CN109206625A - A kind of physics split-phase supermolecule dynamic aggregation object and its application - Google Patents

A kind of physics split-phase supermolecule dynamic aggregation object and its application Download PDF

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CN109206625A
CN109206625A CN201710522414.4A CN201710522414A CN109206625A CN 109206625 A CN109206625 A CN 109206625A CN 201710522414 A CN201710522414 A CN 201710522414A CN 109206625 A CN109206625 A CN 109206625A
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soft segment
hard section
chain
equal
dynamic
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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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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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Abstract

The invention discloses a kind of physics split-phase supermolecule dynamic aggregation objects, wherein containing while having the block polymer molecules of hard section and soft segment；Crystalline phase and/or the phase incompatible with soft segment are mutually mixed and/or can formed each independently between each hard section of the block polymer molecules, to form split-phase physical crosslinking and/or the polymerization based on hard section, each soft segment of the block polymer molecules is unformed shape；Containing at least one ligand groups at least one soft segment of the block polymer molecules, the effect of dynamic metal-ligand is formed with metal center；Moreover, containing hydrogen bond group at least one while that there is hydrogen bond donor and hydrogen bond receptor at least one soft segment of the block polymer molecules, dynamic hydrogen bond action is formed；The dynamic aggregation object has shape memory function, self-repair function and ultra-tough, and in fields such as bio-medical material, military affairs, aerospace, the energy, buildings, tool has been widely used.

Description

A kind of physics split-phase supermolecule dynamic aggregation object and its application
Technical field
The present invention relates to a kind of intellectual materials, and in particular to one kind is dynamic containing the crosslinking of physics split-phase and dynamic supermolecular mechanism State polymer.
Background technique
Crosslinking is that polymer forms three-dimensional net structure to reach raising polymer elasticity, thermal stability and mechanical property etc. The universal method of effect.Crosslinking can be (covalent) crosslinking of chemistry either physics (non-covalent/supermolecule) crosslinking.Physical crosslinking Due to being particularly helpful to promote the processing performance etc. of polymer, become a direction of polymer development.But when only When using traditional physical crosslinking such as such as mutually separating or crystallize, if crosslink density it is lower (chain between crosslinking points is longer/crosslinking Point degree of functionality is lower), then often cross-linked polymer is softer, and mechanical property is bad；And if the higher (crosslinking points of crosslink density Between chain it is longer/crosslinking points degree of functionality is higher), then often lead to that cross-linked polymer is hard and crisp, and easy fracture is so as to cause material Failure, and under the operating temperature of material, after failure, it is necessary to be replaced, can not reuse；And in order to keep material The stability of material, the solution crosslinking temperature of physical crosslinking need to be higher than the operating temperature of material, make to be physical crosslinking the work temperature in material Degree is lower to lack dynamic.
Therefore, it is necessary to develop a kind of novel dynamic aggregation object, so that system there can either be dimensional stability, and have good Good mechanical property, self-repairability and excellent dynamic, to solve problems of the prior art.
Summary of the invention
The present invention is directed to above-mentioned background, in order to make polymer obtain enough toughness, have self-repairability and dynamic, mentions A kind of physics split-phase supermolecule dynamic aggregation object is supplied.For this purpose, we are in dynamic aggregation object comprising having hard section and soft segment knot The block polymer molecules of structure, and introducing has the supermolecular mechanism of dynamic, the i.e. effect of dynamic metal-ligand and dynamic Property hydrogen bond action.The split-phase physical crosslinking that polymer molecule hard section is formed can maintain thermal stability, the mechanical property of dynamic aggregation object Energy, dimensional stability etc., and the metal-ligand effect with dynamic and hydrogen bond action that introduce can be further improved crosslinking Density enhances its stability and mechanical property；Simultaneously have dynamic metal-ligand effect and hydrogen bond action be broken with The dynamic for compensating for and lacking at use temperature based on the physical crosslinking crystallize/mutually separated is re-formed, so that polymer itself has There are certain self-repairability and good toughness.
The present invention can be achieved by following technical solution:
A kind of physics split-phase supermolecule dynamic aggregation object, wherein containing while there is the block polymer of hard section and soft segment point Son；It is mutually mixed between each hard section of the block polymer molecules or respectively independent or to be not only partially mutually mixed part again respective It is separately formed crystalline phase or has the phase incompatible with soft segment again with the incompatible phase of soft segment or existing crystalline phase, be based on being formed The split-phase of hard section is physical crosslinking point, is physical crosslinking or is crosslinked and polymerize, the block polymer to form the split-phase based on hard section Each soft segment of molecule is unformed shape；Contain at least one ligand base at least one soft segment of the block polymer molecules Group forms the effect of dynamic metal-ligand with metal center；Moreover, at least one of the block polymer molecules is soft Contain hydrogen bond group at least one while that there is hydrogen bond donor and hydrogen bond receptor in section, is used to form dynamic hydrogen bond work With.
In one embodiment of the invention, contained by the dynamic aggregation object there is hard section A and soft segment B while Block polymer molecules have under it is various described in structure one kind or appoint several combination:
Wherein, formula (1A) is linear chain structure, and n is hard section-soft segment alternate cells quantity, is more than or equal to 0；
Formula (1B) is linear chain structure, and both ends section is hard section, and n is hard section-soft segment alternate cells quantity, is more than or equal to 0；
Formula (1C) is linear chain structure, and both ends section is soft segment, and n is hard section-soft segment alternate cells quantity, is more than or equal to 0；
Formula (1D) is branched structure, and x is the quantity for the hard section branch chain element being connected on soft segment B；N is hard section-soft segment The quantity of alternate cells is more than or equal to 0；Y is to be connected to hard section on soft segment B-soft segment branch chain element quantity；X, y is greater than Equal to 0, and the sum of x, y are more than or equal to 3；
Formula (1E) is branched structure, and x is the quantity for the hard section branch chain element being connected on soft segment B；N is hard section-soft segment The quantity of alternate cells is more than or equal to 0；Y is to be connected to hard section on soft segment B-soft segment alternately and be to hold point of section with hard section The quantity of branching units；X, y is more than or equal to 0, and the sum of x, y are more than or equal to 3；
Formula (1F) is branched structure, and x is the quantity for the soft segment branch chain element being connected on hard section A；N is soft segment-hard section The quantity of alternate cells is more than or equal to 0；Y is to be connected to soft segment on hard section A-hard section branch chain element quantity；X, y is greater than Equal to 0, and the sum of x, y are more than or equal to 3；
Formula (1G) is branched structure, and x is the quantity for the soft segment branch chain element being connected on hard section A；N is soft segment-hard section The quantity of alternate cells is more than or equal to 0；Y is to be connected to soft segment on hard section A-hard section alternately and be to hold point of section with soft segment The quantity of branching units；X, y is more than or equal to 0, and the sum of x, y are more than or equal to 3；
Formula (1H) is cyclic structure, and n is hard section-soft segment alternate cells quantity, is more than or equal to 1.
In one embodiment of the invention, the main chain of the soft segment of the block polymer molecules is selected from carbochain knot Structure, carbon heterochain structure, carbon chain structure, element chain structure, element heterochain structure, the miscellaneous element chain structure of carbon；The block It is miscellaneous that the main chain of the hard section of polymer molecule is selected from carbon-chain structure, carbon heterochain structure, carbon chain structure, element chain structure, element The miscellaneous element chain structure of chain structure, carbon.
In one embodiment of the invention, the glass transition of each soft segment in the block polymer molecules Temperature is not higher than 25 DEG C.
In one embodiment of the invention, being selected from for the hard section of the block polymer molecules has high-vitrification Amorphous polymer chains section, the polymer segment rich in hydrogen bond group or group, the polymer rich in crystalline phase of transition temperature Segment or group, the polymer segment rich in conjugated structure.
In one embodiment of the invention, in the ligand groups and metal in the block polymer molecules soft segment The dynamic metal-ligand being formed centrally is acted on containing combination one or more in structure shown in the following general formula:
Wherein, X is coordination atom, and M is metal center,It is cyclopentadiene ligand, X is connected with singly-bound in formula Indicate that the coordination atom belongs to the same ligand groups, when containing two or more coordination atoms in a ligand groups When, X is identical atom or different atoms, and X is atom, cation or anion.Wherein, the coordination atom X is selected from Boron, nitrogen, oxygen, sulphur, phosphorus, silicon, arsenic, selenium, tellurium；The metal center M is selected from the gold that can form the effect of dynamic metal-ligand The ionic species of category, compound, chelate and combinations thereof.
In one embodiment of the invention, following constituent is contained in the soft segment of the block polymer molecules At least one of:
In one embodiment of the invention, the dynamic ligand groups in the block polymer molecules soft segment and Between dynamic hydrogen bond group at least containing six skeletal atoms flexible linking group or segment be connected.
In one embodiment of the invention, structural metal-ligand is also contained in the block polymer molecules Effect or structural hydrogen bond action act on and structural hydrogen bond action containing structural metal-ligand simultaneously.
In one embodiment of the invention, the dynamic aggregation object has following any character: ordinary solid, bullet Property body, gel, foam.
In one embodiment of the invention, it further includes following any for constituting the recipe ingredient of the dynamic aggregation object Or appoint it is several can additive or usable object: other polymers, auxiliary agent, filler, sweller.Wherein, the other polymers Selected from it is following any or appoint it is several: natural polymer, synthetic macromolecular compound；The auxiliary agent is selected from following One kind is appointed several: catalyst, initiator, antioxidant, light stabilizer, heat stabilizer, dispersing agent, emulsifier, fire retardant, increasing Tough dose, coupling agent, solvent, lubricant, release agent, plasticizer, thickener, thixotropic agent, levelling agent, colorant, fluorescent whitening agent, Delustering agent, antistatic agent, dehydrating agent, biocide mildewcide, foaming agent, blowing promotor, nucleating agent, rheological agent；The filler choosing From it is following any or appoint it is several: inorganic non-metallic filler, metal packing, organic filler；The sweller is selected from following One kind is appointed several: water, organic solvent, ionic liquid, oligomer, plasticizer；.
In one embodiment of the invention, the dynamic aggregation object is applied to following material or product: selfreparing Property coating, self-repairability plate, self-repairability sealing material, self-repairability block glue, self-repairability conducting resinl, toughness material, Tough elastomer material, flexible material, thermal insulation material, shape-memory material, force snesor, toy, toy filler.
Compared with prior art, the invention has the following advantages:
(1) in the present invention, dynamic aggregation object of the invention includes the dynamic aggregation object molecule with hard section and soft segment, and Simultaneously contain physics split-phase and two kinds of dynamic supermolecular mechanisms, the combination of three can obtain it is abundant collaboration and it is orthogonal Material property.Physics split-phase is provided one strong and stable for dynamic aggregation object as stable polymerized/cross-linked tie point Network structure, polymer can keep balanced structure namely dimensional stability；And dynamic metal-ligand and hydrogen bond supermolecule Effect can spontaneously or under external influence reversible change dynamic structure, and the dynamic change of the two can cooperate with or just It hands over ground to carry out, from for providing dynamic abundant, can get dynamic elastomer/gel etc..Since physics split-phase can lead to It crosses heating and/or solvent is dissociated, even if forming the physical crosslinking based on physics split-phase, material also has good processability Can, therefore selfreparing, moulding, recycling, again processing and utilization are realized largely interior, so that polymer material is with broader Application range and more permanent service life, this cannot achieve in existing polymeric system.Physics split-phase dynamic The structure-rich of polymer, performance multiplicity.
(2) introducing of metal-ligand effect, can obtain the various characteristic properties of metal under suitable condition, including But it is not limited only to ionic conductivity, optical property, magnetism, catalytic, with the performances such as good dynamic and self-repairability The incomparable novel functionality of other materials is obtained simultaneously.
(3) hydrogen bond group for containing while having hydrogen bond donor and hydrogen bond receptor in soft segment, so that block polymer is not having Dynamic hydrogen bond can be effectively formed in the presence of the ingredient of the hydrogen bond group of other hydrogen bonds donors between soft segment, as The collaboration or orthogonal supplement of dynamic metal-ligand effect.
(4) reactive strong, the dynamic response mild condition of dynamic aggregation object dynamic supermolecular mechanism in the present invention.It compares In other dynamic systems, dynamic aggregation object provided by the invention can without catalyst, without the item of high temperature, illumination or specific pH Realize that the synthesis of dynamic aggregation object and dynamic reversibility also reduce use environment while improving preparation efficiency under part Limitation, extend the application range of polymer.
(5) the dynamic aggregation object structure in the present invention and performance have good Modulatory character.By selecting different location Different types of ligand and different metal center atoms and different types of hydrogen bond group, can prepare has difference apparent The dynamic aggregation object that feature, performance are adjustable, widely used；Pass through control physical crosslinking and two kinds of dynamic supermolecular mechanism threes The ratio of ingredient can prepare the dynamic aggregation object of the different properties such as mechanical strength, thermal stability, self-healing properties.In addition, Other additives can also be added according to actual needs during the preparation process to be modified dynamic aggregation object material, extend material Application performance.
With reference to following embodiments explanation, embodiment and the appended claims, these and other features of the invention with And advantage will become obvious.
Specific embodiment
The present invention relates to a kind of physics split-phase supermolecule dynamic aggregation objects, wherein contain while having the embedding of hard section and soft segment Section polymer molecule；Crystallization is mutually mixed and/or can formed each independently between each hard section of the block polymer molecules Mutually and/or the phase incompatible with soft segment, the split-phase with formation based on hard section are physical crosslinking and/or polymerize, the block polymer Each soft segment of molecule is unformed shape；Contain at least one ligand base at least one soft segment of the block polymer molecules Group forms the effect of dynamic metal-ligand with metal center；Moreover, at least one of the block polymer molecules is soft Contain hydrogen bond group at least one while that there is hydrogen bond donor and hydrogen bond receptor in section, forms dynamic hydrogen bond action.
In order to illustrate simplicity the term is indicated using conjunction "and/or" in the description of the invention It may include the option selected from the conjunction "and/or" foregoing description, or described option after conjunction "and/or", Or it is simultaneously selected from described these three situations of option before and after conjunction "and/or".
Heretofore described " polymerization " reaction/action be chain propagation process/effect, namely by intermolecular reaction/ Effect (including covalent chemical reaction and supermolecular mechanism) forms straight chain, branching, ring, two-dimensional/three-dimensional cluster, three-dimensional infinite network The polymer of structure.In the present invention, it is such as not particularly illustrated, supermolecular mechanism only refers to metal-ligand effect and hydrogen bond action.
Term " crosslinking " reaction/action used in the present invention, refer to intermolecular and/or intramolecular by covalent bond and/ Or supermolecular mechanism forms the process with three-dimensional unlimited reticular pattern product.In cross-linking process, polymer chain is general first two Dimension/three-dimensional constantly increases, and gradually forms cluster (can be two dimension or three-dimensional), and developing deeply is three-dimensional infinite network.Cause This, crosslinking can be considered as a kind of special shape of polymerization.In cross-linking process, just reach friendship when a three-dimensional infinite network Connection degree, referred to as gel point, also referred to as percolation threshold.The cross-linking products (contained, similarly hereinafter) more than gel point have three-dimensional nothing Network structure is limited, cross-linked network constitutes an entirety and across entire polymer architecture；In gel point cross-linking products below, It is only lax interchain link structure, and not formed three-dimensional infinite network structure, and is not belonging to across entire polymer architecture The cross-linked network that can constitute an entirety.Unless stated otherwise, the cross-linked structure in the present invention only includes gel point or more Three-dimensional infinite network structure, non-crosslinking structure then includes gel point two-dimensional/three-dimensional cluster structure below and the degree of cross linking is zero Line style and non-linearity structure.
In the present invention, " main polymer chain " refers to having most in polymer architecture if not otherwise indicated The chain of multichain joint number." side chain " refers in polymer architecture with main polymer chain skeleton/cross-linked network chain backbone The molecular weight for being connected and being distributed in its skeleton side is more than the chain structure of 1000Da；Wherein, the branch, bifurcated chain refer to It is the link that the molecular weight come out from main polymer chain skeleton/cross-linked network chain backbone or any other chain bifurcated is more than 1000Da Structure；For the sake of simplicity, the molecular weight of side chain, branch, bifurcated chain if not otherwise indicated, is then collectively referred to as side when being more than 1000Da Chain.Wherein, " side group " refers to being connected in polymer architecture with main polymer chain skeleton/cross-linked network chain backbone The molecular weight for connecing and being distributed in main chain backbone side is short not higher than 1000Da not higher than the chemical group of 1000Da and molecular weight Side chain.For side chain and side group, can have multilevel structure namely side chain that can continue with side group and side chain, the side of side chain Chain can continue have side group and side chain, and side chain therein also includes branch and bifurcated chain isodesmic structure.Wherein, " the end Base " refers to the chemical group for being connected and being located at chain backbone end with polymer chain skeleton in polymer architecture；The present invention In, side group can also have end group under specific condition.
In embodiments of the present invention, block polymer molecules while described with hard section and soft segment, contain The sum of hard section and soft segment is more than or equal to 2, i.e., wherein containing at least one hard section and at least one soft segment.Between each hard section mutually It mixes and/or crystalline phase and/or the phase incompatible with soft segment can be formed each independently, to form the split-phase physics based on hard section Crosslinking and/or polymerization.The physics polymerization makes polymer chain increase (including crosslinking)；The physical crosslinking has polymer Crosslinking physical property after having similar covalent cross-linking, including but not limited to apparent molecular weight increase, elasticity increases or weaken, size Stability increases, mechanical strength enhances etc., and hard section split-phase physical crosslinking is particularly suitable for providing dynamic aggregation object of the invention Balanced structure namely dimensional stability.When hard section quantity is more than or equal to 2 and is connected between each other by soft segment, hard section Crystallization/mutually separation will more efficiently be formed interchain split-phase physical crosslinking, can effectively provide split-phase physical crosslinking intensity, The mechanical property of the balanced structure of polymer and the physics split-phase polymer, therefore preferably comprise at least two hard sections and extremely A few soft segment forms hard section-soft segment alternating structure.
In the present invention, covalent bond and optional structural metal-can be passed through between the hard section and soft segment of same molecule Ligand effect and/or structural hydrogen bond action are connected.The covalent bond refers to traditional covalent bond, in usual temperature (100 DEG C are generally not more than) under degree and (generally less than 1 day) is more difficult in the usual time is broken comprising but be not limited only to lead to Normal 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 Deng.The structural metal-ligand effect and structural hydrogen bond action refer respectively to the normal use in dynamic aggregation object Dissociation/fracture strong metal-ligand effect does not occur in the process and strong hydrogen bonding effect, dynamic are weaker than in normal use process The dynamic metal-ligand effect that can be dissociated and dynamic hydrogen bond action, stability can be higher or lower than crystalline solid It mutually separates the hard phase of formation, preferably higher than crystalline solid and the hard phase for mutually separating formation, stable there is required hard section-to obtain Block polymer molecules of soft segment structure, but in extreme circumstances, such as the effects of high temperature, strong competitive ligand, strong mechanical force under Dissociation/fracture can also occur for structural metal existing for selectivity-ligand effect.During material machine-shaping, appropriate Structural metal-ligand effect existing for the selectivity that temperature or solvent can be broken/dissociate under the conditions of existing etc. and structural Hydrogen bond action is conducive to the machine-shaping and recycling and reusing of material.Wherein, " dissociation/fracture does not occur " also refer to including The effect of the structural metal-ligand and structural hydrogen bond action are formed by not sending out for crystalline solid and the hard phase that mutually separates formation Raw dissociation/fracture.
In embodiments of the present invention, the chain in block polymer molecules with hard section and soft segment while described is opened up Flutterring structure, there is no particular limitation, includes but are not limited to linear chain structure, branched structure (including but not limited to starlike, H-type, tree It is dendritic, pectination, hyperbranched), cyclic structure (including but not limited to monocycle, polycyclic, bridged ring, grommet, torus), two-dimensional/three-dimensional group Clustering architecture and its two kinds or times several combinations, preferably straight chain and branched structure.When there are branched structure, part hard section/ Soft segment can be on main chain, and part hard section/soft segment can be on side chain/branch/bifurcated chain.In embodiments of the present invention, The dynamic aggregation object can only contain a kind of block polymer of topographic morphologies, be also possible to there are many topographic morphologies The block polymer mixture；It also may each be only one kind in other polymers and material composition in its composition to open up The polymer for flutterring form is also possible to the mixture of the polymer there are many topographic morphologies.
In embodiments of the present invention, each in the block polymer molecules with hard section and soft segment while described Hard section can be same or different, and each soft segment can be identical or different；Wherein, hard section and soft segment can wrap each independently again Containing two or more same or different subchain sections；Covalent bond and optional structure can be passed through between each subchain section Property metal-ligand effect and/or structural hydrogen bond action be connected；The subchain section can be with the smaller chain on main chain Section, the smaller segment being also possible on side chain, branch, bifurcated chain；The difference includes but are not limited to chemical composition not Same, molecular weight difference, topological structure is different, steric configuration is different；It can be compatible between each subchain section or mutually separates.In this hair In bright embodiment, each hard section, soft segment and its subchain section can be homopolymer segment and be also possible to copolymer segment, can be The cluster of homopolymerization or the cluster of copolymerization, can be the cross-linked particles of the gel point of homopolymerization or copolymerization or more, can also be function base Group and the above various any combination.
In embodiments of the present invention, there is no particular limitation for the topological structure of any segment in hard section, can be straight Chain structure, branched structure (including but not limited to starlike, H-type, dendroid, pectination, hyperbranched), cyclic structure are (including but unlimited In monocycle, polycyclic, bridged ring, grommet, torus), two-dimensional/three-dimensional cluster structure, the particle more than gel point being crosslinked and its two kinds or Appoint several combinations, but the present invention is not limited only to this, preferably straight chain and branched structure.The topological structure of any segment in soft segment There is no particular limitation, can be linear chain structure, branched structure (including but not limited to starlike, H-type, dendroid, pectination, over-expense Change), cyclic structure (including but not limited to monocycle, polycyclic, bridged ring, grommet, torus), two-dimensional/three-dimensional cluster structure, gel point with The particle of upper crosslinking and its two kinds appoint several combinations, but the present invention is not limited only to this, preferably straight chain, branched structure and group Clustering architecture.
As an example, it is some that the block polymer molecules of the invention as shown in following formula (1A)-(1H) can be enumerated Preferred structure, but the present invention is not limited only to this, wherein and A is hard section, and B is soft segment, different location in same block polymer molecules Hard section A can be the same or different, can be compatible or mutually separate；The soft segment B of different location can phase in same molecule With can also be different, can be compatible or mutually separate:
Wherein, formula (1A) is linear chain structure, and n is hard section-soft segment alternate cells quantity, is more than or equal to 0；It is preferred that n is big In equal to 1；
Formula (1B) is linear chain structure, and both ends section is hard section, and n is hard section-soft segment alternate cells quantity, is more than or equal to 0；
Formula (1C) is linear chain structure, and both ends section is soft segment, and n is hard section-soft segment alternate cells quantity, is more than or equal to 0；It is preferred that n is more than or equal to 1；
Formula (1D) is branched structure, and x is the quantity for the hard section branch chain element being connected on soft segment B；N is hard section-soft segment The quantity of alternate cells is more than or equal to 0；Y is to be connected to hard section on soft segment B-soft segment branch chain element quantity；X, y is greater than Equal to 0, and the sum of x, y are more than or equal to 3；
Formula (1E) is branched structure, and x is the quantity for the hard section branch chain element being connected on soft segment B；N is hard section-soft segment The quantity of alternate cells is more than or equal to 0；Y is to be connected to hard section on soft segment B-soft segment alternately and be to hold point of section with hard section The quantity of branching units；X, y is more than or equal to 0, and the sum of x, y are more than or equal to 3；
Formula (1F) is branched structure, and x is the quantity for the soft segment branch chain element being connected on hard section A；N is soft segment-hard section The quantity of alternate cells is more than or equal to 0；Y is to be connected to soft segment on hard section A-hard section branch chain element quantity；X, y is greater than Equal to 0, and the sum of x, y are more than or equal to 3；It is preferred that y is more than or equal to 1, and the sum of x, y are more than or equal to 3；
Formula (1G) is branched structure, and x is the quantity for the soft segment branch chain element being connected on hard section A；N is soft segment-hard section The quantity of alternate cells is more than or equal to 0；Y is to be connected to soft segment on hard section A-hard section alternately and be to hold point of section with soft segment The quantity of branching units；X, y is more than or equal to 0, and the sum of x, y are more than or equal to 3；It is preferred that y be more than or equal to 1, and the sum of x, y be greater than etc. In 3；
Formula (1H) is cyclic structure, and n is hard section-soft segment alternate cells quantity, is more than or equal to 1；It is preferred that n is more than or equal to 2。
In addition, the structure of the block polymer molecules with hard section and soft segment can also be above-mentioned and enumerate while the present invention Preferred structure any combination and other any appropriate structures, those skilled in the art can be according to the present invention Logic and train of thought, which are given, reasonably to be realized.
In the present invention, the ligand groups (being indicated with L) for forming metal-ligand effect include in polymer Ligand groups (calling " framework counterpart " in the following text) on chain backbone and the ligand groups in polymer chain side group (call " side group in the following text Ligand ") and polymer chain and the ligand (calling " end group ligand " in the following text) of other compound ends.The framework counterpart, refers to At least two atoms in the group directly participate in the building polymer chain skeleton, the polymerization owner including non-covalent Chain, side chain, branch, the lattice chain of the skeleton of bifurcated chain and covalent cross-linking particle, side chain, branch, bifurcated chain skeleton, preferably Noncrosslinking main polymer chain, side chain, branch, bifurcated chain skeleton；The pendant ligands refer to all originals on the group Son is in side group；The end group ligand refers to all atoms on the group on end group.In some circumstances, it holds Ylidene ligands are also pendant ligands or framework counterpart.The ligand groups can be to be generated in polymer polymerizing/cross-linking process, It can be to pre-generate and carry out polymerized/cross-linked again, it is preferably pre-generated.It should be pointed out that in addition to above-mentioned ligand groups, this hair Other ligand groups of building polymer chain skeleton can also be participated in bright polymer containing only one atom.
In embodiments of the present invention, it is described have constituted in soft segment-hard segment structure block polymer molecules it is dynamic The ligand groups (hereinafter referred to as dynamic ligand groups) of state property metal-ligand effect are matched except can be soft segment main chain backbone Body, soft segment main chain end group ligand, soft segment main chain pendant ligands, soft segment lateral chain/branch/bifurcated chain pendant ligands, soft segment lateral chain/ The combination of any one or more in chain/bifurcated chain backbone ligand, soft segment lateral chain/branch/bifurcated end of the chain ylidene ligands, can be with Selectively it is present in other positions in the block polymer molecules with any one or the multiple combinations in following form It sets (but the present invention is not limited only to this): hard section main chain backbone ligand, hard section side chain/branch/bifurcated chain backbone ligand, hard section main chain Pendant ligands, hard section main chain end group ligand, hard section side chain/branch/bifurcated chain pendant ligands, hard section side chain/branch/bifurcated end of the chain Ylidene ligands.It is preferred that with soft segment main chain backbone ligand, soft segment main chain pendant ligands, soft segment lateral chain/branch/bifurcated chain pendant ligands, The group of any one or more in soft segment lateral chain/branch/bifurcated chain backbone ligand, soft segment lateral chain/branch/bifurcated end of the chain ylidene ligands The form of conjunction exists, more preferably in the form of soft segment main chain pendant ligands and/or soft segment lateral chain/branch/bifurcated chain pendant ligands In the presence of gold can be given full play to while not destroying block polymer molecules topological structure and split-phase physical cross-linked network structure Category-ligand dynamic.
