CN109207110A - A kind of hybrid cross-linked dynamic aggregation object - Google Patents

A kind of hybrid cross-linked dynamic aggregation object Download PDF

Info

Publication number
CN109207110A
CN109207110A CN201710524150.6A CN201710524150A CN109207110A CN 109207110 A CN109207110 A CN 109207110A CN 201710524150 A CN201710524150 A CN 201710524150A CN 109207110 A CN109207110 A CN 109207110A
Authority
CN
China
Prior art keywords
cross
linking
dynamic aggregation
aggregation object
linked
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710524150.6A
Other languages
Chinese (zh)
Other versions
CN109207110B (en
Inventor
不公告发明人
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiamen Iron Cloth Mstar Technology Ltd
Original Assignee
Weng Qiumei
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Weng Qiumei filed Critical Weng Qiumei
Priority to CN201710524150.6A priority Critical patent/CN109207110B/en
Publication of CN109207110A publication Critical patent/CN109207110A/en
Application granted granted Critical
Publication of CN109207110B publication Critical patent/CN109207110B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/6266—Polymers of amides or imides from alpha-beta ethylenically unsaturated carboxylic acids
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/06—Flexible foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08K3/16—Halogen-containing compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Abstract

The invention discloses a kind of hybrid cross-linked dynamic aggregation object, the covalent cross-linkings for acting on containing metal-ligand and being formed by covalent bond, wherein more than the gel point that covalent cross-linking reaches covalent cross-linking at least one cross-linked network.Such dynamic aggregation object combines metal-ligand effect and the respective advantage of covalent cross-linking, and by the regulation to reaction materil structure, can prepare structure-rich, the polymer material of performance multiplicity.Metal-ligand acts on the dynamic reversibility that has in dynamic aggregation object, so that polymer reflects the functional characteristics such as stimulating responsive, the effects of selfreparing, shape memory, toughening are played to material in specific structure；And covalent cross-linking imparts polymer with certain strength and stability.The dynamic aggregation object can be used as self-repair material, toughness material, sealing material, shape-memory material, force snesor material etc. and is widely applied.

Description

A kind of hybrid cross-linked dynamic aggregation object
Technical field:
The present invention relates to intelligent polymer fields, and in particular to it is a kind of by covalent bond and metal-ligand effect constitute it is miscellaneous Change crosslinking dynamic aggregation object.
Background technique:
Traditional polymer is generally made of covalent bond, covalent bond due to bond energy with higher, impart polymer with Good stability and stress bearing capacity.Crosslinking is that the materials such as polymer form three-dimensional net structure, obtains elasticity to reach The universal method of body, thermosetting plastics, raising polymer thermostable and mechanical property and other effects.Crosslinking can be chemistry (altogether Valence) crosslinking either physics (non-covalent/supermolecule) crosslinking.Chemical crosslinking promotes polymer thermostable due to being particularly helpful to Property, mechanical property, dimensional stability etc., therefore occupy biggish ratio in the crosslinking of polymer.But when only with change It is also more difficult to embody for extraneous responsiveness and dynamic, it is difficult to meet under the new situation for material when learning covalent cross-linking The development need of material.Chemical crosslinking lacks dynamic, is chemically crosslinked once being formed, and crosslinking will be unable to change in itself, polymeric material The performance of material is immobilized.Physical crosslinking is generally cross-linked to form by noncovalent interaction, and the feature protruded is that have to move The performance of state invertibity, cross-linked structure and polymer has changeability.
For the mechanical property for improving cross-linked polymer, people once attempt building hybridization network structure, such as interpenetrating networks (covalent) structure.In covalent inierpeneirating network structure, in order to obtain enough toughness, generally require to carry out first network Big swelling (such as with solvent or second network), when in use to sacrifice first network (the irreversible fracture of covalent bond) To obtain irreversible toughness.This kind of covalent interpenetrating networks not can be carried out any reparation not only after disruption, lack dynamic yet, It is very restricted its performance and application.
Therefore, it is necessary to develop a kind of novel hybrid cross-linked dynamic aggregation object, so that system can either have dimensionally stable Property, and have good mechanical property and excellent dynamic, to solve problems of the prior art.
