is molded to dynamic aggregation thing.The hybrid mode bag of use Include but be not limited only to solution be stirred, melt be stirred, mediate, banburying, 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, which provides form, to be included but not only 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, flow casting molding, calendering formation, cast molding.
In the preparation process of polymer, dynamic aggregation thing can also be blended with some addible auxiliary agents, filler To form dynamic aggregation thing compound system, but these additives are not necessarily all necessary.
The specific method for preparing dynamic aggregation thing is stirred using solution, typically by shape of the raw material to dissolve or disperse Formula is stirred mixing in the reactor in respective solvent or in common solvent.Generally, hybrid reaction temperature control At 0-200 DEG C, preferably 25-120 DEG C, more preferably 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 mould, at 0-150 DEG C, under preferably 25-80 DEG C of temperature conditionss, places 0- 48h, obtain polymer samples.Reservation solvent can be selected to be made with solution, emulsion, suspension, cream during this as needed Polymer samples existing for the forms such as shape, glue, or selection remove solvent the form such as membranaceous, block is made existing for solid-state gather Compound sample.
When preparing dynamic aggregation thing using the method using compound (IV) as raw material, generally also need to optionally in solvent Middle addition initiator triggers polymerization to obtain dynamic aggregation thing in a manner of polymerisation in solution, or addition dispersant and oil-soluble draw Hair agent is configured to suspension in a manner of suspension polymerisation or slurry polymerization to trigger polymerization to obtain dynamic aggregation thing, or adds and draw Hair agent and emulsifying agent are configured to emulsion in a manner of emulsion polymerization to trigger polymerization to obtain dynamic aggregation thing.Used solution Polymerization, suspension polymerisation, the method for slurry polymerization and emulsion polymerization, are well known to those skilled in the art and widely use Polymerization, can be adjusted according to actual conditions, no longer be developed in details here.
Used solvent, should be carried out according to actual conditions such as reactant, product and courses of reaction in above-mentioned preparation method Selection, include but are not limited to following any solvent or appoint the mixed solvent of several solvents：Deionized water, acetonitrile, acetone, fourth Ketone, benzene,toluene,xylene, ethyl acetate, ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran, methanol, ethanol, chloroform, dichloromethane Alkane, 1,2- dichloroethanes, dimethyl sulfoxide (DMSO), dimethylformamide, dimethyl acetamide, 1-METHYLPYRROLIDONE, acetic acid isopropyl Ester, n-butyl acetate, trichloro ethylene, mesitylene, dioxanes, Tris buffer solutions, citrate buffer solution, acetic acid buffer solution, Phosphate buffer solution, borate buffer solution etc.；It is preferred that deionized water, toluene, chloroform, dichloromethane, 1,2- dichloroethanes, tetrahydrochysene Furans, dimethylformamide, phosphate buffer solution.
In above-mentioned preparation method, the compound liquid concentration structure of reactant, molecular weight, dissolving selected by for being configured Depending on degree and required dispersity, it is not particularly limited, preferable compound liquid concentration is 0.1~10mol/L, more preferably For 0.1~1mol/L.
The specific method for preparing dynamic aggregation thing is stirred using melting, typically directly stirs raw material in the reactor Reaction is stirred after mixing mixing or heating melting, and such a mode is gas, liquid or the relatively low solid of fusing point typically in raw material In the case of use.Generally, hybrid reaction temperature control is at 0-200 DEG C, and preferably 25-120 DEG C, more preferably 25-80 DEG C, mixing is stirred Time control is mixed in 0.5-12h, preferably 1-4h.The product obtained after mixing can be poured into suitable mould, in 0- 150 DEG C, under preferably 25-80 DEG C of temperature conditionss, 0-48h is placed, obtains polymer samples.
When preparing dynamic aggregation thing using the method using compound (IV) as raw material, generally also need to be optionally added into less Initiator is measured in a manner of melt polymerization or gas-phase polymerization to trigger polymerization to obtain dynamic aggregation thing.Melting is poly- used by it Close, the method for gas-phase polymerization, be well known to those skilled in the art and widely used polymerization, can be according to actual feelings Condition is adjusted, and is no longer developed in details here.
The specific method of dynamic aggregation thing is mixed with using melting extrusion, is typically to add the raw material into extruder Row extrusion blending reaction, extrusion temperature are 0-280 DEG C, preferably 50-150 DEG C.Reaction product directly can be cut into conjunction after flow casting molding Suitable size, or obtained extrusion sample is carried out after crushing, utilize injection machine or moulding press to carry out sample preparation.Injection temperature is 0-280 DEG C, preferably 50-150 DEG C, the preferred 60-150MPa of injection pressure；Molding temperature be 0-280 DEG C, preferably 25-150 DEG C, more It is preferred that 25-80 DEG C, preferably clamp time 0.5-60min, 1-10min, the preferred 4-15MPa of molding pressure.Batten can be placed in In suitable mould, at 0-150 DEG C, under preferably 25-80 DEG C of temperature conditionss, 0-48h is placed, obtains final polymer samples.
In the preparation process of dynamic aggregation thing, selected organoboron compound (I), silicon-containing compound (II), chemical combination Thing (III), compound (IV), compound containing other reactive groups can flexible handle into component selections and formula rate Hold, but should be closed according to target material performance and the structure of selected compounds, the reactive group number contained and molecular weight The design and combination of reason.Wherein, the organoboron compound (I) that is added, silicon-containing compound (II), compound (III), compound (IV), the compound containing other reactive groups should ensure that the functional group in reactant system and/or other reactive groups Molar equivalent than in appropriate scope.Contain in organoboron compound (I), silicon-containing compound (II), compound (III) Organic boron acidic group and/or organic boronic ester group and silicone hydroxyl and/or the molar equivalent ratio preferably 0.1 of silicone hydroxyl precursor functional group ~10 scope, more preferably 0.3~3 scope, more preferably 0.8~1.2 scope, wherein, organic boron acidic group and/or organic boron Perester radical functional group molal quantity can be suitably excessive.Contain when in organoboron compound (I), silicon-containing compound (II), compound (III) The molar equivalent ratio of some functional groups is close to 1:When 1, the good dynamic aggregation thing of available extent of reaction height, stability；When The molar equivalent for the functional group contained in organoboron compound (I), silicon-containing compound (II), compound (III) is than deviateing 1:1 When, then it can obtain the preferable dynamic aggregation thing of dynamic.Similarly, when from compound (IV), contain other reactive bases When the compound of group prepares dynamic aggregation thing as reactive component, the molar equivalent ratio of other reactive groups in reactant system Also appropriate scope is should be at, carries out the molar equivalent of other reactive groups of polymerized/cross-linked reaction than preferably 0.1~10 Scope, more preferably 0.3~3 scope, more preferably 0.8~1.2 scope.In actual fabrication process, those skilled in the art Member can be adjusted according to being actually needed.
Organoboron compound (I), siliceous compound (II), compound (III) and compound (IV) are utilized in the present invention , can be with by the design and adjustment to compound structure during preparing the dynamic aggregation thing containing organic boronic estersil key Foundation is needed the functional group of varying number, the molecule segment of different structure, the molecule segment of different molecular weight, reactive base The organic structures such as group, functional groups are incorporated into raw materials of compound, and turn into the structure of dynamic aggregation thing by preparation process Component, so as in regulation and control of the interior realization to dynamic aggregation thing structure in a big way.The diversity of dynamic aggregation thing structure, also cause It embodies abundant different performance, and can the performance according to possessed by polymer be applied to different fields.More attach most importance to Want, those skilled in the art often also can be according to the needs of practical application, structure and performance from source to polymer It is designed；During this, technology people can be turned into if used organic structure (such as organic boron structure, organosilicon structures) Member's regulation and control and effective medium of design dynamic aggregation thing structure.And these above-mentioned advantages and feature, in inorganic compound field In be often difficult to realize, for inorganic compound (such as inorganic boric acid, inorganic borate etc.), often structure is single for it, function Group's number is fixed, and progress is out-phase reaction, is duplicated using the polymer general structure obtained by it, property, and is obtained inorganic Boric acid estersil key easily absorbs water hydrolysis, is used for causing limitation.
Wherein, by being set to structure of functional groups in organoboron compound (I), silicon-containing compound (II), compound (III) Meter, the dynamic aggregation thing with Different Dynamic activity can be prepared.For example, phenyl boric acid/benzene of aminomethyl is connected with using ortho position Phenyl boric acid/borate ester structure that boric acid ester structure or ortho position are connected with amide groups prepares dynamic aggregation thing, the aminomethyl at ortho position Or amide groups can play the effect for promoting dynamic；For another example the boron in organic boron acidic group and/or organic boronic ester group is former After strong electron-withdrawing group (such as fluorine atom, acetate, pyridine radicals, piperidyl) is connected with son, itself and silicone hydroxyl and/or silicone hydroxyl The reaction rate of presoma also greatly improves；Thus resulting dynamic aggregation thing can embody higher dynamic activity, make The organic boronic estersil key obtained in polymer can show dynamic reversibility under conditions of more gently, also make it that dynamic is poly- Compound can be prepared and used under conditions of more gentle, extend the application of polymer.
In the preparation process of dynamic aggregation thing, by regulating and controlling organoboron compound (I), silicon-containing compound (II), chemical combination Functional group number in thing (III), can prepare the dynamic aggregation thing with different crosslinking degrees, and the performance of dynamic aggregation thing Also with crosslinking degree difference and difference.For utilizing the material made by the relatively low dynamic aggregation thing of crosslinking degree, Its usual mechanical strength and mechanical moduli are relatively low, and toughness and ductility are excellent, and heat endurance and dimensional stability are poor, typically exist Soft texture, case hardness are low in macro manifestations, can be stretched on a large scale；Typically can be as fexible film, gluing Agent, fluid sealant use, or are configured to solution or emulsion and are used as coating, impregnating agent.And it is crosslinked journey for utilizing Material made by the higher dynamic aggregation thing of degree, its usual mechanical strength and modulus are higher, toughness, heat endurance, wearability And creep resistance all increases, but ductility can decline, and be with more excellent resilience typically in macro manifestations Property or be presented rigid colloid or solid；It can typically enter as the film with some strength, fiber or bulk material Exercise and use.
In the present invention, prepared at least with a kind of compound with polyfunctional group number with dynamic crosslinking structure Dynamic aggregation thing.During merely using bifunctional compound forming dynamic aggregation thing, by bifunctional compound institute in itself The active function groups number having is less, and when compound molecular weight is larger, these active function groups are possible to because molecule The curling of chain is wound and reaction can not be participated in by being embedded in polymer chain, reduces organic boron acidic group and/or organic boronic ester group Reaction efficiency between functional group and silicone hydroxyl and/or silicone hydroxyl presoma functional group；Meanwhile merely utilize difunctionality dough Compound carries out dynamic aggregation reaction, and obtained is linear dynamic aggregation thing, utilizes the usual power of material made of such polymer Learn intensity and mechanical moduli is relatively low, heat endurance, dimensional stability, solvent resistance are poor, are applied to cause limitation.It is and sharp When being polymerize with polyfunctional compound, dynamic aggregation reactivity point is added, improves dynamic crosslinking efficiency, while So that the dynamic crosslinking point in polymer increases, the utilization rate of dynamic covalent bond in dynamic aggregation thing is improved so that organic boron Possessed dynamic characteristic is embodied sour estersil key well in itself.Meanwhile the obtained dynamic with dynamic crosslinking structure Polymer, when as materials'use, relative to linear dynamic aggregation thing material, the polymeric material of dynamic crosslinking is in power for it Performance, heat endurance, wearability, solvent resistance and creep resistance etc. is learned to be improved, it is poly- so as to extend dynamic The application of compound.
In the preparation process of dynamic aggregation thing, by regulating and controlling organoboron compound (I), silicon-containing compound (II), chemical combination The compliance of strand in thing (III), compound (IV), the compound containing other reactive groups, can prepare has The dynamic aggregation thing of heterogeneity feature, the dynamic aggregation thing of acquisition can have one or more glass transition temperature. For mainly by flexible chain (such as Polyethylene Chain, polyglycol chain, polysiloxane chain, polybutadiene chain, polyacrylic acid chain, polyester Chain etc.) compound that forms and/or the compound of flexible chain can be aggregated into, as the dynamic aggregation thing molecule segment obtained by it Internal rotation is relatively easy, typically (general with relatively low glass transition temperature (being generally not more than 25 DEG C) and relatively low fusing point Not higher than 100 DEG C), good fluidity；Pliability is big, and fragility is low generally macroscopically showing as material, can be stretched and be bent, Dissolubility is preferable, but rigidity, heat resistance and dimensional stability are weaker, can typically enter as gel, adhesive, elastomeric material Exercise and use.For being mainly made up of rigid chain (such as polyacetylene chain, Nomex chain, polyphenylene oxide chain, polybenzothiozole chain etc.) Compound and/or the compound that rigid chain can be aggregated into, as the dynamic aggregation thing obtained by it due to molecule segment internal rotation Relative difficulty is general (to be generally greater than 100 with higher glass transition temperature (being generally greater than 25 DEG C) and higher fusing point DEG C), larger melt viscosity；Material generally macroscopically has larger a rigidity and case hardness, stronger dimensional stability, Heat resistance and chemical resistance, but ductility is relatively low, can typically be used as structural elements.Used when simultaneously Compound containing flexible chain and rigid chain and/or when can aggregate into flexible and rigid chain compound simultaneously, it is obtained Dynamic aggregation thing generally there are the obvious glass transition temperature of multiple difference, polymeric material have moderate rigidity, hardness, Compliance, its mechanical property can be adjusted according to different formulas, typically can be as film, coating, damping material Used.In the present invention, because the dynamic aggregation thing with flexible structure can embody more excellent dynamic reversible Property and tensile toughness, thus preferably by with flexible structure and/or can aggregate into flexible chain organoboron compound (I), Silicon-containing compound (II), compound (III), compound (IV), the compound containing other reactive groups are poly- to prepare dynamic Compound.
In the preparation process of dynamic aggregation thing, by regulating and controlling organoboron compound (I), silicon-containing compound (II), chemical combination Thing (III), compound (IV), the molecular weight of compound containing other reactive groups, can be prepared with different crosslinkings The dynamic aggregation thing of density, it also shows different property features due to the difference of crosslink density.The crosslinking of dynamic aggregation thing Density is lower, and the polymer chain molecular weight between crosslinking points is bigger, on the contrary then smaller.For the relatively low dynamic aggregation of crosslink density Thing, its general glass transition temperature and fusing point are relatively low, and rigidity and case hardness are relatively low, and mechanical strength is low, but can embody Preferable dynamic activity；For the higher dynamic aggregation thing of crosslink density, its general glass transition temperature and fusing point are higher, energy Preferable mechanical strength, toughness and elasticity are enough shown, but dynamic activity can decline.Those skilled in the art can basis It is actually needed and is adjusted.
In addition, in the preparation process of dynamic aggregation thing, can also be by organoboron compound (I), silicon-containing compound (II) mode of functional groups, is introduced in compound (III), compound (IV), the compound containing other reactive groups The performance of dynamic aggregation thing is regulated and controled.For example, improve the hydrolytic resistance of dynamic aggregation thing by introducing hydrophobic group； The fluorescent dynamic aggregation thing of tool is prepared by introducing fluorophor；Dynamic aggregation is improved by introducing antioxidant groups The inoxidizability of thing；The dynamic of dynamic aggregation thing is adjusted by introducing acidic-group or basic group.In another example , can also be by introducing and the similar structure of other polymers when needing dynamic aggregation thing and other polymers being blended Component or coupling group, come reach improve component between compatibility purpose.
All is only that the compound group separation structure in the present invention as raw material can be played to dynamically poly- as previously discussed The PART explanation of compound performance regulation and control, the design for dynamic aggregation thing properity, purposes in the present invention, its is adjustable It is in extensive range, reflect many unexpected actual effects toward contact, it is difficult to accomplish exhaustion, those skilled in the art can To be adjusted according to the thinking of the present invention.
In the preparation process of dynamic aggregation thing, some addible auxiliary agents for being added, it can improve polymer system Standby process, improve product quality and yield, reduce product cost or assign product certain distinctive application performance.Described can The auxiliary agent of addition may be selected from following any or appoint several auxiliary agents：Additive synthesis, including catalyst, initiator；Stabilizing additive, Including antioxidant, light stabilizer, heat stabilizer；Improve the auxiliary agent of mechanical property, including crosslinking agent, toughener, coupling agent；Improve The auxiliary agent of processing characteristics, including lubricant, releasing agent；Softness and the auxiliary agent of lighting, including plasticizer, dynamic regulation agent； Change the auxiliary agent of surface property, including antistatic additive, emulsifying agent, dispersant；Change the auxiliary agent of coloured light, including colouring agent, fluorescence Brightening agent, delustering agent；Fire retardantization and suppression cigarette auxiliary agent, including fire retardant；Other auxiliary agents, including nucleator, rheological agent, thickener, Levelling agent.It should be noted that the crosslinking agent in described addible auxiliary agent, is only needing in chemical combination of the same race or not of the same race Between thing common be covalently attached for can just be used in the case of preparing dynamic aggregation thing is formed using physical/chemical crosslinking means Arrive, such as can rely on organic boronic estersil key or other formation of chemical bond dynamic aggregation things, then not must be added to such help Agent, and the common covalent cross-linking formed must be polymerize below the gel point of covalent cross-linking with obtaining described dynamic crosslinking Thing.