In embodiments of the present invention, may exist one or one on the block polymer molecules chain described in same The above identical or different dynamic ligand groups.Any one or several dynamic ligand groups positioned at any position with drawn The metal center effect entered can form metal-ligand in interchain and/or chain and act on；The interchain metal-ligand effect generates Polymerization and/or crosslinking；Metal-ligand effect generally produces chain inner ring without generating crosslinked action in the chain, but if generating Grommet and/or torus, then can produce crosslinked action；It is preferred that generating interchain and/or chain internal crosslinking.In implementation of the invention In mode, in dynamic polymer systems existing other of selectivity contain polymer or small molecule compound of ligand groups etc. at Ligand groups in point can be located at the dynamic in hard section-soft segment-hard segment structure block polymer molecules Ligand groups form the effect of dynamic metal-ligand with the metal center of introducing jointly.In the present invention, dynamic metal-is matched Body effect can be arbitrary crosslinking degree.It should be pointed out that being not excluded for part in the present invention is formed by dynamic metal- Ligand effect neither forms inter-chain action, does not also form chain inner ring, is only formed and includes but are not limited to grafting, coordination.
In embodiments of the present invention, may exist one or one on the block polymer molecules chain described in same The above identical or different structural ligand groups.The structural metal-ligand effect ligand groups can be with following Being present in the formal character of any one or multiple combinations in form the block polymer molecules, (but the present invention is not It is only limitted to this): soft segment main chain backbone ligand, soft segment main chain pendant ligands, soft segment main chain end group ligand, soft segment lateral chain/branch/point Fork chain framework counterpart, soft segment lateral chain/branch/bifurcated chain pendant ligands, soft segment lateral chain/branch/bifurcated end of the chain ylidene ligands, hard section master It is chain backbone ligand, hard section main chain pendant ligands, hard section main chain end group ligand, hard section side chain/branch/bifurcated chain backbone ligand, hard Section side chain/branch/bifurcated chain pendant ligands, hard section side chain/branch/bifurcated end of the chain ylidene ligands.It is any one or several to be located at arbitrarily The structural ligand groups of position and the effect of introduced metal center can form metal-ligand in interchain and/or chain and act on； The interchain metal-ligand effect generates polymerization and/or crosslinking；In the chain metal-ligand effect generally produce chain inner ring and Crosslinked action is not generated, but if but if generating grommet and/or torus, then it can produce crosslinked action；Preferred structure Property ligand groups only generate interchain polymerization as the end group of soft segment or hard section.In embodiments of the present invention, dynamic is poly- It closes existing other of selectivity in objects system and contains the ligand base in the ingredients such as polymer or the small molecule compound of ligand groups Group can form structure with the metal center of introducing jointly with the structural ligand groups being located in the block polymer molecules Property metal-ligand effect.In the present invention, structural metal-ligand effect can be arbitrary crosslinking degree.It may be noted that It is to be not excluded for part in the present invention to be formed by structural metal-ligand effect neither formation inter-chain action, is not also formed in chain Ring only forms and includes but are not limited to grafting, coordination.
In the present invention, the hydrogen bond group for forming hydrogen bond action includes being present on polymer chain skeleton (packet Include on side chain/branch/bifurcated chain backbone) hydrogen bond group (calling " skeleton hydrogen bond group " in the following text) and in the polymer chain side group Hydrogen bond group (calling " side group hydrogen bond group " in the following text) and the hydrogen bond groups of polymer chain and other compound ends (call " end in the following text Base hydrogen bond group ").The skeleton hydrogen bond group refers to that at least one atom in the group directly participates in described in building Polymer chain skeleton, including main polymer chain, side chain, branch, bifurcated chain skeleton；The side group hydrogen bond group, refers to this All atoms on group are in side group；The end group hydrogen bond group refers to all atoms on the group in end group On.In some circumstances, end group hydrogen bond group is also side group hydrogen bond group and/or skeleton hydrogen bond group.The hydrogen bond group can Being generated in polymer polymerizing/cross-linking process, be also possible to it is pre-generated carry out polymerized/cross-linked again, it is preferably pre-generated.
In embodiments of the present invention, it is described have constituted in soft segment-hard segment structure block polymer molecules it is dynamic The hydrogen bond group (hereinafter referred to as dynamic hydrogen bond group) of state property hydrogen bond action can be with skeleton hydrogen bond group, side group hydrogen bond base The combination of any one or more of the forms such as group, end group hydrogen bond group be present in the soft segment of the block polymer molecules and It is not formed and is mutually separated with soft segment, it is also an option that property is with shapes such as skeleton hydrogen bond group, side group hydrogen bond group, end group hydrogen bond groups The combination of any one or more of formula is present in the hard section of polymer molecule.Since part hydrogen bond does not have directionality and choosing Selecting property can form hydrogen bond action, such as soft segment skeleton hydrogen bond group under specific circumstances between the hydrogen bond group of different location Hydrogen bond action can be formed between soft segment side group hydrogen bond group, the hydrogen bond group in hard section can also be the same as the hydrogen bond base in soft segment Group forms hydrogen bond action, can phase between the hydrogen bond group of identical or different position in identical or different polymer molecule Hydrogen bond action is formed between mutually, it can also be with for example optional other polymers molecule of the other compositions in polymer, filler, small point Hydrogen bond action is formed between hydrogen bond group contained by son etc..As an example, the hydrogen bond action in the present invention includes but is not limited to Such as: forming interchain hydrogen bond crosslinking between the hydrogen bond group in the soft segment lateral chain and/or side group between the soft segment of different molecular；Institute It states and forms soft segment interchain hydrogen in the hydrogen bond group and the soft segment main chain backbone in soft segment lateral chain and/or side group between hydrogen bond group Key crosslinking；Hydrogen bond group and different molecular hard section side chain in the soft segment lateral chain and/or side group and/or the hydrogen bond base in side group Interchain linkage is formed between hydrogen bond group in group and/or hard section main chain backbone；Hydrogen bond group in soft segment lateral chain and/or side group and Hydrogen bond group and hard section side chain in soft segment main chain backbone and/or the hydrogen bond in the hydrogen bond group and hard section main chain backbone in side group Hydrogen bond crosslinks are formed between group；It is independently formed in chain with hydrogen bond between hydrogen bond group in the part side chain and/or side group Ring；Chain inner ring is independently formed with hydrogen bond between hydrogen bond group in the main chain backbone of part；The part side chain and/or side Hydrogen bond group collective effect in base forms chain inner ring etc. with hydrogen bond.In the present invention, being formed by dynamic hydrogen bond crosslinks can To preferably reach the gel infiltration threshold value of hydrogen bond crosslinks or more in any crosslinking degree, i.e., when physics split-phase is crosslinked solution crosslinking only Three-dimensional infinite network can be formed using hydrogen bond crosslinks.
In embodiments of the present invention, may exist one or one on the block polymer molecules chain described in same The hydrogen bond group (hereinafter referred to as structural hydrogen bond group) of the above identical or different structural hydrogen bond action of composition.Described The structural hydrogen bond group property of can choose in the form of skeleton hydrogen bond group, side group hydrogen bond group, end group hydrogen bond group etc. appoint One or more combination of anticipating is present in the soft segment and/or hard section of polymer molecule, and when structural hydrogen bond group is present in It is not separated mutually with the formation of soft phase when in soft segment.It is under specific circumstances, different since part hydrogen bond does not have directionality and selectivity Hydrogen bond action can be formed between the hydrogen bond group of position, therefore, structural hydrogen bond group is preferably located at soft segment and hard section end Base, and be the hydrogen bond group or hydrogen bond group pair with directionality and selectivity, only generate interchain polymerization.In the present invention In, structural hydrogen bond action can be arbitrary crosslinking degree.It is formed by it should be pointed out that being not excluded for part in the present invention Structural hydrogen bond action neither forms inter-chain action in chain, does not also form chain inner ring, is only formed and includes but are not limited to grafting etc. Effect.
The dynamic ligand groups and dynamic hydrogen bond group can be distributed in same block polymerization in the present invention It in the same soft segment of object molecule, can also be distributed in the different soft segments of same block polymer molecules, preferably the dynamic Property ligand groups and dynamic hydrogen bond group between at least containing six skeletal atoms flexible linking group or segment be connected, with More preferably play the synergistic effect of different supermolecular mechanisms.In the present invention, when there are multiple component of polymer, between each ingredient It can be mutually perhaps incompatible；When there are the ingredient of at least one crosslinking, it can mutually disperse between heterogeneity, is mutually interspersed Or part is interspersed, but the present invention is not limited only to this.
In the present invention, except the crystalline phase based on hard section and/or the split-phase physics that mutually constitutes incompatible with soft segment is formed Crosslinking/polymerization is outside physical crosslinking/polymerization, and crosslinking/polymerization that the effect of dynamic metal-ligand generates is also a kind of physics friendship Connection/polymerization, it is also a kind of physical crosslinking/polymerization that dynamic hydrogen bond group, which participates in the supermolecule to be formed hydrogen bond crosslinks/polymerization,；Structure Property crosslinking/polymerization for generating of metal-ligand effect be also a kind of physical crosslinking/polymerization, what structural hydrogen bond group participated in being formed Supermolecule hydrogen bond crosslinks/polymerization is also a kind of physical crosslinking/polymerization.Physical crosslinking/polymerization of the present invention has invertibity, I.e. physical crosslinking/the polymerization is in a heated condition or in good solvent or under other appropriate stimulations, physical crosslinking/polymerization Solution can occur to be crosslinked/depolymerize；In the cooling condition or in poor solvent or after releasing stimulation, physical crosslinking/polymerization It can re-form.
In the present invention, hard section generally than soft segment have higher glass transition temperature and/or formation crystalline phase and/ Or compared with soft segment is incompatible soft segment formed mutually there is better thermal stability and/or higher mechanical strength and/or more Low dissolubility.In embodiments of the present invention, usually there is the soft phase and hard section of soft segment composition in the dynamic aggregation object The hard phase two phase structure constituted；But can be compatible or incompatible by the hard phase of difference that different hard sections are formed, by different soft segments The soft phase of difference of formation can be compatible or incompatible, that is, there may be two even three or three in dynamic aggregation object A above incompatible phase.In embodiments of the present invention, the soft phase that soft segment is constituted mutually is formed by firmly with what hard section was constituted There is no limit including but not limited to spherical, cylindrical shape, helical form, stratiform and combinations thereof forms for phase topological structure (phase morphology). Any phase can also be with other including that between different hard phases, can be dispersed in an other phase between different soft phases Double/more continuous phases for mutually forming interpenetrating, are also possible to mutually independent continuous phase, are also possible to above-mentioned mixed form.At this In the embodiment of invention, preferably soft phase is continuous phase, and hard is mutually that discontinuous phase is dispersed in soft phase, more preferably hard mutually with spherical It is dispersed in soft phase and is physical crosslinking as split-phase, therefore the polymer can more easily have better flexibility and elasticity And be more suitable play supermolecular mechanism dynamic.The size of the discontinuous hard phase is usually more than 100 microns, more excellent Choosing is not more than 10 microns, more preferably no more than 1 micron, most preferably no greater than 100 nanometers.Hard section in dynamic polymer systems Total content is not particularly limited, and preferably accounts between the 1%-50% of gross weight, between the more preferably 5%-35% of gross weight, with convenient Form effective split-phase physical crosslinking.
In embodiments of the present invention, the degree of cross linking for the split-phase physical crosslinking that hard section is formed can be on its gel point Under, the metal-ligand crosslinking formed is acted on by dynamic metal-ligand can be above and below its gel point, by dynamic hydrogen bond base The dynamic hydrogen bond crosslinks that group is formed can also be above and below its gel point；It is preferred that split-phase physical crosslinking and dynamic that hard section is formed The sum of supermolecule crosslinking that supermolecular mechanism is formed is more than total gel point of polymer；The split-phase physics that more preferable hard section is formed The degree of cross linking of crosslinking (contains gel point, similarly hereinafter) on its gel point, to obtain based entirely on the three-dimensional of hard section split-phase physical crosslinking Infinite network, in the case where metal-ligand effect and hydrogen bond action will be completely dissociated, dynamic aggregation object can also keep balance to tie Structure namely dimensional stability.
In embodiments of the present invention, the soft phase of the dynamic aggregation object can not have glass transition temperature, or Person has one or more glass transition temperatures, at least one glass transition temperature is not higher than operating temperature model preferably wherein The lower limit enclosed；The hard phase can also not have glass transition temperature, or have one or more glass transition temperatures, together When can also have one or more solution split-phase physical crosslinking/polymerization temperatures, solution split-phase physical crosslinking/polymerization of preferably any hard section Temperature is higher than the upper limit of operating temperature range.Make its soft segment extremely when the dynamic aggregation object contains the auxiliary agents such as plasticizer or filler When a rare glass transition temperature is not higher than the lower limit of operating temperature range, while the solution crosslinking of hard section/polymerization temperature is high In the upper limit of operating temperature range, the composition also belongs to " the dynamic aggregation object " of meaning of the invention.Wherein, preferably entire soft The glass transition temperature of each component of section is entirely below the lower limit of operating temperature range, help to obtain high poly- of pliability Object is closed, especially with the elastomer of extensive use.Thus obtained elastomer not only has dynamic, and has thermoplasticity Convenient for forming and reprocessing, this thermoplasticity dynamic elasticity body has very important purposes in terms of sealing and power. The glass transition temperature of each soft segment of thermoplasticity dynamic elasticity body is more preferably not higher than 25 DEG C, at room temperature It is used as elastomer.
In embodiments of the present invention, the dynamic of the reversible split-phase physical crosslinking/polymerization of hard section is lower than dynamic Metal-ligand effect and dynamic hydrogen bond action, solution crosslinking/polymerization temperature of more preferable hard section split-phase physical crosslinking/polymerization and Mechanical stability is also respectively higher than the effect of dynamic metal-ligand and the dissociation temperature and mechanics of dynamic hydrogen bond action are stablized Property.In soft segment the dynamic, dissociation temperature of dynamic hydrogen bond action and mechanical stability can be higher than each independently respectively or Lower than dynamic, dissociation temperature and the mechanical stability of the effect of dynamic metal-ligand.Dynamic metal-ligand is acted on and is moved Usually at a lower temperature, preferably no greater than room temperature has dynamic to state property hydrogen bond action；Or it is easy under external force Dissociation/fracture.
In embodiments of the present invention, the chemical composition of hard section is not particularly limited, can be selected from but not limited to master Chain is carbon-chain structure, carbon heterochain structure, carbon chain structure, element chain structure, element heterochain structure, the miscellaneous element chain structure of carbon Polymer segment.The carbon-chain structure is the structure that main chain backbone contains only carbon atom；The carbon heterochain structure is main chain Skeleton contains carbon atom and any or several heteroatomic structures simultaneously, wherein the hetero atom includes but are not limited to Sulphur, oxygen, nitrogen；The carbon chain structure is main chain backbone simultaneously containing carbon atom and any or several Elements Atoms Structure, wherein Elements Atom includes but are not limited to silicon, boron, aluminium；The element chain structure is that main chain backbone has contained only element The structure of atom；The element heterochain structure is main chain backbone simultaneously and only containing at least one hetero atom and at least one member The structure of plain atom；The miscellaneous element chain structure of the carbon is that main chain backbone includes simultaneously carbon atom, hetero atom and Elements Atom Structure.Wherein, preferably carbon-chain structure, carbon heterochain structure, because of its structure-rich, have excellent performance.As an example, the dynamic aggregation The hard section of object can be based on following polymers segment, group or in which appoint several combined segments, but be not limited only to this: have (i.e. glass transition temperature is usually above 40 DEG C, more preferably higher than the upper limit of the operating temperature of material to high glass-transition temperature Not less than 100 DEG C) amorphous polymer chains section, as polystyrene, polymethyl methacrylate, polyvinyl pyridine, hydrogenation are poly- Bornylene, polyethers, polyester, polyether-ether-ketone, poly aromatic carbonic ester, polysulfones etc.；Polymer segment, group rich in hydrogen bond group, Such as polyamide, poly- peptide, the segment rich in urea bond, the segment rich in urethane bond, the segment based on urea groups pyrimidone；It is rich Polymer segment, group containing crystalline phase, as crystallinity polyethylene, crystalline polypropylene, crystalline polyester, crystallinity polyethers, Liquid crystal polymer, mesogenic groups etc.；Ionic polymer segment, such as polyacrylate, poly-methyl acrylate, polyacrylamide Salt, poly styrene sulfonate etc.；Polymer segment rich in conjugated structure, such as polyacetylene, polyphenylacetylene, polyphenyl, polyfluorene, poly- thiophene Pheno etc..Wherein, preferably with the amorphous polymer chains section of high glass-transition temperature, the polymer chain rich in hydrogen bond group Section/group, polymer segment/group rich in crystalline phase, so as to design and regulate and control the block polymer molecules structure and Split-phase physical crosslinking, obtains optimal performance.
In embodiments of the present invention, soft segment polymer chain skeleton can selected from but not limited to main chain be carbon-chain structure, The polymer segment of carbon heterochain structure, carbon chain structure, element chain structure, element heterochain structure, the miscellaneous element chain structure of carbon, it is excellent Carbon-chain structure, carbon heterochain structure, element heterochain structure and the miscellaneous element chain structure of carbon are selected, because of its structure-rich, is had excellent performance.Soft segment Contain hydrogen bond base to polymer chain skeleton (including main chain and side chain/branch/bifurcated chain) and/or side group/end group property of can choose Group.Contained hydrogen bond group is not crystallized and is not separated mutually with soft segment formation, and the number of teeth is preferably no greater than four teeth.Soft segment can be by synthesizing The reaction was continued for macromolecule and/or natural polymer precursor (including import end group and/or pendant active point, import side group and/or side Chain, grafting, chain extension etc.) it obtains, it can also polymerize to obtain by monomer and/or prepolymer/oligomer, or by the above distinct methods phase In conjunction with obtaining.As an example, soft segment polymer chain skeleton can be the segment based on following polymers, but the present invention is not limited only to This: acrylic polymer, saturation of olefins quasi polymer, ethylenic unsaturation hydrocarbon polymer, halogen-containing olefin polymer, Acrylonitrile polymers, vinyl alcohol polymer, silicone-based polymers, ether polymer, esters polymer, Biopolvester class Homopolymer, copolymer, modifier, derivative of polymer etc. etc..
In embodiments of the present invention, ligand groups (being indicated with L) described in metal-ligand effect are selected from ring Pentadiene and the structural unit for containing at least one coordination atom (indicating with X).One coordination atom can with one or Multiple metal centers are (selected from the metal center, metal-organic for including but are not limited to metal ion, metallo-chelate Metal center in metal center, metal inorganic compound, is indicated with M) form one or more coordinate bonds, a metal center One or more coordinate bond can also be formed with one or more coordination atom.One ligand groups is formed with metal center The quantity of coordinate bond be known as the numbers of teeth of ligand groups, in embodiments of the present invention, in the same system, a metal center Metal-ligand effect, different ligands can be formed with one of a tooth ligand, bidentate ligand, tridentate ligand or multiple ligands Between be also possible to by metal center connect cyclization, therefore the present invention can effectively provide type, quantity and performance abundant enough The effect of dynamic metal-ligand, structure shown in the following general formula is some to provide example, but the present invention is not limited only to this:
Wherein, X is coordination atom, and M is metal center,It is cyclopentadiene ligand, in each ligand groups and metal It is a tooth that the heart, which is formed by an X-M key, and X, which is connected, with singly-bound in formula indicates that the coordination atom belongs to the same ligand base Group, when containing two or more coordination atoms in a ligand groups, X can be identical atom and be also possible to difference Atom, selected from including but are not limited to boron, nitrogen, oxygen, sulphur, phosphorus, silicon, arsenic, selenium, tellurium；It is preferred that boron, nitrogen, oxygen, sulphur, phosphorus；More preferably Nitrogen, oxygen；Nitrogen.It should be noted that X exists in the form of anion sometimes.In the present invention, it is preferred to a coordination atom A coordinate bond only is formed with a metal center, therefore contains in ligand groups and can form coordinate bond with same metal center The quantity of coordination atom is the number of teeth of ligand groups.Metal-ligand effect that the ligand groups and metal center are formed (with M-LmIndicate, m indicates the quantity with the ligand groups of the same metal center phase separation) power and the coordination in ligand groups The type and quantity of atom, the type of metal center and valence state and related to ion etc..
In embodiments of the present invention, in order to form crosslinking/polymerization based on metal-ligand effect, a metal It at least wants that metal-ligand effect (i.e. M-L can be formed with ligand groups described in two parts in center2Structure), except nonmetallic Center is already attached on polymer；Can also there are multiple ligands and the same metal center to form metal-ligand effect, wherein Two or more ligand groups can be identical or different.The ligancy of one metal center is limited, the coordination atom of ligand groups More, as soon as the amount of ligand that metal center can be coordinated is fewer, the supermolecule degree of cross linking based on metal-ligand effect is got over It is low；But each ligand is formed by that the more coordinations of the number of teeth are stronger, and dynamic is lower, therefore in the present invention with metal center The ligand groups of preferably more than three teeth form the effect of dynamic metal-ligand, and ligand groups more than preferably three teeth form knot The effect of structure metal-ligand.
In embodiments of the present invention, can only have one kind in a polymer chain or a dynamic polymer systems to match Body can also exist simultaneously any appropriate combination of multiple ligands.A kind of ligand refers to a kind of core ligand knot Structure.One framework counterpart, pendant ligands, end group ligand can have same core ligand structure, their difference exists It is different in the tie point of the core ligand structure access ingredients such as polymer chain or small molecule and/or position.Suitable ligand combination The dynamic aggregation object with particular characteristic can be effectivelyed prepared, such as plays collaboration and/or orthogonal effect, promotes material Comprehensive performance.In the present invention, suitable ligand groups (core ligand structure) can be exemplified below, but the present invention is not limited only to This:
One tooth ligand groups are exemplified below:
-C≡N；
Bidentate ligand group is exemplified below:
Tridentate ligand group is exemplified below:
Tetradentate ligands group is exemplified below:
Multidentate ligand is exemplified below:
It in embodiments of the present invention, can be in ligand groups (core ligand in the case where not influencing coordination property Structure) any suitable location access polymer chain and/or group.
In embodiments of the present invention, the metal center M can be any appropriate metal ion or compound/ The metal center of chelate etc. can be selected from any appropriate ionic species, the chemical combination of any one metal in the periodic table of elements Object/chelate and combinations thereof.
Related metal is preferably the metal in the first subgroup to the 7th subgroup and the 8th race.First subgroup Metal into the 7th subgroup and the 8th race further include lanthanide series metal (i.e. La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and actinide metals (i.e. Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr).
Related metal be more preferably the first subgroup (Cu, Ag, Au), the second subgroup (Zn, Cd), the 8th race (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), group of the lanthanides (La, Eu, Tb, Ho, Tm, Lu), actinium series (Th).Further preferably Cu, Zn, Fe, Co, Ni, Pd, Ag, Pt, Au, La, Ce, Eu, Tb, Th, to obtain stronger dynamic.
In embodiments of the present invention, there is no restriction for related metallo-organic compound, and suitable example can be lifted Under such as:
Other suitable metal organic compounds for being capable of providing metal center include but is not limited to the organic cage of metal-, metal- Organic frame.This metalloid-organic compound can be used alone, or is introduced by suitable covalent chemical on-link mode (OLM) The suitable position of polymer chain.Those skilled in the art can rationally and effectively be realized with logic according to the present invention and train of thought.
In embodiments of the present invention, there is no restriction for related metal inorganic compound, the oxygen of preferably above-mentioned metal Compound, sulfide grain, especially nano particle.
In embodiments of the present invention, can providing the metallo-chelate at suitable metal center, also there is no restriction.It is preferred that Still chelate or some ligands with coordination site vacancy can the chelatings replaced the framework counterpart of the invention Object.
In embodiments of the present invention, there is no particular restriction for the combination of ligand groups and metal center, as long as matching physical efficiency Enough and metal center generates suitable metal-ligand and acts on, but is different what metal center was formed with identical ligand Different metal-ligand effect power and dynamic can be different.Some suitable dynamic metal-ligands effect combinations can be with It is exemplified below, but the present invention is not limited only to this:
Wherein,Indicate with polymer chain, crosslinking link or any other suitable group/atom (including hydrogen original Son) connection.It is such when what is hereinafter occurred againAbove-mentioned definition and range are all continued to use, such as without special case, is no longer repeated Explanation.
In embodiments of the present invention, the hydrogen bond action can be optional tooth number.Wherein, the number of teeth refers to It is donor (H, that is, hydrogen atom) and receptor (Y, that is, receive the electronegative atom of hydrogen atom) institute's shape by hydrogen bond group At hydrogen bond quantity, each H ... Y group is combined into a tooth.In following formula, respectively a schematically illustrate tooth, two teeth and three tooth hydrogen bonds at Key situation.
The bonding situation of one tooth, two teeth and three tooth hydrogen bonds can concrete example it is as follows:
In embodiments of the present invention, the number of teeth of hydrogen bond is not limited.The number of teeth of hydrogen bond is more, and synergistic effect is got over Greatly, the intensity of hydrogen bond is bigger.If the number of teeth for being formed by hydrogen bond is more, intensity is big, then the dynamic of hydrogen bond action is just It is weak, it can be used as structural hydrogen bond and play promotion dynamic aggregation object holding balanced structure and improve mechanical property (modulus and intensity) Effect.If the number of teeth of formed hydrogen bond is few, intensity is low, and the dynamic of hydrogen bond action is just strong, can be used as dynamic hydrogen Key provides dynamic property with the effect of dynamic metal-ligand together.In embodiments of the present invention, preferably more than four teeth Hydrogen bond provides dynamic hydrogen bond action, and hydrogen bonds more than preferably four teeth provides structural hydrogen bond action.
In embodiments of the present invention, the hydrogen bond action can be by existing between any appropriate hydrogen bond group Noncovalent interaction generates, and the hydrogen bond group partially can only contain hydrogen bond donor, or hydrogen bond receptor is only contained in part, Or partly or entirely contain hydrogen bond donor and receptor simultaneously.Wherein, the block polymer with hard section and soft segment structure The soft segment of molecule contains at least one dynamic hydrogen bond group simultaneously containing hydrogen bond donor and receptor so that it can be independently Hydrogen bond action is formed, so that block polymer can be soft in the presence of the ingredient of the hydrogen bond group without other hydrogen bonds donors It is effectively formed dynamic hydrogen bond between section, the collaboration or orthogonal supplement as the effect of dynamic metal-ligand.It is preferably comprised At least one of following constituent:
In embodiments of the present invention, dynamic hydrogen bond group preferably is selected from amide groups, carbamate groups, urea groups, sulphur For carbamate groups and the derivative of the above group etc..
As an example, the hydrogen bond group in following side group and/or end group can be enumerated, but the present invention is not limited only to this.
Wherein, m, n, x are the quantity of recurring group, can be fixed value, are also possible to average value.M, n value range is 0 With the integer for being more than or equal to 1；X value range is the integer more than or equal to 1.