Summary of the invention
For above-mentioned background, the present invention provides a kind of hybrid cross-linked dynamic aggregation object, containing metal-ligand act on And the covalent cross-linking formed by covalent bond；Wherein, covalent cross-linking reaches the gel of covalent cross-linking at least one cross-linked network Or more；Wherein, the form of the hybrid cross-linked dynamic aggregation object be selected from oligomer swell gel, plasticizer swell gel, from Sub- liquid swell gel, elastomer, ordinary solid, foamed material.
In the present invention, covalent cross-linking can have one or more, can also use any appropriate covalent cross-linking knot Structure and combinations thereof.Cross-linked network can have at least one, namely can be single one network, can also have mutually be blended it is more A network can also have multiple networks of interpenetrating.
A kind of hybrid cross-linked dynamic aggregation object provided according to the present invention, can be prepared into the oligomerisation for function admirable Object swell gel, plasticizer swell gel, ionic liquid swell gel, elastomer, ordinary solid and foamed material.It is this dynamic The reversible polymer material of state is able to maintain excellent cyclicity, recoverability, mechanical strength etc., therefore availability is very high, It is worth also especially high.
The present invention can be achieved by following technical solution:
A kind of hybrid cross-linked dynamic aggregation object, the covalent cross-linking for acting on containing metal-ligand and being formed by covalent bond； Wherein, more than the gel point that covalent cross-linking reaches covalent cross-linking at least one cross-linked network；Wherein metal-ligand effect is logical The ligand groups (calling " pendant ligands " in the following text) and introduced metal center crossed in polymer chain side group interact and realize.
In embodiments of the present invention, the ligand groups (being indicated with L) be selected from cyclopentadiene and contain at least one The structural unit of a coordination atom (being indicated with A).One coordination atom can be with one or more metal center (including but not Be only limitted to metal ion, the metal center of metallo-chelate, metal-organic metal center, in metal inorganic compound Metal center, indicated with M) form one or more coordinate bonds, a metal center can also be with one or more coordination Atom forms one or more coordinate bond.The quantity for the coordinate bond that one ligand groups and metal center are formed is known as ligand base The number of teeth of group, in embodiments of the present invention, in the same system, a metal center can be with a tooth ligand, bidentate ligand, three One of tooth ligand or multiple ligands form metal-ligand effect, are also possible to connect by metal center between different ligands Cyclization, therefore the present invention can effectively provide type, quantity and performance dynamic metal-ligand effect abundant enough, following Structure shown in general formula is some to provide example, but the present invention is not limited only to this:
Wherein, A is coordination atom, and M is metal center, and each ligand groups and metal center are formed by an A-M key For a tooth, A, which is connected, with singly-bound in formula indicates that the coordination atom belongs to the same ligand groups, when in a ligand groups When containing two or more coordination atoms, A can be identical atom and be also possible to different atoms, selected from boron, nitrogen, Oxygen, sulphur, phosphorus, silicon, arsenic, selenium, tellurium；It is preferred that boron, nitrogen, oxygen, sulphur, phosphorus；More preferable nitrogen, oxygen；Nitrogen.It should be noted that having When A exist in the form of anion；It is cyclopentadiene ligand.In the present invention, it is preferred to a coordination atom only with a gold Category is centrally formed a coordinate bond, therefore the quantity of the coordination atom contained in ligand groups is the number of teeth of ligand groups.Institute The metal-ligand for stating ligand groups and metal center formation acts on (with M-LxIt indicates, x expression is mutually made with the same metal center The quantity of ligand groups) power in ligand groups the type and quantity of coordination atom, the type of metal center with And valence state and ion pair etc. are related.
The metal center M can be the metal center of any appropriate metal ion or compound/chelate etc., It can be selected from any appropriate ionic species of any one metal, compound/chelate and combinations thereof in the periodic table of elements.
A preferred embodiment (the first polymer network structure) according to the present invention, the dynamic aggregation object is only Containing a cross-linked network, acted on simultaneously containing covalent cross-linking and metal-ligand in this cross-linked network；Wherein covalent cross-linking The degree of cross linking reaches its gel point or more；Cross-linked network polymer chain contains pendant ligands, forms metal-by this pendant ligands and matches Body effect, the degree of cross linking is in its gel point above and below.