Catalyst in described addible auxiliary agent, it can reduce reaction activity by changing reaction path Accelerate the reaction rate of reactant during the course of the reaction.It includes but are not limited to following any or appoints several catalyst：Hydrogen Sodium oxide molybdena, potassium hydroxide, calcium hydroxide, ethylenediamine, triethanolamine, triethylamine, pyridine, 4-dimethylaminopyridine, imidazoles, two Diisopropylethylamine, sodium carbonate, sodium acid carbonate, acetic acid, sulfuric acid, phosphoric acid, carbonic acid, hypochlorous acid, hydrofluoric acid；Wherein, catalyst is excellent Select sodium hydroxide, triethylamine, acetic acid.Catalyst amount used is not particularly limited, generally 0.01-0.5wt.%.
Initiator in described addible auxiliary agent, its can cause in polymerization process monomer molecule activate and Free radical is produced, improves reaction rate, promotes reaction to carry out, includes but are not limited to following any or appoints several initiators： Organic peroxide, such as lauroyl peroxide, benzoyl peroxide (BPO), di-isopropyl peroxydicarbonate, the carbon of peroxidating two Sour dicyclohexyl maleate, dicetyl peroxydicarbonate double (4- tert-butylcyclohexyls) ester, tert butyl peroxy benzoate, tert-butyl hydroperoxides Pivalate, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide；Azo-compound, such as azodiisobutyronitrile (AIBN), occasionally Two different heptonitrile of nitrogen；Inorganic peroxide, such as ammonium persulfate, potassium peroxydisulfate；Wherein, the preferred lauroyl peroxide of initiator, mistake BP, azodiisobutyronitrile, potassium peroxydisulfate.Initiator amount used is not particularly limited, generally 0.1- 1wt.%.
Antioxidant in described addible auxiliary agent, it can delay the oxidizing process of polymer samples, ensure material It can successfully carry out preparing processing 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- (hydroxyl -5- tert-butyl-phenyls of 2- methyl -4) fourth Alkane, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, 2,2 '-di-2-ethylhexylphosphine oxide (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 diamine, 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 BHA (BHA), dibutyl hydroxy toluene (BHT), TBHQ (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 described addible auxiliary agent, it can prevent polymer samples from light aging occurs, extending it makes With the life-span, it includes but are not limited to following any or appoints several light stabilizers：Photomask agent, such as carbon black, titanium dioxide, oxygen Change zinc, calcium sulfite；Ultra-violet absorber, such as ESCALOL 567,2- hydroxyl -4- n-octyloxy hexichol first Ketone, 2- (2- hydroxyl -3,5- di-tert-butyl-phenyls) -5- chlorobenzotriazoles, 2- (2- hydroxy-5-methyl bases phenyl) BTA, 2, 4,6- tri- (2- hydroxyl -4- n-butoxyphenyls) -1,3,5- s-triazine, 2- cyano group -3,3- diphenylacrylate 2- ethylhexyls； Pioneer's type ultra-violet absorber, such as the p- tert-butyl group phenyl ester of salicylic acid, double acid double phenol A ester；UV quenchers, such as double (3, 5- di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester), 2,2 '-thiobis (4- spy's octyl phenol epoxide) nickel；Hindered amine light stabilizer Agent, as double (2,2,6, the 6- tetramethyl piperidine) ester of decanedioic acid, benzoic acid (2,2,6,6- tetramethyl piperidine) ester, three (1,2,2,6, 6- pentamethvls base) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acids (2,4- di-t-butyls Benzene) ester, alkyl phosphoric acid acid amides, N, N '-zinc dibutyl dithiocaarbamate, N, N '-second, n-butyl dithiocarbamate Nickel etc.；Wherein, double (2,2,6,6- tetramethyl piperidine) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid.Used Light stabilizer dosage is not particularly limited, generally 0.01-0.5wt.%.
Heat stabilizer in described addible auxiliary agent, enable to polymer samples during processing or use not Chemical change occurs because heated, or delays these changes to reach the purpose to increase the service life, it includes but not only limited In following any or several heat stabilizers：Lead salts, as lead sulfate tribasic, dibasic lead phosphite, dibasic are stearic Lead plumbate, dibasic phthalic acid lead, tribasic Malaysia lead plumbate, slag lead silicate, lead stearate, lead salicylate, dibasic are adjacent Phthalic acid lead, basic lead carbonate, silica gel co-precipitation lead silicate；Metal soap：As cadmium stearate, barium stearate, calcium stearate, Lead stearate, zinc stearate；Organo-tin compound class, such as di-n-butyltin dilaurate, Bis(lauroyloxy)dioctyltin, Malaysia Sour two (just) butyl tins, double single-ethylhexyl maleate dioctyltins, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital tin C-102, Dimercapto acetic acid isooctyl stannous methide, two mercaptan stannous methides and its compound；Antimony stabilizer, such as mercaptan antimonic salt, sulfydryl second Acid esters mercaptans type, mercapto-carboxylic ester antimony, carboxylate antimony；Epoxy compound species, such as epoxidized oil, epoxy aliphatic ester, asphalt mixtures modified by epoxy resin Fat；Phosphorous acid esters, as the aromatic ester of phosphorous acid three, the alkyl ester of phosphorous acid three, the aralkyl ester of phosphorous acid three, alkane virtue mixed ester, aggretion type are sub- Phosphate；Polyalcohols, such as pentaerythrite, xylitol, mannitol, D-sorbite, trimethylolpropane；Composite thermal stabilizer, Such as it is co-precipitated metallic soap, liquid metal soap compound stabilizer, organotin compound stabilizer；Wherein, heat stabilizer is preferably stearic Sour barium, calcium stearate, di-n-butyltin dilaurate, maleic acid two (just) butyl tin.Heat stabilizer dosage used is without spy Do not limit, generally 0.1-0.5wt.%.
Crosslinking agent in described addible auxiliary agent, for forming the common covalent attachment or common covalent of non-crosslinked property Cluster, namely for increasing with the non-crosslinked property degree of branching that is commonly covalently attached or forming small size cluster, it is included but not It is only limitted to following any or appoints several crosslinking agents：Sulphur, benzoquinones dioxime, 4,4 '-dibenzoyl paraquinonedioxime, ethylenediamine, two Ethene triamine, triethylene tetramine, dimethylaminopropylamine, hexamethylenetetramine, m-phenylene diamine (MPD), phthalic anhydride, maleic two Acid anhydrides, pyromellitic acid dianhydride, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazoles, boron trifluoride complex, positive silicon Acetoacetic ester, methyl silicate, p-methyl benzenesulfonic acid, paratoluensulfonyl chloride, diacrylate -1,4- butanediol esters, dimethacrylate Glycol ester, butyl acrylate, aluminium isopropoxide, zinc acetate, titanium acetylacetone, aziridine, isocyanates, phenolic resin, peroxide Change diisopropylbenzene (DIPB), lauroyl peroxide, peroxidating stearoylketene, benzoyl peroxide, cyclohexanone peroxide, benzoyl peroxide ethyl ketone, Di-t-butyl peroxide, adjacent benzene peroxide dicarboxylate, isopropyl benzene hydroperoxide etc.；Wherein, the preferred sulphur of crosslinking agent, mistake Aoxidize diisopropylbenzene (DIPB) (DCP), benzoyl peroxide (BPO), ethylenediamine (EDA), diethylenetriamine (DETA), phthalic acid Acid anhydride, maleic anhydride.Dosage of crosslinking agent used is not particularly limited, generally 0.1-5wt.%.
Toughener in described addible auxiliary agent, polymer samples fragility can be reduced, increase toughness, improve material Bearing strength, it includes but are not limited to following any or appoints several toughener：Methyl methacrylate-butadiene-benzene second Alkene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modifier, acrylic nitrile-butadiene two Alkene-styrol copolymer, acrylonitrile-butadiene copolymer, the glue of second third, ethylene-propylene diene copolymer, cis-butadiene cement, butadiene-styrene rubber, styrene-fourth Styrene block copolymer etc.；Wherein, the preferred glue of second third of toughener, acrylonitrile-butadiene-styrene copolymer (ABS), SBS (SBS), MBS Resin (MBS), chlorinated polyethylene resin (CPE).Toughener dosage used is not particularly limited, generally 5-10wt.%.
Coupling agent in described addible auxiliary agent, can improve polymer samples and inorganic filler or reinforcing material Interface performance, in plastic processes reduce material melt viscosity, improve the decentralization of filler to improve processing characteristics, And then product is obtained good surface quality and machinery, heat and electrical property, it includes but are not limited to following any or appointed Several coupling agents：Chromium of organic acid complex compound, silane coupler, titanate coupling agent, sulfonyl azide coupling agent, aluminate coupling agent Deng；Wherein, the preferred gamma-aminopropyl-triethoxy-silane of coupling agent (Silane coupling agent KH550), γ-(2,3- the third oxygen of epoxy) third Base trimethoxy silane (silane coupler KH560).Coupling agent dosage used is not particularly limited, generally 0.5- 2wt.%.
Lubricant in described addible auxiliary agent, it is possible to increase the lubricity of polymer samples, reduce friction, reduce Interface Adhesion performance, it includes but are not limited to following any or appoints several lubricants：Saturated hydrocarbons and halogenated hydrocarbon, such as solid Paraffin, microcrystalline wax, atoleine, low molecular weight polyethylene, OPE；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 stearamide；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 described addible auxiliary agent, it can make polymer samples be easy to be stripped, and surface is smooth, clean, It includes but are not limited to following any or appoints several releasing agents：Paraffin hydrocarbon, soaps, dimethicone, ethyl silicon oil, methyl It is phenyl silicone oil, castor oil, used oil, mineral oil, molybdenum disulfide, polyethylene glycol, vinyl chloride resin, polystyrene, silicon rubber, poly- Vinyl alcohol etc.；Wherein, the preferred dimethicone of releasing agent, polyethylene glycol.Releasing agent dosage used is not particularly limited, typically For 0.5-2wt.%.
Plasticizer in described addible auxiliary agent, it can increase the plasticity of polymer samples so that polymer Hardness, modulus, softening temperature and brittle temperature decline, and elongation, flexibility and pliability improve, its include but are not limited to Under it is any or appoint several plasticizer：Phthalates：Dibutyl phthalate, dioctyl phthalate, adjacent benzene two Formic acid di-isooctyl, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, O-phthalic It is double (13) ester of sour butyl benzyl, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid, right Phthalic acid two (2- ethyls) own ester；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyls) own ester；Fatty acid ester Class, such as the own ester of adipic acid two (2- ethyls), decanedioic acid two (2- ethyls) own ester；Epoxy compound species, such as epoxy glycerite esters, ring Oxygen fatty-acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, the own ester of epoxystearic acid (2- ethyls), epoxy Soybean oleic acid 2- ethylhexyls, the own ester of 4,5- epoxies tetrahydrophthalic acid two (2- ethyls), Chinese littleleaf box methyl acetylricinolate； Dihydric alcohol lipid, such as C5~9Sour glycol ester, C5~9Sour Triethylene Glycol；Chloride class, such as afforest paraffin class, chloro fat Acid esters；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester, phenyl alkylsulfonate, inclined benzene three Acid esters, citrate, pentaerythrite and pentaerythritol fatty acid ester etc.；Wherein, plasticizer pref-erable dioctyl phthalate (DOP), Dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), adjacent benzene The isodecyl ester (DIDP) of dioctyl phthalate two, tricresyl phosphate (TCP).Plasticizer consumption used is not particularly limited, generally 5- 20wt.%.
Dynamic regulation agent in described addible auxiliary agent, the dynamic of regulation organic boronic estersil key can be lifted, To obtain the expected performance of optimization, it is usually the compound with free hydroxyl or free carboxyl group, including but not only It is limited to water, sodium hydroxide, alcohol (including silanol), carboxylic acid etc..Dynamic regulation agent dosage used is not particularly limited, generally 0.1-10wt.%.
Antistatic additive in described addible auxiliary agent, the deleterious charge assembled in polymer samples can be guided or disappeared Remove, make it not to producing and life brings inconvenience or endangered, it includes but are not limited to following any or appointed several antistatic Agent：Anionic antistatic agent, such as alkylsulfonate, to ABPS, alkyl phosphate diethanolamine salt, Alkylphenol-polyethenoxy base ether sulfonic acid triethanolamine, to nonyl diphenyl ether potassium sulfonate, the ethanol of alkyl polyoxyethylene base ether sulfonic acid three Double [two (2- the ethylol amines)] phosphates of amine, phosphate derivative, phosphate, phosphoric acid polyethylene oxide alkyl ethers alcohol ester, alkyl, Phosphate derivative, fatty amine sulfonate, butyrate sodium sulfonate；Cationic antistatic agent, such as aliphatic ammonium salt hydrochlorate, lauryl Trimethyl ammonium chloride, dodecyl trimethylamine bromide, N, N- cetyl-ethyl morpholine ethyl-sulfate salt, stearamide propyl (2- ethoxys) dimethylammonium nitrate, alkyl hydroxyethyl dimethylammonium perchlorate, the high chlorine of 2- alkyl -3,3- dihydroxy ethyl imidazolines Hydrochlorate, 2- heptadecyl -3- ethoxy -4- carboxymethyls imidazoline, double (α-ethoxy)-N-3 (dodecyloxy -2- hydroxyls of N, N- Propyl group) first ammonium Methylsulfate salt；Amphoteric ion type antistatic additive, such as alkyl dicarboxyl ammonium methyl second inner salt, lauryl betaine, N, N, N- trialkyl ammonium acetyl (N '-alkyl) amine second inner salt, the polyethylene oxide base-N- ethylphosphonic acids sodium of N- lauryls-N, N- bis-, alkane Salt hydroxide, 2- alkyl -3- ethoxy -3- acetic acid alkali imidazolines quaternary amine alkali, N- alkyl in base two (polyoxyethylene) ammonium second Amino-acid salt；Non-ionic antistatic agent, such as fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide addition product, alkyl phenol Ethylene oxide adduct, tricresyl phosphate polyoxyethylene groups ether-ether, fatty acid monoglyceride, the polycyclic of sorbitan mono-laurate Oxidative ethane addition product；Polymer Antistatic Agent, ethylene oxide propylene oxide addition product, polyethylene glycol such as ethylenediamine-to benzene Dicarboxylic acid esters -3,5- dibenzoates sodium sulfonate copolymers, polyene propionamide N- quaternary ammonium salts substituent, poly- 4- vinyl -1- third Ketone group pyridine phosphoric acid-to butyl phenyl ester salt etc.；Wherein, the preferred lauryl trimethyl ammonium chloride of antistatic additive, hexadecyldimethylamine Base ethoxy quaternary ammonium nitrate (antistatic additive SN), alkyl phosphate diethanolamine salt (antistatic additive P).Antistatic additive used Dosage is not particularly limited, generally 0.3-3wt.%.
Emulsifying agent in described addible auxiliary agent, various compositions in the mixed with polymers liquid comprising auxiliary agent can be improved Surface tension between phase, it is allowed to form uniform and stable dispersion or emulsion, it is preferred for carrying out emulsion polymerization/friendship Connection, it includes but are not limited to following any or appoints several emulsifying agents：Anionic, such as higher fatty acid salt, alkyl sulfonic acid Salt, alkylbenzenesulfonate, Negel, sulphosuccinates, petroleum sulfonate, aliphatic alcohol sulfate, castor oil sulphur Acid esters salt, sulphation butyl ricinoleate salt, phosphate ester salt, fatty acyl-peptide condensation product；Cationic, such as alkylammonium salt, alkyl quaternary Ammonium salt, Fixanol；Amphoteric ion type, such as carboxylic acid ester type, sulfonic acid ester type, sulfuric acid ester type, phosphate type；Nonionic, such as AEO, APES, polyoxyethylene carboxylate, PPOX-ethylene oxide adduct, Fatty acid glyceride, pentaerythritol fatty ester, sorbierite and sorbitan fatty acid ester, sucrose fatty ester, hydramine fat Fat acid amides etc.；Wherein, the preferred neopelex of emulsifying agent, sorbitan fatty acid ester, triethanolamine stearate (Emulphor FM).Emulsifier used is not particularly limited, generally 1-5wt.%.
Dispersant in described addible auxiliary agent, solid flocculation group in mixed with polymers liquid is enabled to be separated into carefully Small particle and be suspended in liquid, it is homogeneous to disperse those and be poorly soluble solid and liquid particles in liquid, while can also prevent The only sedimentation and cohesion of particle, stable suspension is formed, it includes but are not limited to following any or appoints several dispersants：It is cloudy Ionic, such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate；Cationic；Nonionic, such as poly alkyl alcohol Oxygen vinethene, sorbitol anhydride fatty acid APEO；Inorganic type, such as silicate, condensed phosphate；Polymer electrolyte, such as form sediment Powder, gelatin, water-soluble glue, lecithin, carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, lignosulfonates, poly- second Enol, beta-naphthalenesulfonic-acid formaldehyde condensation compound, the ethylene oxide condensate of alkyl phenol formaldehyde condensation product, polycarboxylate etc.；Wherein, divide The preferred neopelex of powder, naphthalene system methylene sulfonate (dispersant N), AEO.Point used Powder dosage is not particularly limited, generally 0.3-0.8wt.%.