As an example, the hydrogen bond on soft segment main chain/side chain (including branch and bifurcated chain) skeleton as described below can be enumerated Group, but the present invention is not limited only to this.
As an example, the hydrogen bond on hard section main chain/side chain (including branch and bifurcated chain) skeleton as described below can be enumerated Group, but the present invention is not limited only to this.
In the present invention, the supermolecule hydrogen bond action, which can be, carries out dynamic supermolecule crosslinking/poly- in dynamic aggregation object It is generated during conjunction；Dynamic supermolecule crosslinking/polymerization is carried out again after being also possible to pre-generated supermolecule hydrogen bond action；It can also After dynamic supermolecule crosslinking/polymerization is formed, to generate supermolecule hydrogen bond action during dynamic aggregation object subsequent forming, but The present invention is not limited only to this.
In embodiments of the present invention, except through forming hydrogen between hydrogen bond group present in the polymer molecule Key effect is outer, can also form hydrogen bond by the hydrogen bond group and the hydrogen bond group in the other components introduced as additive Effect.Such other components that can participate in being formed hydrogen bond action include but is not limited to small molecule, polymer, inorganic material, Contained in hydrogen bond group can be arbitrarily can with the hydrogen bond group formed hydrogen bond group.Between such other components Hydrogen bond can be formed.Such material can be selected from the polymer particles of line style, ring-type, branching, cluster polymer and covalent cross-linking The modified organic and inorganic particle in grain, surface, fiber.
In embodiments of the present invention, except containing containing simultaneously, dynamic metal-ligand is acted on and dynamic hydrogen bond is made Outside with hard section-soft segment structure block polymer molecules ingredient, it can also contain in dynamic aggregation object and only contain dynamic Metal-ligand effect or only containing dynamic hydrogen bond action or without containing any supermolecular mechanism with the block polymer Perhaps incompatible any appropriate other hard sections-soft segment component of polymer of molecular chaperones phase can form metal-ligand effect And/or hydrogen bond action with the component of polymer mutually perhaps incompatible any appropriate component of polymer and other Component of polymer can additionally contain or not contain the small molecule that can form metal-ligand effect and/or hydrogen bond group and fill out Material etc..Other hard sections-soft segment component of polymer can form compatible physics with the block polymer molecules and hand over Networking network, can also form mutually perhaps incompatible mutual blending/interpenetrating/Semi-IPN isostructural cross-linked network.Wherein, this hair Contain while described in bright dynamic metal-ligand effect and dynamic hydrogen bond action have hard section-soft segment structure it is embedding Section polymer molecule accounts for the 5-100% of the dynamic aggregation object group adult gross weight, preferably accounts for the dynamic aggregation object composition gross weight 50-100%.
In embodiment of the present invention, hard section-soft segment structure block polymer contained in the dynamic aggregation object The preparation of molecule can be any appropriate means in technological principle.General there are two types of modes, from monomer, by interior The polymerization of soft segment or hard soft chain segment is successively carried out outside or from outside to inside；Or first it is respectively synthesized end group and/or side group functionalization Then hard section, soft segment or multisection type copolymer directly carry out the reaction between segment, or by other small molecules realization coupling or altogether It is poly-.The preparation of the block polymer molecules can also be the combination based on above two mode, for example, first by hard section or soft Section is prepared into macromole evocating agent, causes the polymerization of adjacent soft segment and hard section, anti-further according to the end group for needing to carry out between segment It answers；For another example, soft segment-hard section di-block copolymer is first generated, then two or more two block molecules are coupled to obtain this hair Bright has hard section-soft segment multi-segment structure polymer molecule.Wherein, the generation or introducing of ligand groups and hydrogen bond group, It can be before soft and hard segments are connected, later or in the process carry out.The polymer containing hard section and soft segment is generated in the ban to be re-introduced into Or when generating the ligand groups and hydrogen bond group, corresponding active site must be contained on polymer segment, includes as example But it is not limited to amino, secondary amino group, hydroxyl, carboxyl, sulfydryl, isocyanate group, epoxy group, ester group, halogen atom, acid halide group, acid Acid anhydride, carbon-carbon double bond, maleimide, triple carbon-carbon bonds, azido, itrile group, hydrazine, tetrazine, succinimide ester.
The polymerization includes but is not limited to polycondensation, addition polymerization, coordination polymerization according to the type of selected prepolymer and opens Cyclopolymerization, addition polymerization include but is not limited to free radical polymerization, active free radical polymerization, anionic polymerisation, cationic polymerization etc..Its In, polymerization process can carry out in a solvent, be also possible to solvent-free bulk polymerization.
The initiation of above-mentioned partial polymerization process needs to use can cause monomer molecule activation in polymerization process Initiator.Different types of initiator can be selected in embodiment of the present invention as needed.For example, selecting monofunctional initiators just In the segment of the segment or both-end exclusive-OR function that prepare single-ended functionalization；For another example, select double/Multifunctional initiator convenient for preparation The segment of double/multiterminal congenerous or double/multiterminal exclusive-OR function；For another example, using the segment or telechelic polymer of single-ended functionalization The macromole evocating agent that segment is prepared can continue to cause the polymerization of other monomers, obtain block copolymer.Wherein, it prepares The polymer segment of single, double, more end-functionalizations has initiator, the reasonable selection chain of active group by reasonable selection itself The functional reagent that transfer agent, reasonable employment can be reacted with initiator residue is realized.
In embodiments of the present invention, partially polymerized reaction also needs to change in polymerization process using catalyst Become reaction path, reduces reaction activity to accelerate the reaction rate of reactant during the reaction.In partial polymerization process also It needs using auxiliary agents such as dispersing agent, emulsifiers.For example, being needed in suspension polymerization using dispersing agent, in emulsion polymerization mistake It needs in journey using emulsifier.The dispersing agent enables in mixed with polymers liquid solid flocculation group to be separated into tiny Particle and be suspended in liquid, those are poorly soluble the solid and liquid particles in liquid for uniform dispersion, while can also prevent The sedimentation and cohesion of grain form stable suspension.The emulsifier can improve each in the mixed with polymers liquid comprising auxiliary agent Kind constitutes the surface tension between phase, is allowed to form uniform and stable dispersion or emulsion, and it is poly- to be preferred for progress lotion It closes.
Specifically, as an example, the available polymerization of the present invention includes but is not limited to: phenylethylene, (methyl) third The heat of olefin(e) acid esters monomer causes general radical polymerization, the light-initiated freedom of phenylethylene, (methyl) acrylic ester monomer Base polymerization, the Iniferter free radical polymerization of vinyl chloride monomer, phenylethylene, (methyl) acrylic ester monomer Atom transfer radical polymerization (ATRP), phenylethylene, (methyl) esters of acrylic acid, the reversible addition-fracture of acrylonitrile monomer Transferring free-radical polymerization (RAFT), nitroxide-mediated stable free-radical polymerization (NMP), ethylene, propylene coordination polymerization, styrene monomer Anionic polymerisation, lactone ring opening polymerization, lactams ring-opening polymerisation, epoxy addition polymerization, cycloolefine ring-opening metathesis polymerization, binary acid Polycondensation between dihydric alcohol, the polycondensation between binary acid and diamine, the click-reaction between binary mercaptan and binary alkene/alkynes Polymerization, the click-reaction polymerization between binary nitrine and binary alkynes, the ring-opening polymerisation of 2- ethyl -2- oxazoline, polyurethane/polyurea are anti- It should wait.
Initiator needed for above-mentioned polymerization and polymerization process, catalyst, other auxiliary agents and reaction condition etc. are all It is open known routine techniques (such as Pan Zuren chief editor, " polymer chemistry (enhanced edition) "), those skilled in that art can be with It is reasonably selected and is combined as needed.
In embodiments of the present invention, the reaction that the generation or introducing of framework counterpart group can use includes but not only limits In with Types Below: isocyanates reacts with amino/hydroxyl/sulfydryl/carboxyl, the nucleophilic of the electrophilic substitution reaction of heterocycle, heterocycle Substitution reaction, double bond (including acrylate, acrylamide etc.) radical reaction, nitrine-alkynes click-reaction, sulfydryl-double bond/alkynes Click-reaction, the reaction of urea-amine, amidation process, tetrazine-norbornene reaction, active ester are reacted with amino；It is preferred that different Cyanate is reacted with amino/hydroxyl/sulfydryl, double bond radical reaction, nitrine-alkynes click-reaction, sulfydryl-double bond/alkynes are clicked Reaction, the reaction of urea-amine, amidation process, active ester are reacted with amino；More preferable isocyanates and amino/hydroxyl/mercapto The reaction of base, double bond radical reaction, nitrine-alkynes click-reaction, sulfydryl-double bond/alkynes click-reaction.
In embodiments of the present invention, the generation or introducing of side group or end group ligand groups can be using any appropriate anti- Answer, include but are not limited to Types Below: esterification, isocyanates react with amino/hydroxyl/sulfydryl/carboxyl, heterocycle Electrophilic substitution reaction, the nucleophilic substitution of heterocycle, double bond radical reaction, the side chain reaction of heterocycle, nitrine-alkynes are clicked instead It answers, sulfydryl-double bond/alkynes click-reaction, the reaction of urea-amine, amidation process, tetrazine-norbornene reaction, active ester and ammonia The reaction of base；It is preferred that esterification, isocyanates are reacted with amino/hydroxyl/sulfydryl, nitrine-alkynes click-reaction, urea-amine Reaction, amidation process, the reacting of active ester and amino, sulfydryl-double bond/alkynes click-reaction；More preferable esterification, isocyanide Acid esters reacts with amino/hydroxyl/sulfydryl, sulfydryl-double bond/alkynes click-reaction, nitrine-alkynes click-reaction.
In embodiments of the present invention, the introducing of metal center can carry out on any suitable opportunity.At least one Lower three kinds of methods can introduce before introducing/generation ligand, and the combination of metal-ligand effect can be formerly formed with ligand Object is re-introduced into, and can also be re-introduced into after the preparation for completing polymer molecule.It is preferred that being introduced after generating ligand groups.
In embodiments of the present invention, the generation or introducing of hydrogen bond group can use any appropriate reaction, including but Be not limited only to Types Below: isocyanates reacts with amino/hydroxyl/sulfydryl/carboxyl, double bond (including acrylate, acryloyl Amine etc.) radical reaction, double bond cyclization, epoxy react with amino/hydroxyl/sulfydryl, nitrine-alkynes click-reaction, sulfydryl- Double bond/alkynes click-reaction, the reaction of urea-amine, esterification, amidation process, the reaction of tetrazine-norbornene, active ester with Amino/reaction of hydroxyl/sulfydryl, silicone hydroxyl condensation reaction；Preferred isocyanate reacts with amino/hydroxyl/sulfydryl, urea- The reaction of amine, active ester are reacted with amino/hydroxyl/sulfydryl；More preferable isocyanates is reacted with amino/hydroxyl/sulfydryl.Hydrogen The generation or introducing of key group can have the reaction type of one or more, reaction means, and the hydrogen bond action between hydrogen bond group can To have one or more of types, structure.
In embodiments of the present invention, the reaction that can use such as following form between segment terminal-reactive group connects It connects the soft segment hard section of the block polymer molecules or obtains the covalent bond in segment: isocyanates and amino/hydroxyl/sulfydryl, The reaction of carboxyl, epoxy and amino/hydroxyl/sulfydryl, the reacting of phenolic aldehyde, nitrine-alkynes click-reaction, sulfydryl-double bond/alkynes are clicked anti- It answers, the reaction of urea-amine, amidation process, esterification, tetrazine-norbornene reaction, active ester and amino/hydroxyl/sulfydryl Reaction, silicone hydroxyl condensation reaction.
Those skilled in the art can also select suitable preparation means according to the understanding of the present invention, reach ideal Purpose.
In the present invention, the dynamic aggregation object and the form containing its composition can be ordinary solid, elastomer, Gel, foam etc..When containing small molecule in the composition of the dynamic aggregation object, the boiling point of selected small molecule is preferably higher than 100 DEG C, the character of material is largely volatilized and changed to avoid small molecule.Wherein, what is contained in ordinary solid and foamed material can Dissolution small-molecular-weight component content is generally not more than 10wt%, and the small-molecular-weight component content contained in gel is generally not less than 50wt%.Ordinary solid and elastomer are because have better mechanical property, preparation method also most easy, more preferably. Foam is more highly preferred to due to the characteristics such as light.
In embodiments of the present invention, dynamic aggregation object gel can by sweller (including water, organic solvent, One of oligomer, plasticizer, ionic liquid or combinations thereof) in carry out crosslinking acquisition, can also have been prepared in dynamic aggregation object Swelling acquisition is carried out at rear recycling sweller.Certainly, the present invention not only limit and this, those skilled in the art can be according to this hair Bright logic and train of thought, is rationally and effectively realized.
In embodiments of the present invention, can be introduced in dynamic aggregation object with it is soft mutually compatible but with it is hard mutually incompatible Sweller prepares dynamic aggregation object gel.The sweller can include but is not limited to water, organic solvent, ionic liquid, oligomerisation Object, plasticizer.Wherein, oligomer can also be considered as plasticizer.Hydrogel, organic solvent swelling are become using water-swellable system System be known as organogel, the system of ionic liquid swelling is known as ionic liquid gel, and the system of oligomer swelling is referred to as neat Polymers swell gel, the system for being plasticized solvent swell are known as plasticizer swell gel；Wherein, ionic liquid, oligomer and plasticizer The gel of swelling is also referred to as organogel.
A kind of dynamic aggregation object gel provided by the present invention, preferred ion liquid gel, oligomer swell gel and increasing Mould solvent swell gel, more preferable plasticizer swell gel.Gel has the advantages that softness, and plasticizer is because boiling point is high, stablizes Property it is good and there is advantage.
A kind of preferred preparation method of dynamic aggregation object ionic liquid gel of the invention, including but not limited to following step It is rapid: the raw material for preparing dynamic aggregation object and ionic liquid being blended, the mass fraction 0.5 for preparing the raw material of dynamic aggregation object is made ~70%, it is polymerize by the appropriate means, is coupled or other kinds of chemical reaction is made one after reaction Kind dynamic aggregation object ionic liquid gel.The preferred preparation method of another dynamic aggregation object ionic liquid gel of the invention, Including but not limited to following steps: the raw material of the block polymer and metal center is swollen in into the solvent containing ionic liquid In, make the mass fraction 0.5~70% of the block polymer, sufficiently removes solvent after swelling, that is, a kind of dynamic aggregation is made Object ionic liquid gel.It is to be based on that the block polymer molecules for preparing ionic liquid gel, which are preferably polymer soft segment skeleton, Polymer, fluorine containing acrylic ester monomer replace the polymer segment of poly- saturation of olefins, polymer containing acrylonitrile.
A kind of preferred preparation method of dynamic aggregation object oligomer swell gel of the invention, including but not limited to following step Rapid: the raw material and oligomer that will prepare dynamic aggregation object are blended, make to prepare the mass fraction 0.5 of the raw material of dynamic aggregation object~ 70%, it is polymerize by the appropriate means, is coupled or one kind is made after reaction in other kinds of chemical reaction The gel of dynamic aggregation object oligomer swelling.The preferred preparation side of another dynamic aggregation object oligomer swell gel of the invention Method, including but not limited to following steps: the raw material in the block polymer and metal is swollen in containing the molten of oligomer In agent, make the mass fraction 0.5~70% of the block polymer, sufficiently remove solvent after swelling, that is, it is poly- that a kind of dynamic is made Close the gel of object oligomer swelling.
A kind of preferred preparation method of dynamic aggregation object plasticizer swell gel of the invention, including but not limited to following step Rapid: the raw material and plasticizer that will prepare dynamic aggregation object are blended, make to prepare the mass fraction 0.5 of the raw material of dynamic aggregation object~ 70%, it is polymerize by the appropriate means, is coupled or one kind is made after reaction in other kinds of chemical reaction The gel of dynamic aggregation object plasticising solvent swell.The preferred preparation side of another dynamic aggregation object plasticizer swell gel of the invention Method, including but not limited to following steps: the raw material of the block polymer and metal center is swollen in containing plasticizer In solvent, make the mass fraction 0.5~70% of the block polymer, sufficiently removes solvent after swelling, that is, a kind of dynamic is made The gel of polymeric plasticizer swelling.It is base that the block polymer for preparing plasticizer swell gel, which is preferably polymer soft segment, Polymer in vinyl-chloride-containing monomer, the polymer containing norbornene monomer, the monomer containing saturation of olefins polymer polymer Segment.
In embodiments of the present invention, another preferred configuration of dynamic aggregation object and its composition is foamed material.
In embodiments of the present invention, the structure of dynamic aggregation object foamed material is related to open-celled structure, hole-closing structure, half Open three kinds of semi-closure structure etc..It in open-celled structure, is interconnected between abscess and abscess, or connection completely, one-dimensional or three-dimensional can By gas or liquid, abscess diameter is 0.01 to 3mm etc..Hole-closing structure has individual blisters structure, inner cell and abscess Between there is wall film to separate, the overwhelming majority be not interconnected, abscess diameter be 0.01 to 3mm etc..The existing phase of contained abscess It is intercommunicated and to have mutual disconnected structure be then half open-celled structure.
In embodiments of the present invention, foaming method according to the difference of foaming agent used can be divided into physical blowing method and Chemical blowing process two major classes.
Physical blowing method is that dynamic aggregation object is made to foam using the method for physics, and general there are three types of methods: (1) first will Inert gas is dissolved under stress in dynamic aggregation object, releases gas using decompression, thus in the material formed stomata and Foaming；(2) by foam and heating is allowed to vaporization to the low-boiling point liquid dissolved in polymer or its material composition；(3) Hollow sphere and/or foamable polymer microballoon are added in material composition, during forming dynamic aggregation object or it Afterwards, it forms foaming body and foams.Physical blowing agent advantage of lower cost, especially carbon dioxide used in physical blowing method and The cost of nitrogen is low, and can be fire-retardant, pollution-free, therefore application value is higher；It is right and without residue after physical blowing agent foaming The influence of material property is little.It is then most simple in technique using the method for addition hollow sphere.
Chemical blowing process is that gas is generated using chemical method to make dynamic aggregation object foam, and general there are two types of methods: (1) The chemical foaming agent being added in dynamic aggregation object (raw material) heat to be allowed to decompose and releases gas and foams；(2) may be used To be foamed using the gas that releases of chemical reaction mutually occurs between raw material components, such as carbonate reacts release with sour Carbon dioxide out.
Partial polymer is polymerizeing or is occurring that gas can be generated in other chemical reaction processes in the present invention, does not need at this time Additionally use foaming agent.The physical blowing agent advantage of lower cost as used in physical blowing method, and can be fire-retardant, pollution-free, and And without residue after physical blowing agent foaming, the influence to foamed polymer physical performance is little, therefore in embodiments of the present invention In, preferred physical blowing.Gel like material is particularly suitable for foaming using hollow sphere and/or foamable polymer microballoon.
In addition to using the above-mentioned usual way for preparing foam, freeze-drying can also be used to prepare foamed material. The method for preparing foamed material using freeze-drying, include the following steps: will to swell in it is soft it is mutually compatible, with hard mutually or not Hold and the dynamic aggregation object of volatile solvent freezes, is then escaping solvent in a manner of distillation close under vacuum condition.? During solvent escapes and after evolution, dynamic aggregation object can maintain the shape before freezing, thus obtain porous spongy Foamed material.
A kind of embodiment for preparing dynamic aggregation object foamed material is to fill dynamic aggregation object, foaming agent and other auxiliary agents Divide mixing, injects and complete foaming in mold.Wherein, prepare foamed material the block polymer be preferably based on polyurethane, The polymer of polyureas, i.e., using urethane bond and urea bond as the polymer of linking group, preferably wherein soft segment is to be based on Saturation of olefins, unsaturated olefin, alkenyl halide, polyethers, polyester, silicon rubber, polyacrylate based polymer, polyvinyl acetate The polymer of based polyalcohol, polyacrylonitrile based polyalcohol.
Dynamic aggregation object foamed material provided by the present invention further relates to: by welding, gluing, cutting, matching plane, perforation, The dynamic aggregation object foamed material, is transformed into any shape that needs by coining, lamination and hot forming, for example, pipe, stick, Sheath, container, ball, piece, volume and band；Purposes of the dynamic aggregation object foamed material in floating installation；The dynamic aggregation object Purposes of the foamed material in any required shape of insulation；It, will by lamination, bonding, fusion and other interconnection techniques Known to the dynamic aggregation object foamed material and sheet material, film, foam, fabric, stiffener and those skilled in the art Other materials are combined into complicated interlayer structure together；Use of the dynamic aggregation object foamed material in washer or sealing On the way；The purposes of the dynamic aggregation object foamed material in packaging material or in a reservoir.It, can about dynamic aggregation object of the invention The dynamic aggregation object of foaming is such a type, is allowed to through extrusion, injection molding, compression moulding or those of skill in the art Known other forming techniques deform them.
In embodiments of the present invention, it in the range of not interfering the object of the invention, can according to circumstances select to add Or using other polymers, auxiliary agent, filler, sweller collectively as dynamic aggregation object recipe ingredient, or in dynamic aggregation Play the role of improving processing performance in the preparation process of object.
Wherein, the other polymers can play in system as additive and improve material property, assign material Material new capability improves materials'use and economic benefit, has the function that material comprehensively utilizes.Addible other polymers, It can be selected from natural polymer, synthetic macromolecular compound.The present invention is to the character of added polymer and is had Some molecular weight can be oligomer or high polymer according to the difference of molecular weight, not according to polymeric species without limitation Together, it can be homopolymer or copolymer, should be prepared in the specific use process according to the performance of target material and actually The needs of journey and selected.
When the other polymers are selected from natural polymer, it can be selected from following any or appoint several days Right high-molecular compound: natural rubber, chitosan, chitin, native protein, polysaccharide etc..
When the other polymers are selected from synthetic macromolecular compound, it can be selected from following any or appoint several: Polytrifluorochloroethylene, haloflex, chliorinated polyvinyl chloride, polyvinyl chloride, Vingon, low density polyethylene (LDPE), middle density Polyethylene, high density polyethylene (HDPE), ultra-high molecular weight polyethylene, melamine formaldehyde resin, polyamide, polyacrylic acid, polypropylene Acid esters, polyacrylamide, polyacrylonitrile, polybenzimidazoles, polyethylene terephthalate, polybutylene terephthalate Ester, polycarbonate, polyethylene glycol, polyester, polyether sulfone, polyarylsulfone (PAS), polyether-ether-ketone, tetrafluoroethylene-perfluoro propane copolymer, polyamides Imines, polyacrylate, polyacrylonitrile, polyphenylene oxide, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high-impact polyphenyl second Alkene, polysulfones, polytetrafluoroethylene (PTFE), polyurethane, polyureas, polyvinyl acetate, ethylene-propylene copolymer, ethane-acetic acid ethyenyl ester are total Polymers, AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, vinyl chloride-acetate Ester copolymer, polyvinylpyrrolidone, epoxy resin, phenolic resin, Lauxite, unsaturated polyester (UP), polyisoprene, gather it is suitable Butadiene, styrene-butadiene copolymer, hycar, poly- (the chloro- 1,3- butadiene of 2-), isobutene-are different Pentadiene copolymer, ethylene-propylene-Isosorbide-5-Nitrae-hexadiene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene- Ethylidene norbornene copolymer, dimethyl silicone polymer, Polymethyl methacrylate, polymethylphenylsiloxane, poly- methyl Vinyl benzene radical siloxane, poly- methyl ethylene trifluoropropyl siloxane, vinylidene-chlorotrifluoroethylene, inclined fluorine second Alkene-hexafluoropropylene copolymer, vinylidene-tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene propylene copolymer, polycyclic oxygen Chloropropane, epichlorohydrin ethylene oxide copoymer, epoxychloropropane-ethylene oxide-propylene oxide copolymer etc..
Wherein, the auxiliary agent may include but be not limited to the combination of following one or more, such as additive synthesis, including catalysis Agent, initiator；Stabilizing additive, including antioxidant, light stabilizer, heat stabilizer, dispersing agent, emulsifier, fire retardant；Improve The auxiliary agent of mechanical property, including toughener, coupling agent；Improve the auxiliary agent of processing performance, including solvent, lubricant, release agent, increasing Mould agent, thickener, thixotropic agent, levelling agent；Change the auxiliary agent of coloured light, including colorant, fluorescent whitening agent, delustering agent；Other are helped Agent, including antistatic agent, biocide mildewcide, foaming agent, foam stabiliser, nucleating agent, rheological agent etc..
Catalyst in the auxiliary agent can reduce reaction activity by changing reaction path to accelerate to react The reaction rate of object during the reaction.It includes but are not limited to following any or appoints several catalyst: 1. polyurethane closes At with catalyst: amines catalyst, such as triethylamine, triethylenediamine, bis- (dimethylaminoethyl) ethers, 2- (2- dimethylamino- Ethyoxyl) ethyl alcohol, trimethyl hydroxyethylammonium propane diamine, N, bis- (dimethylamine propyl) isopropanolamines of N-, N- (dimethylamino-propyl) two Isopropanolamine, N, N, N '-trimethyl-N '-ethoxy diamine ethylether, tetramethyl dipropylenetriamine, N, N- dimethyleyelohexane Amine, N, N, N ', N '-tetramethyl Alkylenediamine, N, N, N ', N ', N '-five methyl diethylentriamine, N, N- dimethyl ethanol Amine, N-ethylmorpholine, 2,4,6- (dimethylamino methyl) phenol, trimethyl-N-2- hydroxypropyl caproic acid, N, N- dimethyl benzylamine, N, N- dimethyl cetylamine etc.；Organometallic catalysts, such as stannous octoate, dibutyltin dilaurate, dioctyl tin two Laurate, zinc Isoocatanoate, isooctyl acid lead, potassium oleate, zinc naphthenate, cobalt naphthenate, ferric acetyl acetonade, phenylmercuric acetate, propionic acid Benzene mercury, bismuth naphthenate, sodium methoxide, potassium octanoate, potassium oleate, calcium carbonate etc.；2. polyolefin catalyst for synthesizing: such as Ziegler- Natta catalyst, π-allyl nickel, alkyl lithium catalyst, metallocene catalyst, aluminium diethyl monochloride, titanium tetrachloride, tri-chlorination Titanium, boron trifluoride etherate, magnesia, dimethylamine, stannous chloride, triethylamine, tetraphenylboron sodium, antimony oxide, sesquialter Ethylmercury chloride aluminium, vanadium oxytrichloride, triisobutyl aluminium, nickel naphthenate, naphthenic acid rare earth etc.；3. CuAAC catalysts: by monovalence Copper compound and amine ligand share concerted catalysis；Monovalence copper compound can be selected from Cu (I) salt, as CuCl, CuBr, CuI, CuCN, CuOAc etc.；Also selected from Cu (I) complex compound, such as [Cu (CH3CN)4]PF6、[Cu(CH3CN)4]OTf、CuBr(PPh3)3Deng；Amine Ligand can be selected from three [(1- benzyl -1H-1,2,3- triazole-4-yl) methyl] amine (TBTA), three [(1- tert-butyl -1H-1,2,3- Triazole-4-yl) methyl] amine (TTTA), three (2- benzimidazole methyl) amine (TBIA), hydration bathophenanthroline disulfonic acid sodium etc.；④ Thiol-ene catalysts: photochemical catalyst, such as dimethoxybenzoin, 2- hydroxy-2-methyl phenylacetone, 2,2- dimethoxy Base -2- phenyl acetophenone etc.；Nucleopilic reagent catalyst, such as ethylenediamine, triethanolamine, triethylamine, pyridine, 4- dimethylamino pyrrole Pyridine, imidazoles, diisopropyl ethyl amine etc..Catalyst amount used is not particularly limited, generally 0.01-0.5wt%.