Another preferred embodiment (second polymer network structure) according to the present invention, the dynamic aggregation object Only contain a cross-linked network, is acted on simultaneously containing covalent cross-linking and metal-ligand in this cross-linked network；Meanwhile it being crosslinked Also contain supermolecule hydrogen bond action in network；Wherein, the degree of cross linking of covalent cross-linking is more than its gel point；Cross-linked network polymer Chain contains pendant ligands, forms metal-ligand effect by this pendant ligands, the degree of cross linking is in its gel point above and below； The degree of cross linking of supermolecule hydrogen bond action is in its gel point above and below.
Another preferred embodiment (the third polymer network structure) according to the present invention, the dynamic aggregation object contain There are two cross-linked network, one of cross-linked network only contains covalent cross-linking, and wherein the degree of cross linking reaches gel point or more；Another Network only contains metal-ligand effect, forms metal-ligand effect, the degree of cross linking by the pendant ligands on polymer chain More than its gel point.
Another preferred embodiment (the 4th kind of polymer network structure) according to the present invention, the dynamic aggregation object Containing there are two cross-linked network, one of cross-linked network contains covalent cross-linking and metal-ligand effect simultaneously, wherein covalently hands over The degree of cross linking of connection reaches its gel point or more；Another cross-linked network only contains-metal-ligand effect.
Another preferred embodiment (the 5th kind of polymer network structure) according to the present invention, the dynamic aggregation object Containing there are two cross-linked network, one of cross-linked network contains covalent cross-linking and metal-ligand effect simultaneously, wherein covalently hands over The degree of cross linking of connection reaches its gel point or more；Another cross-linked network only contains supermolecule hydrogen bond action.
Another preferred embodiment (the 6th kind of polymer network structure) according to the present invention, the dynamic aggregation object Containing there are two cross-linked network, one of cross-linked network only contains covalent cross-linking and its degree of cross linking more than its gel point；In addition One cross-linked network only contains metal-ligand effect；Also contain supermolecule hydrogen bond action at least one cross-linked network simultaneously.
Another preferred embodiment (the 7th kind of polymer network structure) according to the present invention, the dynamic aggregation object Containing there are three cross-linked network, one of cross-linked network only contains covalent cross-linking and its degree of cross linking more than its gel point, in addition One cross-linked network only contains metal-ligand effect, and third cross-linked network only contains supermolecule hydrogen bond action.
Another preferred embodiment (the 8th kind of polymer network structure) according to the present invention, the dynamic aggregation object Containing there are two cross-linked network, one of cross-linked network contains covalent cross-linking simultaneously and metal-ligand acts on, and covalent cross-linking The degree of cross linking is more than its gel point；Another cross-linked network contains covalent cross-linking and supermolecule hydrogen bond action simultaneously, and covalently The degree of cross linking of crosslinking is more than its gel point.
Another preferred embodiment (the 9th kind of polymer network structure) according to the present invention, the dynamic aggregation object Containing there are two cross-linked network, one of cross-linked network only contains covalent cross-linking and its degree of cross linking more than its gel point；In addition One cross-linked network contains covalent cross-linking and metal-ligand effect simultaneously, and the degree of cross linking of covalent cross-linking is more than its gel point.
In addition to the embodiment of above-mentioned nine kinds of hybridization network structures, the present invention can also have other diversified hydridization nets Network structural implementation, can contain in an embodiment there are three or its above identical or different network, the same net Can be containing different covalent cross-linkings and/or different metal-ligand effects in network, while also optionally containing identical or different Supermolecule hydrogen bond action, the ingredient containing metal-ligand and/or supermolecule hydrogen bond action is also possible to noncrosslinking ingredient point It dissipates in a network.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, the optional supermolecule hydrogen bond action, by being present in dynamic aggregation object Chain backbone (including side chain/branch/bifurcated chain), side group appoint in end group and to form hydrogen bond between one or more hydrogen bond group It constitutes.The hydrogen bond group preferably comprises following constituent:
At least one of further preferably following constituent:
At least one of further preferably following constituent:
Wherein,Indicate with polymer chain, crosslinking link or any other suitable group/atom (including hydrogen original Son) connection.