Colouring agent in described addible auxiliary agent, polymeric articles can be made to show required color, increase Surface color and polish, it includes but are not limited to following any or appoints several colouring agents：Inorganic pigment, as titanium white, chrome yellow, cadmium red, Iron oxide red, molybdate red, ultramarine, chrome green, carbon black；Organic pigment, such as lithol red BK directions, lake red C, red, good base R is red, phthalocyanine Red, fast carmine HF3C, the bright red R of plastics and the not red BR of clo, forever solid orange HL, Fast Yellow G, vapour bar plastics Huang R, permanent yellow 3G, Permanent yellow H2G, phthalocyanine blue B, dark green, plastics purple RL, nigrosine；Organic dyestuff, such as thioindigo red, vat yellow 4GF, indanthrene blue RSN, slag rhodamine toner, Oil Yellow etc.；Wherein, the selection of colouring agent is depending on color sample demand, it is not necessary to especially limit It is fixed.Colorant concentrations used are not particularly limited, generally 0.3-0.8wt.%.
Fluorescent whitening agent in described addible auxiliary agent, contaminated material can be made to obtain the sparkling of similar fluorite Effect, it includes but are not limited to following any or appoints several fluorescent whitening agents：Stilbene-based, coumarin type, pyrazoline Type, benzo oxygen nitrogen type, BIDA type etc.；Wherein, (fluorescence increases the preferred stilbene biphenyl sodium disulfonate of fluorescent whitening agent White agent CBS), 4,4- double (5 methyl -2- benzoxazolyls) talan (fluorescent whitening agent KSN), 2,2- (4,4 '-talan Base) dibenzoxazine (fluorescent whitening agent OB -1).Fluorescent whitening agent dosage used is not particularly limited, generally 0.002- 0.03wt.%.
Delustering agent in described addible auxiliary agent, when enabling to incident light arrival polymer surfaces, occur unrestrained anti- Penetrate, produce the matt and delustring outward appearance of low gloss, it includes but are not limited to following any or appoints several delustering agents：Settle sulphur Sour barium, silica, aqueous gypsum powder, talcum powder, titanium dioxide, poly- methyl carbamide resin etc.；Wherein, the preferred titanium dioxide of delustering agent Silicon.Delustering agent dosage used is not particularly limited, generally 2-5wt.%.
Fire retardant in described addible auxiliary agent, by increasing capacitance it is possible to increase the flame resistance of material, its include but are not limited to Under it is any or appoint several fire retardants：Phosphorus system, such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, phosphoric acid Toluene diphenyl ester；Halogen phosphoric acid ester, such as three (2,3- dibromopropyl) phosphates, tricresyl phosphate (2,3- dichloro the third) ester；Organic halogen Compound, such as high chlorine contents chlorinated paraffin, 1,1,2,2- tetrabromoethane, deca-BDE, the decane of perchloro- ring penta；Inorganic combustion inhibitor, Such as antimony oxide, aluminium hydroxide, magnesium hydroxide, Firebrake ZB；Reactive flame retardant, such as chlorendic anhydride, double (2,3- dibromos third Base) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride etc.；Wherein, the preferred deca-BDE of fire retardant, tricresyl phosphate Phenyl ester, tricresyl phosphate, phosphate toluene diphenyl ester, antimony oxide.Amount of flame-retardant agent used is not particularly limited, typically For 1-20wt.%.
Nucleator in described addible auxiliary agent, crystallization speed can be accelerated by changing the crystallization behavior of polymer Rate, increase crystal density and promote fine grain size, reach and shorten material molding cycle, improve the product transparency, surface The purpose of the physical and mechanical properties such as gloss, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance, it include but It is not limited only to following any or appoints several nucleators：Benzoic acid, adipic acid, sodium benzoate, talcum powder, p-phenolsulfonic acid's sodium, Silica, benzylidene sorbitol and its derivative, EP rubbers, ethylene propylene diene rubber etc.；Wherein, the preferred dioxy of nucleator SiClx, benzylidene sorbitol (DBS), ethylene propylene diene rubber.Nucleator dosage used is not particularly limited, generally 0.1- 1wt.%.
Rheological agent in described addible auxiliary agent, it can ensure that polymer has good brushing during film Property and appropriate coating thickness, prevent storage when solid particle sedimentation, it is possible to increase its redispersibility, it includes but not only limited In following any or several rheological agents：Inorganic, such as barium sulfate, zinc oxide, alkaline earth oxide, calcium carbonate, chlorination Lithium, sodium sulphate, magnesium silicate, aerosil, waterglass, colloidal silica；Organo-metallic compound, as aluminum stearate, Aluminium alkoxide, titanium chelate, aluminium chelate compound；Organic, such as organobentonite, rilanit special, rilanit special/amide waxe, fibre Tie up plain derivative, isocyanate derivates, hydroxy compounds, acrylic emulsion, acrylic copolymer, polyvinyl alcohol, polyethylene Wax, cellulose esters etc.；Wherein, the preferred organobentonite of rheological agent, Tissuemat E, hydrophobically modified alkalescence swellable emulsions (HASE), alkali-swellable emulsions (ASE).Rheological agent dosage used is not particularly limited, generally 0.1-1wt.%.
Thickener in described addible auxiliary agent, the good thixotropy of mixed with polymers liquid and appropriate can be assigned Denseness, so as to meet many demands such as its stability and application performance during production, storage and use, it is wrapped Include but be not limited only to following any or appoint several thickeners：Lower-molecular substance, such as soap, AEO sulphur Hydrochlorate, alkyldimethylamine oxide, fatty monoethanol amide, fatty diglycollic amide, aliphatic acid Isopropamide, dehydration mountain Pears alcohol tricarboxylic ester, glycerol trioleate, coamidopropyl glycine betaine, 2- alkyl-N- carboxymethyl-N- hydroxyethyl imidazoles quinoline, Titanate coupling agent；Polymer substance, such as bentonite, artificial hectorite, fine particle silica, colloidal aluminum, plant polyose class, micro- life It is thing polysaccharide, animal protein, cellulose family, starch, marine alga acids, poly-methyl acrylate, methacrylic acid copolymer, suitable Anhydride copolymer, crotonic acid-copolymers, polyacrylamide, polyvinyl pyrrolidone, polyvinyl alcohol, polyethers, polyvinyl methyl ether urethane are gathered Compound etc.；Wherein, the preferred hydroxyethyl cellulose of thickener, coconut oil diethanol amide, acrylic acid-methacrylic acid copolymer. Thickener dosage used is not particularly limited, generally 0.1-1.5wt.%.
It levelling agent in described addible auxiliary agent, can ensure that the flat smooth of polymer coating film is uniform, improve and apply Film surface quality, dicoration is improved, it includes but are not limited to following any or appoints several levelling agents：Polydimethylsiloxanes Alkane, PSI, cellulose acetate butyrate, polyacrylate, organic siliconresin etc.；Wherein, levelling agent is preferred Dimethyl silicone polymer, polyacrylate.Levelling agent dosage used is not particularly limited, generally 0.5-1.5wt.%.
In the preparation process of dynamic aggregation thing, the preferred initiator of addible auxiliary agent, antioxidant, light stabilizer, heat are steady Determine agent, toughener, plasticizer, emulsifying agent, dispersant, fire retardant, dynamic regulation agent.
Described addible filler, it primarily serves following effect in polymer samples：1. reduce molded article Shrinkage factor, improve dimensional stability, surface smoothness, flatness and the zero diopter of product or without photosensitiveness etc.；2. adjust material Viscosity；3. meeting different performance requirement, such as raising material impact intensity and compressive strength, hardness, rigidity and modulus, raising are resistance to Mill property, improve heat distortion temperature, improve electric conductivity and thermal conductivity etc.；4. improve the coloring effect of pigment；5. assign photostability And chemical resistance；6. playing compatibilization, cost can be reduced, improves the competitiveness of product commercially.
Described addible filler, it may be selected from following any or appoint several fillers：Inorganic non-metallic filler, metal are filled out Material, organic filler.
Described addible inorganic non-metallic filler, include but are not limited to following any or appoint several：Calcium carbonate, Clay, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon, quartz, mica powder, clay, asbestos, asbestos fibre, just Feldspar, chalk, lime stone, blanc fixe, gypsum, graphite, carbon black, graphene, CNT, molybdenum disulfide, slag, flue Ash, wood powder and shell powder, diatomite, red mud, wollastonite, silica-alumina carbon black, aluminium hydroxide, magnesium hydroxide, flyash, oil shale powder, Swelling perlite powder, conductive black, vermiculite, iron cement, white clay, alkali mud, boron mud, glass microballoon, resin microbeads, foam microspheres, glass Glass powder, cement, glass fibre, carbon fiber, quartz fibre, charcoal core boron fibre, titanium diboride fiber, calcium titanium fiber, carbon silicon are fine Dimension, ceramic fibre, whisker etc..
Described addible metal packing, include but are not limited to following any or appoint several：Conductive metal filler, Metallic particles, metal and alloyed powder, carbon steel, stainless steel, stainless steel fibre etc..
Described addible organic filler, include but are not limited to following any or appoint several：1. naturally organic fill out Material, as fur, natural rubber, cotton, velveteen, fiber crops, jute, flax, asbestos, cellulose, cellulose acetate, shellac, chitin, Chitosan, lignin, starch, protein, enzyme, hormone, raw lacquer, timber, wood powder, shell powder, glycogen, xylose, silk etc.；2. synthesize Resin extender, such as AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, acetate fiber Element, polytrifluorochloroethylene, haloflex, chliorinated polyvinyl chloride, epoxy resin, ethylene-propylene copolymer, ethylene-acetate second Enoate copolymer, high density polyethylene (HDPE), high impact polystyrene, low density polyethylene (LDPE), medium density polyethylene, melamine-first Urea formaldehyde, polyamide, polyacrylic acid, polyacrylamide, polyacrylonitrile, polyarylsulfone (PAS), polybenzimidazoles, poly terephthalic acid fourth two Alcohol ester, makrolon, dimethyl silicone polymer, polyethylene glycol, polyester, polysulfones, polyether sulfone, polyethylene terephthalate, Phenolic resin, tetrafluoroethylene-perfluoro propane copolymer, polyimides, PMA, polymethacrylonitrile, poly- methyl-prop E pioic acid methyl ester, polyformaldehyde, polyphenylene oxide, polypropylene, polyphenylene sulfide, PPSU, polystyrene, polytetrafluoroethylene (PTFE), polyurethane, poly- second Enol, polyvinyl acetate, polyvinyl butyral resin, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, Vingon, Polyvinyl formal, polyvinylpyrrolidone, Lauxite, ultra-high molecular weight polyethylene, unsaturated polyester (UP), polyether-ether-ketone Deng；3. synthetic rubber filler, such as isoprene rubber, butadiene rubber, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, second Third rubber, silicon rubber, fluorubber, lactoprene, polysulfide rubber, polyurethane rubber, epichlorohydrin rubber, thermoplastic elastomer (TPE) Deng；4. synthetic fibers filler, such as viscose fiber, CUP, diethyl ester fiber, triethyl fiber, Fypro, poly- carbonic acid Ester fiber, vinal, polyester fiber, polyurethane fiber, polyacrylonitrile fibre, vinylon, polychlorostyrene second Alkene fiber, polyolefine fiber, fluorofibre, polytetrafluoroethylene fibre, aromatic polyamide fibre, aramid fiber or aramid fiber are fine Dimension etc..
Wherein, the wire feeding of addition does not limit, mainly depending on required material property, preferably calcium carbonate, sulphur Sour barium, talcum powder, carbon black, graphene, glass microballoon, glass fibre, carbon fiber, natural rubber, chitosan, starch, protein, Polyethylene, polypropylene, polyvinyl chloride, vinyl-vinyl acetate copolymer, polyvinyl alcohol, isoprene rubber, butadiene rubber, butylbenzene Rubber, nitrile rubber, neoprene, butyl rubber, EP rubbers, silicon rubber, thermoplastic elastomer (TPE), Fypro, poly- carbon Acid esters fiber, vinal, polyester fiber, polyacrylonitrile fibre；Amount of filler used is not particularly limited, generally 1-30wt.%.
In the preparation process of dynamic aggregation thing, special limit is not done to the addition of dynamic aggregation thing each component raw material Fixed, those skilled in the art can be adjusted according to actual preparation situation and target polymerization physical performance.
For the first and second of each component raw material prepared in embodiment, matching somebody with somebody for following parts by weight is referred to Than：
Wherein, the preferred parts by weight proportioning of each component raw material is：
For the third and the 4th kind of each component raw material prepared in embodiment, matching somebody with somebody for following parts by weight is referred to Than：
Wherein, the preferred parts by weight proportioning of each component raw material is：
For the 5th kind of each component raw material prepared in embodiment, the proportioning of following parts by weight is referred to：
Wherein, the preferred parts by weight proportioning of each component raw material is：
Described dynamic aggregation physical performance is adjustable on a large scale, can be applied to every field, has broad application prospects, Military aerospace equipment, functional paint and coating, biological medicine, bio-medical material, the energy, building, bionical, intellectual material etc. are led Domain, all embody the application effect to attract people's attention.
For example, by using dilatancy possessed by dynamic aggregation thing, it is explosion-proof etc. that well recovery, fuel oil can be applied to Aspect；Also making damping shock absorber can be applied to, for various motor vehicles, plant equipment, bridge, building vibrations every From, polymeric material when vibrated, the big energy that can dissipate plays damping, so as to effectively relax vibration body Vibrations；Stress response possessed by dynamic aggregation thing can also be used, as energy-absorbing buffering material, applied to buffering package Material, athletic protective article, the police protective materials of surge guard product and army etc., so as to reduce article or human body outside Power effect lower suffered vibrations and impact, including shock wave caused by blast etc.；Pass through dynamic possessed by dynamic aggregation thing Invertibity and rate of stressing dependence, prepare the polymeric material of stress sensitive type, a part, which can apply to preparation, to be had The toy and body-building material of mobility and the magic effect of elasticity conversion, it may also be used for prepare the speed lockup of road and bridge Device.
For another example making full use of self-repairability possessed by dynamic aggregation thing, can prepare with self-repair function Binding agent, the gluing applied to various types of materials；It can also be used for preparing with good plasticity and the polymerization of reparation can be reclaimed Thing blocks glue；Based on the dynamic reversibility of organic boronic estersil key, it can design and prepare the scratch-resistant with self-repair function Coating, so as to extend the service life of coating, realize the long-effective corrosion protection to matrix material；By suitable compositional selecting and Formula design, can prepare polymer pad or polymer plate with self-repair function, be damaged so as to mimic biology body Recover from injury the principle closed so that material can carry out self-healing to internal or outer damage, eliminate hidden danger, extend material Service life, huge application potential is shown in the field such as military project, space flight, electronics, bionical.
For another example carried out using organic boronic estersil key as key can be sacrificed in use, it can pass through suction under external force Receive substantial amounts of energy and assign polymeric material with excellent toughness, it is hereby achieved that the splendid thin polymer film of toughness, fibre Dimension or sheet material, are widely used in the fields such as military affairs, space flight, motion, the energy, building.
Dynamic aggregation thing of the present invention is described further with reference to some embodiments.Specific implementation Example is of the invention to be further described, non-limiting protection scope of the present invention.
Embodiment 1
Utilize the small molecule organoboron compound (I) containing four-functional group and the siliceous chemical combination of the small molecule containing difunctional Thing (II) prepares the dynamic aggregation thing with dynamic crosslinking structure.
A certain amount of organoboron compound (a) is weighed (to be initiator, triethylamine for catalyst using AIBN, utilize vinyl Boric acid, vinylboronic acid dibutyl ester and 1,6- ethanthiols are made by thiol-ene click-reactions) to be dissolved in tetrahydrofuran molten 0.8mol/L solution is configured in agent；Measure tetrahydrofuran solutions of the 40ml dissolved with organoboron compound and pour into dried and clean Flask in, add 4ml deionized water, be added dropwise to a little acetic acid and be well mixed, then be slowly added into the siliceous of 5.02g wherein Compound (b) (is raw material using dimethylallylchlorosilane, the mercaptan of 1, the 10- last of the ten Heavenly stems two, is by initiator, triethylamine of AIBN Catalyst, it is made by thiol-ene click-reactions).Above-mentioned mixed solution is constantly stirred under the conditions of 60 DEG C, with The progress of stirring, the viscosity of solution constantly rises, and after stirring 4h, obtains homogeneous dynamic aggregation logistics body, utilizes rotating flow Become maximum elastance G ' of the instrument to polymer fluidmaxWith minimal elastic modulus G 'minTested, wherein, test temperature is 25 DEG C, test frequency scope is 0.1~100rad/s, measures the maximum elastance G ' of polymer fluidmaxFor 8.91 × 103Pa, minimal elastic modulus G 'minFor 7.13Pa, dynamic aggregation thing imparts polymer fluid with the effect of " shear thickening ". This polymer can be applied to the explosion-proof of flammable liquid, after increasing the polymer in a liquid, flammable liquid uses in stirring During due to viscosity increase, splashing is not likely to produce, so as to add security.Petroleum production engineering is can also be applied to, increases the displacement of reservoir oil The viscosity of displacing phase in technique, so as to improve oil recovery factor.