Initiator in the auxiliary agent can cause monomer molecule to activate in polymerization process and generate free Base improves reaction rate, and reaction is promoted to carry out, and includes but are not limited to following any or appoints several initiators: 1. free radical Polymerization initiator: organic peroxide, such as lauroyl peroxide, benzoyl peroxide (BPO), dicetyl peroxydicarbonate diisopropyl Bis- (4- tert-butylcyclohexyl) esters of ester, di-cyclohexylperoxy di-carbonate, dicetyl peroxydicarbonate, tert-butyl hydroperoxide benzoic acid Ester, tert-butyl hydroperoxide pivalate, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide；Azo-compound, such as azo two Isobutyronitrile (AIBN), azobisisoheptonitrile；Inorganic peroxide, such as ammonium persulfate, potassium peroxydisulfate；2. living polymerization causes Agent: such as 2,2,6,6- tetramethyl -1- oxygroup piperidines, 1- chloro-1-phenyl ethane/stannous chloride/bis- pyridines ternary system；3. from Son polymerization initiator: such as butyl lithium, sodium/naphthalene system, boron trifluoride/aqueous systems, tin tetrachloride/alkyl halide system；4. matching Position polymerization initiator: such as titanium tetrachloride/triethyl aluminum system, two zirconium cyclopentadienyl of dichloro/methylaluminoxane system；5. ring-opening polymerisation With initiator: such as sodium methoxide, potassium methoxide, ethylenediamine, hexamethylene diisocyanate, stannous octoate.Wherein, the preferred mistake of initiator Aoxidize lauroyl, benzoyl peroxide, azodiisobutyronitrile, potassium peroxydisulfate.Initiator amount used is not particularly limited, and one As be 0.1-1wt%.
Antioxidant in the auxiliary agent can delay the oxidation process of polymer samples, guarantee that material can be suitable It is processed and is prolonged its service life sharply, include but are not limited to following any or appoint several antioxidant: Hinered phenols, Such as 2,6 di tert butyl 4 methyl phenol, 1,1,3- tri- (- 4 hydroxyl -5- tert-butyl-phenyl of 2- methyl) butane, four [β-(3,5- Di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol)；Sulfur-bearing by Hinder phenols, such as 4,4 '-thiobis-[3 methy 6 tert butyl phenol], 2,2 '-thiobis-[4- methyl-6-tert-butylphenol]； Triazine system hindered phenol, such as 1,3,5- bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl]-perhydro-s-triazines；Trimerization isocyanide Acid esters Hinered phenols, such as three (3,5- di-tert-butyl-4-hydroxyl benzyl)-triisocyanates；Amine, such as N, N '-two (betanaphthyl) P-phenylenediamine, N, N '-diphenyl-para-phenylene diamine, N- phenyl-N '-cyclohexyl p-phenylenediamine；Sulfur-bearing class, such as thiodipropionic acid dilauryl Osmanthus ester, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, three nonyl benzene of phosphorous acid Ester, three [2.4- di-tert-butyl-phenyl] phosphite esters etc.；Wherein, the preferred tea polyphenols of antioxidant (TP), butylated hydroxy anisole (BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), three [2.4- di-tert-butyl-phenyl] phosphite esters (irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters (antioxidant 1010).Used Antioxidant dosage is not particularly limited, generally 0.01-1wt%.
Light stabilizer in the auxiliary agent can prevent polymer samples from light aging occurs, prolong its service life, It includes but are not limited to following any or appoints several light stabilizers: photomask agent, such as carbon black, titanium dioxide, zinc oxide, sulfurous Sour calcium；Ultraviolet absorbing agent, such as ESCALOL 567,2-hydroxy-4-n-octoxybenzophenone, 2- (2- hydroxyl Base -3,5- di-tert-butyl-phenyl) -5- chlorobenzotriazole, 2- (2- hydroxy-5-methyl base phenyl) benzotriazole, (the 2- hydroxyl of 2,4,6- tri- Base -4- n-butoxyphenyl) -1,3,5- s-triazine, 2- cyano -3,3- diphenylacrylate 2- ethylhexyl；Pioneer's type is ultraviolet Light absorbers, such as the p- tert-butyl phenyl ester of salicylic acid, double acid double phenol A ester；UV quenchers, such as bis- (3,5- bis- tertiary fourths Base -4- benzylphosphonic acid mono ethyl ester), 2,2 '-thiobis (4- spy's octyl phenol oxygroup) nickel；Hindered amine light stabilizer, such as the last of the ten Heavenly stems two Bis- (2,2,6,6- tetramethyl piperidine) esters of acid, benzoic acid (2,2,6,6- tetramethyl piperidine) ester, three (1,2,2,6,6- pentamethyl piperazines Piperidinyl) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acid (2,4- di-tert-butyl) ester, alkyl Phosphoamide, N, N '-zinc dibutyl dithiocaarbamate, N, positive fourth positive group aminodithioformic acid nickel of N '-two etc.；Its In, bis- (2,2,6, the 6- tetramethyl piperidine) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid.Light used is stablized Agent dosage is not particularly limited, generally 0.01-0.5wt%.
Heat stabilizer in the auxiliary agent enables to polymer samples in processing or use process not due to heated Chemical change occurs, or delays these variations to achieve the purpose that prolong the service life comprising but it is not limited only to following A kind of or several heat stabilizers: lead salts, such as lead sulfate tribasic, dibasic lead phosphite, dibasic lead stearate, disalt Base phthalic acid lead, tribasic Malaysia lead plumbate, slag lead silicate, lead stearate, lead salicylate, dibasic phthalic acid Lead, basic lead carbonate, silica gel are co-precipitated lead silicate；Metal soap: such as cadmium stearate, barium stearate, calcium stearate, stearic acid Lead, zinc stearate；Organo-tin compound class, such as di-n-butyltin dilaurate, Bis(lauroyloxy)dioctyltin, maleic acid two (just) butyl tin, double single-ethylhexyl maleate dioctyltins, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital tin C-102, two mercaptos Guanidine-acetic acid isooctyl stannous methide, two mercaptan stannous methides and its compound；Antimony stabilizer, such as mercaptan antimonic salt, mercaptoacetate Mercaptans type, mercapto-carboxylic ester antimony, carboxylate antimony；Epoxy compound species, such as epoxidized oil, epoxy aliphatic ester, epoxy resin；It is sub- Phosphoric acid ester, such as three aromatic ester of phosphorous acid, three alkyl ester of phosphorous acid, three aralkyl ester of phosphorous acid, alkane virtue mixed ester, aggretion type phosphorous acid Ester；Polyalcohols, such as pentaerythrite, xylitol, mannitol, D-sorbite, trimethylolpropane；Composite thermal stabilizer, such as altogether Precipitate metallic soap, liquid metal soap compound stabilizer, organotin compound stabilizer etc.；Wherein, the preferred barium stearate of heat stabilizer, Calcium stearate, di-n-butyltin dilaurate, maleic acid two (just) butyl tin.Heat stabilizer dosage used does not limit especially It is fixed, generally 0.1-0.5wt%.
Dispersing agent in the auxiliary agent enables to solid flocculation group in mixed with polymers liquid to be separated into tiny particle And be suspended in liquid, those are poorly soluble the solid and liquid particles in liquid for uniform dispersion, while can also prevent particle Sedimentation and cohesion form stable suspension comprising but be not limited only to following any or appoint several dispersing agents: anionic, Such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate；Cationic；It is non-ionic, such as aliphatic alcohol polyethenoxy Ether, sorbitol anhydride fatty acid polyoxyethylene ether；Inorganic type, such as silicate, condensed phosphate；Polymer electrolyte, such as starch, bright Glue, water-soluble glue, lecithin, carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, lignosulfonates, polyvinyl alcohol Deng.Wherein, the preferred neopelex of dispersing agent, naphthalene system methylene sulfonate (dispersing agent N), aliphatic alcohol polyethenoxy Ether, dispersant dosage used are not particularly limited, generally 0.3-0.8wt%.
Emulsifier in the auxiliary agent can improve in the mixed with polymers liquid comprising auxiliary agent between various composition phases Surface tension is allowed to form uniform and stable dispersion or emulsion comprising but be not limited only to following any or appoint several Kind emulsifier: anionic, such as higher fatty acid salt, alkylsulfonate, alkylbenzene sulfonate, Negel, succinic acid Sulfonated ester, petroleum sulfonate, aliphatic alcohol sulfate, castor oil salt, sulphation butyl ricinoleate salt, phosphate ester salt, Fatty acyl-peptide condensation product；Cationic, such as alkylammonium salt, alkyl quaternary ammonium salts, Fixanol；Amphoteric ion type, such as carboxylate Type, sulfonic acid ester type, sulfuric acid ester type, phosphate type；It is non-ionic, such as fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, rouge Fat acid polyoxyethylene ester, polypropylene oxide-ethylene oxide adduct, fatty acid glyceride, pentaerythritol fatty ester, sorbierite And sorbitan fatty acid ester, sucrose fatty ester, hydramine fatty acid amide etc..Wherein, preferably neopelex, lose Water Span, triethanolamine stearate (Emulphor FM), emulsifier used are not particularly limited, generally For 1-5wt%.
Fire retardant in the auxiliary agent can increase the flame resistance of material comprising but be not limited only to following any Or appoint several fire retardants: phosphorus system, such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate hexichol Ester；Halogen phosphoric acid ester, such as three (2,3- dibromopropyl) phosphates, tricresyl phosphate (2,3- dichloro the third) ester；Organohalogen compounds are such as high Chlorinty chlorinated paraffin, 1,1,2,2- tetrabromoethane, deca-BDE, penta decane of perchloro- ring；Inorganic fire retardants, such as three oxidations two Antimony, aluminium hydroxide, magnesium hydroxide, zinc borate；Reactive flame retardant, such as chlorendic anhydride, bis- (2,3- dibromopropyl) anti-butylene two Acid esters, tetrabromobisphenol A, tetrabromophthalic anhydride etc.；Wherein, the preferred deca-BDE of fire retardant, triphenyl phosphate, tricresyl phosphate Toluene ester, phosphate toluene diphenyl ester, antimony oxide.Amount of flame-retardant agent used is not particularly limited, generally 1-20wt%.
Toughener in the auxiliary agent can reduce polymer samples brittleness, increase toughness, and it is strong to improve material carrying Degree comprising but be not limited only to following any or appoint several toughener: methyl methacrylate-butadiene-styrene copolymerization Resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modifier, acrylonitrile-butadiene-benzene second Alkene copolymer, acrylonitrile-butadiene copolymer, the third glue of second, ethylene-propylene diene copolymer, cis-butadiene cement, butadiene-styrene rubber, styrene-butadiene-benzene Ethylene block copolymer etc.；Wherein, preferred the third glue of second of toughener, acrylonitrile-butadiene-styrene copolymer (ABS), benzene second Alkene-butadiene-styrene block copolymer (SBS), Methyl Methacrylate-Butadiene-Styrene Copolymer resin (MBS), Chlorinated polyethylene resin (CPE).Toughener dosage used is not particularly limited, generally 5-10wt%.
Coupling agent in the auxiliary agent can improve the interface characteristics of polymer samples and inorganic filler or reinforcing material Can, the viscosity of material melt is reduced in plastic processes, improves the dispersion degree of filler to improve processing performance, and then make to make Product obtain good surface quality and machinery, heat and electrical property comprising but be not limited only to following any or appoint several couplings Agent: chromium of organic acid complex compound, silane coupling agent, titanate coupling agent, sulfonyl azide coupling agent, aluminate coupling agent etc.；Wherein, The preferred gamma-aminopropyl-triethoxy-silane of coupling agent (Silane coupling agent KH550), γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy Base silane (silane coupling agent KH560).Coupling agent dosage used is not particularly limited, generally 0.5-2wt%.
Solvent in the auxiliary agent, adjustable viscosity are convenient for technological operation, make in product preparation process or in preparing With.Its include but are not limited to it is following any or appoint it is several: hydro carbons (such as hexamethylene, heptane), halogenated hydrocarbon (such as methylene chloride, Chloroform, tetrachloromethane), aromatic hydrocarbons (such as toluene, dimethylbenzene), ketone (such as acetone, methyl ethyl ketone), ethers (such as ether, tetrahydro furan Mutter, dioxane), esters (such as ethyl acetate, butyl acetate), glycol ether-ether (such as ethylene glycol ether acetate, propylene glycol list first Ether acetate), dimethylformamide (DMF), N-Methyl pyrrolidone (NMP) etc..Solvent usage used is not particularly limited, Generally 1-200wt%.
Lubricant in the auxiliary agent can be improved the lubricity of polymer samples, reduce friction, reduce Interface Adhesion Performance comprising but be not limited only to following any or appoint several lubricants: saturated hydrocarbons and halogenated hydrocarbon, such as solid paraffin, micro- Spar wax, atoleine, low molecular weight polyethylene, oxidized polyethylene wax；Fatty acid, such as stearic acid, hydroxy stearic acid；Fat Esters of gallic acid, such as fatty acid low-carbon-ester, polyol esters of fatty acids, native paraffin, ester type waxes and saponified wax；Aliphatic amide type is such as hard Acyl amine or stearic amide, oleamide or oleamide, erucyl amide, N, N '-ethylene bis stearamide；Fatty alcohol and polynary Alcohols, such as stearyl alcohol, cetanol, pentaerythrite；Metal soap, as lead stearate, calcium stearate, barium stearate, magnesium stearate, Zinc stearate etc.；Wherein, the preferred solid paraffin of lubricant, atoleine, stearic acid, low molecular weight polyethylene.Lubrication used Agent dosage is not particularly limited, generally 0.5-1wt%.
Release agent in the auxiliary agent, it can make polymer samples be easy to demould, and surface is smooth, clean comprising but It is not limited only to following any or appoints several release agents: paraffin hydrocarbon, soaps, dimethicone, ethyl silicon oil, aminomethyl phenyl silicon Oil, castor oil, used oil, mineral oil, molybdenum disulfide, polyethylene glycol, vinyl chloride resin, polystyrene, silicon rubber, polyvinyl alcohol Deng；Wherein, the preferred dimethicone of release agent, polyethylene glycol.Release agent dosage used is not particularly limited, generally 0.5- 2wt%.
Plasticizer in the auxiliary agent can increase the plasticity of polymer samples, so that the hardness of polymer, mould Amount, softening temperature and brittle temperature decline, elongation, flexibility and flexibility improve comprising but be not limited only to following any Kind appoints several plasticizer: Phthalates: dibutyl phthalate, dioctyl phthalate, phthalic acid two Different monooctyl ester, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, phthalic acid fourth benzyl Bis- (13) esters of ester, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid, terephthaldehyde Sour two (2- ethyl) own esters；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyl) own ester；Fatty acid ester, such as The own ester of adipic acid two (2- ethyl), decanedioic acid two (2- ethyl) own ester；Epoxy compound species, such as epoxy glycerite esters, epoxy rouge Fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, the own ester of epoxystearic acid (2- ethyl), epoxy soybean Oleic acid 2- ethylhexyl, the own ester of 4,5- epoxy tetrahydrophthalic acid two (2- ethyl), Chinese littleleaf box methyl acetylricinolate, binary Alcohol lipid, such as the sour glycol ester of C5~9, the sour Triethylene Glycol of C5~9；Class containing chlorine such as afforests paraffin class, chlorinated fatty acid Ester；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester；Phenyl alkylsulfonate, trimellitic acid Ester, citrate, pentaerythrite and pentaerythritol fatty acid ester etc.；Wherein, plasticizer pref-erable dioctyl phthalate (DOP), neighbour Dibatyl phithalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), adjacent benzene two Formic acid diisodecyl ester (DIDP), tricresyl phosphate (TCP).Plasticizer consumption used is not particularly limited, generally 5- 20wt%.
Thickener in the auxiliary agent, can assign the good thixotropy of mixed with polymers liquid and consistency appropriate, and one As used during production of the invention and semi-finished product store comprising but be not limited only to following any or appoint several thickenings Agent: lower-molecular substance, such as fatty acid salt, fatty alcohol polyoxyethylene ether sulfate, alkyldimethylamine oxide, fatty acid monoethanol Amide, fatty diglycollic amide, fatty acid Isopropamide, anhydro sorbitol tricarboxylic ester, glycerol trioleate, coconut monoethanolamide Propyl betaine, 2- alkyl-N- carboxymethyl-N- hydroxyethyl imidazole quinoline, titanate coupling agent；Polymer substance, such as bentonite, manually Hectorite, fine particle silica, colloidal aluminum, plant polyose class, microbial polysaccharide class, animal protein, cellulose family, starch, Seaweed acids, poly-methyl acrylate, methacrylic acid copolymer, cis-butenedioic anhydride copolymer, crotonic acid-copolymers, polyacrylamide, Polyvinyl pyrrolidone, polyvinyl alcohol, polyethers, polyvinyl methyl ether urethane polymer etc.；Wherein, the preferred hydroxy ethyl fiber of thickener Element, coconut oil diethanol amide, acrylic acid-methacrylic acid copolymer.Thickener dosage used is not particularly limited, generally For 0.1-1.5wt%.
Thixotropic agent in the auxiliary agent is added in hydridization dynamic polymer systems, increases the thixotropy of polymeric system. Include but are not limited to following any or appoint several: gas-phase silica, rilanit special, bentonite, silicic acid anhydride, silicic acid are derivative Object, urea derivative etc..Thixotropic agent dosage used is not particularly limited, generally 0.5-2wt%.
Levelling agent in the auxiliary agent can guarantee the flat and smooth uniform of polymer coating film, improve film coated surface matter Amount improves dicoration comprising but be not limited only to following any or appoint several levelling agents: dimethyl silicone polymer, poly- methyl Phenyl siloxane, cellulose acetate butyrate, polyacrylate, organic siliconresin etc.；Wherein, the preferred poly dimethyl of levelling agent Siloxanes, polyacrylate.Levelling agent dosage used is not particularly limited, generally 0.5-1.5wt%.
Colorant in the auxiliary agent can make polymeric articles show required color, increase surface color and polish, It includes but are not limited to following any or appoints several colorants: inorganic pigment, such as titanium white, chrome yellow, cadmium red, iron oxide red, molybdenum chromium Red, ultramarine, chrome green, carbon black；Organic pigment, such as lithol red BK directions, lake red C, red, good base R is red, phthalocyanine is red, Yong Guyang The bright red R of red HF3C, the plastics and not red BR of Crow, forever solid orange HL, Fast Yellow G, vapour bar plastics Huang R, permanent yellow 3G, permanent yellow H2G, Phthalocyanine blue B, dark green, plastics purple RL, nigrosine；Organic dyestuff, such as thioindigo red, vat yellow 4GF, indanthrene blue RSN, slag rose Rare essence, Oil Yellow etc.；Wherein, the selection of colorant does not need to be particularly limited to depending on color sample demand.Coloring used Agent dosage is not particularly limited, generally 0.3-0.8wt%.
Fluorescent whitening agent in the auxiliary agent can make contaminated substance obtain the sparkling effect of similar fluorite, It includes but are not limited to following any or appoints several fluorescent whitening agents: Stilbene-based, coumarin type, pyrazoline type, benzo Oxygen nitrogen type, phthalimide type etc.；Wherein, the preferred stilbene biphenyl sodium disulfonate (fluorescent whitening agent of fluorescent whitening agent CBS), bis- (5 methyl -2- benzoxazolyl) talan (fluorescent whitening agent KSN) of 4,4-, 2,2- (4,4 '-diphenylethyllene) Double benzoxazoles (fluorescent whitening agent OB -1).Fluorescent whitening agent dosage used is not particularly limited, generally 0.002- 0.03wt%.
Delustering agent in the auxiliary agent when incident light being enabled to reach polymer surfaces, occurs diffusing reflection, generates low The matt and delustring appearance of gloss comprising but be not limited only to following any or appoint several delustering agents: sedimentation barium sulfate, dioxy SiClx, aqueous gypsum powder, talcum powder, titanium dioxide, poly- methyl carbamide resin etc.；Wherein, the preferred silica of delustering agent.Used disappears Photo etching dosage is not particularly limited, generally 2-5wt%.
The deleterious charge assembled in polymer samples can be guided or be eliminated, make it by the antistatic agent in the auxiliary agent Production and life are not brought inconvenience or are endangered comprising but be not limited only to following any or appoint several antistatic agents: yin from Subtype antistatic agent, such as alkylsulfonate, to Sodium Nonylphenoxypropane Sulfonate, alkyl phosphate diethanolamine salt, alkyl phenol Polyoxyethylene groups ether sulfonic acid triethanolamine, to nonyl diphenyl ether potassium sulfonate, alkyl polyoxyethylene base ether sulfonic acid triethanolamine, phosphoric acid Ester derivant, phosphate, phosphoric acid polyethylene oxide alkyl ethers alcohol ester, alkyl bis- [two (2- ethylol amine)] phosphates, 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- hydroxyl second Base) dimethylammonium nitrate, alkyl hydroxyethyl dimethylammonium perchlorate, 2- alkyl -3,3- dihydroxy ethyl imidazoline perchlorate, 2- Heptadecyl -3- ethoxy -4- carboxymethyl imidazoline, N, bis- (α-ethoxy)-N-3 (dodecyloxy -2- hydroxypropyl) first of N- Ammonium Methylsulfate salt；Amphoteric ion type antistatic agent, such as alkyl dicarboxyl methyl ammonium second inner salt, lauryl betaine, N, N, N- tri- Alkylammonium acetyl (N '-alkyl) amine second inner salt, bis- polyethylene oxide base-N- ethylphosphonic acid sodium of N- lauryl-N, N-, alkyl two Salt hydroxide, -3 ethoxy -3- acetic acid alkali imidazoline quaternary amine alkali of 2- alkyl, N- alkyl amino acid in (polyoxyethylene) ammonium second Salt；Non-ionic antistatic agent, such as fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide addition product, alkyl phenol epoxy second The polyethylene oxide of alkane addition product, tricresyl phosphate polyoxyethylene groups ether-ether, fatty acid monoglyceride, sorbitan mono-laurate Addition product；Polymer Antistatic Agent, ethylene oxide propylene oxide addition product, polyethylene glycol-terephthalic acid (TPA) such as ethylenediamine Ester -3,5- dibenzoate sodium sulfonate copolymers, polyene propionamide N- quaternary ammonium salt substituent, poly- 4- vinyl -1- acetonyl pyrrole Pyridine phosphoric acid-is to butyl phenyl ester salt etc.；Wherein, the preferred lauryl trimethyl ammonium chloride of antistatic agent, octadecyldimethyl hydroxyl second Base quaternary ammonium nitrate (antistatic agent SN), alkyl phosphate diethanolamine salt (antistatic agent P).Antistatic agent dosage used does not have It is particularly limited to, generally 0.3-3wt%.
Dehydrating agent in the auxiliary agent, can moisture in removing system comprising but be not limited only to it is following any or Appoint several: oxazolidine compound (such as 3- Ethyl-2-Methyl -2- (3- methyl butyl) -1,3- oxazolidine), different to Methyl benzenesulfonyl Cyanate, triethyl orthoformate, vinyl silanes, calcium oxide etc..Dehydrating agent dosage used is not particularly limited, generally 0.1-2wt%.
Biocide mildewcide in the auxiliary agent can inhibit the growth of bacterium, and the appearance for keeping product clean and tidy extends and uses Service life；Or protection user, the health for promoting user, such as reduce tinea pedis.It includes organic matter and inorganic matter, including but It is not limited only to following any or appoints several: isothiazolinone derivatives, such as 5-Chloro-2-methyl-4-isothiazolin-3-one, 2- Methyl -4- isothiazoline -3- ketone, N- normal-butyl -1,2- benzisothiazole-3-ketone, octylisothiazolinone, 2,4,4- tri- Chlorine-2-hydroxyl-diphenyl ether, 2- (4- thiazolyl) benzimidazole, copper 8-quinolinolate or bis- (8-hydroxyquinoline base) copper；It is organic Tin compound, such as tributyl-tin fumarate, tributyltin acetate, bis- (tributyl tin) sulfide, bis- (tributyl tin) tin oxide； N, N- dimethyl-N '-phenyl (fluorine dichloromethyl is thio) sulfonamide；Inorganic compound or compound, such as nano silver, nano-silica Change titanium, nano silica, nano zine oxide, superfine cupper powder, inorganic antiseptic YY-Z50, XT inorganic antiseptic, composite antibacterial Agent KHFS-ZN.Biocide mildewcide dosage used is not particularly limited, generally 0.5-2wt%.
Foaming agent in the auxiliary agent can make polymer samples foaming pore-forming, to obtain light, heat-insulated polymerization Object material comprising but be not limited only to following any or appoint several foaming agents: physical blowing agent, such as carbon dioxide, nitrogen, argon Gas, methane, ethane, propane, butane, iso-butane, pentane, neopentane, hexane, isopentane, heptane, isoheptane, acetone, benzene, first Benzene, methyl ether, ether, petroleum ether, chloromethanes, methylene chloride, dichloroethylene, dicholorodifluoromethane, trifluorochloromethane, hydrogen chlorine fluorine Hydrocarbon -22, hydrochlorofluorocarbons -142b, hydrofluorocarbons -134a, hydrofluorocarbons -152a, chlorofluorocarbons -11, chlorofluorocarbons -12, Chlorofluorocarbons -114；Inorganic foaming agent, as sodium bicarbonate, ammonium carbonate, ammonium hydrogen carbonate, carbonate ammonia natrium, azido compound, hydroboration close Object etc.；Organic foaming agent, such as N, N '-dinitrosopentamethlyene tetramine, N, N '-dimethyl-N, N '-dinitroso terephthaldehyde Amide, azodicarbonamide, barium azo-biscarbonate, two diisopropyl carbonate of azo, azodicarbonamide potassium formate, two isobutyl of azo Nitrile, 4,4 '-oxobenzenesulfonyl hydrazide, 3,3 '-disulfonyl hydrazide diphenyl sulphone (DPS)s, 1,3- benzene Erhuang hydrazides, benzene sulfonyl hydrazide, three diazanyls three Piperazine, p-toluene sulfonylsemicarbazide, biphenyl -4,4 '-disulfonyl nitrine, diazo aminobenzene；Physical microballoon/granule foaming agent, such as The expandable microballoon of the companies such as Akzo Nobel production.Wherein, the preferably environmentally friendly carbon dioxide of foaming agent, nitrogen, argon Gas and sodium bicarbonate, ammonium carbonate, azodicarbonamide (blowing agent AC), N, five methine tetramine (foaming agent of N '-dinitro H), N, N '-dimethyl-N, N '-dinitrosoterephthalamine (foaming agent NTA), physical microballoon foaming agent.Hair used Infusion dosage is not particularly limited, generally 0.1-30wt%.