Constitute that the raw material components of dynamic aggregation object further include following any or any two can additive: other polymers, Auxiliary agent, filler；
Wherein, addible other polymers are selected from following any or appoint several: natural polymer, synthesis tree Rouge, synthetic rubber, synthetic fibers；
Wherein, addible auxiliary agent is selected from following any or appoints several: catalyst, initiator, antioxidant, light are stablized Agent, heat stabilizer, chain extender, toughener, coupling agent, lubricant, release agent, plasticizer, foaming agent, antistatic agent, emulsifier, Dispersing agent, colorant, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, rheological agent, thickener, levelling agent, antibacterial agent；
Wherein, addible filler be selected from it is following any or appoint several fillers: inorganic non-metallic filler, metal packing, Organic filler.
In embodiments of the present invention, a kind of hybrid cross-linked dynamic aggregation object is applied to following product: self-repairability Material, sealing material, toughness material, adhesive, toy material, shape-memory material, force snesor material, energy storage device material Material.
Compared with prior art, the invention has the following advantages:
(1) present invention in dynamic aggregation object structure-rich, performance multiplicity.It is existed simultaneously in a polymeric system altogether Valence crosslinking and metal-ligand effect and optional supermolecule hydrogen bond action, the advantages of making full use of and combine each effect.Its In, covalent cross-linking provides a strong and stable network structure for dynamic aggregation object, and polymer can keep balanced structure, That is dimensional stability；And metal-ligand effect then provide one for dynamic aggregation object can spontaneously or can under external influence The dynamic structure of inversion, to realize " being association of activity and inertia " of metal-ligand effect and covalent bond, the table in polymer network Reveal synergistic effect.Due to no intermolecular phorogenesis and key energy to failure is generally higher in traditional cross-linked structure, need substantially Toughness is provided by the elongation between crosslinking points when segment stress, therefore the general toughness of obtained cross-linked polymer relatively has Limit, and after introducing metal-ligand effect in the polymer, metal-ligand effect under external force can be with " can sacrifice key " Form is broken, and provides enough toughness for cross-linked polymer, so that cross-linked polymer is to possess cross-linked structure intrinsic While mechanical strength and stability, also possess excellent tensile toughness and tear resistance.
(2) the dynamic aggregation object structure in the present invention and performance have good Modulatory character.Ligand groups various structures, By selecting different pendant ligands and different metal center atoms, can prepare with different appearance features, performance is adjustable, Widely used dynamic aggregation object；Pendant ligands group can be moved independently of polymer chain, have better flexibility, It not will cause microphase-separated and crystallization in dynamic aggregation object, guarantee that polymer has enough dynamics, meanwhile, side group is matched Body group is able to use existing compound and is synthesized by simply chemical reaction, preparation method multiplicity；By controlling not The metal-ligand effect of same type can make material have the characteristics such as fluorescence, stress discoloration；Pass through control covalent cross-linking and gold The ratio of both category-ligand effects ingredient, can prepare mechanical strength, thermal stability, fluorescence, creep-resistant property, review one's lessons by oneself The functional different dynamic aggregation objects such as renaturation energy.This is very inside traditional covalent cross-linking and supermolecule cross-linking system What difficulty was accomplished.
(3) dynamic aggregation object dynamic property in the present invention is good, dynamic response mild condition.Metal-ligand effect and Hydrogen bond action belongs to two different supermolecular mechanisms, exists simultaneously in dynamic aggregation object, can produce under the action of the external world The effect of raw quadrature-synergy.Compared to other dynamic systems, dynamic aggregation object provided by the invention can be not necessarily to catalyst, be not necessarily to Synthesis and the dynamic reversibility that dynamic aggregation object is realized under conditions of high temperature, illumination or specific pH, are improving preparation efficiency Meanwhile the limitation of use environment is also reduced, extend the application range of polymer.In addition, during the preparation process can also root Other additives are added according to actual needs to be modified dynamic aggregation object material, extend the application performance of material.
With reference to following embodiments explanation, embodiment and the appended claims, these and other features of the invention with And advantage will become obvious.