Embodiment 2
Utilize the small molecule organoboron compound (I) containing four-functional group and the siliceous chemical combination of the macromolecular containing difunctional Thing (II) prepares the dynamic aggregation thing with dynamic crosslinking structure.
Added in the three-necked flask of dried and clean 15ml phenyl boric acids end-blocking polyethylene glycol (a) (with polyethylene glycol 400, 2 bromo propionyl bromide is raw material, and triethylamine is catalyst, the polyethylene glycol of double bromine end-blockings is prepared, then by itself and 2- aminomethyl phenyl boron Final product is made by hydrocarbyl reaction in acid), 80 DEG C are heated to, is added dropwise to a small amount of deionized water and acetic acid wherein, so The methoxy silane modified silicon oil (b) for being added dropwise to 42ml in the state of stirring afterwards (with dimethylvinylmethoxysiiane, glues Degree is about that 2000mPas end hydrogen-based silicone oil is raw material, and Si―H addition reaction is carried out under Pt catalytic conditions and is made), in the shape of heating 30min is stirred under state, after each component is sufficiently mixed uniformly, adds 2ml triethylamines, continues to react 2h, obtains having necessarily viscous The polymer fluid of degree.The apparent viscosity of polymer fluid is tested using rotation viscometer, wherein, test temperature 25 DEG C, constant shear rate is 0.1s-1, the apparent viscosity for measuring polymer fluid is 22,680mPas.Utilize rotational rheometer To the maximum elastance G ' of polymer fluidmaxWith minimal elastic modulus G 'minTested, wherein, test temperature is 25 DEG C, Test frequency scope is 0.1~100rad/s, measures the maximum elastance G ' of polymer fluidmaxFor 7.78 × 104Pa, most Small elastic modulus G 'minFor 31.78Pa.The dynamic aggregation logistics body of this structure embodies obvious dynamic characteristic and " shearing increases It is thick " property, it can apply on textile or in foams, be fabricated to defense of resistance to impact articles for use, such as take as motion Dress is used as motion with protection pad.
Embodiment 3
Utilize the macromolecular organoboron compound (I) containing four-functional group and the siliceous chemical combination of the small molecule containing difunctional Thing (II) prepares the dynamic aggregation thing with dynamic crosslinking structure.
15ml borate end capped polyether (a) is added in the three-necked flask of dried and clean (by (bromomethyl) boric acid two The polyetheramine that isopropyl ester is about 2000 with molecular weight is made by hydrocarbyl reaction), 90 DEG C are heated to, adds 3ml deionization Water, a small amount of acetic acid is added dropwise to, after stirring, is added dropwise to 21ml methylhydroxy silicone oil (b) (viscosity is about 30mPas), After each component is sufficiently mixed 30min by stirring, 2ml triethylamines are added, continues to react 3h in the state of heating stirring, obtains To the dynamic aggregation logistics body with larger viscosity.The apparent viscosity of polymer fluid is tested using rotation viscometer, Wherein, test temperature is 25 DEG C, and constant shear rate is 0.1s-1, the apparent viscosity for measuring polymer fluid is 51,400mPa s.A beaker separately is taken, wherein addition 80ml deionized water, 0.8g neopelexes, 0.4g hydroxy ethyl fibers Element, 0.2g stearic acid and 0.2g oleic acid, after stirring by mixing, take 30ml polymer fluids to pour into beaker, carry out fast It is stirred, is stirred after 30min fastly, obtains the milky white liquid with certain viscosity, then add 0.2g wherein Ground titanium dioxide, ultramarine, soft carbon mixed-powder in advance, 0.2g organobentonites, 0.2g dimethyl silicone polymers, 0.2g dibutyl tin laurates, particle fluorescence brightening agent KSN, 20mg light stabilizer 770, after being uniformly mixed, in room temperature After placing 12h, then the aqueous emulsion paint being made up of dynamic aggregation thing is can obtain, coating is directly carried out coated on surface of bottom material After drying, then scratch-resistant, the coating of peelable regeneration can be formed.
Embodiment 4
Utilize the macromolecular organoboron compound (I) containing four-functional group and the siliceous chemical combination of the macromolecular containing difunctional Thing (II) prepares the dynamic aggregation thing with dynamic crosslinking structure.
The PolyTHF (a) for weighing 15.1g phenyl boric acids end-blocking (using 3- amino phenyl boric acid as raw material, itself and dibromo is sealed The PolyTHF (molecular weight is about 2000) at end is made by hydrocarbyl reaction) it is added in the three-necked flask of dried and clean, The hydroxy-end capped methyl phenyl silicone oil (b) (molecular weight is about 12,000) for weighing 8.5g is added in three-necked flask, is being stirred In the state of by temperature be raised to 100 DEG C mixed after, add 1ml triethylamines, continue react 3h.After reaction terminates, had There are the viscous samples of certain viscosity, polymer samples are poured into suitable mould, be placed in 80 DEG C of baking ovens under vacuum In continue react 4-6h, be cooled to afterwards room temperature place 30min, finally give glue polymer samples.Polymer samples exist It can on a large scale be stretched under slower rate of extension, produce creep；If but Rapid stretching, demonstrate flexibility feature, uses Finger being capable of Fast Restoration after pressing it.It is made into the dumbbell pattern of 80.0 × 10.0 × (2.0~4.0) mm sizes Bar, extension test is carried out using cupping machine, rate of extension 50mm/min, measure sample tensile strength for 0.67 ± 0.14MPa, stretch modulus are 0.79 ± 0.39MPa, and elongation at break is up to 1003 ± 312%.This material can make quality The toy of color similar plasticine different, that there is magic elasticity.
Embodiment 5
Using the micromolecular compound (IV) containing an organic boronic estersil key and other reactive groups and contain two Other individual reactive group micromolecular compounds prepare the dynamic aggregation thing with dynamic crosslinking structure.
The boric acid estersil compound (a) for weighing 0.1mol (is made using lithium methide, vinyl lithium and trimethylborate reaction Ethylene methacrylic ylboronic acid；Using ethylene methacrylic ylboronic acid, dimercaptosuccinic acid as raw material, pass through thiol-ene points under the conditions of 80 DEG C After hitting the obtained intermediate product of reaction, it is condensed with aminoethylaminoisobutyl dimethyl methoxy silane under the conditions of 50 DEG C Reaction is made), 0.01mol 4-Aminobutanoicacids (b), 0.05mol dicyclohexylcarbodiimide condensing agents, 5mmol catalyst 4- bis- Methylamino pyridine is dissolved in 80ml deionized water, after being uniformly mixed, reacts 5h under reflux conditions.Reaction terminates Afterwards, normal pressure filters off the dicyclohexyl urea of generation, then sloughs solvent by depressurizing suction filtration and obtain white residue, after being purified To the solid dynamic aggregation thing of paste.Obtained dynamic aggregation thing soft surface, there is relatively low melt viscosity and higher heat Stability, it can be used as a kind of additive with lubricant effect, lubrication of the material under high shear forces can be lifted Performance.
Embodiment 6
Using the small molecule organoboron compound (I) containing difunctional and other reactive groups and contain three officials Can group and dynamic aggregation of small molecule silicon-containing compound (II) preparation with dynamic crosslinking structure of other reactive groups Thing.
60ml tetrahydrofuran solvent is added in the reaction bulb of dried and clean, after sealing, using bubbling argon deoxygenation 1h, Then 0.3g acetenyl pinacol borates (a) are added using syringe, the silane (b) that 0.66g contains azido group (utilizes 11- bromoundecanes base trichlorosilane is made with reaction of sodium azide), 0.28ml DIPEA, 19mg Cu (PPh3)3Br is into reaction bulb.Reaction bulb is heated to 60 DEG C, 12h is reacted in the state of stirring.After the completion of reaction, it will react Liquid filter except solvent obtains head product, utilizes n-hexane/dichloromethane (3:1) decontamination is eluted, final product is obtained after drying. Product is dissolved in tetrahydrofuran, adds a certain amount of methanol, can obtain the gel with mechanics sensitiveness, can be answered For damping material.
Embodiment 7
It is siliceous using the small molecule organoboron compound (I) containing trifunctional and two kinds of small molecules containing trifunctional Compound (II) prepares the dynamic aggregation thing with dynamic crosslinking structure.
Itself and hydrobromic acid (using 1- hydroxyl boron heterocycle propylene as raw material, are passed through into addition reaction system by organoboron compound (a) Obtain the bromo- 1- hydroxyls boron heterocycle propane of 2-；With 1,3,5- triacryl hexahydro -1,3,5-triazines, 2- aminoothyl mercaptans for raw material, AIBN is initiator, and triethylamine is catalyst, by thiol-ene click-reactions be made intermediate product after, then with the bromo- 1- hydroxyls of 2- Base boron heterocycle propane is made by hydrocarbyl reaction) it is dissolved in tetrahydrofuran solvent, it is configured to 0.4mol/L solution；Take one Itself and hydrobromic acid (using the chloro- amyl- 3- alkene of 1- methyl-sila ring of 1- as raw material, are passed through addition reaction by quantitative silicon-containing compound (b) The chloro- 1- methyl-silacyclopentans of the bromo- 1- of 3- are made；Using triallylamine, 2- aminoothyl mercaptans as raw material, AIBN is initiator, Triethylamine is catalyst, by thiol-ene click-reactions be made intermediate product after, then with the chloro- 1- methyl-silas of the bromo- 1- of 3- Pentamethylene is made by hydrocarbyl reaction) it is dissolved in tetrahydrofuran solvent, it is configured to 0.2mol/L solution；Meanwhile take one Quantitative silicon-containing compound (c) is (using trimethylolpropane tris (3-thiopropionate), the chloro- vinyl-silacyclobutanes of 1- as original Material, AIBN is initiator, and triethylamine is catalyst, is made by thiol-ene click-reactions) it is dissolved in tetrahydrofuran solvent It is configured to 0.2mol/L solution.The organoboron compound solution that 20ml has been configured is added in the beaker of dried and clean, 6ml's Deionized water, a small amount of acetic acid is added dropwise to, 20ml silicon-containing compound (b) solution and containing for 20ml are added dropwise under stirring Silicon compound (c) solution, after being stirred under the conditions of 50 DEG C, then 3ml triethylamine is added dropwise to, continues to react 4h, reacting During solution viscosity constantly rise, until reaction terminate after, obtain the polymer samples of certain viscosity.Will be sticky Polymer samples are poured into suitable mould, are placed in 24h in 50 DEG C of vacuum drying ovens and are dried, and are cooled to room temperature placement afterwards 30min, the polymer samples finally given jelly, have certain elasticity, and can be extended within the specific limits.Made Into the dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes, extension test, stretching speed are carried out using cupping machine Rate is 50mm/min, and it is 1.28 ± 0.52MPa to measure sample tensile strength, and stretch modulus is 1.79 ± 0.89MPa, extension at break Rate is 392 ± 73%.In addition, obtained product also has good plasticity, different shape can be positioned over according to being actually needed Mould in, and slightly apply certain stress under the conditions of certain temperature, you can according to mould molding be polymerization of different shapes Produce product.In the present embodiment, after the polymer samples that broken can be reclaimed, section part is bonded (optional during this Select and section carried out slightly to soak), it is placed in 50 DEG C of mould and applies certain pressure placement 6-8h, the crackle of sample joint place disappears Lose, polymer can be made to a kind of gasket material again and used, embody the self-repairability of polymeric material and recyclable Property.
Embodiment 8
Utilize the micromolecular compound (III) containing trifunctional, the small molecule organoboron compound containing four-functional group (I), small molecule silicon-containing compound (II) system containing multi-functional small molecule silicon-containing compound (II) and containing difunctional The standby dynamic aggregation thing with dynamic crosslinking structure.
8.28g compounds (a) are added in the beaker of dried and clean (with vinyl boronic acids pinacol ester, the sulphur of the 1,10- last of the ten Heavenly stems two Alcohol, dimethylvinylmethoxysiiane are raw material, and AIBN is initiator, and triethylamine is catalyst, is clicked on by thiol-ene Reaction obtains), 15.92g double (Isosorbide-5-Nitrae-phenylene) hypoboric acid (b) of 4,4'- oxygen, 60ml DMF is added, is entered under the conditions of 80 DEG C Row heating, and solid is dissolved in a solvent well mixed by stirring.In the state of stirring, 4ml deionized water is added, A small amount of acetic acid, after being well mixed, then the 1 of 2.64g is slowly added to successively, 1,3,3,5,5- six ethyoxyl -1,3, the silicon generations of 5- tri- Hexamethylene (c), the siloxanes (d) of ten tetramethyl -1,11- dichloros of 12.48g six.After being stirred 30min, 2.5ml three second are added Amine, reacted under the conditions of 110 DEG C, in course of reaction, solution viscosity constantly rises, after heating response 4h, polymer is molten Liquid is poured into suitable mould, is placed in 24h in 80 DEG C of vacuum drying ovens and is carried out removing solvent, is cooled to room temperature afterwards and is placed 30min, most The hard polymer samples of bulk are obtained eventually, and polymer has certain intensity and rigidity, but toughness and ductility are poor.Will The dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes is made in it, carries out extension test using cupping machine, draws It is 10mm/min to stretch speed, and it is 2.12 ± 0.34MPa to measure sample tensile strength, and stretch modulus is 3.97 ± 1.12MPa, by it Placement 12h in 80 DEG C of moulds is placed in after broken to be molded again, can be as glass system by the use of its recyclable characteristic Product substitute is used.
Embodiment 9
Using containing multi-functional small molecule organoboron compound (I) and the siliceous chemical combination of the macromolecular containing trifunctional Thing (II) prepares the dynamic aggregation thing with dynamic crosslinking structure.
The silane-modified polycaprolactams (b) of 10.13g are added in three-necked flask, and (using acryloyl chloride as initiator, NaOH is Catalyst, the polycaprolactam for triggering caprolactam ring-opening polymerisation to be blocked into alkene list, then by itself and thiopurine methyltransferase triethoxy For silane using AIBN as initiator, triethylamine is catalyst, and final product is obtained by thiol-ene click-reactions), 1.53g's Organoboron compound (a) (by propylene ylboronic acid diisopropyl ester and 1,3,5-triazines -2,4, the mercaptan of 6- tri- using AIBN as initiator, Triethylamine is catalyst, is made by thiol-ene click-reactions), 100ml DMF solvents, be heated to 80 DEG C be stirred it is molten Solution, adds 10ml deionized water, is added dropwise to a little acetic acid, continue after being stirred 30min, 4ml triethylamines is added, 80 Continue stirring reaction 3h under the conditions of DEG C, solution viscosity constantly rises during reaction, until after reaction terminates, has obtained one Determine the polymer fluid of viscosity.Maximum elastance G ' using rotational rheometer to polymer fluidmaxWith minimal elastic mould Measure G 'minTested, wherein, test temperature is 25 DEG C, and test frequency scope is 0.1~100rad/s, measures polymer fluid Maximum elastance G 'maxFor 4.49 × 104Pa, minimal elastic modulus G 'minFor 23.24Pa, dynamic aggregation thing has dilatant Property, its viscosity rises under shear stress, and modulus improves, and this polymer can be applied to well recovery, or applied Surface of bottom material is overlying on to be used to prepare energy-absorbing material.
Embodiment 10
Using the cyclic macromolecular compound (IV) containing an organic boronic estersil key and other reactive groups, contain The micromolecular compound of two other reactive groups prepares the dynamic aggregation thing with dynamic crosslinking structure.
40ml tetrahydrofuran solvent is added in the three-necked flask of dried and clean, after sealing, utilizes bubbling argon deoxygenation 1h, 3.4g ring-type organic boronic estersil compounds (a) then are added (by 11- bromoundecane base dimethyl chlorides using syringe Condensation reaction is carried out with 2- bromoethyls methyl-boric acid after silane hydrolyzate and the organic boronic estersil compound that both ends are bromine is made, then The organic boronic estersil compound that both ends are azido group is made in itself and reaction of sodium azide；The butadiene of terminal hydroxy group is oligomeric Thing (molecular weight is about 800) passes through with 5- alkynyls caproic acid under dicyclohexylcarbodiimide, DMAP catalytic condition The butadiene oligomer that both ends are alkynyl is made in esterification, then by its organic boronic estersil with both ends for azido group Compound is made using the tetrahydrofuran of excess as solvent under cuprous iodide, DIPEA catalytic condition), 2ml 20% acetic acid aqueous solution, be heated under argon gas protection 50 DEG C place 30min after, add 0.05g 1, pungent two mercaptan (b) of 8-, 0.03g photochemical catalysts DMPA, 0.2g triethylamine.Make after reactant is completely dissolved, to be kept stirring for state response 2h by stirring, Then 10min is reacted under ultraviolet light again, after the completion of reaction, reaction solution is poured into suitable mould, is placed in 50 DEG C 24h is further reacted and except solvent in vacuum drying oven, finally can obtain the polymeric colloid of viscosity, its surface strength and Hardness is relatively low, but it can be stretched on a large scale and not broken (elongation at break is up to 1500%).In the present embodiment, Can be as super PUR or self-adhesive at room temperature materials'use, and when defect can occur on its surface, by heating to it Repaired, and can be reclaimed by the dissociation (forming non-crosslinked property branched polymer) of organic boronic estersil key.