Blowing promotor in the auxiliary agent comprising but be not limited only to foamed promoter, frothing inhibitor, foam and stablize Agent etc..The foamed promoter comprising but be not limited only to it is following any or appoint it is several: urea, stearic acid, lauric acid, Salicylic acid, tribasic lead sulfate, dibasic lead phosphite, lead stearate, cadmium stearate, zinc stearate, zinc oxide, ZB- 530,KZ-110,MS-1；The frothing inhibitor comprising but be not limited only to following any or appoint several: maleic acid, richness Horse acid, stearyl chloride, phthalyl chloride, maleic anhydride, phthalate anhydride, hydroquinone, naphthalenediol, aliphatic amine, amide, Oxime, isocyanates, mercaptan, thiophenol, thiocarbamide, sulfide, sulfone, cyclohexanone, acetylacetone,2,4-pentanedione, hexacholorocyclopentadiene, dibutyl Malaysia Sour tin etc.；The foam stabiliser comprising but be not limited only to it is following any or appoint it is several:: silicone oil, sulfonated aliphatic alcohol, Alpha-sulfonated fatty acid, NaLS, dodecyldimethylamine oxide, alkylolamides, polyethylene glycol oxide, alkylaryl are poly- Ethylene oxide alcohol, tridecyl ether, Polyoxyethylene sorbitan glycerol monolaurate, siloxanes-ethylene oxide are embedding Section copolymer etc..Blowing promotor dosage used is not particularly limited, generally 0.05-10wt%.
Nucleating agent in the auxiliary agent can accelerate crystalline rate, increase knot by the crystallization behavior of change polymer Brilliant density and promote fine grain size, reach and shorten material molding cycle, improves the product transparency, lustrous surface, tension The purpose of the physical mechanical properties such as intensity, rigidity, heat distortion temperature, impact resistance, creep resistance comprising but be not limited only to Under it is any or appoint several nucleating agents: benzoic acid, adipic acid, sodium benzoate, talcum powder, p-phenolsulfonic acid's sodium, silica, two Benzal D-sorbite and its derivative, EP rubbers, ethylene propylene diene rubber etc.；Wherein, the preferred silica of nucleating agent, two benzals D-sorbite (DBS), ethylene propylene diene rubber.Nucleating agent dosage used is not particularly limited, generally 0.1-1wt%.
Rheological agent in the auxiliary agent can guarantee that polymer has good brushability and appropriate during film Coating thickness, the sedimentation of solid particle, can be improved its redispersibility comprising but be not limited only to following when preventing storage A kind of or several rheological agents: inorganic, such as barium sulfate, zinc oxide, alkaline earth oxide, calcium carbonate, lithium chloride, sulfuric acid Sodium, magnesium silicate, fumed silica, waterglass, colloidal silicon dioxide；Organo-metallic compound, as aluminum stearate, aluminium alkoxide, Titanium chelate, aluminium chelate compound；Organic, such as organobentonite, rilanit special/amide waxe, isocyanate derivates, acrylic acid Lotion, acrylic copolymer, polyethylene wax, cellulose esters etc.；Wherein, the preferred organobentonite of rheological agent, polyethylene wax, hydrophobic Modified alkaline swellable emulsions (HASE), alkali-swellable emulsions (ASE).Rheological agent dosage used is not particularly limited, and one As be 0.1-1wt%.
The filler primarily serves following effect in polymer samples: 1. reducing the shrinking percentage of molded article, mentions Dimensional stability, surface smoothness, flatness and the zero diopter of high product or without photosensitiveness etc.；2. adjusting the viscosity of material；③ Meet different performance requirement, such as improves material impact intensity and compressive strength, hardness, rigidity and modulus, improve wearability, improve Heat distortion temperature improves electric conductivity and thermal conductivity etc.；4. improving the coloring effect of pigment；5. assigning photostability and chemically-resistant being rotten Corrosion；6. playing compatibilization, cost can be reduced, improves product competitiveness in the market.
The filler, selected from following any or appoint several fillers: inorganic non-metallic filler, organic is filled out at metal packing Material.
The inorganic non-metallic filler includes but are not limited to following any or appoints several: calcium carbonate, clay, sulphur It is sour barium, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, asbestos, asbestos fibre, orthoclase, white Chalk, lime stone, blanc fixe, gypsum, graphite, carbon black, graphene, graphene oxide, fullerene, carbon nanotube, molybdenum disulfide, Slag, flue dust, wood powder and shell powder, diatomite, red mud, wollastonite, silica-alumina carbon black, aluminium hydroxide, magnesium hydroxide, flyash, Oil shale powder, swelling perlite powder, conductive black, vermiculite, iron cement, white clay, alkali mud, boron mud, glass microballoon, resin microbeads, 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..
The metal packing includes but are not limited to following any or appoints several: metal powder, fiber comprising But it is not limited only to copper, silver, nickel, iron, gold etc. and its powder, the fiber of alloy；Nano-metal particle comprising but be not limited only to receive Rice gold particle, nano-Ag particles, nanoparticle palladium, nano iron particles, nano cobalt granule, nano nickle granules, nanometer Fe3O4Particle, Nanometer γ-Fe2O3Particle, nanometer MgFe2O4Particle, nanometer MnFe2O4Particle, nano Co Fe2O4Particle, nano Co Pt3Particle, Nanometer Fe Pt particle, nanometer Fe Pd particle, ferronickel bimetallic magnetic nanoparticle and other in infrared or ultraviolet or electromagnetism The lower nano-metal particle etc. that can be generated heat of effect；Liquid metal comprising but it is not limited only to mercury, gallium, gallium indium liquid alloy, gallium Indium tin liquid alloy, other gallium base liquid metal alloys；Metallo-organic compound molecule or crystal and other infrared or purple The substance etc. that can be generated heat under outer or electromagnetic action.
The organic filler includes but are not limited to following any or appoints several: 1. natural organic filler, such as natural Rubber, cotton, velveteen, fiber crops, jute, flax, asbestos, cellulose, cellulose acetate, lignin, starch, wood powder etc.；2. synthesizing 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, polycarbonate, dimethyl silicone polymer, polyethylene glycol, polyester, polysulfones, polyether sulfone, polyethylene terephthalate, Phenolic resin, tetrafluoroethylene-perfluoro propane copolymer, polyimides, polymethyl acrylate, polymethacrylonitrile, poly- methyl-prop E pioic acid methyl ester, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, polytetrafluoroethylene (PTFE), polyurethane, polyvinyl alcohol, gathers polyphenylene oxide Vinyl acetate, polyvinyl butyral, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, Vingon, polyethylene Alcohol formal, polyvinylpyrrolidone, Lauxite, ultra-high molecular weight polyethylene, unsaturated polyester (UP), polyether-ether-ketone etc.；3. closing At gum filler, as isoprene rubber, butadiene rubber, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, EP rubbers, Silicon rubber, fluorubber, lactoprene, polyurethane rubber, epichlorohydrin rubber, thermoplastic elastomer (TPE) etc.；4. synthetic fibers are filled out Material, such as viscose fiber, copper ammonia fiber, diethyl ester fiber, triethyl fiber, Fypro, polycarbonate, polyvinyl alcohol Fiber, polyester fiber, polyurethane fiber, polyacrylonitrile fibre, vinylon, polyvinyl chloride fibre, polyolefin are fine Dimension, fluorofibre, polytetrafluoroethylene fibre, aromatic polyamide fibre, aramid fiber or aramid fiber etc.；5. foamed polymer Composition granule and expandable polymer beads.
Wherein, wire feeding does not limit, mainly depending on required material property, preferably calcium carbonate, barium sulfate, cunning Mountain flour, carbon black, graphene, (hollow) glass microballoon, foam microspheres, expandable particles, glass fibre, carbon fiber, metal powder, day Right rubber, protein, resin microbeads, amount of filler used are not particularly limited, generally 1-30wt%.
The preferred antioxidant of auxiliary agent, light stabilizer, heat stabilizer, toughening in the preparation process of dynamic aggregation object material Agent, plasticizer, foaming agent, fire retardant.The preferred calcium carbonate of filler, barium sulfate, talcum powder, carbon black, glass microballoon, graphene, glass Glass fiber, carbon fiber.
Wherein, the sweller may include but be not limited to water, organic solvent, ionic liquid, oligomer, plasticizer.Its In, oligomer can also be considered as plasticizer.
Organic solvent in the sweller is selected from as an example and includes but is not limited to any of the following or appoint several Kind: hydro carbons (such as hexamethylene, heptane), halogenated hydrocarbon (such as methylene chloride, chloroform, tetrachloromethane), aromatic hydrocarbons (such as toluene, dimethylbenzene), Ketone (such as acetone, methyl ethyl ketone), ethers (such as ether, tetrahydrofuran, dioxane), esters (such as ethyl acetate, acetic acid fourth Ester), glycol ether-ether (such as ethylene glycol ether acetate, propylene glycol monomethyl ether acetate), dimethylformamide (DMF), N- methyl Pyrrolidones (NMP) etc..
Ionic liquid in the sweller is generally made of organic cation and inorganic anion, as an example, sun It includes but is not limited to that alkyl quaternary ammonium ion, alkyl quaternary are seen imidazol ion, the N- alkyl that ion, 1,3- dialkyl group replace that ion, which is selected from, Substituted pyridinium ion etc.；Anion be selected from include but is not limited to for halide ion, tetrafluoroborate ion, hexafluoro-phosphate radical from Son also has CF3SO3 -、(CF3SO2)2N-、C3F7COO-、C4F9SO3 -、CF3COO-、(CF3SO2)3C-、(C2F5SO2)3C-、 (C2F5SO2)2N-、SbF6 -、AsF6 -Deng.In ionic liquid used in the present invention, the preferred glyoxaline cation of cation, anion It is preferred that hexafluorophosphoricacid acid ions and tetrafluoroborate ion.
Oligomer in the sweller is selected from as an example and includes but is not limited to any of the following or appoint several: Polyethylene glycol oligomer, polyvinyl alcohol oligomer, polyvinyl acetate ester oligomer, polyacrylic acid N-butyl oligomer, liquid stone Wax etc.
Plasticizer in the sweller is selected from as an example and includes but is not limited to any of the following or appoint several: Phthalates: dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisooctyl phthalate (DIOP), dibutyl phthalate (DHP), diisooctyl phthalate (DIDP), diisononyl phthalate (DINP), neighbour Phthalic acid butyl benzyl, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid are bis- (13) Ester, terephthalic acid (TPA) two (2- ethyl) own ester；Phosphoric acid ester, as tricresyl phosphate (TCP), phosphoric acid (hexichol -2- ethyl) oneself Ester；Fatty acid ester, such as the own ester of adipic acid two (2- ethyl), decanedioic acid two (2- ethyl) own ester；Epoxy compound species, such as epoxy Glyceride type, epoxy fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidised soybean oil, epoxystearic acid (2- second Base) own ester, epoxy soybean oleic acid 2- ethylhexyl, the own ester of 4,5- epoxy tetrahydrophthalic acid two (2- ethyl), Chinese littleleaf box acetyl Methyl ricinolcic acid, dihydric alcohol lipid, such as C5~9Sour glycol ester, C5~9Sour Triethylene Glycol；Class containing chlorine such as afforests stone Wax class, chloro fat acid esters；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester；Petroleum sulphur Acid phenenyl ester, trimellitate, citrate, pentaerythrite and pentaerythritol fatty acid ester etc..Wherein, the preferred DBP, DOP of plasticizer, DIOP, DIDP, DINP, TCP, epoxidised soybean oil.Wherein, epoxidised soybean oil is that a kind of environment-friendly type plastic of function admirable increases Mould agent, epoxidation reaction preparation occurs for refined soybean oil and peroxide, in polymer product resistance to volatilization, it is not easy to migrate, Not easy to lose, this is to keeping product light, thermal stability and to prolong the service life be highly beneficial.Epoxidised soybean oil toxicity pole It is small, it is allowed for the packaging material of food and medicine by many countries, is that the unique of Food and Drug Adminstration of the US's approval can For the epoxy plasticiser of packaging material for food, therefore it is more highly preferred to.
In the preparation process of dynamic aggregation object, special limit is not done to the dosage of dynamic aggregation object each component raw material Fixed, those skilled in the art can be adjusted according to practical preparation situation and target polymerization physical performance.
The manufacturing method of composition of the invention is not particularly limited, for example, roller, kneader, extruder, ten thousand can be passed through Additive is blended with dynamic aggregation object as needed for energy blender etc., then carries out the subsequent operation such as foam.
Dynamic aggregation object of the invention due to it includes having the block polymer molecules of hard section and soft segment simultaneously, hard section and Soft segment can form physics split-phase, and what hard section was formed mutually can be used as physical crosslinking/polymerization, be conducive to the machine-shaping of material with Recycling.The block polymer molecules also contain dynamic supermolecular mechanism, when dynamic supermolecular mechanism forms interchain linkage When, dynamic aggregation object obtained all has good self-healing properties.Simultaneously because the presence of dynamic supermolecular mechanism, it can To increase the toughness of material.By suitable component selection and formula design, can prepare with shape memory and selfreparing The splendid polymer material of the material and toughness of function, as shape memory clamping plate, the sensor of stress sensitive, self-repairability apply Layer, self-repairability block glue and conducting resinl, self-repairability sealing element etc., in bio-medical material, military affairs, aerospace, energy The fields such as source, building tool has been widely used.Further, since dynamic aggregation object of the invention contains at least two supermolecules work With that is, at least one dynamic metal-ligand effect and at least one dynamic hydrogen bond action can make resulting polymers material With level multiple performance abundant.Due to the self-repairability and recuperability of material, making for material can also be greatly reduced With cost, be conducive to the utilization rate and energy-saving and emission-reduction that improve resource.
Dynamic aggregation object material of the present invention is described further below with reference to some specific embodiments.Specifically Embodiment is that present invention be described in more detail, non-limiting protection scope of the present invention.
Embodiment 1
By commercial styrene-butadiene-styrene triblock copolymer (SBS), 4- pyridine methyl mercaptan, 2- (tertiary butyloxycarbonyl Base-amino) ethyl mercaptan and photoinitiator benzil dimethyl ketal (BDK) react in tetrahydrofuran, keep polybutadiene chain The molar ratio of alkenyl and 4- pyridine methyl mercaptan, 2- (t-butoxycarbonyl-amino) ethyl mercaptan and BDK is about 50:5:5:1 in section, Obtain the present invention modified SBS containing hydrogen bond group and ligand groups simultaneously.By commercially available SBS, 4- pyridine methyl mercaptan and light-initiated Agent BDK reacts in tetrahydrofuran, and the molar ratio of alkenyl and 4- pyridine methyl mercaptan and BDK is about in holding polybutadiene segments Silver nitrate solution is added in 50:5:1 after complete reaction, and keeping the molar ratio of silver ion and pyridyl group is about 1:2, obtains soft segment In only containing the modified SBS of ligand groups.Commercially available SBS, 2- (t-butoxycarbonyl-amino) ethyl mercaptan and photoinitiator b DK are existed It is reacted in tetrahydrofuran, keeps mole of alkenyl and 2- (t-butoxycarbonyl-amino) ethyl mercaptan and BDK in polybutadiene segments Than being about 50:5:1, soft segment is obtained only containing the modified SBS of hydrogen bond group.Contain hydrogen bond base while weighing obtained by 30 mass parts Group and the modified SBSs of ligand groups, the resulting modified SBS containing ligand groups of 20 mass parts, 20 mass parts it is resulting containing The modified SBS of hydrogen bond group and the unmodified SBS of 40 mass parts, addition silver nitrate solution, holding silver ion and pyridyl group rub You remove solvent after being sufficiently mixed than being about 1:2.Again by gained mixture and 25 mass parts of naphthenic oil, 17 mass of precipitated calcium carbonate Part, 25 mass parts of polystyrene, 8 mass parts of polyvinyl acetate, 0.8 mass parts of antioxidant 264,2 mass parts of AC foaming agent are mixed It closes uniformly, is squeezed out with screw extruder, be then kneaded slice on a mill, foam 8 minutes and form at 170 DEG C of 20MPa, Dehydration 2 hours are kept the temperature again, obtain dynamic aggregation object foamed product.
Performance: tensile strength 12.7MPa is broken rate elongation 910%；Density: 83kg/m3.This foamed material has very Good toughness and wearability is good, can be used for thermal insulation material processed.
Embodiment 2
Under the conditions of anhydrous and oxygen-free, ethyl isocyanate is reacted with the 1-APD of equimolar equivalent, is obtained Side group has the diol compound 2a of urea groups.By 3 molar equivalents [2,2':6', 2 "-terpyridyls] -5,5 "-dimethanol, 5 moles Equivalents of compound 2a is reacted with the polycaprolactone of the both ends carboxy blocking of 7 molar equivalents, in bicyclic ethyl carbodiimide (DCC) and Under the catalysis of 4-dimethylaminopyridine (DMAP), it is hydroxy-end capped containing terpyridyl framework counterpart group and side urea groups to obtain both ends Polyester segment.With benzoyl peroxide (BPO) for initiator, thioacetic acid is chain-transferring agent in 90-100 DEG C of initiation styrene Polymerization, keep initiator, monomer, chain-transferring agent molar ratio be 1:30:1, obtain the polystyrene of single-ended carboxy blocking.By 1 The resulting copolymer segment of molar equivalent and the single-ended carboxylic acid-terminated polystyrene mixing of 2 molar equivalents, are to urge with DCC and DMAP Agent after complete reaction, is added liquor zinci chloridi, keeps mole of zinc ion and ligand groups using methylene chloride as solvent Than being about 1:2, polystyrene-poly caprolactone of the invention-polystyrene three-stage polymer is obtained.
Performance: tensile strength 23.4MPa is broken rate elongation 1190%.This material has good toughness and intensity, can It is used to prepare and squeezes out profile, plate, blow molding or cast film, tablet, wire rod and cable cover.
Embodiment 3
Isocyanates ethyl acrylate is reacted in methylene chloride with n-propylamine, nafoxidine respectively, is kept different The molar ratio of cyanate and amino is 1:1, obtains acrylate monomer 3a, the 3b containing urea bond and the derivative containing urea bond.By etc. rub The acrylic acid and 6- hydroxymethyl quinoline of your equivalent react under the catalysis of DCC and DMAP, obtain the acrylate containing ligand groups Monomer 3c.First by 1 molar equivalent AIBN, 1 molar equivalent cumyl dithiobenzoic acid ester (dithiobenzoic acid 2- phenyl propyl- 2- Base ester) and 30 molar equivalent sodium p styrene sulfonates be dissolved in tetrahydrofuran, after sealing keep anhydrous and oxygen-free low pressure, in ultraviolet lamp Light initiation polymerization is carried out in room temperature under irradiation.After monomer reaction wait be added is complete, add containing 50 molar equivalent propylene Sour N-butyl, 10 molar equivalent 3a, 5 molar equivalent 3b and 10 molar equivalent 3c mixed solution the reaction was continued.After polymerization, It is poly- to obtain modified polyacrylate-of the polypropylene ester end for dithiobenzoic acid ester and containing side hydrogen bond group and side ligand groups Sodium styrene sulfonate two-part polymer.Under the conditions of anhydrous and oxygen-free, by the resulting dithiobenzoic acid ester sealing end of 1 molar equivalent Two-part copolymer, 20 molar equivalent tributylphosphines and 50 molar equivalent acrylic acid are dissolved in tetrahydrofuran, and 20 molar equivalents are added Sodium borohydride, at room temperature react 20 hours, product is deposited in methanol, obtain polypropylene ester end be carboxyl polystyrene Sodium sulfonate-polyacrylate two-part copolymer.Under nitrogen protection, 70 molar equivalent 2- bromine isobutyl acylbromides and 1 mole are worked as Amount beta-cyclodextrin is dissolved in methylene chloride, obtains 21 functions in 0 DEG C of reaction under the catalysis of 100 molar equivalent triethylamines and causes Agent.Using resulting 21 functional initiator of 1 molar equivalent as initiator, using 4- amylene-1-ol as chain-transferring agent, cause 315 Molar equivalent styrene polymerization is obtained with 21 hydroxy-end capped arm polystyrene.Resulting 21 arm of 1 molar equivalent is poly- Styrene and the resulting polyacrylate end of 21 molar equivalents are kayexalate-polypropylene ester two-part copolymerization of carboxyl Object is dissolved in methylene chloride, is catalyst with DCC and DMAP, appropriate cadmium chloride solution is added after fully reacting, obtains the present invention Dynamic aggregation object.
Performance: tensile strength 5.9MPa is broken rate elongation 1320%.This material can be used for preparing adhesive, block glue.
Embodiment 4
At -78 DEG C, 1 molar equivalent δ-valerolactone is instilled into the tetrahydrofuran containing 1 molar equivalent lithium diisopropylamine Solution after stirring, is added the toluene solution of the 3- propargyl bromide containing 1.1 molar equivalents, is reacted at -40 DEG C. After reaction, by crude product at 140 DEG C short-path distillation, obtain internal ester monomer 4a.Under the conditions of anhydrous and oxygen-free, successively to reaction vessel Bipyridine, cuprous bromide, ethyl-alpha-bromopropionate and styrene is added, holding molar ratio is 1:1:1:20, at 110 DEG C Under reacted.Tetrahydrofuran dissolution is added in resulting polystyrene after reaction, using Lithium Aluminium Hydride as reducing agent, at room temperature instead It answers 6 as a child to precipitate in methyl alcohol and obtained hydroxy-end capped polystyrene 4b.Under anhydrous condition, by resulting polystyrene 4b with The internal ester monomer 4a of 50 molar equivalents and the 6-caprolactone of 50 molar equivalents react at 110 DEG C under the catalysis of stannous octoate, Obtain two-part copolymer 4c.Under inert gas protection, 1 molar equivalent styrene-maleic anhydride copolymer and 6 moles are worked as Amount gained two-part copolymer 4c is dissolved in dimethylbenzene, is added with stirring catalyst paratoluenesulfonic acid sodium salt, is stirred to react in 105 DEG C, Obtain styrene-maleic anhydride copolymer grafting (modified poly ester-polystyrene) multisection type copolymer.Bromomethane is dissolved in four Hydrogen furans, is added excessive sodium azide, and reaction obtains compound triazonmethane.By resulting multisection type copolymer and nitrine first Alkane, 2,5- dehydration -1- nitrine -1- deoxy-D-glucose alcohol are dissolved in tetrahydrofuran, keep alkynyl and triazonmethane, 2,5- dehydration - The molar ratio of 1- nitrine -1- deoxy-D-glucose alcohol is that 5:3:2 reacts at 35 DEG C under the catalysis of cuprous iodide and pyridine Obtain the multisection type copolymer that polyester segments side group contains triazolyl and pendant hydroxyl group.By resulting multisection type polymer and isocyanic acid second Ester reaction, keeping the molar ratio of pendant hydroxyl group and isocyanate group is 1:1, under the catalysis of dibutyl tin dilaurate (DBTDL) Obtain the multisection type copolymer that polyester segments side group contains triazolyl and side carbamateyl.Gained copolymer is dissolved in containing suitable The solution for measuring copper chloride removes solvent to get dynamic aggregation object of the invention is arrived after being sufficiently stirred.
Performance: tensile strength 21.5MPa is broken rate elongation 630%.This dynamic aggregation object is with good toughness and certainly Prosthetic, and there is multiple transition temperature, it is used as the material simultaneously with selfreparing and shape memory function.
Embodiment 5
Under nitrogen protection, 10 molar equivalent ethylene glycol monoallyl ethers (average molecular weight about 500Da) and 1 mole are worked as It measures potassium methoxide to be blended, the epoxy prapanol of 70 molar equivalents is slowly added dropwise at 95 DEG C, obtaining end group is that hydroxyl has branched structure Olefinic monomer 5a.Under nitrogen protection, by end group be hydroxyl have branched structure olefinic monomer 5a with and hydroxyl equimolar work as The ethyl isocyanate of amount reacts in methylene chloride under the catalysis of DBTDL, obtains olefinic monomer 5b.By 5b and 1- mercapto glycerol Equimolar is blended, and 1wt% photoinitiator 2 is added, 2- dimethoxy -2- phenyl acetophenone, illumination 30 divides under 300W ultraviolet lamp Clock obtains diol compound 5c.By glycol 5c, 3 molar equivalent maleic acid hydrazides, 20 molar equivalent 1,6- obtained by 2 molar equivalents oneself Glycol, the mixing of 23 molar equivalent Adipoyl Chlorides, under the catalysis of triethylamine, obtaining both ends is that hydroxyl has cladodification side group and cladodification The modified poly ester of side group end amido-containing acid ester base.By 2 molar equivalent α-acetyl group-gamma-butyrolacton and 3 molar equivalent carbonic acid Guanidine is dissolved in ethyl alcohol, using triethylamine as catalyst, back flow reaction 16 hours.Insoluble matter is dispersed in water by filtering reacting solution, is used PH value is adjusted to 6-7 by hydrochloric acid, and after stirring 30 minutes, is filtered and cleaned, obtain compound 5d.200 mass parts are resulting Polyester, 2 mass parts 1,4- butanediols, 2 mass parts DBTDL, 1 mass parts organic silicone oil, 50 mass parts montmorillonites, 60 mass parts two Chloromethanes, 10 mass parts ends contain the polyethylene glycol and ferrous ion of 4,4'- benzidine -2,2'- disulfonic acid ligand The organic cage of the metal of formation, 35 mass parts water are sufficiently blended at 35 DEG C, are denoted as component A.By 200 mass parts toluene diisocynates Ester, 50 mass part compound 5d after abundant blending and stirring 40 hours, are cooled to 35 DEG C, are denoted as component B in 90 DEG C.By component A with Component B is mixed according to 1.2:1 mass ratio, is quickly stirred to bubble is generated, is then injected into mold rapidly, at room temperature instead It answers 30 minutes, then keeps the temperature 2 hours at 120 DEG C, obtain a kind of hard polyurethane ester group foamed material.
Performance: tensile strength 24MPa is broken rate elongation 1360%；Density: 103kg/m3.The product has excellent tough Property and good self-repairability, can be used for manufacturing thermal insulation material, insulating materials.
Embodiment 6
Under anhydrous condition, the toluene of reactor volume 14% is added in reactor and 1 atmospheric pressure of maintenance by ethylene full of 2L And the butadiene toluene solution (9wt%) of volume 0.95%.It is added in 40 DEG C and contains catalyst 6a, AliBu3[Ph3C][B (C6F5)4] 20 milliliters of catalyst solution, meanwhile, the butadiene first of reactor volume 6% is instilled with 6 milliliters of speed per minute Benzole soln (9wt%).After butadiene solution is all added dropwise, 20 milliliters of acidified methanols are rapidly added, and product is sunk in ethanol It forms sediment, obtains ethylene-butylene random copolymer.By resulting random copolymer and 2 mercapto ethanol and photoinitiator b DK four It is reacted in hydrogen furans, keeping the molar ratio of alkenyl and 2 mercapto ethanol and BDK is about 50:5:1, obtains the second with pendant hydroxyl group Alkene-butadiene random copolymer.4- (4- hydroxy phenyl) -2,3- benzodiazine -1- ketone and 4- nitro-chlorobenzene are dissolved in DMF, 1,2- dihydro -2- (4- nitrobenzophenone) -4- [4- (4-nitrophenoxy)-phenyl]-benzodiazine-is obtained under the catalysis of potassium carbonate 1- ketone.By gained compound under the catalysis of platinum-carbon, with one hydration hydrazine reaction, obtain synthesis polyarylamine one of monomer, 1,2- Dihydro -2- (4- aminophenyl) -4- [4- (4- amino-benzene oxygen)-phenyl]-benzodiazine -1- ketone.It, will under the conditions of anhydrous and oxygen-free The resulting polyarylamine monomer of 5 molar equivalents is sufficiently mixed with 6 molar equivalent terephthalic acid (TPA)s, is with triphenyl phosphite and pyridine Dehydrating agent reacts 3 hours using N-Methyl pyrrolidone and calcium chloride as medium at 100 DEG C.Reaction solution is through sedimentation, washing, purification Obtain the polyarylamine of carboxy blocking.The ethylene-butylene random copolymer and a certain amount of polyarylamine, 4- carboxyl of pendant hydroxyl group will be had Oxazolidone and carboxyl -2 4'-, 2 ': 6 ', 2 "-terpyridyls react under the catalysis of DCC and DMAP, keep hydroxyl, poly- virtue The molar ratio of amine, 4- carboxyl oxazolidone and carboxyl -2 4'-, 2 ': 6 ', 2 "-terpyridyls is 5:1:2:2, obtains ethylene-fourth Two olefinic random copolymers are grafted polyarylamine.By resulting polymers and suitable scandium chloride solution blending, except obtaining this hair after solvent Bright dynamic aggregation object.