Specific embodiment
A kind of hybrid cross-linked dynamic aggregation object of the present invention, the dynamic aggregation object are made containing metal-ligand The covalent cross-linking formed with and by covalent bond, wherein covalent cross-linking reaches the solidifying of covalent cross-linking at least one cross-linked network More than glue point, wherein metal-ligand acts through ligand groups in polymer chain side group and introduced metal center is mutual It acts on and realizes；Wherein, it is solidifying to be selected from oligomer swell gel, plasticising solvent swell for the form of the hybrid cross-linked dynamic aggregation object Glue, ionic liquid swell gel, elastomer, ordinary solid, foamed material.
Term " polymerization " reaction/action used in the present invention refers to that the reactant of lower molecular weight passes through polycondensation, adds The reaction formations such as poly-, ring-opening polymerisation form the propagation process/effect with the product of higher molecular weight.Wherein, reactant can Thinking (can spontaneously be polymerize with polymerizing power, or can be polymerize in initiator or outside plus under capable of acting on) The compounds such as monomer, oligomer, prepolymer.Homopolymer is known as by a kind of product that reactant is polymerize.By two kinds Or the product that two or more reactants are polymerize is known as copolymer." polymerization " in the present invention comprising anti- Answer linear growth process, branching process, annulation process and the cross-linking process etc. of object strand；In embodiments of the present invention In, " polymerization " includes caused by the noncovalent interaction of bonding and metal-ligand effect with hydrogen bond action as covalent bond Propagation process.
Term " crosslinking " reaction/action used in the present invention refers to leading between reactant molecule and/or in reactant molecule The physical action of chemical bonds, metal-ligand effect and the optional supermolecule hydrogen bond action crossed between covalent bond forms three-dimensional The process of unlimited reticular pattern product.In cross-linking process, polymer chain is general first to be increased in two-dimensional/three-dimensional direction, gradually Two dimension or three-dimensional cluster are formed, developing deeply is three-dimensional infinite network structure.It should be noted that the cross-linked structure in the present invention, Its three-dimensional infinite network structure for refering in particular to gel point or more (containing gel point, similarly hereinafter), and non-crosslinking structure then refers to line style, ring The structures such as shape, branching and gel point two dimension below, three-dimensional cluster structure.Heretofore described " gel point " is (also referred to as Percolation threshold), reactant is referred in cross-linking process, and viscosity is uprushed, and starts gel phenomenon occur, is started crosslinking for the first time and is reached Reflecting point when to a three-dimensional infinite network.When there are a variety of crosslinked actions, except covalent cross-linking is at least one network It is outer to reach its gel point or more, other crosslinked actions can be in its gel point above and below.
In embodiments of the present invention, covalent cross-linking can have one or more than one kinds of, also can be using any Suitable covalently cross-linked structure (including but not limited to chemical structure, topological structure, the degree of branching) and combinations thereof.In reality of the invention It applies in mode, cross-linked network can have at least one, namely can be single one network, be also possible to mutually be blended multiple Network is also possible to multiple networks of interpenetrating, and the invention is not limited thereto.But in embodiments of the present invention, described total It is more than the gel point that valence crosslinking must reach covalent cross-linking at least one network, that is, if an only cross-linked network, Then the degree of cross linking of covalent covalent cross-linking therein must reach gel point or more.In this way, just may be used for polymer of the invention Even if polymer can also keep balanced structure, namely in the normal state may be used to guarantee in the case where only one network To be the insoluble structure not melted.
In embodiments of the present invention, the metal-ligand effect in any one network can have any crosslinking journey Degree preferably reaches the gel point that metal-ligand acts on or more.In the present invention, if not illustrating, metal-ligand effect It refers in particular to crosslinking degree and reaches its gel point or more.
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, " branch ", " bifurcated chain " Refer to 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's Chain structure；For the sake of simplicity, the molecular weight of side chain, branch, bifurcated chain if not otherwise indicated, then unitedly calls when being more than 1000Da For side chain." side group ", refer in polymer architecture with main polymer chain skeleton/cross-linked network chain backbone/side chain, The molecular weight that branch, bifurcated chain backbone are connected and are distributed in chain backbone side is not higher than the chemical group and molecular weight of 1000Da Short chain not higher than 1000Da.For side chain and side group, can have multilevel structure namely side chain can continue with side group and Side chain, the side chain of side chain can continue have side group and side chain, and side chain therein also includes branch and bifurcated chain isodesmic structure.It is described " end group ", refer in polymer architecture with polymer chain skeleton be connected and be located at chain backbone end chemical group； In the present invention, side group can also have end group under specific condition.