Embodiment 11
Using containing multi-functional small molecule organoboron compound (I), contain the siliceous chemical combination of multi-functional small molecule Thing (II), using the small molecule organoboron compound (I) containing four-functional group and other reactive groups, contain tetrafunctional The small molecule silicon-containing compound (II) of group and other reactive groups, the compound system containing two other reactive groups The standby dynamic aggregation thing with dynamic crosslinking structure.
The mixture of a certain amount of organoboron compound (a) and organoboron compound (c) is weighed (with trimethylolpropane tris (3-thiopropionate), propylene ylboronic acid diisopropyl ester are raw material, and AIBN is initiator, and triethylamine is catalyst, is passed through Thiol-ene click-reactions are made) it is dissolved in tetrahydrofuran solvent, it is configured to 0.3mol/L solution；Weigh a certain amount of contain The mixture of silicon compound (b) and silicon-containing compound (d) is (with trimethylolpropane tris (3-thiopropionate), methylpropenyl Dichlorosilane is raw material, and AIBN is initiator, and triethylamine is catalyst, is made by thiol-ene click-reactions) it is dissolved in four In hydrogen THF solvent, 0.3mol/L solution is configured to.Under argon gas protective condition, 20ml is added in the flask of dried and clean The organoboron compound solution configured, 20% a small amount of acetic acid aqueous solution is added dropwise to, is heated to 60 DEG C, is dripped under stirring 20ml silicon-containing compound solution is added, after stirring, then is added dropwise to 3ml triethylamine, after reacting 30min, adds 0.18g Allyl ether (e), 0.05g photochemical catalyst DMPA, after making reactant dissolving completely by stirring, state response 2h is kept stirring for, Then 10min is reacted under ultraviolet light again, then pours into reaction solution in suitable mould, is placed in 60 DEG C of vacuum drying ovens 24h is further reacted and dried, and is cooled to room temperature afterwards and is placed 30min.The polymer samples of agar shape are finally given, Sample has certain elasticity and toughness, can be extended within the specific limits, and pressing is carried out to it with finger can quick resilience. The dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes is made into, extension test is carried out using cupping machine, Rate of extension is 50mm/min, and it is 2.13 ± 0.61MPa to measure sample tensile strength, and stretch modulus is 2.94 ± 1.05MPa, is broken Elongation is split for 327 ± 46%.In addition, obtained product also has good plasticity, can be positioned over not according to being actually needed In the mould of similar shape, and slightly apply certain stress under the conditions of certain temperature, you can according to mould molding be different shape Polymeric articles.In the present embodiment, polymer can be made to resilience packing ring and resilience pad is used.
Embodiment 12
Using containing multi-functional macromolecular organoboron compound (I) and containing the siliceous chemical combination of multi-functional macromolecular Thing (II) prepares the dynamic aggregation thing with dynamic crosslinking structure.
15g amylenes ylboronic acid-methyl methacrylate-butyl acrylate copolymer (a) is added in three-necked flask (with mistake Potassium sulfate is initiator, and 4- amylenes ylboronic acid, methyl methacrylate, butyl acrylate are raw material, are obtained by emulsion polymerization To), 100ml acetone solvents, be heated to 50 DEG C be stirred dissolving after, add 10ml deionized water, be added dropwise to a little second Acid, be slowly added into the silane-modified polycaprolactones (b) of 2.5g (using allyl alcohol as initiator, stannous octoate is catalyst, trigger ε- Caprolactone ring-opening polymerisation obtains the polycaprolactone of alkene list end-blocking, then it is obtained with acroleic acid esterification to the gathering in oneself of the double end-blockings of alkene Ester, then by its with γ-mercaptopropyl trimethoxysilane using AIBN as initiator, triethylamine is catalyst, passes through thiol-ene points Hit reaction and obtain final product), after being stirred 30min, 2ml triethylamines are added, continue stirring reaction 2h under the conditions of 50 DEG C. After reaction terminates, solvent is sloughed by depressurizing suction filtration and obtains white residue, dynamic aggregation thing is obtained after being purified.Take 10g Polymer samples are scattered in 40ml deionized water, add 0.4g neopelexes, 0.2g hydroxyethyl celluloses, 0.1g stearic acid and 0.1g oleic acid, after heating stirring is well mixed, obtain the polyacrylate dispersion with certain viscosity.It can incite somebody to action Obtained dynamic aggregation thing emulsion is used as building external paint, can also be fabricated to good adhesion, scrub resistance, solvent resistant Property, the latex film of water resistance, can also be fabricated to functional fabric finishing agent, finishing agent, be alternatively arranged as the softness of leather Finishing agent is used.
Embodiment 13
Utilize the macromolecular organoboron compound (I) containing trifunctional, the siliceous chemical combination of the macromolecular containing trifunctional Thing (II) and dynamic aggregation thing of macromolecular silicon-containing compound (II) preparation with dynamic crosslinking structure containing trifunctional.
By three arm polysiloxanes (a) of boric acid end-blocking (using 3- bromo- 4- (bromomethyl) benzaldehydes as raw material, by itself and methyl Tri-phenyl-phosphorus bromide, potassium tert-butoxide react 24h at room temperature, then are warming up to 100 DEG C in water/dioxane in the mixed solvent reaction 24h, then it is reacted with tert-butyl chloro-silicane, imidazoles to 20h in DMF solvent, then by itself and methanol, methoxyl methyl chlorine 4h is reacted in tetrahydrofuran solvent, then using Mg as catalyst, is heated to 60 DEG C of reaction 3h, then adds butyl borate room temperature 8h is reacted, 2- (methylol) phenyl boric acid ring-type monoesters ethene is obtained after purification；With the octamethylcy-clotetrasiloxane, (diformazan of phenyl three Radical siloxane base) silane is raw material, the concentrated sulfuric acid is catalyst, passes through ring-opening polymerisation method and synthesizes three end hydrogen-based polysiloxanes, then will It is made with 2- (methylol) phenyl boric acid ring-type monoesters ethene under Pt catalytic conditions by hydrosilylation) it is dissolved in tetrahydrochysene In THF solvent, 0.2mol/L solution is configured to, and therefrom takes 20ml samples to be added in the flask of dried and clean, is added 4ml deionized water, a small amount of acetic acid is added dropwise to, be well mixed；Take a certain amount of three Silante terminated arm PPOXs (b) (using glycerine, expoxy propane as raw material, BFEE is catalyst, is blocked by cation ring-opening polymerization synthesis of hydroxy Three arm PPOXs, then it is obtained into three arm PPOX triacrylates with acrylic acid by esterification, then by its Respectively with 1,2- dithioglycols, dimethyl vinyl chlorosilane by being made after thiol-ene click-reactions) it is dissolved in tetrahydrochysene furan Mutter in solvent, be configured to 0.1mol/L solution, and take 20ml to be added dropwise in flask；Take a certain amount of Silante terminated poly- silicon of three arms (using octamethylcy-clotetrasiloxane, (dimethyl siloxane) silane of phenyl three as raw material, the concentrated sulfuric acid is catalyst to oxygen alkane (c), is led to Cross ring-opening polymerisation method and synthesize three end hydrogen-based polysiloxanes, then it is passed through under Pt catalytic conditions with dimethyl vinyl chlorosilane Hydrosilylation is made) it is dissolved in tetrahydrofuran solvent, 0.2mol/L solution is configured to, and take 20ml to be added dropwise to flask In.Mixed solution is stirred under the conditions of 50 DEG C, then adds 1.5ml triethylamines, is continued after stirring 1h, solution viscosity is opened Begin to rise, continue after reacting 1h, the polymer solution with certain viscosity is poured into mould, is placed in 24h in 50 DEG C of baking ovens It is dried, is cooled to room temperature afterwards and places 30min, the polymer samples of the transparent membrane finally given.It is cut into The dumbbell shape batten of 80.0 × 10.0 × (0.08 ± 0.02) mm sizes, extension test, stretching speed are carried out using cupping machine Rate is 50mm/min, and it is 2.14 ± 0.35MPa to measure sample tensile strength, and stretch modulus is 2.83 ± 1.34MPa, extension at break Rate is 673 ± 121%.Right angle is produced according to QB/T 1130-91 plastic quarter tear resistance test methods to try without scarfing type standard Sample carries out film splitting performance test, and it is 4.72 ± 0.38MPa to measure sample cross direction tear strength, machine direction tear 4.93 ±0.52MPa.Thin polymer film shows more excellent combination property, has certain tensile strength and good tear-proof Performance, and can largely be stretched.After thin polymer film is cut, section part is placed in 50 DEG C of mould and is bonded After 2-4h, the crackle of section part disappears, and sample film forming again, has self-repair function.Such dynamic aggregation thing can be applied to Function film is prepared, or can be used as the pad pasting of automobile and furniture, can also be used as stretch wrappers, its Scratch-resistant and it can be recycled and reuse.
Embodiment 14
Using containing multi-functional macromolecular organoboron compound (I), contain multi-functional small molecule organoboration Compound (I) and contain multi-functional macromolecular silicon-containing compound (II) prepare with dynamic crosslinking structure dynamic aggregation thing.
22.4ml four arm ester type compounds (a) of organic boric acid ester end-blocking are added in three-necked flask (by isopropenyl Pinacol borate is catalyst by initiator, triethylamine of AIBN with four -3-thiopropionate of pentaerythrite, passes through thiol- Ene click-reactions are made), 120 DEG C are heated under stirring, 5mg BHT antioxidant is added, then weighs 13.12g boric acid Four arm compounds (b) of end-blocking (are raw material using 2- formylphenylboronic acids, ammonia, toluene is solvent, is reacted by Petasis 2- aminomethyl phenyl boric acid is synthesized, then it is made with tetrabromo season amylalcohol by hydrocarbyl reaction) it is added in three-necked flask, pass through Stirring makes it well mixed；29.6ml four arm polysiloxanes (c) are measured again (with octamethylcy-clotetrasiloxane, four (dimethyl-silicons Epoxide) silane is raw material, the concentrated sulfuric acid is catalyst, and four end hydrogen-based polysiloxanes are synthesized by ring-opening polymerisation method, then by itself and first Base methylvinyldiethoxysilane under Pt catalytic conditions by hydrosilylation after hydrolyze again it is obtained) be added dropwise to mixed liquor In；After reactant is well mixed, 2ml triethylamines are added, mixing liquid is reacted into 1h at 120 DEG C under nitrogen guard mode Afterwards, mixed liquor has certain viscosity, now adds 1g titanium alloy powders, 1g ceramic powders, 2g calcium sulfate, after stirring, after Continue and react 2h at 120 DEG C, obtain thick polymer samples, be poured into suitable mould, and sample is placed in 100 DEG C 4-6h is placed in vacuum drying oven further to be reacted, and is cooled to room temperature afterwards and is placed 30min.Bulk is finally given, is in Hard, surface has the polymer samples of certain glossiness.It is made into 80.0 × 10.0 × (2.0~4.0) mm sizes Dumbbell shape batten, using cupping machine carry out extension test, rate of extension 10mm/min, measuring sample tensile strength is 5.21 ± 0.88MPa, stretch modulus are 10.76 ± 1.37MPa.Polymer samples surface is smooth, with certain intensity and just Property.It is placed in after being crushed in 100 DEG C of moulds after placing 6-8h, sample can be again compressing.Polymeric material can be used for Orthopaedics therapy, product and equipment are corrected as orthopaedics.
Embodiment 15
Using containing multi-functional macromolecular organoboron compound (I), the siliceous chemical combination of the macromolecular containing difunctional Thing (II), the macromolecular silicon-containing compound (II) containing simple function group prepare the dynamic aggregation thing with dynamic crosslinking structure.
Taking a certain amount of dendritic organoboron compound (a), (using DMPA as light trigger, ultraviolet light is light source, by second Sulfydryl boric acid is made by thiol-ene click-reactions with 1,2- dithioglycols in ene boric acid；It is purple using DMPA as light trigger Outer light is light source, by triallylamine and 1, after one-level intermediate product is made by thiol-ene click-reactions in 2- dithioglycols, Thiol-ene click-reactions are continued through with triallylamine again two level intermediate product are made, afterwards again with 1,2- dithioglycols Three-level intermediate product is made by thiol-ene click-reactions, then is reacted with triallylamine and level Four intermediate product is made, finally Pass through thiol-ene click-reactions with sulfydryl boric acid and final product be made) it is dissolved in toluene solvant and is configured to 0.1mol/L's Solution；Meanwhile take a certain amount of dimethyl hydroxyl silicon oil (b) (molecular weight is about 4000) to dissolve by heating and be configured in toluene solvant 0.8mol/L solution；Take a certain amount of polyether modified silicon oil (c) (Methyl Hydrogen Polysiloxane Fluid for being about 2000 using molecular weight and insatiable hunger Carried out with polyethers under Pt catalytic conditions after intermediate product is made in Si―H addition reaction, then continue with Vinyldimethylethoxysilane Final product is obtained by Si―H addition reaction) dissolve by heating the solution that 0.8mol/L is configured in toluene solvant.Respectively take 20ml organic Boron compound solution and two kinds of silicon oil solutions are added in the flask of dried and clean, are added dropwise to 20% a small amount of acetic acid aqueous solution, After being stirred under the conditions of 80 DEG C, 2ml triethylamines are added, continue stirring reaction 2h under the conditions of 80 DEG C.After reaction terminates, Polymer samples are poured into suitable mould, sample is placed in into 24h in 50 DEG C of baking ovens carries out removing solvent, is cooled to room afterwards Temperature places 30min, finally gives the polymer samples of transparent membrane.It is cut into 80.0 × 10.0 × (0.08 ± 0.02) mm The dumbbell shape batten of size, extension test is carried out using cupping machine, rate of extension 50mm/min, it is strong to measure sample stretching It is 4.23 ± 0.94MPa to spend for 2.65 ± 0.45MPa, stretch modulus, and elongation at break is 864 ± 157%.According to QB/T 1130-91 plastic quarter tear resistance test methods produce right angle and carry out film splitting performance test without scarfing type standard specimen, It is 7.25 ± 1.01MPa to measure sample cross direction tear strength, and machine direction tear is 7.54 ± 1.69MPa.Thin polymer film is soft It is soft, and there is certain tensile strength, modulus and good tear resistance, meanwhile, table of the film in terms of tensile toughness It is now very excellent.After thin polymer film is cut, section part is placed in 50 DEG C of mould after being bonded 2-4h, section part Crackle disappears, and sample film forming again, embodies self-repairability.Inflatable packer buffering can be prefabricated into by carrying out structure design to it Packaging material is used, and buffer protection function is played to packaged product, and material is also quite convenient for recovery.
Embodiment 16
Using containing multi-functional macromolecular organoboron compound (I) and containing the siliceous chemical combination of multi-functional macromolecular Thing (II) prepares the dynamic aggregation thing with dynamic crosslinking structure.
Taking a certain amount of acrylic acid-organic boronic copolymer (a), (using 2- formylphenylboronic acids, allylamine as raw material, toluene is Solvent, synthesis 2- (allylamine) methylphenylboronic acid is reacted by Petasis, then it is entered under AIBN initiation conditions with acrylic acid Row is free-radical polymerized to be obtained) solution that 0.4mol/L is configured in deionized water is dissolved in, therefrom take 40ml to be added to drying clean It is stand-by in net beaker.A certain amount of vinyl pyrrolidone-silane copolymer (b) is taken (using AIBN as initiator, by vinylpyridine Pyrrolidone and vinyl silane triisopropoxide pass through free-radical polymerized be made) it is dissolved in deionized water and is configured to 0.4mol/L Solution, therefrom take 40ml solution to be slowly added under stirring equipped with acrylic acid-organic boronic aqueous copolymers solution In beaker.Solution has been added, 30min is stirred to mixed liquor, after making each component well mixed, a small amount of triethylamine has been added dropwise to, is placed in Heating response is carried out in 50 DEG C of water-baths.With the progress of reaction, mixture solution viscosity constantly raises, and after reacting 30min, adds Enter Fes of the 3.2g Jing Guo the surface modification of silane coupling A 1513O4Particle and 1.5g hydroxyethyl celluloses, to mixed liquor ultrasound 1min, make Fe3O4Particle is uniformly dispersed wherein, then continues to carry out constantly stirring reaction to liquid in a heated condition.Instead After answering 90min, mixed liquor is poured into suitable mould, is placed in 50 DEG C of baking ovens and is placed 24h and be dried and further Reaction, finally gives and is dispersed with Fe3O4The magnetic dynamic aggregation thing gel of particle.It is made into 80.0 × 10.0 × (2.0~ 4.0) the dumbbell shape batten of mm sizes, extension test is carried out using cupping machine, rate of extension 50mm/min, measures sample Tensile strength is 1.42 ± 0.34MPa, and stretch modulus is 2.03 ± 0.92MPa, and elongation at break is 1031 ± 180%.Pass through Aminomethyl phenyl boric acid structure is introduced into reactant so that obtained organic boronic estersil key has good dynamic response, After the polymer samples recovery broken, it is only necessary to placing 4-6h in 50 DEG C of mould can be molded again, meanwhile, polymer coagulates Glue has also embodied excellent tensile toughness.In the present embodiment, obtained magnetic gel can show under magnetic fields Go out elongation, shrink or a variety of deformation such as bending, and possessed excellent in toughness causes the net of gel in the process to gel in itself Network structure can't be damaged.Dynamic aggregation thing gel can rely on its unique pliability and permeability to be widely used in targetting The fields such as insoluble drug release, cell separation are with marking, protein is adsorbed and separated.