Performance: tensile strength 2.9MPa is broken rate elongation 1440%.The product operating temperature range is wide, is especially suitable for work Make the big product of temperature range, such as the component in aerospace vehicle.
Embodiment 7
The poly- second that 20 molar equivalent 2,2-, bis- (allyloxymethyl)-n-butyl alcohol and 10 molar equivalent both ends alkenyls are blocked Glycol (average molecular weight is about 500) is under the catalysis of the Hoveyda-Grubbs generation catalyst of 0.3 molar equivalent in 80 DEG C The reaction of diene metathesis polymerization is carried out, side group is obtained and contains hydroxyl skeleton modified polyether containing double bonds.By gained polyethers and one Quantitative isoxazole -5- carboxylic acid reaction, keeping the molar ratio of hydroxyl and isoxazole -5- carboxylic acid in polyethers is 3:2, obtains side group and contains There are hydroxyl and isoxazolyl skeleton modified polyether containing double bonds.Using stannous octoate as catalyst, it is with resulting modified polyether Initiator causes the ring-opening polymerisation of levorotatory lactide in toluene in 100 DEG C, keeps hydroxyl and lactide monomer in modified polyether Molar ratio be 1:30, reaction obtain modified polyether grafting Poly L-lactic acid copolymer.By gained copolymer and a certain amount of 4- Methyl-triazolidine -3,5- diketone is dissolved in tetrahydrofuran, and double bond and 4- methyl-triazolidine -3,5- diketone in polyethers is kept to rub You sufficiently react after stirring than being 2:1, obtain the modified polyether grafting Poly L-lactic acid that polyether segment side group contains hydrogen bond group Gained copolymer is dissolved in the solution containing appropriate copper trifluoromethanesulfcomposite by copolymer, is sufficiently stirred, except after solvent up to this hair Bright dynamic aggregation object.
Performance: tensile strength 16.3MPa is broken rate elongation 1610%.The product has excellent toughness, good simultaneously Self-repairability and good biological degradability, also there is potential application value in terms of biomaterial.
Embodiment 8
Under nitrogen protection, by 5 molar equivalent bisphenol-As, 6 molar equivalent dichloro diphenyl sulfones are dissolved in N-Methyl pyrrolidone, Using toluene as dehydrating agent, Carbon Dioxide calcium is salt forming agent, is warming up to 140 DEG C and reacts 1 hour, the water that present invention generates is by toluene Take out of and separate, then heat to 160 DEG C react 4 hours, then to 180 DEG C react 4 hours.To after the reaction was completed, be cooled to room Temperature is added 2 molar equivalent para-aminophenol, toluene and potassium carbonate, repeats the above process.Crude product obtains both ends through ethanol precipitation For the polysulfones of amino.Under nitrogen protection, 11 molar equivalent 2- bromine isobutyl acylbromides and 5 molar equivalent ethylene glycol are dissolved in dichloromethane Alkane obtains dual initiator 1,2- bis- (bromine isobutyl acyl-oxygens) in 0 DEG C of reaction under the catalysis of 12 molar equivalent triethylamines.Anhydrous and oxygen-free Under the conditions of, 10 molar equivalent n-BMAs are dissolved in toluene, using cuprous bromide and PMDETA as catalyst, are rubbed with 1 That equivalent 1,2- bis- (bromine isobutyl acyl-oxygens) are initiator, are reacted 6 hours at 90 DEG C, and the poly- methyl of both ends bromine atom sealing end is obtained Acrylate segment.The resulting polymethacrylates segment of 1 molar equivalent and 4 molar equivalent 2 mercapto ethanols are dissolved in diformazan Base sulfoxide (DMSO) reacts in 40 DEG C under the catalysis of triethylenediamine, obtains the hydroxy-end capped polymethylacrylic acid in both ends N-butyl.By 5 molar equivalent 2,6- pyridine dimethanols, 5 molar equivalent 1H- imidazoles -4,5- dimethanols, 20 molar equivalent adipyls Chlorine is blended, and after sufficiently reacting under the catalysis of triethylamine, adds the hydroxy-end capped polymethylacrylic acid in 11 molar equivalent both ends N-butyl obtains skeleton and contains the hydroxy-end capped polyester of hydrogen bond group and ligand groups both ends.Under the conditions of anhydrous and oxygen-free, 3 are rubbed That resulting polyester of equivalent, 6 molar equivalent isophorone diisocyanate are reacted under the catalysis of DBTDL in 60 DEG C.Wait react After completely, the resulting polysulfones of 4 molar equivalents is added, the reaction was continued, obtains modified polymethyl acid-polysulfones multisection type copolymerization Object.The Vinalac 5920 that the resulting both ends of 1 molar equivalent are hydroxyl is dissolved in methylene chloride, with 2 molar equivalents Pyridine-3-carboxylic acid acyl chlorides reacts under the catalysis of triethylamine, obtains Vinalac 5920 of the both ends containing pyridyl group.By 80 Copolymer obtained by mass parts be sufficiently stirred with 20 Vinalac 5920s of the mass parts both ends containing pyridyl group swell in containing In Isosorbide-5-Nitrae-dioxane solvent of appropriate ruthenic chloride, it is placed in mold and is freezed at -80 DEG C completely, pumping is opened at -50 DEG C Pump maintains dry air pressure less than 50 μ atm24 hours, and obtained foamed material is placed in 20 DEG C of vacuum ovens to dry, pumping Whole solvents are taken to obtain corresponding foamed material.
Performance: 25 DEG C: tensile strength 21.5MPa, it is broken rate elongation 4.7%；75 DEG C: tensile strength 16.2MPa, fracture are prolonged Long rate 1280%；Density: 83kg/m3.The product is being higher than under room temperature with splendid toughness, can be used for preparation work temperature Degree is higher than the product of room temperature, is also used as filtering material or carrier uses, while can provide catalytic performance.
Embodiment 9
1 molar equivalent ethamine, 2.5 molar equivalent dithiothreitol (DTT)s (DTT), 6 molar equivalent γ-thiobutryolacatone are added The mixed solution of ethyl alcohol and 0.5M sodium bicarbonate (the two volume ratio is 1:1).Reaction is carried out in 50 DEG C under nitrogen protection, is obtained Compound 9a.8 4,4 '-difluoro benzophenones of molar equivalent and diphenyl sulphone (DPS) (the two mass ratio is about 1:4) are existed under nitrogen protection 180 DEG C are sufficiently blended, and the hydroquinone of 12 molar equivalents, the nothing of the Anhydrous potassium carbonate of 1 molar equivalent and 10 molar equivalents is added Aqueous sodium carbonate is to slowly warm up to 250 DEG C, is warming up to 290 DEG C after isothermal reaction 30 minutes again and reacts 1 hour, obtains hydroxy-end capped Polyether-ether-ketone segment.Under the conditions of anhydrous and oxygen-free, using cyclo-octene as monomer, using Grubbs bis- generations catalyst as catalyst, with Maleic acid is chain-transferring agent, and keeping the molar ratio of catalyst, chain-transferring agent and monomer is 1:4000:20000.It is with tetrahydrofuran Solvent reacts 2 hours at 40 DEG C.Polymerization reaction is quenched with vinyl ethyl ether, and precipitated product in methyl alcohol, obtains two end groups For the polycyclic octene of carboxyl.The resulting polyether-ether-ketone of 3 molar equivalents and the resulting polycyclic octene of 4 molar equivalents are dissolved in dichloromethane Alkane obtains polyether-ether-ketone-polycyclic octene multisection type copolymer using DCC and DMAP as catalyst.1 molar equivalent is resulting more The compound 9a of segmentation copolymer and 10 molar equivalents, 3 molar equivalent 2 pyrazinyl ethyl mercaptans, 2 molar equivalent pyridazine -3- mercaptan It is dissolved in toluene, the azo-bis-isobutyl cyanide (AIBN) of 0.1 molar equivalent is added, is reacted at 60 DEG C, after complete reaction, is added suitable The nitric acid gold solution of amount obtains dynamic aggregation object of the invention.Anti-aging agent is added into the resulting dynamic aggregation object of 100 mass parts D1 mass parts, 8 mass parts of 1 mass parts of accelerant CZ, 6 mass parts of paraffin oil and blowing agent H, are sufficiently mixed and are placed in mold, It foams 20 minutes at 125 DEG C, continues to keep the temperature 15 minutes at 150 DEG C after cooling and demolding, obtain corresponding foamed product.
Performance: tensile strength 3.7MPa is broken rate elongation 1450%；Density: 97kg/m3.The product has splendid tough Property, it can be used for preparing all kinds of daily necessities and product component.
Embodiment 10
1 molar equivalent (4- ethenylphenyl) methanol and 1.1 molar equivalent pyridines are dissolved in anhydrous methylene chloride, at 0 DEG C The bromo- 2- methyl propionyl bromide of 1 molar equivalent 2-, concentrate solution after reaction 3 hours are instilled, filtering is cleaned with silicagel column, obtains benzene second Vinyl monomer 10a.The acrylic acid of equimolar equivalent and 4- pyridinemethanol are reacted under the catalysis of DCC and DMAP, obtains containing and match The acrylate monomer 10b of body group.By the acrylic acid of equimolar equivalent and pyridazine -3- base methanol DCC and DMAP catalysis Lower reaction obtains the acrylate monomer 10c containing ligand groups.Using 1 molar equivalent AIBN as initiator, by 90 molar equivalent benzene The resulting phenylethylene macromonomer 10a copolymerization of ethylene, 10 molar equivalents, obtains polystyrene macromolecular initiator.It is anhydrous Under oxygen free condition, side group bromine atom and acrylic acid N-butyl, esters of acrylic acid in gained polystyrene macromolecular initiator are kept The molar ratio of monomer 3a, 10b, 10c are 1:10:10:5:5, under the catalysis of cuprous bromide and pentamethyl-diethylenetriamine, in first Reacted under the conditions of 80 DEG C in benzene, after complete reaction after, the solution for containing appropriate thorium nitrate is added, it is poly- to obtain dynamic of the invention Close object.
Performance: tensile strength 7.8MPa is broken rate elongation 1120%.The product has good toughness and self-repairability, It can be used for preparing durability adhesive etc..
Embodiment 11
Using 1 molar equivalent methyl tosylate as initiator, cause 20 molar equivalents 2- normal-butyl -2- oxazoline and The cation ring-opening polymerization of the 2- cyclobutenyl -2- oxazoline of 10 molar equivalents obtains part side group containing alkene using water as chain terminating agent Poly- (the 2- oxazoline) of base.Resulting poly- (2- oxazoline), 3- sulfydryl -1- propyl alcohol, photoinitiator b DK is anti-in tetrahydrofuran It answers, keeping the molar ratio of side alkenyl and 3- sulfydryl -1- propyl alcohol and BDK in poly- (2- oxazoline) segment is 5:5:1, obtains side group Poly- (2- oxazoline) containing hydroxyl.Under the conditions of anhydrous and oxygen-free, a certain amount of resulting modification poly- (2- oxazoline) is dissolved in pyridine, 2- bromine isobutyl acylbromide is slowly added dropwise under 0 DEG C of stirring, keeps mole of pendant hydroxyl group and 2- bromine isobutyl acylbromide in poly- (2- oxazoline) Than for 1:1, then it is warming up to room temperature reaction 24 hours, obtains side group brominated poly- (2- oxazoline).Under the conditions of anhydrous and oxygen-free, keep The molar ratio of bromine and styrene monomer is 1:20 in gained poly- (2- oxazoline), in cuprous bromide and pentamethyl-diethylenetriamine (PMDETA) under catalysis, in 100 DEG C of progress bulk polymerizations, crude product is dissolved in tetrahydrofuran after reaction, through alumina filter After be deposited in methanol, obtain poly- (2- oxazoline) grafted polystyrene.By 4- hydroxybutyl acrylate and equimolar equivalent third Olefin(e) acid ethyl ester is dissolved in methylene chloride, reacts under the catalysis of DBTDL, obtains the acrylic ester monomer of amido-containing acid ester base 11a.The hydroxy-ethyl acrylate of equimolar equivalent and amyl- 2, the 4- diene -5- acyl chlorides of ring are reacted under the catalysis of triethylamine, obtained Acrylic ester monomer 11b containing cyclopentadienyl group.Under the conditions of anhydrous and oxygen-free, gained poly- (2- oxazoline) is kept to be grafted polyphenyl second The molar ratio of bromine and n-butyl acrylate, acrylate monomer 11a, acrylate monomer 11b, acrylate monomer 10b in alkene Under the catalysis of cuprous bromide and PMDETA, it is polymerize in 60 DEG C for 1:10:15:10:5 using anisole as solvent, is reacted After acetone is added, methanol is deposited in after alumina filter, obtain poly- (2- oxazoline) grafting (polystyrene-modified polypropene Acid esters).Under the conditions of anhydrous and oxygen-free, keeping gained graft copolymer middle-end bromide and the molar ratio of methyl methacrylate is 1: 20, under the catalysis of cuprous bromide and PMDETA, in 70 DEG C of progress bulk polymerization polymerizations, crude product is dissolved in ether after reaction, It is deposited in methanol, obtains poly- (2- oxazoline) grafting (polystyrene-modified polyacrylate-polymethyl methacrylate).It takes Above-mentioned 00 mass parts of copolymer 1 and the alkyl-blocked polyethylene glycol oligomer of 100 mass parts and suitable nickel chloride solution fill Point be blended, except after solvent up to multisection type polymer polyethylene glycol oligomer swell gel.
Performance: tensile strength 1.3MPa is broken rate elongation 970%.The product has good toughness, can be used for applying Layer, adhesive.
Embodiment 12
6- amino -1- hexanol and methylchloroformate are reacted in methylene chloride, using anhydrous sodium bicarbonate as catalyst, control The molal quantity ratio of amino and methylchloroformate processed is 10:11, obtains compound 12a.Under nitrogen protection, by high molecular weight Buddhist nun Imperial 6 (average molecular weight about 50000), the n-Decylamine of equimolar equivalent and are placed in closed appearance with the diphenyl sulphone (DPS) of the quality such as nylon 6 It in device, is reacted at 235 DEG C, obtains single-ended amino-terminated low molecular weight nylon 6 (average molecular weight about 3000).By low-density Polyethylene (average molecular weight is about 50000) is dissolved in dimethylbenzene, the maleic anhydride of 100 molar equivalents is added, when solution temperature liter To after 130 DEG C, the initiator cumyl peroxide for being dissolved in dimethylbenzene is added, it is poly- that low-density is obtained after isothermal reaction 1 to 3 hour Vinyl Graft maleic anhydride.By the single-ended of the resulting grafted low density polyethylene maleic anhydride of 1 molar equivalent and 10 molar equivalents Amino-terminated low molecular weight nylon 6 melt blending at 200 DEG C is obtained low with 6 side chain of maleic anhydride side group and nylon Density polyethylene.The resulting low density polyethylene (LDPE) of 1 molar equivalent is dissolved by heating in dimethylbenzene, the 2 of 50 molar equivalents are added, Bis- pyridine amine of 2'- and appropriate paratoluenesulfonic acid sodium salt, are stirred to react in 130 DEG C, obtain with side ligand groups, side carboxyl and nylon The low density polyethylene (LDPE) of 6 side chains.Gained polyethylene is reacted under the catalysis of DCC and DMAP with compound 12a, is obtained with side The low density polyethylene (LDPE) of 6 side chain of ligand groups, side hydrogen bond group and nylon.By gained polyethylene and suitable trifluoromethanesulfonic acid europium Solution blending, except obtaining dynamic aggregation object of the invention after solvent.By the resulting modified low-density polyethylene of 100 mass parts, 20 The odium stearate of mass parts, the sodium bicarbonate of 5 mass parts and 0.1 mass parts vaseline oil are sufficiently blended, and extrusion molding obtains phase The foamed product answered.
Performance: tensile strength 4.1MPa is broken rate elongation 1120%；Density: 55kg/m3.The light good toughness of the product, can Using as toy packing material or organic electroluminescence emitting red light flexible material.
Embodiment 13
It is the L-PEI (average molecular weight is about 300Da) and 4 molar equivalents of amino by 5 molar equivalent both ends 2,2'- bipyridyl -4,4'- diacid chlorides react under the catalysis of triethylamine, and obtaining both ends is that amino contains framework counterpart and skeleton The L-PEI of hydrogen bond.Under nitrogen protection, by the resulting L-PEI of 1 molar equivalent and 8 molar equivalent L- Alanine-N- carboxyl-ring inner-acid anhydride is dissolved in dimethylformamide, and reacts at room temperature.After complete reaction, methanol extraction is used Product obtains polypeptide-polyethyleneimine-polypeptide three-stage polymer.By 100 mass parts resulting polymers and 3 mass parts stones Black alkene is blended, and suitable frerrous chloride and liquor zinci chloridi is added, and keeps the molar ratio of framework counterpart and iron ion, zinc ion to be 9:2:1.It is pressed and molded except blend is placed in mold after solvent, obtains dynamic aggregation Tetramune of the invention.
Performance: tensile strength 2.5MPa is broken rate elongation 970%.The product has good toughness, can be used as function painting Layer, adhesive, it may also be used for prepare the film with heat, electricity, stress sensing function.
Embodiment 14
Under the conditions of anhydrous and oxygen-free, ethyl isocyanate is reacted with the Isosorbide-5-Nitrae of equimolar equivalent-pentadiene -3- amine, obtains side Base band has the double olefin compound 14a of urea groups.By pure and mild 1H- benzimidazole -5- acyl chlorides the urging in triethylamine of 1,4- pentadiene -3- Change lower reaction, obtains the double olefin compound 14b that side group contains benzimidazolyl.By 1 molar equivalent 2,2'- bipyridyl -4,4'- Dimethanol reacts under catalysis of the DCC with DMAP with 2 molar equivalent acrylic acid, obtains ligand compound 14c.
Under the conditions of anhydrous and oxygen-free, by 1 molar equivalent 1,3- diaminourea and 2 molar equivalents 2,4-TDI is dissolved in ethyl alcohol, It reacts 16 hours at room temperature, obtains the triuret intermediate that both ends are isocyanate group.Intermediate obtained by 1 molar equivalent is dissolved in DMSO, the hydroxy-ethyl acrylate of 2 molar equivalents obtain the segment rich in hydrogen bond group that both ends are allyl in 60 DEG C of reactions 14d。
By the polyethylene glycol of 3 molar equivalent diallyls sealing end, 2 molar equivalent compound 14a, 1 molar equivalent compound 14b, 3 molar equivalent compound 14c, 4 molar equivalent segment 14d, 14 molar equivalents 1,2- dithioglycol mix in DMF, with Benzoin dimethylether is photoinitiator, in the UV lamp illumination reaction.After fully reacting, 2 molar equivalent methyl acrylates are added Sealing end, obtains the multisection type copolymer based on polythiaether.Before solvent, the 1- second containing aforementioned raw material gross weight phase homogenous quantities is added The carbon nanotube and suitable tetrafluoro boric acid of base -3- methyl imidazolium tetrafluoroborate and gross mass 4% are ferrous, after mixing Except solvent is to get the dynamic aggregation object based on polyethers/1- ethyl-3-methylimidazole tetrafluoroborate ionic gel.
The modulus of the ionic liquid gel of embodiment preparation can achieve 8 times in 59kPa, strain, and fracture strength exists 97kPa.This ionic liquid gel stability is good, mechanical property is strong, can be applied to dye solar cell, brake, super The fields such as capacitor, artificial-muscle and electrochromic device are also used as the sensing materials such as electricity, stress.
Embodiment 15
By 1 molar equivalent ethylene glycol, 100 molar equivalent ethylene oxide, 45 molar equivalents (S)-(oxiranylmethyl) ammonia Base t-butyl formate, 40 molar equivalent 3- [(acetparaminosalol) phenoxy group] -1,2 epoxy prapane, 15 molar equivalent 3- (epoxies Ethane -2- base) pyridine hybrid reaction preparation both ends are that pendant hydroxyl groups contain the poly- of carbamate groups, amide groups and pyridyl group Ether.By the resulting polyethers of 4 molar equivalents (being calculated as 100 mass parts), appropriate organic metal framework [Zn4O(BDC)3] (MOF-5, The molar ratio of middle zinc ion and pyridyl group be 1:6), 2 mass parts DBTDL, 1 mass parts organic silicone oil, 50 parts by mass Methylene chloride, 30 mass parts water are sufficiently blended at 35 DEG C, are denoted as component A.6 molar equivalent urea are instilled into 9 molar equivalent 4,4- diisocyanates Ester dicyclohexyl methyl hydride after abundant blending and stirring 24 hours, is cooled to 35 DEG C, is denoted as component B in 70 DEG C.By component A and component B Mixing is quickly stirred to bubble is generated, then free foaming, then gained foam is kept the temperature to dehydration at 120 DEG C, and hard section is obtained Dynamic aggregation object aperture flexible foam for contracting triuret soft segment based on polyethers.
Performance: tensile strength 2.1MPa is broken rate elongation 1380%；Density: 59kg/m3.The light softness of the product, can make For the filler of toy etc..
Embodiment 16
By the bromo- 1- propyl alcohol of 3- and excessive reaction of sodium azide, 3- azido -1- propyl alcohol is obtained.It will be obtained by 2 molar equivalents Azide and 1 molar equivalent 2, (acetenyl) pyridine of 6- bis- carry out nitrine-alkynes click-reaction, obtain compound 16a.
At 0 DEG C, 1 molar equivalent 16a and 2 molar equivalent pyridines are dissolved in anhydrous tetrahydro furan, by 2 molar equivalent 2- bromines third Acylbromide is slowly dropped into solution under nitrogen protection.Solution temperature is warmed to room temperature, after reaction 16 hours, crosses and filters out precipitating.It will filter After liquid concentration removes solvent, is recrystallized in ethyl alcohol, obtain intermediate product 16b.By 1 molar equivalent 16b and 3 molar equivalent sodium iodides Be dissolved in acetone respectively, and two solution be mixed and stirred for rapidly, after complete reaction, filter precipitating, remove solvent, by crude product with Methylene chloride is that washing lotion recrystallizes in methyl alcohol after the removal of impurities of short silicagel column, obtains bifunctional initiator 16c.Under oxygen free condition, Using Sodium Thiosulfate as catalyst, sodium bicarbonate is auxiliary agent, and resulting 16c is initiator, carries out vinyl chloride monomer in water Polymerization, keep monomer, catalyst, auxiliary agent, initiator molar ratio be 100:2:2.2:1, with Celvol 540 (0.293g/mL) It is stabilizer with Methocel K100 (0.11g/mL), is reacted at 25 DEG C, obtain the polychlorostyrene second that both ends are blocked with iodine atom Alkene.Abovementioned steps are repeated, 16b are replaced with 2 bromopropionic acid methyl esters, reaction obtains the single-ended polyvinyl chloride for iodine atom sealing end.By institute Single-ended polyvinyl chloride and 4- acetylamino benzenethiol, 4- sulfydryl benzyl alcohol for iodine atom sealing end to be dissolved in hexamethylene anti-at 60 DEG C It answers 12 hours, keeping the molar ratio of side group chlorine atom and 4- acetylamino benzenethiol, 4- sulfydryl benzyl alcohol is about 20:1:1, is obtained The modified polyvinyl chloride of amide groups containing side and pendant hydroxyl group.Gained modified polyvinyl chloride and suitable Isonicotinic acid are reacted, protected The molar ratio for holding pendant hydroxyl group and carboxyl is that 1:1 obtains side group and contain ligand groups and hydrogen simultaneously under the catalysis of DCC and DMAP The single-ended polyvinyl chloride for iodine atom sealing end of key group.
Under the conditions of anhydrous and oxygen-free, the polyvinyl chloride that the resulting both ends of 1 molar equivalent are blocked with iodine atom, 2 molar equivalents Copper, 6 molar equivalent three (2- dimethylaminoethyl) amine, 30 molar equivalent methyl methacrylates are dissolved in DMSO, stir in 25 DEG C Reaction is added tetrahydrofuran, precipitating and water/methanol mixed solution, it is poly- to obtain polymethyl methacrylate-after complete reaction Vinyl chloride-polymethyl methacrylate three-stage copolymer.Under the conditions of anhydrous and oxygen-free, 1 molar equivalent three-stage of gained is copolymerized Object, 2 molar equivalent sodium sulfites, 2.2 molar equivalent sodium bicarbonates and 10 molar equivalent allyl hydroxyethyl ethers are dissolved in DMSO, It is reacted 4 hours at 70 DEG C, concentrated reaction solution is precipitated in methyl alcohol, is obtained with hydroxy-end capped three-stage copolymer.It repeats The step replaces three-stage copolymer with the single-ended polyvinyl chloride by iodine atom sealing end, and reaction obtains the poly- of one-ended hydroxy sealing end Vinyl chloride.2,4-TDI of polyvinyl chloride and equimolar equivalent that gained one-ended hydroxy blocks is dissolved in methylene chloride, in TDBDL Catalysis under, reaction obtain one end with isocyanate-terminated polyvinyl chloride.By one end obtained by 3 molar equivalents with isocyanates Base sealing end polyvinyl chloride and 2 molar equivalent, four arm polymer be dissolved in methylene chloride, under the catalysis of TDBDL, reaction obtain with The multisection type polymer of polyvinyl chloride or polymethyl methacrylate sealing end.By resulting 100 mass parts of dynamic aggregation object, epoxy 70 mass parts of soybean oil, 50 mass parts of tricresyl phosphate, 20 mass parts of polyvinylpyrrolidone microballoon and appropriate fluoroform Sulfonic acid ferrous iron is uniformly mixed, and is placed in mold and is kept the temperature 30 minutes in 180 DEG C, obtains corresponding dynamic aggregation object plasticizer after cooling Swell gel.
Performance: tensile strength 27MPa is broken rate elongation 830%.The product also has one in addition to good intensity, toughness Fixed hygroscopicity can be used as Osteological material use.
Embodiment 17
By allyl hydroxyethyl ether and 5- chloromethyl -2- oxazolidone, 1:1 is dissolved in toluene in molar ratio, is to urge with potassium carbonate Agent, using tetrabutylammonium bromide as consisting of phase-transferring agent, obtaining one end is the compound 17a that allyl one end is oxazolidone.By 1, 4- diiodo-benzene alkynyl, then with 4- iodoaniline, obtain the amino-terminated conjugation segment 17b in both ends.1 molar equivalent is conjugated "-terpyridyl -4- formic acid carries out acylation reaction, obtains both ends with terpyridyl base for segment 17b and 2 molar equivalents 2,2':6', 2 The conjugation segment 17c of sealing end.