In embodiments of the present invention, the pendant ligands, refer to all atoms on the group in side group, Pendant ligands can be before polymerized/cross-linked, later or in the process generate.The characteristics of based on side group, usually polymerized/cross-linked it Preceding and/or generate later, quantity, structure and generation can be than relatively freely controlling.Since side group has more than skeletal chain Motility well, therefore the metal-ligand effect formed by pendant ligands is easier to obtain dynamic.
In embodiments of the present invention, the ligand groups (being indicated with L) be selected from cyclopentadiene and contain at least one The structural unit of a coordination atom (being indicated with A).One coordination atom can be with one or more metal center (including but not Be only limitted to metal ion, the metal center of metallo-chelate, metal-organic metal center, in metal inorganic compound Metal center, indicated with M) form one or more coordinate bonds, a metal center can also be with one or more coordination Atom forms one or more coordinate bond.The quantity for the coordinate bond that one ligand groups and metal center are formed is known as ligand base The number of teeth of group, in embodiments of the present invention, in the same system, a metal center can be with a tooth ligand, bidentate ligand, three One of tooth ligand or multiple ligands form metal-ligand effect, are also possible to connect by metal center between different ligands Cyclization, therefore the present invention can effectively provide type, quantity and performance dynamic metal-ligand effect abundant enough, following Structure shown in general formula is some to provide example, but the present invention is not limited only to this:
Wherein, A is coordination atom, and M is metal center, and each ligand groups and metal center are formed by an A-M key For a tooth, A, which is connected, with singly-bound in formula indicates that the coordination atom belongs to the same ligand groups, when in a ligand groups When containing two or more coordination atoms, A can be identical atom and be also possible to different atoms, including but not only limit In boron, nitrogen, oxygen, sulphur, phosphorus, silicon, arsenic, selenium, tellurium；It is preferred that boron, nitrogen, oxygen, sulphur, phosphorus；More preferable nitrogen, oxygen；Nitrogen.It needs to illustrate , A exists in the form of anion sometimes；It is cyclopentadiene ligand.In the present invention, it is preferred to which a coordination atom is only A coordinate bond is formed with a metal center, therefore the quantity of the coordination atom contained in ligand groups is ligand groups The number of teeth.The metal-ligand that the ligand groups and metal center are formed acts on (with M-LxIt indicates, in x expression and the same metal The quantity of the ligand groups of heart phase separation) power and the type and quantity of coordination atom in ligand groups, metal center Type and valence state and ion pair etc. are related.
In embodiments of the present invention, in order to form the crosslinking based on metal-ligand effect, a metal center is extremely It wants that metal-ligand effect (i.e. M-L can be formed with ligand groups described in two parts less2Structure), there can also be multiple match Body and the same metal center form metal-ligand effect, and two of them or multiple ligand groups can be identical or different.One The ligancy of metal center is limited, and the coordination atom of ligand groups is more, and the amount of ligand that a metal center can be coordinated is got over It is few, it is lower based on metal-ligand effect supermolecule degree of cross linking；But each ligand is formed by the number of teeth with metal center and gets over More coordinations are stronger, and dynamic is lower, therefore the ligand groups of three teeth are preferably more than in the present invention.
In embodiments of the present invention, can only have in the side group of polymer chain or a dynamic polymer systems A kind of ligand can also exist simultaneously any appropriate combination of multiple ligands.A kind of ligand, refers to a kind of core Ligand structure, pendant ligands, end group ligand can have same core ligand structure, they are the difference is that core is matched Body structure accesses the tie point and/or position difference of polymer chain or small molecule.Suitable ligand combination can effectively be made The standby dynamic aggregation object with particular characteristic, such as collaboration and/or orthogonal effect are played, promote the comprehensive performance of material.It closes Suitable pendant ligands group (core ligand structure) can be exemplified below, but the present invention is not limited only to this:
In embodiments of the present invention, in addition to containing the above pendant ligands, other pendant ligands, institute can also be contained simultaneously The other pendant ligands stated are exemplified below, but the present invention is not limited only to this:
In embodiments of the present invention, when there are the polymer of non-covalent or small molecules in dynamic polymer systems When compound, the core ligand structure can also be made in the polymer of the non-covalent or the end of small molecule compound For end 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 also 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 is more preferably the first subgroup (Cu, Ag, Au) metal, the second subgroup (Zn, Cd) metal, the 8th race (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt) metal, group of the lanthanides (La, Eu, Tb, Ho, Tm, Lu) metal, actinium series (Th) metal.Into One step is 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, can providing the metallic compound at suitable metal center, there is no restriction, optional From metallo-organic compound, metal inorganic compound, metallo-chelate etc..