Embodiment 17
The dynamic aggregation thing with dynamic crosslinking structure is prepared using containing multi-functional macromolecular compound (III).
60ml organic boronics-silane-modified silicone oil (a) (methyl for being about 60,000 with molecular weight is added in three-necked flask Sulfydryl silicone oil, vinyl boronic acids dimethyl ester, methyl vinyl diethoxysilane are raw material, using DMPA as light trigger, Under the conditions of ultraviolet light, be made by thiol-ene click-reactions), be warming up to 80 DEG C it is well mixed after, add going for 4ml Ionized water, a small amount of acetic acid is added dropwise to, polymerisation is carried out under stirring.During polymerization, the viscosity of silicone oil is not It is disconnected to rise, after reacting 90min, the polymeric liquid with larger viscosity can be obtained, is poured into suitable mould, is placed in Continue to react 4h in 80 DEG C of vacuum drying ovens, be cooled to room temperature afterwards and place 30min, finally give soft surface and with larger viscous The transparent polymer sample of property.Surface of polymer material intensity is relatively low, has unformed property, under external force, material is easier to Extend, and embody good tensile toughness, can largely be stretched and not broken (elongation at break exceedes 2000%).When there is defect on its surface, it is placed in 60 DEG C of vacuum drying ovens and heats 2-4h, defect disappears.In the present embodiment, The special hydrolysis of dynamic key in dynamic aggregation thing, can keep pellucidity for a long time, can be using polymer as carrying selfreparing Super PUR or the self-adhesive at room temperature materials'use of characteristic, it can also be used to be used for as the medium of speed lockup's device bridge and Road construction.
Embodiment 18
Using containing multi-functional macromolecular organoboron compound (I) and containing the siliceous chemical combination of multi-functional macromolecular Thing (II) prepares the dynamic aggregation thing with dynamic crosslinking structure.
25g phenyl boric acid modification by copolymerization isoprene rubbers (a) are weighed (using AIBN as initiator, by isoprene and 3- vinyl Phenyl boric acid is obtained by free-radical polymerized), the silane-modified polysilsesquioxanes (b) of 4g (using mercaptopropyltriethoxysilane as original Material, ferric trichloride, HCl are catalyst, and hydrolytic condensation obtains sulfhydryl modified polysilsesquioxane, then by itself and methyl ethylene two Chlorosilane, vinylcyclopropane is using DMPA as light trigger, under the conditions of ultraviolet light, is clicked on by thiol-ene anti- Should be made) be added to and carry out mixing 20min in small-sized internal mixer after, add 5g white carbons, 6g titanium dioxides, 0.05g barium stearates, 0.15g stearic acid continues to be kneaded 20min.After additive is sufficiently mixed uniformly with sizing material, takes out the material after being kneaded and cooled down, It is placed in twin-roll machine and suppresses flakiness, is cooled down at room temperature, cut-parts.Obtained polymer flake is dipped in 90 DEG C of water It is crosslinked, is then taken out, 6h is placed in 80 DEG C of vacuum drying ovens and is further reacted and dried, is cooled to room temperature afterwards 30min to be placed, sample is removed from the molds, finally gives the dynamic aggregation thing material of rubbery state, it has good plasticity, Product of different shapes can be prepared into according to die size, and stretching extension can be carried out interior in a big way, is embodied very excellent Different tensile toughness.The dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes is made into, utilizes cupping machine Extension test is carried out, rate of extension 50mm/min, it is 1.02 ± 0.31MPa to measure sample tensile strength, and stretch modulus is 1.52 ± 0.44MPa, elongation at break are 1207 ± 342%.After surface of polymer material is delineated with blade, put After placing 4-6h in 80 DEG C of vacuum drying ovens, cut disappears and (may be selected that surface is carried out slightly to soak during this), sample energy Enough carry out selfreparing.This polymeric material can keep soft under normal conditions, and interim rigidity is shown when being impacted, and After an impact, become normal flexible state again again, using stress response characteristic possessed by sample, rubber can be made into Base pressure sensitive pads use.
Embodiment 19
Using containing multi-functional macromolecular organoboron compound (I), contain the siliceous chemical combination of multi-functional macromolecular Thing (II), the dynamic aggregation thing with dynamic crosslinking structure is prepared containing multi-functional macromolecular compound (III).
3.64g borate esters modification EP rubbers (a) is weighed (using low molecule amount EPM as raw material, to utilize Oxidation dibenzoyl is carried out after reaction forms small cluster structure, then in cluster surface grafting maleic anhydride as crosslinking agent, then plus Enter 4- aminobenzene pinacol borates and final product be made by amidation process) it is added in the beaker of dried and clean, pour into 40ml xylene solvent carries out heating stirring, adds 4ml deionized water, is added dropwise to a small amount of acetic acid, then weigh 2.48g Silane-modified EP rubbers (b) (using low molecule amount EPM as raw material, crosslinking agent is used as by the use of dibenzoyl peroxide Carry out after reaction forms small cluster structure, then in cluster surface grafting maleic anhydride, add 3- aminopropyltriethoxy dimethoxys Final product is made by amidation process in silane), 3.12g borate esters-silane-modified EP rubbers (c) be (with low molecule amount EPM is raw material, is carried out using dibenzoyl peroxide as crosslinking agent after reaction forms small cluster structure, then Cluster surface grafting maleic anhydride, add 4- aminobenzenes pinacol borate, 3- aminopropyltriethoxy dimethoxysilanes pass through Final product is made in amidation process), it is slowly added under stirring in beaker, is heated to 80 DEG C and is stirred 30min Afterwards, 1.0mg BHT antioxidant is added, 2ml triethylamines, continues to be stirred reaction 3h under the conditions of 80 DEG C, obtains sticky gather Compound liquid, it is placed in suitable mould, 24h is placed in 80 DEG C of vacuum drying ovens and carries out removing solvent, is cooled to room afterwards Temperature places 30min, is removed from the molds sample, finally gives the dynamic aggregation thing of rubber-like.It is made into 80.0 × 10.0 × The dumbbell shape batten of (2.0~4.0) mm sizes, extension test is carried out using cupping machine, rate of extension 50mm/min, is surveyed Sample tensile strength is 3.53 ± 0.69MPa, stretch modulus is 4.38 ± 1.34MPa, elongation at break up to 947 ± 274%.Polymer samples not only embody certain intensity, and show very excellent toughness, can be as one Kind sealing strip, sealing ring or elastic buffer pad are used；In use, material shows good viscoelastic Property, there is good isolation vibrations and stress buffer effect, while also show excellent hydrolytic resistance.When its surface occurs When damaged, the healing of breakage can be achieved by heating so as to be molded again, realize the selfreparing and recycling of material.
Embodiment 20
Using the macromolecular organoboron compound (I) containing four-functional group and contain the siliceous chemical combination of multi-functional macromolecular Thing (II) prepares the dynamic aggregation thing with dynamic crosslinking structure.
The ester modified polybutadiene (a) of 7.2g boric acid is weighed respectively in the beaker of dried and clean (with Amino End Group 1,3- to gather Butadiene, (bromomethyl) boric acid diisopropyl ester are raw material, are made by hydrocarbyl reaction), 2.4g surfaces carry silicone hydroxyl Silica (b), then 40ml benzene solvents are added wherein, after being stirred by mixing under the conditions of 50 DEG C, add 16mg Neopelex, 8mg hydroxypropyl cellulose, be heated to 70 DEG C continue react 2h, will have certain viscosity afterwards Mixed liquor be placed in suitable mould in 50 DEG C of vacuum drying ovens dry 24h, finally give the poly- fourth for being dispersed with silica Diene polymer.The dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes is made into, is entered using cupping machine Row extension test, rate of extension 50mm/min, it is 1.87 ± 0.42MPa to measure sample tensile strength, stretch modulus 2.74 ± 0.82MPa, elongation at break are 502 ± 149%.After the polymer samples broken are reclaimed, placed in 80 DEG C of mould 4-8h can be molded again.In the present embodiment, polymer samples can be made to a kind of fluid sealant or recuperability elastic pellet is played Tool is used, and it can embody good toughness and elasticity, and can be according to the production for needing to be pressed into different shape size Product, sample that is damaged or no longer needing may be recovered, new product are made and uses.
Embodiment 21
Using containing multi-functional macromolecular organoboron compound (I) and containing the siliceous chemical combination of multi-functional macromolecular Thing (II) prepares the dynamic aggregation thing with dynamic crosslinking structure.
Weigh the boric acid modified polystyrene (a) of 8.5g and (using AIBN as initiator, utilize styrene and 4- vinyl benzene boron Acid is made by free-radical polymerized) it is added in the beaker of dried and clean, 80ml toluene solvant is poured into wherein, is heated to 50 After DEG C being dissolved by stirring, the glass micro-fibers (b) that 1.5g surfaces carry silicone hydroxyl are added in beaker, add 6mg The neopelex of Silane coupling agent KH550,6mg, continue after stirring 30min, add 4mg hydroxypropyl cellulose, It is heated to 80 DEG C to continue to react 3h, mixed liquor is placed in suitable mould in 50 DEG C of vacuum drying ovens dries 24h afterwards, finally Obtain being dispersed with the bulk polymer sample of glass micro-fibers, it has higher case hardness and certain mechanical strength, quality Harder, elasticity and toughness are poor, are tapped with hammer after crushing, and observation finds that the glass micro-fibers in matrix are combined with matrix Closely.Broken material is put into mould and is heated to 180 DEG C, the compression molding 5min under 5MPa pressure, it is made into 80.0 × The dumbbell shape batten of 10.0 × (2.0~4.0) mm sizes, extension test, rate of extension 10mm/ are carried out using cupping machine Min, it is 4.24 ± 1.73MPa to measure sample tensile strength, and stretch modulus is 9.12 ± 3.08MPa, and it has good resistance toization Medicine is learned, can enter exercise using obtained polymeric material as glassware substitute, hard packing box, dalle With.
Embodiment 22
Using the macromolecular compound (IV) containing multiple organic boronic estersil keys and other multiple reactive groups, contain Prepared by the micromolecular compound (IV) of one organic boronic estersil key and two other reactive groups have dynamic crosslinking structure Dynamic aggregation thing.
17.4g boric acid estersil polymer (a) is weighed (using benzoyl peroxide as initiator, by propylene, propylene ylboronic acid Diisopropyl ester is carried out under the conditions of 80 DEG C after radical polymerization obtains intermediate product, by itself and thiopurine methyltransferase dimethylethoxysilane It is dissolved in tetrahydrofuran/water mixed solvent, using triethylamine as catalyst, it is obtained most that ester exchange reaction is carried out under the conditions of 80 DEG C End-product), (methyl is made using lithium methide, vinyl lithium and trimethylborate reaction in 3.92g boric acid estersil compound (b) Vinyl boronic acids；Using ethylene methacrylic ylboronic acid, 5- hexenyldimethylchlorosilanes as raw material, chloroform/water mixed liquor is solvent, three Ethamine is catalyst, and condensation reaction is carried out under the conditions of 50 DEG C and is made), 0.2g plasticizer DOPs, 0.05g dimethicones add Into the three-necked flask of dried and clean, 100 DEG C of stirring meltings are heated under nitrogen protective condition, after being well mixed, are added 0.04g AIBN, 0.5g triethylamines, react 4h under 100 DEG C of nitrogen protective conditions.After reaction terminates, it is suitable to be poured into In mould, it is placed under vacuum in 80 DEG C of vacuum drying ovens and continues to react 4-6h, is cooled to room temperature afterwards and places 30min, most The gluey polymer samples of hard are obtained eventually.Polymer samples have certain intensity and compressibility, can be within the specific limits Stretched.The dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes is made into, is carried out using cupping machine Extension test, rate of extension 50mm/min, it is 3.84 ± 0.88MPa to measure sample tensile strength, stretch modulus is 6.03 ± 1.42MPa, elongation at break are 473 ± 46%.Sample after breaking applies stress in section part and (may be selected during this to disconnected Face slightly soak), being placed in 80 DEG C of moulds section after heating 6-8h can bond again, have self-healing properties, also can root Material is molded again according to mould of different shapes.This material can be carried out as stress loading material in fine mould Use, play bearing stress effect while, there is certain deformability again, play cushioning effect, its it is cracked or When damaged, it can also be repaired by heating.
Embodiment 23
Using the macromolecular compound (III) containing polyfunctional group and other multiple reactive groups, contain difunctional The dynamic aggregation thing with dynamic crosslinking structure is prepared with the small molecule silicon-containing compound (II) of other reactive groups.
Weigh polybutadiene epoxy resin (a) (the poly- fourth for being about 2000 with molecular weight of 25g borate esters-silane-modified Diene epoxy resin is raw material, by its respectively with 4- aminobenzenes pinacol borate, methylaminopropyl dimethyl methoxy silane It is made by epoxide group ring-opening reaction) it is added in three-necked flask, 80 DEG C are warming up to, after leading to nitrogen insulation 1h, adds 0.5g Triethylamine, 1.8g γ-mercapto hydroxypropyl methyl dimethoxysilane (b) is slowly added under stirring, after reacting 2h, then be added dropwise to A small amount of 20% acetic acid aqueous solution, carries out cross-linking reaction under stirring.During reaction, on the viscosity of liquid is continuous Rise, after reacting 2h, obtain thick yellow polymer sample, be now poured into suitable mould, be placed in 80 DEG C Continue to react 4h in vacuum drying oven, be cooled to room temperature afterwards and place 30min, finally give the polymer samples of similar maltose, Its intensity is relatively low, but has larger sticky and very good tensile toughness, can largely be stretched and not broken (elongation at break is up to 1000%).In the present embodiment, can be used polymer as electronic package material or adhesive, During use, it can be recycled and reused, polymer samples have longer service life.
Embodiment 24
Using containing multi-functional macromolecular organoboron compound (I) and containing the siliceous chemical combination of multi-functional macromolecular Thing (II) prepares the dynamic aggregation thing with dynamic crosslinking structure.
Weighing 23g organic boronic modified silicon rubbers (a), (using methyl mercapto silicon rubber, vinyl boronic acids as raw material, DMPA makees For light trigger, under the conditions of ultraviolet light, be made by thiol-ene click-reactions), the silanol-modified silicon rubber (b) of 10g (using methyl vinyl silicone rubber, γ-mercapto hydroxypropyl methyl dimethoxysilane as raw material, DMPA is as light trigger, in ultraviolet light Under the conditions of irradiation, be made by thiol-ene click-reactions), 2g methyl silicone rubber particles are added in small-sized internal mixer and are kneaded After 20min, add 10g silica, 12g titanium dioxides, 1.75g di-iron trioxides, 0.035g silicone oil and continue to be kneaded 30min, make Obtain additive to be sufficiently mixed uniformly with sizing material, take out sizing material afterwards, be placed in twin-roll machine and suppress flakiness, carry out at room temperature cold But, cut-parts.Obtained polymer flake is dipped in 90 DEG C of water and is crosslinked, is then taken out, is put in 80 DEG C of vacuum drying ovens Put 6h further to be reacted and dried, be cooled to room temperature afterwards and place 30min, be removed from the molds sample, finally give The dynamic plugging glue of soft rubber-like.The dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes is made into, profit Extension test is carried out with cupping machine, rate of extension 50mm/min, it is 2.33 ± 0.27MPa to measure sample tensile strength, Stretch modulus is 3.04 ± 0.52MPa, and elongation at break is 843 ± 264%.Polymer samples not only embody very excellent Tensile toughness, also with good plasticity and resilience；Product of different shapes can be prepared into according to die size, to its table After face is pressed, recess can reply rapidly, when its surface occurs damaged, can be again molded, realized by heating Recycle.Obtained silastic product can be fabricated to all kinds of seals, or using its good damping property and Insulating properties, it is fabricated to Rubber sleeper pad accessory and is applied to railway traffic.
Embodiment 25
Using containing multi-functional macromolecular organoboron compound (I), contain the siliceous chemical combination of multi-functional macromolecular Thing (II) prepares the dynamic aggregation thing with dynamic crosslinking structure.