The octamethylcy-clotetrasiloxane of 1 molar equivalent and 1 molar equivalent tetramethyl-ring tetrasiloxane are blended in acetic acid, It is reacted under the sulphuric acid catalysis of 0.02 molar equivalent in 130 DEG C.Sufficiently after reaction, reaction solution is stood and is cooled down, chlorination is used Sodium water solution and calcium carbonate aqueous solution are washed till neutrality, obtain both ends after sloughing solvent and low-boiling-point substance with hydroxy-end capped hydrogeneous poly- silicon Oxygen alkane.By the hydroxy-end capped hydrogen containing siloxane in 1 molar equivalent both ends and 2 molar equivalent 2,2':6', 2 "-terpyridyl -4- first Acid reacts under the catalysis of DCC and DMAP, obtains the hydrogen containing siloxane blocked with terpyridyl base.It is catalysis with chloroplatinic acid Agent exists the polysiloxanes containing 3 molar equivalent silicon hydrogen with 2 molar equivalent compound 17a and 1 molar equivalent 4-vinylpridine It is reacted 3 hours at 90 DEG C in cyclohexanone, obtains one end with what terpyridyl base blocked and contain side ligand groups and side hydrogen bond base The polysiloxanes of group.By 100 mass parts of gained polysiloxanes, conjugation segment 17c30 mass parts, 20 mass parts of hollow glass micro-ball And suitable zinc chloride be sufficiently blended after inject mold, up to accordingly containing the foamed product of tiny balloon after compression molding.
Performance: tensile strength 1.7MPa is broken rate elongation 1780%；Density: 148kg/m3.The toughness of products is good, simultaneously With certain hygroscopicity, thermal insulation material can be used as.
Embodiment 18
Cyanuric acid and the chloro- 1- hexene of 6- keep molar ratio 4:1, are dissolved in anhydrous dimethyl sulphoxide, under potassium carbonate catalysis It is stirred to react at 80 DEG C 15 hours, obtains the olefinic monomer 18a of hydrogen bonds group.10 molar equivalent compound 18a are added Reaction vessel is cooled to 5 DEG C by toluene, and 13 molar equivalent cyclopentadiene are added dropwise in low temperature.It is warming up to back after being added dropwise Stream temperature continues to be stirred to react, and obtains compound 18b.Replace compound 18a as raw material weight using 4- methyl -5- vinylthiazole This multiple step, obtains compound 18c.Under the conditions of anhydrous and oxygen-free, by 1 molar equivalent initiator 2, the double tertiary fourths of 6- diisopropyl imines Oxygroup molybdenum is dissolved in toluene, and 5 molar equivalent regulator trimethyl phosphorus and 30 molar equivalent crystalline polymer monomer norbornene are added, After reaction 1 hour, the glassy polymers monomer methyl tetracyclododecen of 20 molar equivalents is added.After the reaction was continued 1 hour, add Enter 600 molar equivalent rubbery feel polymer monomer 5- n-hexyl -2- norbornene, 200 molar equivalent monomer 18b and 100 moles Equivalent monomer 18c.Finally, 0.5 molar equivalent coupling agent m-terephthal aldehyde is added, after fully reacting, product is sunk in methyl alcohol Shallow lake obtains five block copolymers.Resulting five block copolymer is dissolved in hexamethylene, using platinum as catalyst, is carried out at 100 DEG C Catalytic hydrogenation, obtaining end section be crystalline state-glassy state di-block copolymer interlude is rubbery state random copolymer based on hydrogen Change multiterminal section-mono- interlude multisection type polymer of polynorbornene.Resulting polymers and suitable scandium chloride solution are total to It is mixed, except being pressed and molded after solvent, obtain dynamic aggregation Tetramune of the invention.
Performance: tensile strength 13.8MPa is broken rate elongation 2230%.The product has splendid toughness, and resilience is good, Set resistant is small, can carry out large range of stretching, can be used for preparing conveyor components etc..
Embodiment 19
With 1 molar equivalent benzoyl peroxide (BPO) for initiator, 1 molar equivalent thioacetic acid is chain-transferring agent 90 DEG C cause 30 molar equivalent n-BMAs polymerization, obtain the Vinalac 5920 of single-ended carboxy blocking.? Under nitrogen protection, amination dimethyl siloxane 19a (average molecular weight about 10000Da, x:y are about 3:2) is added in urea, is protected The molar ratio for holding urea and amino is 7:10, after 160 DEG C, heat preservation about 1 hour are to slowly warm up under stirring, are down to room temperature, obtain Part amino is converted into the modified dimethyl polysiloxane of imidazoline ketone group.By resulting dimethyl silicone polymer in condensing agent 2- In the presence of ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline with 4- pyridazine carboxylic acid carry out acylation reaction, keep side amino with The molar ratio of carboxyl is 3:2, obtains modified dimethyl polysiloxane 19b.
By resulting dimethyl silicone polymer 19b in condensing agent 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline In the presence of with the Vinalac 5920 of single-ended carboxy blocking carry out acylation reaction, keep the molar ratio of side amino and carboxyl For 1:1, modified dimethyl polysiloxane grafting Vinalac 5920 is obtained.Resulting polymers and moderate amount of sulfuric acid copper are molten Liquid is blended, except obtaining dynamic aggregation object of the invention after solvent.
Performance: tensile strength 1.5MPa is broken rate elongation 1490%.The product has splendid toughness, can be applied to electricity The seal protection waterproof of the component of sub- product, such as the waterproof seal plug in handset earphone hole；Also act as graphene, carbon nanotube Wait the substrate of electricity, heat, strain gauge.
Embodiment 20
With 1 molar equivalent 4,4'- azo bis- (4- cyano amylalcohols) is that initiator draws using 4- amylene-1-ol as chain-transferring agent 20 molar equivalent methyl methacrylate polymerizations are sent out, the hydroxy-end capped polymethyl methacrylate in both ends is obtained.Under anhydrous condition, Using the resulting polymethyl methacrylate of 1 molar equivalent as macromolecular dual initiator, using stannous octoate as catalyst, causes 50 and rub Ring-opening polymerisation of the 6-caprolactone of that equivalent α-chloro- 6-caprolactone and 50 molar equivalents at 110 DEG C, obtaining both ends is hydroxyl Three-stage copolymer.By polystyrene that gained three-stage copolymer and one end are hydroxyl, 1:1 is blended in molar ratio, in DCC and Reaction obtains polystyrene-modified poly ester-polymethyl methacrylate-five sections of modified poly ester-polystyrene under the catalysis of DMAP Formula copolymer.(acetenyl) pyridine of 2,6- bis- of 1 molar equivalent triazonmethane and 10 molar equivalents is carried out nitrine-alkynes to click instead It answers, obtains compound 20a.By the bromo- 1- propyl alcohol of 3- and excessive reaction of sodium azide, 3- azido -1- propyl alcohol is obtained.By gained Azide and compound 20a carry out nitrine-alkynes click-reaction, obtain compound 20b.
The copolymer that polyester segment side group contains chlorine atom is dissolved in dimethylformamide, 2 molar equivalent of chlorine atom is added Sodium azide, reaction obtain the copolymer that side group contains azido.Gained side group is contained to the copolymer of azido, 4- (2- Propine amino) t-butyl perbenzoate and compound 20a be dissolved in tetrahydrofuran, keep azido, 4- (2- propine amino) benzoic acid The molar ratio of the tert-butyl ester and compound 20a are that 5:4:1 reacts at 35 DEG C and gathered under the catalysis of cuprous iodide and pyridine Ester segment contains the five-part form polymer of side hydrogen bond group and side ligand groups.The polycaprolactone of single-ended carboxy blocking is (average Molecular weight about 1000Da) and compound 20b reacted under the catalysis of DCC and DMAP, obtain single-ended gathering in oneself for ligand groups Ester.By gained five-part form polymer, it is single-ended be sufficiently blended for the polycaprolactone of ligand groups and suitable liquor zinci chloridi, protect Hold the ligand groups in five-part form polymer, it is single-ended be the polycaprolactone of ligand groups, the molar ratio of zinc ion is 3:1:2.It removes Solvent is placed in mold, is pressed and molded to get dynamic aggregation Tetramune of the invention is arrived.
Performance: tensile strength 27.6MPa is broken rate elongation 1320%.This material, which removes, has splendid toughness, due to it With multiple transition temperature, it is alternatively arranged as shape-memory material.
Embodiment 21
By 1 molar equivalent 2- vinyl terephthalic acid (TPA) and 2.1 molar equivalent triphenylphosphines be dissolved in anhydrous pyridine obtain it is molten Liquid A.2.1 molar equivalent 4- metoxyphenols and 2.2 molar equivalent carbon trichlorides are dissolved in anhydrous pyridine and obtain solution B.It will be molten Liquid B is slowly dropped into solution A, obtains liquid crystal monomer vinyl terephthalic acid (TPA) di-p-methoxy phenyl ester (MPCS) in 60 DEG C of reactions. The ethyl isocyanate of equimolar equivalent and N- (2- ethoxy) acrylamide are dissolved in chloroform, system is reacted under the catalysis of TDBDL Obtain the acrylamide monomers 21a containing carbamate groups.By the tetrazoleacetic acid of equimolar equivalent and N- (2- ethoxy) Acrylamide reacts under the catalysis of DCC and DMAP is made the acrylamide monomers 21b containing ligand groups.In nitrogen protection Under, 13 molar equivalent 2- bromine isobutyl acylbromides and 3 molar equivalent pentaerythrites are dissolved in methylene chloride, in 15 molar equivalent triethylamines Catalysis under in 0 DEG C of reaction obtain tetrafunctional initiator.Under the conditions of anhydrous and oxygen-free, the resulting tetrafunctional initiator of 1 molar equivalent, 2 molar equivalent cuprous bromides, 2 molar equivalent PMDETA, 400 molar equivalent acrylamides, 200 molar equivalent monomer 21a, 40 rub Your equivalent monomer 21b sequentially adds reaction vessel, and reaction obtains the four arm polymer based on polyacrylamide at 80 DEG C.It is anhydrous Under oxygen free condition, by 4 molar equivalent stannous chlorides, 4 molar equivalent PMDETA and 200 molar equivalent monomer MPCS are placed in reaction and hold Device is added the chlorobenzene solution containing modified polyacrylamide obtained by 1 molar equivalent, reacts and obtained with side chain type liquid crystal at 110 DEG C Macromolecule is the polymer with four arms asteroids for holding section.By resulting polymer and etc. quality 1- butyl -3- methyl Limidazolium hexafluorophosphate, suitable trifluoromethanesulfonic acid europium solution are sufficiently blended, except obtaining corresponding ionic gel after solvent.
The modulus of the ionic liquid gel of embodiment preparation can achieve 19 times in 27kPa, strain, and fracture strength exists 62kPa, the product not only have good conductivity and mechanical strength, and can be in very wide temperature range and electrochemical window Interior stabilization can be made into a kind of ideal electrolyte.
Embodiment 22
Under nitrogen protection, 2 molar equivalent methyl p-hydroxybenzoates are dissolved in tetrahydrofuran, catalyst of triethylamine is added After be uniformly mixed.In 0 to the 5 DEG C of tetrahydrofuran solution of instillation containing 1 molar equivalent paraphthaloyl chloride, keeps and to react 10 small Shi Hou obtains liquid crystal hard section 22a.Under the conditions of 90 DEG C of anhydrous no air, limonene oxide and catalyst 22b are dissolved in toluene, Keeping the molar ratio of limonene oxide and catalyst is 50:1, and 10bar carbon dioxide, fully reacting are passed through into reaction vessel Afterwards, crude product with methanol is precipitated to obtain poly- limonene carbonic ester segment.By the poly- limonene carbonic ester segment of gained and 1,3- third Glycol is dissolved in toluene, and catalyst 1,5,7- tri- azabicyclic [4.4.0] decyl- 5- alkene is added, reacts 3 hours, obtains at 80 DEG C Average molecular weight is about 2000 both ends with hydroxy-end capped poly- limonene carbonic ester segment 22c.Under nitrogen protection, by 1 mole The poly- limonene carbonic ester 22c of equivalent of hydroxyl groups sealing end and the liquid crystal hard section 22a of 1.1 molar equivalents are blended and carry out ester exchange reaction simultaneously Methanol is distilled out, obtains the poly- limonene carbonic ester multisection type polymer of liquid crystal-after complete reaction.
By the poly- limonene carbonic ester multisection type polymer of liquid crystal-and 15 molar equivalents containing 100 molar equivalent side alkenyls 4- methyl -4H-3- sulfydryl -1,2,4- triazole, 25 molar equivalent 3- sulfydryl -1,2,4- triazoles, 60 molar equivalent 3- sulfydryls N-butyl propionate is dissolved in tetrahydrofuran and is sufficiently blended, and reacts, obtains in the presence of photoinitiator b DK and under the irradiation of ultraviolet lamp Poly- limonene carbonic ester side group contains the polymer there are two types of triazol radical.By the poly- limonene carbonic acid of the resulting liquid crystal-of 70 mass parts The fibre of polyester-polystyrene copolymer, suitable nickel chloride solution and 5 mass parts obtained in ester, 30 mass parts embodiments 2 The nanocrystalline blending of dimension element obtains the dynamic aggregation object alloy product with inierpeneirating network structure except forming after solvent.
Performance: tensile strength 13.4MPa is broken rate elongation 1730%.The product primary raw material is renewable raw materials, can be wide It is general to be used as non-returnable container film, everyday articles etc..
Embodiment 23
Under the conditions of anhydrous and oxygen-free, by the isocyanates ethyl acrylate of ethyl mercaptan and equimolar equivalent under triethylamine catalysis It is reacted in methylene chloride, obtains the acrylate monomer 23a containing thio carbamate groups.By acrylic acid and imidazo [1,2-A] pyridin-3-yl methanol reacts under the catalysis of DCC and DMAP, obtains acrylate monomer 23b.Anhydrous and oxygen-free condition Under, solvent methyl phenyl ethers anisole, 1 molar equivalent paratoluensulfonyl chloride, 2 molar equivalent PMDTA and 30 are successively added into reaction vessel to rub You are added 1 molar equivalent stannous chloride, react 12 hours at 60 DEG C equivalent methyl tert-butyl acrylate after mixing, then The mixture of 50 molar equivalent n-butyl acrylates and 50 molar equivalent monomer 23a and 30 molar equivalent monomer 23b is added, it will Reaction system is maintained at reacted 12 hours at 60 DEG C after, add 15 molar equivalent styrene monomers, be warming up to 80 DEG C reaction 48 Hour.After reaction, reaction solution is blended with tetrahydrofuran, is first filtered with neutral alumina column, then tetrahydrofuran shower. After filtrate is collected and is concentrated, is obtained polyacrylate side group in triplicate with methanol extraction and contain hydrogen bond group and ligand base Polymethyl tert-butyl acrylate-polyacrylate copolymer-polystyrene three-stage that group's polystyrene end is blocked with chlorine atom Copolymer.The three-stage copolymer of the resulting chlorine atom sealing end of 1 molar equivalent is dissolved in dimethylformamide, 2 moles is added and works as The sodium azide of amount, reaction obtain the three-stage copolymer of azido sealing end.By three sections of the sealing end of azido obtained by 2 molar equivalents Formula copolymer and 1 molar equivalent 1,5- hexadiine are dissolved in tetrahydrofuran, anti-at 35 DEG C under the catalysis of cuprous iodide and pyridine It should obtain polymethyl tert-butyl acrylate-polyacrylate copolymer-polystyrene-polypropylene acid ester copolymer-poly- methyl-prop Enoic acid ter-butyl ester five-part form copolymer.The resulting five-part form copolymer of 1 molar equivalent is dissolved in 1,2- dichloroethanes, 30 is added and rubs That equivalent trifluoroacetic acid, is stirred to react at 60 DEG C.Completely to the hydrolysis of polymethyl tert-butyl acrylate segment, it is total to obtain five-part form Polymers.Gained copolymer is blended with suitable lanthanum nitrate hexahydrate, except being pressed and molded after solvent, obtains dynamic aggregation of the invention Tetramune.
Performance: tensile strength 6.9MPa is broken rate elongation 1420%.The product has splendid toughness, while having shape Shape memory function is suitable for preparing each type component.
Embodiment 24
The furans of equimolar equivalent and maleimide are reacted in methylene chloride, furans-maleimide is obtained and adds Close object.Under the conditions of anhydrous and oxygen-free, a certain amount of monomer furans-maleimide amine adduct and cyclo-octene are mixed, control two The ratio of person's molal quantity is about 1:10, using Grubbs bis- generations catalyst as catalyst, using maleic acid as chain-transferring agent, keeps catalysis The molar ratio of agent, chain-transferring agent and monomer is 1:4000:20000.Using tetrahydrofuran as solvent, reacted 2 hours at 40 DEG C.With Polymerization reaction is quenched in vinyl ethyl ether, and precipitated product in methyl alcohol, and obtaining two end groups is that carboxyl skeleton contains maleimide Modification polycyclic octene.Polycyclic octene obtained by 5 molar equivalents and 4 molar equivalent 1,8- benzodiazine -2,7- diaminos are being condensed Acylation reaction is carried out in the presence of agent 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline, two end groups is obtained and contains for carboxyl The modification polycyclic octene of framework counterpart group and hydrogen bond group.It is to cause with 1 molar equivalent 4,4'- azo bis- (4- cyano amylalcohols) Agent causes 20 molar equivalent styrene polymerizations, obtains the hydroxy-end capped polyphenyl second in both ends using 4- amylene-1-ol as chain-transferring agent Alkene.The resulting modified polycyclic octene of 2 molar equivalents and the resulting polystyrene of 3 molar equivalents are dissolved in methylene chloride, with DCC and DMAP is catalyst, obtains multisection type copolymer.By 1 molar equivalent both ends be amino polyisobutene (average molecular weight is about 2000) it is dissolved in methylene chloride, is reacted under the catalysis of pyridine with the chloroacetic chloride of 2 molar equivalents, the poly- of both ends amide-containing is obtained Isobutene hydrogen bond connects auxiliary agent.The polyisobutene (average molecular weight about 2000) that 1 molar equivalent both ends are hydroxyl is dissolved in dichloro Methane reacts under the catalysis of triethylamine with the pyridine-3-carboxylic acid acyl chlorides of 2 molar equivalents, it is different containing gathering for pyridyl group to obtain both ends Butylene.By above-mentioned 00 mass parts of multisection type copolymer 1,30 mass of polystyrene-polybutadiene-thermoplastic polystyrene elastomer Part, polyisobutene hydrogen bond connect 20 mass parts of auxiliary agent, both ends 20 mass parts of polyisobutene and suitable chlorination containing pyridyl group Platinum solution blending, except obtaining dynamic aggregation object alloy after solvent.Gained alloy is calculated as 100 mass parts, adds azo diformazan 5.5 mass parts of amide are placed in mold after 1 mass parts of lead sulfate tribasic are sufficiently mixed, and are plasticized under 170 DEG C of 3.5MPa pressure Foaming, is heat-treated 8 minutes at 100 DEG C, cooling and demolding obtains corresponding foamed product later.
Performance: tensile strength 3.6MPa is broken rate elongation 920%；Density: 105kg/m3.The product has good tough Property, can be used for preparation can be used as device outer case, electrical component, auto parts and components and sealing element.
Embodiment 25
Polycyclic octene obtained in embodiment 9 is subjected to hydrogenation reaction, obtains the polyethylene that both ends are carboxyl.By 1 mole The resulting polyethylene of equivalent and 2 molar equivalent 2,2':6', 2 "-terpyridyl -4'- amine is in condensing agent 2- ethyoxyl -1- ethoxy carbon Acylation reaction is carried out in the presence of acyl group -1,2- dihydroquinoline, obtains the polyethylene that both ends are terpyridine ligand group.It is anhydrous Under oxygen free condition, 1 molar equivalent azo dimethyl N-2- hydroxyl butyl propionamide is dissolved in toluene, the vinegar of 105 molar equivalents is added Vinyl acetate.It reacts 16 hours at a reflux temperature, obtains the polyvinyl acetate that both ends are hydroxyl.It will be obtained by 1 molar equivalent "-terpyridyl -4- formic acid is blended, anti-under the catalysis of DCC and DMAP for polyvinyl acetate and 2 molar equivalents 2,2':6', 2 It answers, obtains the polyvinyl acetate that both ends are terpyridine ligand group.Gained polyvinyl acetate is dissolved in tetrahydrofuran, is added Enter the methanol solution containing potassium hydroxide, react at room temperature, obtains vinylacetate-vinylalcohol random copolymer.By gained Vinylacetate-vinylalcohol random copolymer and 2-[4-morpholinodithio acetic acid, imidazoles -4- acetic acid be blended, keep polymer side hydroxyl The molar ratio of base and 2-[4-morpholinodithio acetic acid, imidazoles -4- acetic acid is 3:1:2, reacts and is contained under the catalysis of DCC and DMAP The modified polyvinyl acetate of side ligand groups and side hydrogen bond group.By the resulting polyethylene of 5 molar equivalents with contain 10 moles The cobaltous dichloride solution of equivalent cobaltous dichloride is sufficiently blended, and adds 5 molar equivalent modified polyvinyl acetates and suitable Cobaltous dichloride solution (being 1:6 with the molar ratio of thiazolyl) is sufficiently mixed except obtaining dynamic aggregation object of the invention after solvent.
Performance: tensile strength 5.8MPa is broken rate elongation 870%.The toughness of products is splendid, can be used as all kinds of daily necessities with And self-repairability plug and sealing element etc..
Embodiment 26
The 2- ethylbutanoyl chlorine of 4,4 '-di-2-ethylhexylphosphine oxides (phenyl isocyanate) and equimolar equivalent is dissolved in dimethylbenzene, slowly Instill the xylene solution containing 1.5 molar equivalent triethylamines.After reacting 4 hours at a reflux temperature, -15 DEG C are cooled to, filter Insoluble matter is removed, except the crude product for obtaining the 26a containing compound after solvent.Under the conditions of anhydrous and oxygen-free, by 1 molar equivalent aniline and containing 1 The crude product of molar equivalent compound 26a is dissolved in toluene, reacts 2 hours at 4 DEG C, the centre insoluble in toluene is obtained by filtration Body.The N- aminoethyl piperazine of 1 molar equivalent is dissolved in DMF, is reacted 1 hour at 20 DEG C, with water sedimentation, obtains production not soluble in water Object 26b.Compound 26b is dissolved in acetone, and the equivalent containing equimolar intermediate 26a crude product reaction, after twenty minutes, use ring Hexane precipitation obtains intermediate.Under nitrogen protection, the N- aminoethyl piperazine of intermediate and equimolar equivalent is dissolved in anhydrous DMF reacts 1 hour at 20 DEG C, with water sedimentation, obtains product 26c not soluble in water.
Under the catalysis of DBTDL, by hydroxy-end capped low point of methyl diphenylene diisocyanate and equimolar equivalent one end Son amount poly-β-hybroxybutyric acid is dissolved in DMF and reacts to obtain with isocyanate-terminated polyester.To the isocyanide containing 1 molar equivalent 1 molar equivalent compound 26c is added in the polyester liquid of perester radical sealing end, after complete reaction, obtains two sections based on polyester Formula polymer.Resulting polymers and maleic anhydride are dissolved in chlorobenzene, make the initial mass volumetric concentration 3% of maleic anhydride.? 130 DEG C of addition benzoyl peroxides make the initial concentration 0.2% of benzoyl peroxide, are kept for thermotonus 6 hours, are obtained Modified poly-β-hybroxybutyric acid grafted maleic anhydride.Under inert gas protection, resulting modified poly-β-hybroxybutyric acid is connect Branch maleic anhydride, 3- amino -1,2,4- triazole, 5- amino oxazole are dissolved in dimethylbenzene, keep maleic anhydride side group, 3- amino - 1,2,4- triazole, 5- amino oxazole molar ratio be 3:2:1, be stirred to react in 80 DEG C, obtain modified poly-β-hybroxybutyric acid Multisection type polyester in segment side group containing amide-triazol radical, oxazolyl.It can by 00 mass parts of multisection type copolymer 1, biology Degradation polyester PHB100 mass parts, 50 mass parts of biodegradable polyesters tiny balloon and proper amount of nano grade ferroso-ferric oxide are total Mold is injected after mixed, is pressed and molded to get the dynamic aggregation object foamed product based on biodegradable polyesters containing tiny balloon.
Performance: tensile strength 27MPa is broken rate elongation 1450%；Density: 165kg/m3.The product has splendid tough Property and good biodegradability, can be used for manufacturing the magnetic lightweight toy of tool.
Embodiment 27
Under the conditions of anhydrous and oxygen-free, using 1 molar equivalent cumyl dithiobenzoic acid ester as chain-transferring agent, cause at 140 DEG C 30 molar equivalent styrene polymerizations.After reaction 6 hours, precipitates, and filtered with ethanol washing, put down in frost anhydrous methanol The right about 20 polystyrene macromolecular chain-transferring agent of homopolymerization.By the resulting polystyrene macromolecular chain tra nsfer of 1 molar equivalent Agent, 150 molar equivalent acrylonitrile, 1 molar equivalent AIBN are dissolved in DMF, react 48 hours at 65 DEG C, and obtaining polyacrylonitrile end is The polystyrene-polypropylene nitrile two-part copolymer of dithiobenzoic acid ester.It, will be obtained by 1 molar equivalent under the conditions of anhydrous and oxygen-free Dithiobenzoic acid ester sealing end two-part copolymer, 20 molar equivalent tributylphosphines and 50 molar equivalent acrylic acid are dissolved in four The sodium borohydride of 20 molar equivalents is added in hydrogen furans, reacts 20 hours at room temperature, product is deposited in methanol, obtains poly- third Alkene nitrile end is polystyrene-polypropylene nitrile-two-part copolymer of carboxyl.Two-part copolymer and 1 obtained by 2 molar equivalents is rubbed Your equivalent both ends are that the polystyrene of hydroxyl is dissolved in methylene chloride, using DCC and DMAP as catalyst, obtain polystyrene-poly third Alkene nitrile-polystyrene-polypropylene nitrile-polystyrene five-part form copolymer.By five-part form copolymer, triazonmethane, 2,5- dehydration- 1- nitrine -1- deoxy-D-glucose alcohol, zinc chloride are dissolved in DMF, keep itrile group, triazonmethane, 2,5- dehydration -1- in copolymer Nitrine -1- deoxy-D-glucose alcohol, zinc chloride molar ratio be 10:2:1:15, by reaction solution at room temperature ultrasound 5 minutes enable Each component is warming up to 125 DEG C and is stirred to react after being sufficiently mixed, convert tetrazole base and pendant hydroxyl group for part itrile group.It will be resulting Side group contains the copolymer of hydroxyl under the catalysis of DBTDL and ethyl isocyanate reaction, keeps pendant hydroxyl group and ethyl isocyanate Molar ratio is 1:1, obtains the five-part form copolymer that side group contains tetrazole base and carbamate groups.Gained five-part form is copolymerized 100 mass parts of object with it is abundant containing hydrogen bond group and 60 mass parts of the modified SBS of ligand groups simultaneously obtained in embodiment 1 It is blended, suitable silver nitrate solution is added, except obtaining polystyrene, modified polyacrylonitrile, three groups of modified polybutadiene after solvent Divide polymer alloy.