In embodiments of the present invention, the suitable metallo-organic compound that can provide suitable metal center 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, the oxide of the preferably above-mentioned metal of related metal inorganic compound, vulcanization Composition granule, especially nano particle.
In embodiments of the present invention, the metallo-chelate that can provide suitable metal center preferably has coordination site empty Scarce chelate or some ligands can the chelate replaced the pendant ligands of the invention.
In embodiments of the present invention, there is no particular restriction for the combination of pendant ligands and metal center, as long as side group is matched Body can generate suitable metal-ligand with metal center and act on.Some suitable combinations can be exemplified below, but this hair It is bright to be not limited only to this:
In embodiments of the present invention, in addition to containing metal-ligand effect, also optionally make containing supermolecule hydrogen bond With.Wherein supermolecule hydrogen bond action plays the role of including interchain linkage, interchain polymerization, cyclization etc. in chain.
The optional supermolecule hydrogen bond action in the present invention, it is total generally by the atom Z big with electronegativity The connected hydrogen atom of valence and electronegativity is big, radius is small atom Y, using hydrogen as medium, generate the hydrogen of Z-H ... Y shape formula between Z and Y Key link, wherein described Z, the Y is the atom that any appropriate electronegativity is big and radius is small, can for same element also with For not same element, the atoms such as F, N, O, C, S, Cl, P, Br, I, more preferably F, N, O atom, more preferably O, N can be selected from Atom.Wherein, the supermolecule hydrogen bond action can be used as ring formation in supermolecule polymerization and/or crosslinking and/or chain and deposit Namely hydrogen bond can only play to connect two or more chain segment units and play to increase and polymer chain dimensions but not play super Molecule cross-link effect or hydrogen bond only play the crosslinking of interchain supermolecule, or only play in chain and appoint in ring formation or three of the above It anticipates two or more combination.The present invention is also not excluded for hydrogen bond and plays the role of grafting.
In embodiments of the present invention, the hydrogen bond can be optional tooth number.Wherein, the number of teeth refer to by The donor (H, that is, hydrogen atom) and receptor (Y, that is, receive the electronegative atom of hydrogen atom) of hydrogen bond group are formed by Hydrogen bond quantity, each H ... Y group are combined into a tooth.In following formula, the hydrogen of the schematically illustrate tooth of difference, two teeth and three tooth hydrogen bond groups Key bonding situation.
The bonding situation of one tooth, two teeth and three tooth hydrogen bonds can concrete example it is as follows:
The number of teeth of hydrogen bond is more, and synergistic effect is bigger, and the intensity of hydrogen bond is bigger.In embodiments of the present invention, right The number of teeth of hydrogen bond does not limit.If the number of teeth of hydrogen bond is more, intensity is big, then the dynamic of supermolecule hydrogen bond action is with regard to weak, Can play the role of that dynamic aggregation object is promoted to keep balanced structure and improve mechanical property (modulus and intensity).If hydrogen bond The number of teeth is few, then intensity is low, and the dynamic of supermolecule hydrogen bond action can be provided with regard to strong together with metal-ligand supermolecular mechanism Dynamic property.In embodiments of the present invention, the supermolecule hydrogen bond action of preferably more than four teeth.Hydrogen bond action certain condition Under may be constructed strong non-covalent, can as the useful supplement of covalent cross-linking, on the one hand play increase balanced structure it is steady Qualitative and mechanical strength effect, on the other hand promotes toughness based on its non-covalent character.