5.28g acrylamide-boric acid copolymer (a) is weighed in the beaker of dried and clean (with 3- bromopropyls boric acid, alkene Propylamine is raw material, after (3- (allyl amino) propyl group) boric acid is made by hydrocarbyl reaction, then by itself and N, N- dimethyl propylenes Acrylamide carries out radical polymerization and obtains final product using AIBN as initiator), and 40ml deionized water is added wherein, Constantly stirring and dissolving is placed under the conditions of 50 DEG C, after dissolving completely, is added dropwise to a small amount of 1mol/L NaOH solution wherein；Weigh 5.20g acrylamide-silane copolymer (b) (using 2- acrylic acid -3- (diethoxymethylsilane base) propyl diester as raw material, AIBN is initiator, and it is passed through with N,N-DMAA and is made after radical polymerization) be added slowly to acrylamide- In boric acid copolymer solution, its dissolving is mixed by being stirred continuously in the process, after dissolving completely, sequentially adds 1.08g Graphene powder, 0.05g neopelexes, after stirring 30min under the conditions of 50 DEG C, the ethoxy for adding 0.02g is fine Mixed solution, is placed under the conditions of 50 DEG C continues to react afterwards by dimension element.With the progress of reaction, on the viscosity of solution is continuous Rise, after heating response 2.5h, obtain thick polymer samples, be placed on 24h in 50 DEG C of baking ovens and be dried except molten Agent, then dried sample is placed in mould, it is compressing at 80 DEG C.It is made into 80.0 × 10.0 × (2.0~4.0) The dumbbell shape batten of mm sizes, extension test is carried out using cupping machine, rate of extension 50mm/min, measures sample stretching Intensity is 2.08 ± 0.56MPa, and stretch modulus is 2.83 ± 1.22MPa, and elongation at break is 434 ± 87%.It will can break After polymer samples are reclaimed, it is placed in placement 6-8h in 80 DEG C of mould and is molded again.In the present embodiment, can be by polymer Sample is made a kind of compound dynamic polymer bond pad of graphene and used, and this heat-conducting pad can be pressed into according to needs The product of different shape size, sample that is damaged or no longer needing may be recovered, new product are made and uses.
Embodiment 26
Using containing multi-functional macromolecular organoboron compound (I) and containing the siliceous chemical combination of multi-functional macromolecular Thing (II) prepares the dynamic aggregation thing with dynamic crosslinking structure.
A certain amount of boric acid modified polynorbornene (a) is taken (using vinyl boronic acids, cyclopentadiene as raw material, to pass through Diels-Alder reactions are made boric acid modified ENB, then by its with ENB with metallocene catalyst/methyl alumina Alkane is catalyst system and catalyzing, is made by polyaddition reaction) dissolve by heating the molten of 0.8mol/L is configured in o-dichlorohenzene solvent Liquid, therefrom take 50ml to be added in the flask of dried and clean, be added dropwise to a small amount of deionized water and acetic acid stir it is stand-by.Take A certain amount of silane-modified polynorbornene (b) (using methyl vinyl diethoxysilane, cyclopentadiene as raw material, passes through Diels-Alder reactions are made silane-modified ENB, then by its with ENB with metallocene catalyst/methyl alumina Alkane is catalyst system and catalyzing, is made by polyaddition reaction) dissolve by heating the molten of 0.8mol/L is configured in o-dichlorohenzene solvent Liquid, therefrom take in the boric acid modified polynorbornene mixed solution that 50ml has been configured before being slowly added into, entirely adding During, solution is in 80 DEG C of condition of water bath heating, and is well mixed mixed liquor by being stirred continuously.Solution addition is completed Afterwards, continue to stir 30min, then add 4ml triethylamines, be heated to 100 DEG C of stirring reaction 3h, obtain dynamic aggregation thing solution. Using electrostatic spinning technique, the needle tubing equipped with dynamic aggregation thing solution is done into positive pole, circular aluminium sheet does negative pole, adjusts between electric field Distance, apply voltage, the drop of syringe needle is become spindle by spherical and is formed injection stream by regulation, it is molten in spinning process Agent part is volatilized, and polymer fiber is obtained on receiving screen, and then fiber is placed in 60 DEG C of vacuum drying ovens and dries 12h, is obtained Dynamic aggregation fibres product.Fibre diameter is observed using microscope, the polymer fiber diameter for finding to obtain is in 1 ~2 μm of scope.Obtained polynorbornene fiber can be used to make the integrated electricity of human organ, electronic package material or silicon The erosion resistant on road, there is huge application prospect in nanometer tubing, optical fiber, integrated circuit connection.
Embodiment 27
Using containing multi-functional macromolecular organoboron compound (I) and containing the siliceous chemical combination of multi-functional macromolecular Thing (II) prepares the dynamic aggregation thing with dynamic crosslinking structure.
30g borates-ethylene copolymer (a) is taken (using AIBN as initiator, by isopropenyl boric acid frequency under the conditions of 80 DEG C That alcohol ester and ethene carry out random copolymerization and are made), 15g Silane-ethylene copolymers (b) are (using AIBN as initiator, in 80 DEG C of conditions It is lower methyl vinyl diethoxysilane and ethene are subjected to random copolymerization to be made), 5g polyethylene, 1g fire retardants TPP, 0.5g tri- Aoxidize two antimony, 0.5g stearic acid, 0.05g irgasfos 168s, 0.1g antioxidant 1010s, 0.1g di-n-butyltin dilaurates, After 0.25g dimethicones are well mixed, it is added in small-sized extruder and carries out extrusion blending, extrusion temperature is 140-160 DEG C, After obtained extrusion batten is granulated, sample preparation is carried out using small injecting machine, injection temperature is 140-160 DEG C, then will Obtained thin slice batten is placed in 90 DEG C of water and is crosslinked, and then takes out, is placed in mould, under 120 DEG C of nitrogen protective conditions Place 4-6h to be dried and further react, finally give the dynamic aggregation thing sample with fire resistance.Made Into the dumbbell shape batten of 80.0 × 10.0 × (2.0~4.0) mm sizes, extension test, stretching speed are carried out using cupping machine Rate is 50mm/min, and it is 5.98 ± 1.23MPa to measure sample tensile strength, and stretch modulus is 9.51 ± 2.13MPa, extension at break Rate is 147 ± 36%, and sample has certain mechanical property and good anti-flammability.In addition, obtained sample is also with good Good plasticity, can be according to the polymeric articles that mould molding of different shapes is different outward appearances.In the present embodiment, will can gather Flame-proof sheet material use is made in compound sample, and it can be recycled and reused.
Embodiment 28
Using containing multi-functional macromolecular organoboron compound (I) and containing the siliceous chemical combination of multi-functional macromolecular Thing (II) prepares the dynamic aggregation thing with dynamic crosslinking structure.
60g vinyl chloride-boric acid ester copolymer (a) is taken (using AIBN as initiator, by vinyl chloride and propylene ylboronic acid diisopropyl Ester is made by radical polymerization), 30g vinyl chloride-silane copolymer (b) is (using AIBN as initiator, by propylene base trichlorosilane With vinyl chloride pass through it is free-radical polymerized be made), 10g polyvinyl chloride, 20g o-phthalic acid dibutyl esters, 10g MBS toughener, 1g Stearic acid, 0.1g irgasfos 168s, 0.2g antioxidant 1010s, 0.2g di-n-butyltin dilaurates, the mixing of 0.5g dimethicones After uniformly, it is added in small-sized extruder and carries out extrusion blending, extrusion temperature is 120-140 DEG C, and obtained extrusion batten is carried out After granulation, sample preparation is carried out using small injecting machine, injection temperature is 130-150 DEG C, is then placed in obtained thin slice batten Be crosslinked in 90 DEG C of water, then take out, be placed in mould, under 100 DEG C of nitrogen protective conditions place 4-6h be dried with And the further dynamic aggregation thing sample for reacting, finally giving toughness reinforcing.It is made into 80.0 × 10.0 × (2.0~4.0) mm The dumbbell shape batten of size, extension test is carried out using cupping machine, rate of extension 50mm/min, it is strong to measure sample stretching It is 15.94 ± 2.17MPa to spend for 10.49 ± 1.22MPa, stretch modulus, and elongation at break is 773 ± 106%, polymer samples With good pliability, large range of stretching can be carried out.In addition, obtained product also has good plasticity, can root According to the polymeric articles that mould molding of different shapes is different outward appearances.In the present embodiment, polymer samples can be made resistance to The hose material of bending is used, and after its appearance is damaged, it can be recycled and reused.
Embodiment 29
Using the small molecule organoboron compound (I) containing four-functional group, contain multi-functional macromolecular organoboration Compound (I) and the small molecule silicon-containing compound (II) containing difunctional, contain multi-functional macromolecular silicon-containing compound (II) the dynamic aggregation thing with dynamic crosslinking structure is prepared.
Weigh a certain amount of 2,5- hypoboric acid thiophene (a) to be dissolved in toluene solvant, be configured to 0.2mol/L solution；Claim Take a certain amount of chloropropene-phenyl boric acid copolymer (b) (using chloropropene, 4- vinylphenylboronic acids as raw material, AIBN is initiator, Obtained by radical polymerization) it is dissolved in toluene solvant, it is configured to 0.05mol/L solution；Respectively take two kinds of organic borons of 20ml Compound solution is added in the beaker of dried and clean, adds 4ml deionized waters and a small amount of acetic acid, adds 10mg BHT Antioxidant, after being well mixed, it is slowly added to 1.72g diphenyl silanediols (c), 4.70g chloropropenes-silicon successively under stirring (using chloropropene, styrene ethyl trimethoxy silane as raw material, AIBN is initiator to alkyl copolymer (d), passes through radical polymerization It is made), it is heated to 80 DEG C and mixed solution is slowly stirred, after making every component dissolving well mixed, is added dropwise to the second of 2ml tri- Amine continues stirring reaction.The viscosity of solution constantly rises with the progress of stirring, after hybrid reaction 2h, obtains the polymerization of paste Thing sample, now it is poured into suitable mould, is placed in 50 DEG C of vacuum drying ovens and dries 24h, be cooled to room temperature afterwards and put 30min is put, the polymer samples of the agaroid shape finally given, sample surfaces are pressed with finger, sample can be very fast Ground resilience, good elasticity is shown, in addition, sample can also be extended within the specific limits.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, It is 2.97 ± 0.36MPa to measure sample tensile strength, and stretch modulus is 4.77 ± 1.43MPa, elongation at break is 576 ± 137%.In the present embodiment, polymer samples can be made to a kind of fluid sealant or recuperability elastic pellet is used, its It can embody good toughness and elasticity, and can be damaged or no longer according to the product for needing to be pressed into different shape size The sample needed may be recovered, and new product is made and uses.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair The equivalent structure or equivalent flow conversion that bright description is made, or directly or indirectly it is used in other related technology necks Domain, it is included within the scope of the present invention.

Claims (14)

  1. A kind of 1. dynamic aggregation thing with dynamic crosslinking structure, it is characterised in that its polymer chain skeleton in cross-linked network On, either on the cross linked chain synthetism frame between polymer chain or simultaneously on polymer chain skeleton between polymer chain Contain organic boronic estersil key on cross linked chain synthetism frame；Wherein, described organic boronic estersil key, it has following structure：
    Wherein, a boric acid estersil key is at least formed between boron atom and silicon atom, and at least one carbon atom leads in structure Cross boron carbon key with boron atom to be connected, and at least one organic group passes through in the boron carbon key connection to boron atom；Described Polymerization linking point of the organic boronic estersil key as dynamic aggregation thing, either it is crosslinked linking point or simultaneously as polymerization link Put and be crosslinked linking point and exist, be the necessary condition to form/maintain dynamic aggregation thing structure.
  2. 2. the dynamic aggregation thing according to claim 1 with dynamic crosslinking structure, it is characterised in that its at least with Lower one or more of compounds obtain as raw material：
    Organoboron compound (I), it contains organic boron acidic group or organic boronic ester group or organic boron acidic group and organic boron The combination of perester radical；Silicon-containing compound (II), it contains silicone hydroxyl or silicone hydroxyl presoma or silicone hydroxyl and silicone hydroxyl The combination of presoma；Compound (III), it contains organic boron acidic group or organic boronic ester group or organic boron acidic group simultaneously Combination and silicone hydroxyl or silicone hydroxyl presoma or the group of silicone hydroxyl and silicone hydroxyl presoma with organic boronic ester group Close；Compound (IV), it contains organic boronic estersil key and other reactive groups；Wherein, organoboron compound (I), contains Silicon compound (II), compound (III) contain at least one functional group；Wherein, organoboron compound (I) or siliceous chemical combination Thing (II) does not prepare described dynamic aggregation thing separately as raw material；
    Wherein, the organic boron acidic group contained in raw materials of compound, refer to by boron atom and be connected with the boron atom one The structural motif that hydroxyl is formed, and boron atom therein is at least connected with a carbon atom by boron carbon key, and at least one Individual organic group passes through in the boron carbon key connection to boron atom；
    Wherein, the organic boronic ester group contained in raw materials of compound, refer to by boron atom, an oxygen being connected with the boron atom The structural motif that atom and the alkyl being connected with the oxygen atom or silylation are formed, and boron atom therein at least with a carbon Atom is connected by boron carbon key, and at least one organic group passes through in the boron carbon key connection to boron atom；
    Wherein, the silicone hydroxyl contained in raw materials of compound, refer to by silicon atom and a hydroxyl being connected with the silicon atom The structural motif formed；
    Wherein, the silicone hydroxyl presoma contained in raw materials of compound, refer to by silicon atom and be connected with the silicon atom one Individual hydrolyzable obtains the structural motif that the group of hydroxyl is formed, wherein, the group that hydrolyzable obtains hydroxyl is selected from halogen, cyanogen Base, oxygen cyano group, thiocyanogen, alkoxy, amino, sulfate group, boric acid ester group, acyl group, acyloxy, acylamino-, ketoxime base, alkoxide Base；
    Wherein, the functional group contained in raw materials of compound, refer in the hydroxyl or organic boronic ester group in organic boron acidic group Ester group or silicone hydroxyl in hydroxyl or silicone hydroxyl presoma in hydrolyzable obtain hydroxyl group or they Combination；Wherein, a hydroxyl in organic boron acidic group is a functional group, and an ester group in organic boronic ester group is one Individual functional group, a hydroxyl in silicone hydroxyl are a functional group, and a hydrolyzable in silicone hydroxyl presoma obtains hydroxyl Group be a functional group；
    Wherein, other reactive groups in raw materials of compound contained, refer to that reaction can be performed the derivatization, or gathered The group of common covalent bond of the conjunction/cross-linking reaction generation in addition to organic boronic estersil key, its be selected from hydroxyl, phenolic hydroxyl group, carboxyl, Acyl group, amide groups, acyloxy, amino, aldehyde radical, sulfonic group, sulfonyl, sulfydryl, alkenyl, alkynyl, cyano group, piperazine base, oximido, hydrazine Base, guanidine radicals, halogen, isocyanate groups, anhydride group, epoxide group, acrylate group, acrylamide group, Malaysia acyl Imine group, n-hydroxysuccinimide group, ENB group, azo group, azido group, heterocyclic group.