Performance: tensile strength 19.3MPa is broken rate elongation 1270%.This elastomeric material have splendid toughness and Self-repairability can be used for preparing profile, plate, film, the tablet etc. with self-repair function.
Embodiment 28
Using 1 molar equivalent methyl tosylate as initiator, cause 20 molar equivalents 2- oxazolyl phenyl quinoline sun from Sub- ring-opening polymerisation obtains poly- (the 2- oxazolyl phenyl quinoline) that one end is hydroxyl using water as chain terminating agent.By 10 molar equivalent 1,6- oneself Hexanediol diglycidyl ether, 2 molar equivalent 2,2'- bipyridyl -4,4'- dimethanols, 7 molar equivalent polyethylene glycol oligomers (divide 500) son amount is about sufficiently mixed with the catalyst boron trifluoride ether of polyethylene glycol quality 1%, react at 80 DEG C, obtain side Base is hydroxyl both ends with the epoxy polymer of epoxy radicals end-blocking.By hydroxy-end capped poly- of resulting epoxy polymer and gained one end (2- oxazolyl phenyl quinoline) is sufficiently mixed, and keeping molar ratio is about 1:2, in 160 DEG C under the catalysis of catalyst boron trifluoride ether Lower reaction 2 hours obtains poly- (2- oxazolyl phenyl quinoline)-polyethers-poly- (2- oxazolyl phenyl quinoline) copolymerization of the polyethers section containing pendant hydroxyl group Object.Gained copolymer and 4'- methyl -2,2'- bipyridyl -4- formic acid, imidazoles -4- acetic acid are blended, side hydroxyl in copolymer is kept The molar ratio of base and 4'- methyl -2,2'- bipyridyl -4- formic acid, imidazoles -4- acetic acid is 3:1:2, under the catalysis of DCC and DMAP Reaction obtains poly- (2- oxazolyl phenyl quinoline)-polyethers-poly- (2- oxazolyl phenyl of the polyethers section containing side bipyridyl and side imidazolyl Quinoline) copolymer.Take above-mentioned 00 mass parts of gained copolymer 1, alkyl-blocked 100 mass parts of polyethylene glycol oligomer and appropriate Copper-bath be blended, except dynamic aggregation object polyethylene glycol oligomer swell gel can be obtained after solvent.
Performance: tensile strength 790kPa is broken rate elongation 780%.The gel can use making coatings, adhesive.
Embodiment 29
Using 1 molar equivalent hydroxyethyl methacrylate as initiator, using boron fluoride as catalyst, cause 100 molar equivalents Ethylene oxide, 50 molar equivalents (S)-(oxiranylmethyl) t-butyl carbamate cation ring-opening polymerization, preparation one end are Alkenyl one end is the modified polyether that the side group of hydroxyl contains carbamate groups.The resulting modified polyether of 1 molar equivalent and 1 are rubbed You are dissolved in methylene chloride by the polystyrene (see embodiment 2) of the single-ended carboxy blocking of equivalent, using DCC and DMAP as catalyst, obtain Polyethers end is polystyrene-modified polyether two-part copolymer of alkenyl.Under the conditions of anhydrous and oxygen-free, sequentially added to reaction vessel PMDETA, cuprous bromide, ethyl-alpha-bromopropionate and methyl methacrylate, holding molar ratio are
1:1:1:20 is reacted at 70 DEG C.Tetrahydrofuran is added in resulting polymethyl methacrylate after reaction Dissolution, using Lithium Aluminium Hydride as reducing agent, reacting 6 at room temperature, as a child precipitating obtained the hydroxy-end capped poly- methyl in one end in methyl alcohol Methyl acrylate.Under anhydrous condition, by the 6-caprolactone of resulting polymethyl methacrylate and 50 molar equivalents and 10 moles The internal ester monomer 4a of equivalent reacts at 110 DEG C under the catalysis of stannous octoate, obtains polyester end and is contained with hydroxy-end capped side group The polyester of acetylene bond-polymethyl methacrylate two-part copolymer.Resulting two-part copolymer and triazonmethane are dissolved in four Hydrogen furans, keeping the molar ratio of alkynyl and azido is that 1:1 reacts at 35 DEG C under the catalysis of cuprous iodide and pyridine Polyester-polymethyl methacrylate the two-part for containing triazolyl to polymethyl methacrylate end with bromine atom sealing end side group is total Polymers.Under nitrogen protection, 1 molar equivalent modified poly ester-polymethyl methacrylate two-part copolymer and 10 moles are worked as Amount thiocarbamide, which is dissolved in DMF and is heated to 100 DEG C, to be kept for 24 hours.Sodium hydrate aqueous solution of the addition containing 10 molar equivalents, and It is kept for 24 hours at 110 DEG C.Sulfuric acid is instilled again, and the reaction was continued 5 hours, and obtaining polymethyl methacrylate end is sulfydryl sealing end Two-part copolymer.Polystyrene-modified polyether two-part copolymer obtained by 1 molar equivalent and 1 molar equivalent is resulting poly- Methyl methacrylate-modified poly ester two-part copolymer and 2% photoinitiator b DK are dissolved in tetrahydrofuran, and reaction obtains Polystyrene-modified polyether-polymethyl methacrylate-modified poly ester four-part form copolymer.By gained copolymer and appropriate three Fluorine methanesulfonic acid ferrous solution is blended, and except mold is packed into after solvent, mold is placed in autoclave, is passed through dry supersaturation two Carbonoxide, decompression makes its expanded foamed molding after pressurization 12 minutes, and corresponding foamed product is obtained after demoulding.
Performance: tensile strength 13.2MPa is broken rate elongation 1310%；Density: 91kg/m3.The product has splendid tough Property and shape memory function, can be used for manufacture have shape memory function thermal insulation material, insulating materials.
Embodiment 30
Under anhydrous and oxygen-free stirring, by 1 molar equivalent 1, the bromo- 2- propyl alcohol of 3- bis- is instilled at -78 DEG C works as containing 1 mole The tetrahydrofuran solution of bis- (cyclopentadiene) nickel is measured, and is stirred to react at 0 DEG C, compound 30a is obtained after removal of impurities.By acrylic acid It is reacted under the catalysis of DCC and DMAP with the resulting compound 30a of equimolar equivalent, obtains acrylic ester monomer 30b.? Under anhydrous and oxygen-free stirring, by 1 molar equivalent 1,3- dibromopropane is instilled at -78 DEG C contains the bis- (rings penta 2 of 1 molar equivalent Alkene) nickel tetrahydrofuran solution, and be stirred to react at 0 DEG C, compound 30c obtained after removal of impurities.By 3- aminomethylpiperidine and wait Molar equivalent isocyanates ethyl acrylate is dissolved in methylene chloride, and reaction obtains acrylic ester monomer 30d at room temperature.By propylene Acyl chlorides and equimolar equivalent 4- hydroxy-2-pyrrolidinone are dissolved in methylene chloride, and reaction obtains acrylic acid under the catalysis of triethylamine Esters monomer 30e.
Under the conditions of anhydrous and oxygen-free, keep initiator 2 bromopropionic acid methyl esters and n-butyl acrylate, acrylate monomer 30b, The molar ratio of acrylate monomer 30d is 1:10:15:15, under the catalysis of cuprous bromide and PMDETA, is polymerize in 70 DEG C, instead It should obtain modified polyacrylate.Under the conditions of anhydrous and oxygen-free, bromine and styrene monomer in gained modified polyacrylate are kept Molar ratio is 1:20, under the catalysis of cuprous bromide and PMDETA, is polymerize in 100 DEG C, it is poly- that reaction obtains modified polyacrylate- Styrene.Copolymer obtained by 1 molar equivalent and 25 molar equivalent 5- amino -1- amylalcohols are dissolved in DMSO, react 30 points in 40 DEG C Clock.Reaction solution is instilled into methylene chloride, with hydrochloric acid, sodium bicarbonate solution and water washing, is gathered after anhydrous magnesium sulfate is dry Styrene end is the copolymer of hydroxyl.Gained copolymer is reacted under catalysis of the DCC with DMAP with acrylic acid, obtains acrylic acid Macro molecules monomer.Under the conditions of anhydrous and oxygen-free, initiator 2 bromopropionic acid methyl esters and n-butyl acrylate, resulting propylene are kept Esters of gallic acid macromonomer, acrylate monomer 30b, acrylate monomer 30e molar ratio be 1:40:10:15:15, in bromine Change under cuprous and PMDETA catalysis, polymerize in 70 DEG C, reaction obtains modified polyacrylate grafting, and (polystyrene-modification is poly- Acrylate).100 mass parts resulting polymers and the dicyclopentadienyl nickel monomer 30c of 5 mass parts are subjected to two cyclopentadienyls in 20 DEG C in pyridine The ring-opening polymerisation of nickel compound obtains dynamic aggregation object of the invention.
Performance: tensile strength 6.7MPa is broken rate elongation 1460%.The product has splendid toughness, can be used for making It makes adhesive, block glue.
Embodiment 31
It is the polystyrene-polypropylene of dithiobenzoic acid ester by 1 molar equivalent polyacrylonitrile end under the conditions of anhydrous and oxygen-free Nitrile two-part copolymer (see embodiment 27), 20 molar equivalent tributylphosphines and 50 molar equivalent hydroxy-ethyl acrylates are dissolved in tetrahydro The sodium borohydride of 20 molar equivalents is added in furans, reacts 20 hours at room temperature, product is deposited in methanol, obtains polypropylene Nitrile end is the polystyrene-polypropylene nitrile two-part copolymer of hydroxyl.It is thio with three using di-tert-butyl peroxide as initiator Carbonic ester is chain-transferring agent, and the polymerization of isoprene is carried out at 125 DEG C, obtains polyisoprene Macromolecular chain transfer agent.With AIBN is initiator, and using resulting polyisoprene as chain-transferring agent, using Isosorbide-5-Nitrae-dioxane as solvent, benzene is carried out at 60 DEG C Vinyl polymerization obtains polyisoprene end with the polyisoprene-polystrene two-part copolymer of carboxy blocking.By acrylonitrile End is polystyrene-polypropylene nitrile two-part copolymer and the equimolar equivalent polyisoprene end of hydroxyl with the poly- of carboxy blocking Isoprene-polystyrene two-part copolymer is dissolved in methylene chloride, using DCC and DMAP as catalyst, obtains polystyrene-poly Isoprene-polyacrylonitrile-polystyrene four-part form polymer.Resulting four-part form polymer and compound 9a and light are drawn Hair agent benzil dimethyl ketal (BDK) reacts in tetrahydrofuran, keeps alkenyl and compound 9a in polyisoprene segments And the molar ratio of BDK is about 50:5:1, obtains the four-part form polymer in polyisoprene segments containing side amide groups.By four Segmentation copolymer, triazonmethane, zinc chloride are dissolved in DMF, keep the molar ratio of itrile group in copolymer, triazonmethane, zinc chloride to be Reaction solution is warming up to 125 DEG C after ultrasound enables each component be sufficiently mixed in 5 minutes at room temperature and is stirred to react, by part by 10:2:15 Itrile group is converted into tetrazole base, obtains the four-part form dynamic aggregation object containing side hydrogen bond group and side ligand groups.By gained four Segmentation copolymer is blended with appropriate copper chloride solution, except obtaining dynamic aggregation object of the invention after solvent.
Performance: tensile strength 23.5MPa is broken rate elongation 640%.This material has good toughness and selfreparing Property, can be used for preparing has self-repair function profile, plate, film, tablet etc..
Embodiment 32
By polyethers end be alkenyl side group contain carbamate groups polystyrene-modified polyether two-part copolymer (see Embodiment 29) it is reacted under collective effect of the BDK with ultraviolet light with the thioacetic acid of equimolar equivalent, carboxylic is converted by alkenyl Base.By the polyester end of the polystyrene of resulting carboxy blocking-modified polyether two-part copolymer and equimolar equivalent with hydroxyl Sealing end side group contains polyester-polymethyl methacrylate two-part copolymer (see embodiment 29) of triazolyl in DCC and DMAP Catalysis under react, obtain polystyrene-modified polyether-polyester-polymethacrylate copolymer.By gained copolymer and fit Trifluoromethanesulfonic acid cerium solution blending is measured, except obtaining dynamic aggregation object of the invention after solvent.
Performance: tensile strength 16.7MPa is broken rate elongation 880%.This material, which removes, has good toughness and selfreparing Property, also there is shape memory function, can be used for preparing has multi-functional components.
Embodiment 33
Using 1 molar equivalent p-methyl benzenesulfonic acid propynyl ester as initiator, 1 molar equivalent hexynic acid is terminator, carries out 10 and rubs The cation ring-opening polymerization of your equivalent 2- (3- ethylheptyl) -2- oxazoline, obtains poly- (the 2- oxazole that both ends are blocked with alkynyl Quinoline).In anhydrous conditions, by 1 molar equivalent compound 33a and 1 molar equivalent 2,6- diisopropyl phenylisocyanate is dissolved in four Hydrogen furans reacts 16 hours at room temperature, obtains the UPy derivative that one end is alkenyl.The UPy that resulting one end is alkenyl is spread out Biology reacts under collective effect of the BDK with ultraviolet light with the thioacetic acid of equimolar equivalent respectively, converts carboxyl for alkenyl. By the 6- heptynoic acid of equimolar equivalent and propargylamine in condensing agent 2- ethyoxyl -1- ethoxy carbonic acyl radical -1,2- dihydroquinoline In the presence of carry out acylation reaction, obtain both ends be alkynyl compound 33b.
Take poly- (the 2- oxazoline) and 9 molar equivalents of 5 molar equivalent compound 33b, 5 molar equivalent both ends propinyls sealing end 11 polyethylene glycol of both ends azido sealing end carry out nitrine-alkyne reaction, obtain modified polyether that both ends blocks with alkynyl/gather (2- oxazoline) copolymer.By one end be polystyrene (see embodiment 4) that hydroxy-end capped one end is bromine atom with it is excessive Reaction of sodium azide, obtaining one end is the polystyrene that hydroxyl one end is azido.Take polystyrene and 1 obtained by 2 molar equivalents The resulting modified polyether of molar equivalent/poly- (2- oxazoline) copolymer carries out nitrine-alkynes click-reaction, obtains both ends and is sealed with hydroxyl Polystyrene-the modified polyether at end/poly- (2- oxazoline) copolymer-polystyrene three-stage copolymer.By resulting three-stage Copolymer reacts under the catalysis of DCC and DMAP with the UPy derivative that one end is carboxyl, and it is poly- to obtain UPy- polystyrene-modification Ether/poly- (2- oxazoline) copolymer-polystyrene-UPy copolymer.Gained copolymer is blended with suitable copper chloride solution, Except solvent obtains dynamic aggregation object of the invention.
Performance: tensile strength 18.7MPa is broken rate elongation 1450%.This material has splendid toughness, can be used for making Standby all kinds of articles for daily use.
Embodiment 34
With 1 molar equivalent initiator 2,2- dibutyl -2- tin -1,3- cyclic heptane dioxide is initiator and 30 molar equivalents Levorotatory lactide is dissolved in toluene, obtains the hydroxy-end capped Poly L-lactic acid in both ends in 100 DEG C of reactions.2- chlorine cyclohexanone is dissolved in two Chloromethanes is added metachloroperbenzoic acid (mCPBA), and keeping the molar ratio of 2- chlorine cyclohexanone and mCPBA is 10:12, reacts To the chloro- 6-caprolactone of α-.Under anhydrous condition, chloro- 60 molar equivalent of 6-caprolactone of α-is dissolved in 60 molar equivalent of 6-caprolactone Toluene, using stannous octoate as catalyst, in 20 DEG C under hydroxy-end capped Poly L-lactic acid causes at 1 molar equivalent initiator both ends Reaction is obtained polyester side group and contains chlorine atom and be total to hydroxy-end capped modified poly ester-Poly L-lactic acid-modified poly ester three-stage Polymers.The three-stage copolymer that resulting polyester segment side group contains chlorine atom is dissolved in dimethylformamide (DMF), was added The sodium azide of amount, reaction obtain the copolymer that side group contains azido.Side group is contained to copolymer, the 2- alkynes third of azido Base-N- butyl carbamate, 2- ethynyl pyridine are dissolved in tetrahydrofuran, keep azido, 2- propargyl-N- butylamino first Acid esters, 2- ethynyl pyridine molar ratio be 10:7:3 react and gathered at 35 DEG C under the catalysis of cuprous iodide and pyridine Ester segment contains the three-stage copolymer of side carbamateyl, side ligand groups.Gained copolymer is dissolved in containing appropriate sulphur In the solution of sour copper, be sufficiently stirred, except after solvent up to dynamic copolymers of the invention.
Performance: tensile strength 15.5MPa is broken rate elongation 1520%.The product have excellent toughness and it is good from Prosthetic, the product also have good biological degradability, also there is potential application value in terms of biomaterial.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks Domain is included within the scope of the present invention.

Claims (15)

1. a kind of physics split-phase supermolecule dynamic aggregation object, which is characterized in that the dynamic aggregation object contains while having hard The block polymer molecules of section and soft segment；It is mutually mixed between each hard section of the block polymer molecules or respectively independent or both Part be mutually mixed not only part form crystalline phase or the phase incompatible with soft segment or existing crystalline phase each independently but also have with it is soft The incompatible phase of section is physical crosslinking point to form the split-phase based on hard section, to form the split-phase physical crosslinking based on hard section or hand over Connection and polymerization, each soft segment of the block polymer molecules are unformed shape；At least one of the block polymer molecules Containing at least one ligand groups in soft segment, the effect of dynamic metal-ligand is formed with metal center；Moreover, described is embedding Contain hydrogen bond group at least one while that there is hydrogen bond donor and hydrogen bond receptor at least one soft segment of section polymer molecule, It is used to form dynamic hydrogen bond action.
2. a kind of physics split-phase supermolecule dynamic aggregation object according to claim 1, which is characterized in that dynamic described in wherein One of structure described in block polymer molecules with hard section A and soft segment B while contained by state polymer are various under having Kind appoints several combinations:
Wherein, formula (1A) is linear chain structure, and n is hard section-soft segment alternate cells quantity, is more than or equal to 0；
Formula (1B) is linear chain structure, and both ends section is hard section, and n is hard section-soft segment alternate cells quantity, is more than or equal to 0；
Formula (1C) is linear chain structure, and both ends section is soft segment, and n is hard section-soft segment alternate cells quantity, is more than or equal to 0；
Formula (1D) is branched structure, and x is the quantity for the hard section branch chain element being connected on soft segment B；N is hard section-soft segment alternating The quantity of unit is more than or equal to 0；Y is to be connected to hard section on soft segment B-soft segment branch chain element quantity；X, y is more than or equal to 0, and the sum of x, y are more than or equal to 3；
Formula (1E) is branched structure, and x is the quantity for the hard section branch chain element being connected on soft segment B；N is hard section-soft segment alternating The quantity of unit is more than or equal to 0；Y is to be connected to hard section on soft segment B-soft segment alternately and be to hold the branched chain of section with hard section The quantity of unit；X, y is more than or equal to 0, and the sum of x, y are more than or equal to 3；
Formula (1F) is branched structure, and x is the quantity for the soft segment branch chain element being connected on hard section A；N is soft segment-hard section alternating The quantity of unit is more than or equal to 0；Y is to be connected to soft segment on hard section A-hard section branch chain element quantity；X, y is more than or equal to 0, and the sum of x, y are more than or equal to 3；
Formula (1G) is branched structure, and x is the quantity for the soft segment branch chain element being connected on hard section A；N is soft segment-hard section alternating The quantity of unit is more than or equal to 0；Y is to be connected to soft segment on hard section A-hard section alternately and be to hold the branched chain of section with soft segment The quantity of unit；X, y is more than or equal to 0, and the sum of x, y are more than or equal to 3；
Formula (1H) is cyclic structure, and n is hard section-soft segment alternate cells quantity, is more than or equal to 1.
3. a kind of physics split-phase supermolecule dynamic aggregation object according to claim 1, which is characterized in that dynamic described in wherein One of structure described in block polymer molecules with hard section A and soft segment B while contained by state polymer are various under having Kind appoints several combinations:
Wherein, formula (1A) is linear chain structure, and n is hard section-soft segment alternate cells quantity, is more than or equal to 1；
Formula (1B) is linear chain structure, and both ends section is hard section, and n is hard section-soft segment alternate cells quantity, is more than or equal to 0；
Formula (1C) is linear chain structure, and both ends section is soft segment, and n is hard section-soft segment alternate cells quantity, is more than or equal to 1；
Formula (1D) is branched structure, and x is the quantity for the hard section branch chain element being connected on soft segment B；N is hard section-soft segment alternating The quantity of unit is more than or equal to 0；Y is to be connected to hard section on soft segment B-soft segment branch chain element quantity；X, y is more than or equal to 0, and the sum of x, y are more than or equal to 3；
Formula (1E) is branched structure, and x is the quantity for the hard section branch chain element being connected on soft segment B；N is hard section-soft segment alternating The quantity of unit is more than or equal to 0；Y is to be connected to hard section on soft segment B-soft segment alternately and be to hold the branched chain of section with hard section The quantity of unit；X, y is more than or equal to 0, and the sum of x, y are more than or equal to 3；
Formula (1F) is branched structure, and x is the quantity for the soft segment branch chain element being connected on hard section A；N is soft segment-hard section alternating The quantity of unit is more than or equal to 0；Y is to be connected to soft segment on hard section A-hard section branch chain element quantity；X is more than or equal to 0, y More than or equal to 1, and the sum of x, y are more than or equal to 3；
Formula (1G) is branched structure, and x is the quantity for the soft segment branch chain element being connected on hard section A；N is soft segment-hard section alternating The quantity of unit is more than or equal to 0；Y is to be connected to soft segment on hard section A-hard section alternately and be to hold the branched chain of section with soft segment The quantity of unit；X is more than or equal to 0, y and is more than or equal to 1, and the sum of x, y are more than or equal to 3；
Formula (1H) is cyclic structure, and n is hard section-soft segment alternate cells quantity, is more than or equal to 2.
4. a kind of physics split-phase supermolecule dynamic aggregation object according to claim 1, which is characterized in that the block is poly- The main chain of the soft segment of adduct molecule is selected from carbon-chain structure, carbon heterochain structure, carbon chain structure, element chain structure, element heterochain The miscellaneous element chain structure of structure, carbon；The main chain of the hard section of the block polymer molecules be selected from carbon-chain structure, carbon heterochain structure, Carbon chain structure, element chain structure, element heterochain structure, the miscellaneous element chain structure of carbon.
5. a kind of physics split-phase supermolecule dynamic aggregation object according to claim 1, which is characterized in that the block is poly- The glass transition temperature of each soft segment in adduct molecule is not higher than 25 DEG C.
6. a kind of physics split-phase supermolecule dynamic aggregation object according to claim 1, which is characterized in that the block is poly- The hard section of adduct molecule is selected from the amorphous polymer chains section with high glass-transition temperature, the polymerization rich in hydrogen bond group Object segment or group, the polymer segment rich in crystalline phase or group, the polymer segment rich in conjugated structure.
7. a kind of physics split-phase supermolecule dynamic aggregation object according to claim 1, which is characterized in that the block is poly- The dynamic metal-ligand effect that ligand groups and metal center in adduct molecule soft segment are formed is containing knot shown in the following general formula One or more combination in structure:
Wherein, X is coordination atom, and M is metal center,It is cyclopentadiene ligand, X is connected table with singly-bound in formula Show that the coordination atom belongs to the same ligand groups, when containing two or more coordination atoms in a ligand groups, X It is identical atom or different atoms, X is atom, cation or anion.
8. a kind of physics split-phase supermolecule dynamic aggregation object according to claim 7, which is characterized in that matching described in wherein Position atom X is selected from boron, nitrogen, oxygen, sulphur, phosphorus, silicon, arsenic, selenium, tellurium；The metal center M, which is selected from, can form dynamic metal- The ionic species of metal of ligand effect, compound, chelate and combinations thereof.
9. a kind of physics split-phase supermolecule dynamic aggregation object according to claim 1, which is characterized in that the block is poly- Contain at least one of following constituent in the soft segment of adduct molecule:
10. a kind of physics split-phase dynamic aggregation object according to claim 1, which is characterized in that the block polymer At least to connect containing six the flexible of skeletal atom between dynamic ligand groups in molecule soft segment and dynamic hydrogen bond group It connects base or segment is connected.
11. a kind of physics split-phase supermolecule dynamic aggregation object according to claim 1, which is characterized in that the block Also match containing structural metal-ligand effect or structural hydrogen bond action or simultaneously containing structural metal-in polymer molecule Body effect and structural hydrogen bond action.
12. a kind of physics split-phase supermolecule dynamic aggregation object described in any claim in -11 according to claim 1, special Sign is that the dynamic aggregation object has following any character: ordinary solid, elastomer, gel, foam.
13. a kind of physics split-phase supermolecule dynamic aggregation object described in any claim in -11 according to claim 1, special Sign is, constitutes the recipe ingredient of the dynamic aggregation object and further includes following any or appoint and several additive or can be used Object: other polymers, auxiliary agent, filler, sweller.
14. a kind of physics split-phase supermolecule dynamic aggregation object according to claim 13, which is characterized in that described other Polymer is selected from following any or appoints several: natural polymer, synthetic macromolecular compound；The auxiliary agent is selected from It is any below or appoint it is several: catalyst, initiator, antioxidant, light stabilizer, heat stabilizer, dispersing agent, emulsifier, resistance Fire agent, toughener, coupling agent, solvent, lubricant, release agent, plasticizer, thickener, thixotropic agent, levelling agent, colorant, fluorescence Brightening agent, delustering agent, antistatic agent, dehydrating agent, biocide mildewcide, foaming agent, blowing promotor, nucleating agent, rheological agent；Described Filler is selected from following any or appoints several: inorganic non-metallic filler, metal packing, organic filler；The sweller is selected from It is any below or appoint it is several: water, organic solvent, ionic liquid, oligomer, plasticizer.
15. a kind of physics split-phase supermolecule dynamic aggregation object described in any claim in -11,14 according to claim 1, It is characterized in that, the dynamic aggregation object is applied to following material or product: self-repairability coating, is reviewed one's lessons by oneself at self-repairability plate Renaturation sealing material, self-repairability block glue, self-repairability conducting resinl, toughness material, tough elastomer material, flexible material, Thermal insulation material, shape-memory material, force snesor, toy, toy filler.
CN201710522414.4A 2017-06-30 2017-06-30 A kind of physics split-phase supermolecule dynamic aggregation object and its application Pending CN109206625A (en)

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CN112724410A (en) * 2020-12-29 2021-04-30 南京邮电大学 Bipyridine-based metal coordination self-repairing material and preparation method thereof
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CN112973459B (en) * 2021-03-09 2022-08-05 万华化学集团股份有限公司 Fluoropolymer hollow fiber porous membrane and preparation method thereof
CN113789100A (en) * 2021-07-19 2021-12-14 河南省路嘉路桥股份有限公司 Waterproof material for concrete matrix and preparation method thereof
CN113522357A (en) * 2021-08-20 2021-10-22 山东瑞博龙化工科技股份有限公司 Ionic liquid catalyst and preparation method and application thereof
CN115161011A (en) * 2022-07-20 2022-10-11 上海电力大学 High-stability perovskite phase CsPbI 3 Nanocrystalline and preparation method thereof
CN115161011B (en) * 2022-07-20 2024-03-01 上海电力大学 High-stability perovskite phase CsPbI 3 Nanocrystalline and preparation method thereof
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