  3. 3. the dynamic aggregation thing according to claim 2 with dynamic crosslinking structure, it is characterised in that described organic boron Compound (I), it is with following representation：
    Wherein, A is to contain organic boron acidic group or organic boronic ester group or the mould of organic boron acidic group and organic boronic ester group Block；M be modules A number, m >=1；L is the substituted radical on individual module A, or the company between two or more modules As Group is connect, it is selected from following any or several structures：Small molecule alkyl, molecular weight of the molecular weight no more than 1000Da are more than 1000Da polymer chain residue, singly-bound, hetero atom linker, molecular weight are no more than 1000Da divalence or multivalence small molecule hydrocarbon Base, molecular weight are more than 1000Da divalence or multivalence polymer chain residue；Wherein, during m=1, L is the substitution on individual module A Group, it is in small molecule alkyl of the molecular weight no more than 1000Da, polymer chain residue of the molecular weight more than 1000Da It is any or appoint it is several；m>When 1, linking groups of the L between two or more modules As, it is selected from singly-bound, hetero atom connects The divalence of the divalence of base, molecular weight no more than 1000Da or multivalence small molecule alkyl, molecular weight more than 1000Da or multivalence polymerization Any of thing chain residue is appointed several；P be group L number, p >=1；
    Described silicon-containing compound (II), it is with following representation：
    Wherein, G is to contain silicone hydroxyl or silicone hydroxyl presoma or the module of silicone hydroxyl and silicone hydroxyl presoma；N is mould Block G number, n >=1；J is the substituted radical on individual module G, or the linking group between two or more module G, It is selected from following any or several structures：Hydrogen atom, heteroatom group, molecular weight are no more than 1000Da small molecule hydrocarbon The polymer chain residue of base, molecular weight more than 1000Da, molecular weight are no more than 1000Da inorganic molecules chain residue, molecular weight Inorganic macromolecular chain residue, singly-bound, hetero atom linker, molecular weight more than 1000Da are no more than 1000Da divalence or multivalence The divalence of small molecule alkyl, molecular weight more than 1000Da or multivalence polymer chain residue, molecular weight are no more than 1000Da divalence Or polyvalent mineral small molecule chain residue, molecular weight are more than 1000Da divalence or polyvalent mineral macromolecular chain residue；Wherein, n=1 When, J is the substituted radical on individual module G, and it is selected from small point that hydrogen atom, heteroatom group, molecular weight are no more than 1000Da The polymer chain residue of sub- alkyl, molecular weight more than 1000Da, inorganic molecules chain residue of the molecular weight no more than 1000Da, divide Any of the inorganic macromolecular chain residue of son amount more than 1000Da is appointed several；n>When 1, J be two or more module G it Between linking group, its be selected from singly-bound, hetero atom linker, molecular weight be no more than 1000Da divalence or multivalence small molecule hydrocarbon Base, molecular weight more than 1000Da divalence or multivalence polymer chain residue, molecular weight no more than 1000Da divalence or multivalence without Any of the divalence of machine small molecule chain residue, molecular weight more than 1000Da or polyvalent mineral macromolecular chain residue are appointed several Kind；Q be group J number, q >=1；
    Described compound (III), it is with following representation：
    Wherein, A is to contain organic boron acidic group or organic boronic ester group or the mould of organic boron acidic group and organic boronic ester group Block；X be modules A number, x >=1；G is to contain silicone hydroxyl or silicone hydroxyl presoma or silicone hydroxyl and silicone hydroxyl forerunner The module of body；Y be module G number, y >=1；T is between two or more A or between two or more G or A and G Between linking group, its be selected from it is following any or appoint several structures：Singly-bound, hetero atom linker, molecular weight are no more than 1000Da divalence or multivalence small molecule alkyl, molecular weight are more than 1000Da divalence or multivalence polymer chain residue；V is group T number, v >=1；
    Described compound (IV), it is with following representation：
    Wherein, E is the module containing organic boronic estersil key；U be module E number, u >=1；Y is the substitution on individual module E Group, or the linking group between the substituted radical on individual module E and two or more module E, and at least one base Group Y is connected with the boron atom of organic boronic estersil key, and at least one group Y is connected with the silicon atom of organic boronic estersil key；Its In, at least one other reactive group is contained at least one group Y, and contain in all group Y other are anti- Answering property group number is more than or equal to 2；Described group Y, it is selected from following any or several structures：Molecular weight is no more than The polymer chain residue of 1000Da small molecule alkyl, molecular weight more than 1000Da, singly-bound, hetero atom linker, molecular weight are not Divalence or multivalence small molecule alkyl, molecular weight more than 1000Da are more than 1000Da divalence or multivalence polymer chain residue；Its In, during u=1, Y is the substituted radical on individual module E, and it is selected from small molecule alkyl, the molecule that molecular weight is no more than 1000Da Any of the polymer chain residue of amount more than 1000Da is appointed several；u>When 1, Y be individual module E on substituted radical and Linking group between two or more module E, it is selected from small molecule alkyl, molecular weight of the molecular weight no more than 1000Da and is more than Any of 1000Da polymer chain residue appoints several and singly-bound, hetero atom linker, molecular weight to be no more than Any in the 1000Da divalence of divalence or multivalence small molecule alkyl, molecular weight more than 1000Da or multivalence polymer chain residue Kind is appointed several；R be group Y number, r >=2；
    Wherein, the modules A containing organic boron acidic group, it is selected from following any or several structures：
    Wherein, K1For the group being joined directly together with boron atom, it is selected from following any structure：Hydrogen atom, heteroatom group, divide Small molecule alkyl of the son amount no more than 1000Da, molecular weight are more than 1000Da polymer chain residue；Wherein, the ring-type knot in A4 Structure is the nonaro-maticity containing at least one organic boron acidic group or armaticity boron heterocyclic group；The cyclization of cyclic structure in A4 is former Son is each independently carbon atom, boron atom or other hetero atoms, and at least one ring member nitrogen atoms are boron atom and formed organic Boronate, and at least one ring member nitrogen atoms connect with group L or group T-phase；Boron atom in the various structures at least with one Carbon atom is connected by boron carbon key, and at least one organic group passes through in the boron carbon key connection to boron atom；
    The described modules A containing organic boronic ester group, it is selected from following any or several structures：
    Wherein, K2For the group being joined directly together with boron atom, it is selected from following any structure：Hydrogen atom, heteroatom group, divide Small molecule alkyl of the son amount no more than 1000Da, molecular weight are more than 1000Da polymer chain residue；R1、R2、R3、R4、R6For with The monovalent organic group or monovalence organosilicon radical that oxygen atom is joined directly together, it is direct by carbon atom or silicon atom and oxygen atom It is connected, it is selected from following any structure：Small molecule alkyl of the molecular weight no more than 1000Da, molecular weight are no more than 1000Da's Small molecule silylation, molecular weight are more than 1000Da polymer chain residue；R5Divalence to be joined directly together with two oxygen atoms has Machine group or divalence organosilicon radical, it is joined directly together by carbon atom or silicon atom with oxygen atom, and it is selected from following any Structure：Molecular weight no more than the divalence small molecule silylation of 1000Da divalence small molecule alkyl, molecular weight no more than 1000Da, Molecular weight is more than 1000Da diatomic polymer chain residue；Wherein, the cyclic structure in B5 is to contain at least one organic boronic The nonaro-maticity or armaticity boron heterocyclic group of ester group；The ring member nitrogen atoms of cyclic structure in B5 be each independently carbon atom, Boron atom or other hetero atoms, and at least one ring member nitrogen atoms are boron atom and form organic boronic ester group, and it is at least one into Annular atom connects with group L or group T-phase；Boron atom in the various structures at least passes through boron carbon key phase with a carbon atom Even, and at least one organic group passes through in the boron carbon key connection to boron atom；
    The described module G containing silicone hydroxyl, it is selected from following any or several structures：
    Wherein, K3、K4、K5、K6、K7For the group being joined directly together with silicon atom, it is each independently selected from following any structure： The small molecule alkyl of hydrogen atom, heteroatom group, molecular weight no more than 1000Da, molecular weight are residual more than 1000Da polymer chain The inorganic molecules chain residue of base, molecular weight no more than 1000Da, molecular weight are more than 1000Da inorganic macromolecular chain residue；Its In, the cyclic structure in C7, C8, C9 is the nonaro-maticity containing at least one silicone hydroxyl or armaticity sila cyclic group；C7、 The ring member nitrogen atoms of cyclic structure in C8, C9 are each independently carbon atom, silicon atom or other hetero atoms, and it is at least one into Annular atom is silicon atom and forms silicone hydroxyl, and at least one ring member nitrogen atoms connect with group J or group T-phase；
    The described module G containing silicone hydroxyl presoma, it is selected from following any or several structures：
    Wherein, K8、K9、K10、K11、K12For the group being joined directly together with silicon 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 1000Da polymer The inorganic molecules chain residue of chain residue, molecular weight no more than 1000Da, molecular weight are residual more than 1000Da inorganic macromolecular chain Base；X1、X2、X3、X4、X5、X6、X7、X8、X9、X10、X11、X12、X13、X14For the hydrolyzable groups being joined directly together with silicon atom, its Selected from halogen, cyano group, oxygen cyano group, thiocyanogen, alkoxy, amino, sulfate group, boric acid ester group, acyl group, acyloxy, acylamino-, Ketoxime base, alkoxide group；Wherein, the cyclic structure in D7, D8, D9 be the nonaro-maticity containing at least one silicone hydroxyl presoma or Armaticity sila cyclic group；The ring member nitrogen atoms of cyclic structure in D7, D8, D9 be each independently carbon atom, silicon atom or its His hetero atom, and at least one ring member nitrogen atoms are silicon atom and form silicone hydroxyl presoma, and at least one ring member nitrogen atoms and base Group J or group T-phase connect；
    The described module E containing organic boronic estersil key, it is selected from following any or several structures：
    Wherein, K13、K16、K20For the group being joined directly together with boron atom, it is each independently selected from following any structure：Hydrogen The small molecule alkyl of atom, heteroatom group, molecular weight no more than 1000Da, molecular weight are residual more than 1000Da polymer chain Base；K14、K15、K17、K18、K19、K21For the group being joined directly together with silicon 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 1000Da polymer The inorganic molecules chain residue of chain residue, molecular weight no more than 1000Da, molecular weight are residual more than 1000Da inorganic macromolecular chain Base.
  4. 4. the dynamic aggregation thing according to claim 3 with dynamic crosslinking structure, it is characterised in that described hetero atom Group, it is selected from following any group：It is halogen, hydroxyl, mercaptan, carboxyl, nitro, primary amine groups, silicon substrate, phosphorus base, triazole, different Oxazole, amide groups, imide, thioamides base, enamine base, carbonate group, thiocarbonic acid ester group, dithiocarbonic acids ester group, Trithiocarbonic acid ester group, carbamate groups, thiocarbamate base, dithiocarbamate groups, thioester substrate, monothioester Base, dithioesters base, ortho acid ester group, phosphate-based, phosphorous acid ester group, hypophosphorous acid ester group, phosphonate group, phosphoryl, phosphorous acyl Base, secondary phosphoryl, thiophosphoryl, thio phosphorous acyl group, thio secondary phosphoryl, phosphorus silane ester group, silane ester group, phosphoamide, Thioamides, phosphamide, phosphoramidite, pyrophosphoramide, endoxan, ifosfamide, thio-phosphamide, orthosilicic acid base, partially Silicic acid base, secondary silicic acid base, boronate, metaboric acid base, rhizome of Chinese monkshood acyl group, peptide bond, acetal, cyclic ketal, mercaptal, azepine acetal, nitrogen Heterocycle acetal, nitrogen thia acetal, ithioacetals, hemiacetal, hemimercaptol, azepine hemiacetal, ketal, thioketal, azepine Ketal, azacyclo- ketal, nitrogen thia ketal, acylhydrazone key, oxime key, sulfime ether, semicarbazones key, thiosemicarbazone key, 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, isourea base, isothiourea group, allophanate group, thioallophanate base, Guanidine radicals, amidino groups, amino guanidine radicals, amido-amidinate, imido acidic group, imidic acid thioester substrate, nitroxyl, nitrosyl radical, sulfonic group, sulfonic acid Ester group, sulfinat, sulfoamido, sulfonamido, sulfonyl hydrazino, sulfonylurea group, maleimide；
    Described molecular weight is no more than 1000Da small molecule alkyl, its any, any unsaturation in the following group Form, any substituted form or any by hydridization form：C1-71Alkyl, ring C3-71Alkyl, phenyl, benzyl, aromatic hydrocarbons Base；
    Described molecular weight is more than 1000Da polymer chain residue, and it is selected from homopolymerization or the carbochain polymer of copolymerized form is residual Base, heterochain polymer residue, elemento-organic polymer residue；
    Described molecular weight is no more than 1000Da small molecule silylation, its any, any insatiable hunger in the following group With form, any substituted form or any by hydridization form：Silicon-carbon alkane chain residue, siloxane chain residue, silicon sulphur Alkane chain residue, silazane chain residue；
    Described molecular weight is no more than 1000Da inorganic molecules chain residue, and it is any, any in the following group Unsaturated form, any substituted form or any by hydridization form：Chain sulphur residue, 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, boron-oxygen chain residue；
    Described molecular weight be more than 1000Da inorganic macromolecular chain residue, its in the following group it is any, any not Saturated form, any substituted form or any by hydridization form：Chain sulphur polymer residue, polysilane chain are residual Base, polysiloxane chain residue, polysulfide silicon chain residue, polysulfide nitrogen chain residue, polyphosphoric acid chain residue, polyphosphazene chain residue, polychlorostyrene generation Phosphonitrile chain residue, polyborane chain residue, poly- boroxane chain residue；It is or any inorganic big with residue in the following group Molecule or any inorganic macromolecular with residue being modified by surface：Zeolite-type molecular sieves, aluminium phosphate molecular sieve, phosphoric acid Zirconium molecular sieve, heteropolyacid salt molecular sieve, diamond, graphite, carbon fiber, white phosphorus, red phosphorus, five phosphorous oxides, molybdenum sulfide, titanium dioxide Silicon, silicon disulfide, silicon nitride, carborundum, talcum, kaolin, montmorillonite, mica, asbestos, feldspar, cement, glass, quartz, pottery Porcelain, boron oxide, nitridation sulphur, calcium silicide, silicate, glass fibre, beryllium oxide, magnesia, mercury oxide, boron hydride, boron nitride, Boron carbide, aluminium nitride, diaspore, gibbsite, corundum, titanium dioxide；
    Described singly-bound, it is selected from boron boron singly-bound, carbon-carbon single bond, carbon nitrogen singly-bound, nitrogen nitrogen singly-bound, boron carbon single bond, boron nitrogen singly-bound, boron Silicon singly-bound, silicon silicon singly-bound, silicon-carbon singly-bound, silicon nitrogen singly-bound；
    Described hetero atom linker, it is selected from following any or several combination：Ether, sulfenyl, disulfide group, thioether Base, divalence tertiary amine groups, trivalent tertiary amine groups, divalence silicon substrate, trivalent silicon substrate, tetravalence silicon substrate, divalence phosphorus base, three valent phosphors base, divalence boron Base, trivalent boryl.
  5. 5. the dynamic aggregation thing according to claim 2 with dynamic crosslinking structure, it is characterised in that form dynamic aggregation The raw material components of thing also include following any or any two can additive：Auxiliary agent, filler；
    Wherein, addible auxiliary agent is selected from following any or several auxiliary agents：Catalyst, initiator, antioxidant, light are stable Agent, heat stabilizer, crosslinking agent, toughener, coupling agent, lubricant, releasing agent, plasticizer, dynamic regulation agent, antistatic additive, breast Agent, dispersant, colouring agent, fluorescent whitening agent, delustering agent, fire retardant, nucleator, rheological agent, thickener, levelling agent；
    Wherein, addible filler is selected from following any or several fillers：It is inorganic non-metallic filler, metal packing, organic Filler.
  6. 6. the dynamic aggregation thing with dynamic crosslinking structure according to any one of claim 2 to 5, it is characterised in that It participates in reaction generation organic boronic estersil key by least following components and obtained：
    At least one organoboron compound (I), at least one silicon-containing compound (II)；Wherein, organoboron compound (I) and siliceous Compound (II) contains two or more functional groups, and at least one organoboron compound (I) or at least one silicide-comprising Compound (II) contains three or more than three functional groups.
  7. 7. the dynamic aggregation thing with dynamic crosslinking structure according to any one of claim 2 to 5, it is characterised in that It participates in reaction generation organic boronic estersil key by least following components and common covalent bond obtains：
    At least one organoboron compound (I), at least one silicon-containing compound (II)；Wherein, organoboron compound (I) and siliceous Compound (II) contains one or more functional groups, and at least one organoboron compound (I) or at least one silicide-comprising Compound (II) contains one or more other reactive groups.
  8. 8. the dynamic aggregation thing with dynamic crosslinking structure according to any one of claim 2 to 5, it is characterised in that It participates in reaction generation organic boronic estersil key by least following components and obtained：At least one compound (III)；Wherein, change Compound (III) contains two or more functional groups.
  9. 9. the dynamic aggregation thing according to claim 8 with dynamic crosslinking structure, it is characterised in that participate in reaction generation The compound component of organic boronic estersil key also includes：
    At least one organoboron compound (I), either at least one silicon-containing compound (II) or at least one organic boron chemical combination The combination of thing (I) and at least one silicon-containing compound (II)；
    Wherein, organoboron compound (I), silicon-containing compound (II) contain two or more functional groups, and at least oneization Compound (III) or at least one organoboron compound (I) or at least one silicon-containing compound (II) contain three or more than three Functional group.
  10. 10. the dynamic aggregation thing with dynamic crosslinking structure according to any one of claim 2 to 5, it is characterised in that It participates in reaction generation organic boronic estersil key by least following components and common covalent bond obtains：At least one compound (III)；Wherein, compound (III) contains two or more functional groups.
  11. 11. the dynamic aggregation thing according to claim 10 with dynamic crosslinking structure, it is characterised in that participate in reaction life Also include into the compound component of organic boronic estersil key and common covalent bond：
    At least one organoboron compound (I), either at least one silicon-containing compound (II) or at least one organic boron chemical combination The combination of thing (I) and at least one silicon-containing compound (II)；
    Wherein, organoboron compound (I), silicon-containing compound (II) contain one or more functional groups, and at least oneization Compound (III) or at least one organoboron compound (I) or at least one silicon-containing compound (II) contain one or more Other reactive groups.
  12. 12. the dynamic aggregation thing with dynamic crosslinking structure according to any one of claim 2 to 5, it is characterised in that It participates in reaction by least following components and generates common covalent bond acquisition：
    At least one compound (IV) containing at least one organic boronic estersil key and at least one other reactive group.
  13. 13. the dynamic aggregation thing according to claim 12 with dynamic crosslinking structure, it is characterised in that participate in reaction life Compound component into common covalent bond also includes：
    It is at least one not contain organic boronic estersil key but the compound containing at least one other reactive group；Wherein, change Other reactive groups contained in compound can participate in reacting with other reactive groups contained in compound (IV).
  14. 14. the dynamic aggregation thing with dynamic crosslinking structure according to any one of claim 1 to 5, it is characterised in that It is applied to following product：Damper, padded coaming, defense of resistance to impact material, athletic protective article, army and police's protective article, from Prosthetic coating, self-repairability sheet material, self-repairability binding agent, toughness material, toy.
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