In embodiments of the present invention, the supermolecule hydrogen bond action can be by between any appropriate hydrogen bond group Existing noncovalent interaction generates.Wherein, the hydrogen bond group can only contain hydrogen bond donor, or only containing hydrogen bond by Body, or contain hydrogen bond donor and receptor simultaneously, preferably contain hydrogen bond donor and receptor simultaneously.Wherein, the hydrogen bond group is excellent Choosing contains following constituent:
At least one of further preferably following constituent:
At least one of further preferably following constituent:
Wherein,Indicate with polymer chain, crosslinking link or any other suitable group/atom (including hydrogen original Son) connection.In embodiments of the present invention, hydrogen bond group preferably is selected from amide groups, carbamate groups, urea groups, thio ammonia Carbamate base and the derivative of the above group etc..
In the present invention, the hydrogen bond group can be only present on polymer chain skeleton (including side chain/branch/point Fork chain), referred to as skeleton hydrogen bond group；Also it can be only present in polymer chain side group (also including the multilevel structure of side group), referred to as Side group hydrogen bond group；Also it can be only present on polymer chain/small molecule end group, referred to as end group hydrogen bond group；It can also be simultaneously On being present at least two in polymer chain skeleton, polymer chain side group, polymer chain/small molecule end group.When existing simultaneously In polymer chain skeleton, polymer chain side group, polymer chain/small molecule end group at least two on when, under specific circumstances, Hydrogen bond can be formed between the hydrogen bond group of different location, such as skeleton hydrogen bond group can be formed between side group hydrogen bond group Hydrogen bond.
Wherein, suitable skeleton hydrogen bond group citing such as (but the present invention is not limited only to this):
Wherein, suitable side group hydrogen bond group/end group hydrogen bond group is in addition to it can have above-mentioned skeleton hydrogen bond group structure, More citings such as (but the present invention is not limited only to this):
Wherein, m, n are the quantity of repetitive unit, can be fixed value, are also possible to average value, preferably smaller than 20, more excellent Choosing is less than 5.
It in the present invention, can be same containing one or more kinds of hydrogen bond groups in same polymeric system It can also be a kind of or more containing that can contain in one or more kinds of hydrogen bond group namely dynamic aggregation object in cross-linked network The combination of kind hydrogen bond group.The hydrogen bond group can be formed by the reaction between any appropriate group, such as: it is logical The covalent reaction crossed between carboxyl, acyl halide group, anhydride group, ester group, amide groups, isocyanate groups and amino is formed；It is logical Cross isocyanate groups and hydroxyl, sulfydryl, the covalent reaction between carboxyl are formed；Pass through succinimide group and amino, hydroxyl Covalent reaction between base, sulfydryl is formed.
The structure-rich of dynamic aggregation object in the present invention, performance multiplicity.It can be existed simultaneously in a polymeric system Covalent cross-linking and ligand metal effect and optional supermolecule hydrogen bond action, the balance for providing material using covalent cross-linking are steady Determine structure, metal-ligand effect and optional supermolecule hydrogen bond action provide the dynamic property of material.Metal-ligand work is used as The toughness of material can be improved for key can be sacrificed；There is dynamic reversibility again, material can be assigned after being destroyed by external force Repair ability；Furthermore dynamic reversibility is capable of providing shape memory function again.This is to be difficult to reality in existing polymeric system Existing.
In the present invention, the supermolecule hydrogen bond action in cross-linked network can have any appropriate degree of cross linking, can be with It, can also be below its gel point more than its gel point.The supermolecule hydrogen bond action can be to carry out in dynamic aggregation object It is generated during covalent cross-linking, also can carry out supermolecule when polymer chain carries out covalent cross-linking by the hydrogen bond group Hydrogen bond action；Covalent cross-linking is carried out again after being also possible to pre-generated supermolecule hydrogen bond action；It can also be formed in covalent cross-linking Afterwards, supermolecule hydrogen bond action is generated during dynamic aggregation object subsequent forming.
In embodiments of the present invention, dynamic aggregation object can be made of one or more cross-linked networks.When dynamic When polymer is only made of a cross-linked network, contain the covalent cross-linking and gold simultaneously in the cross-linked network structure Category-ligand effect.It, can be by two or more mutual blendings when dynamic aggregation object is made of two or more cross-linked networks Cross-linked network constitute, can also be made of two or more mutually interspersed cross-linked networks, can also be by two or more portions The cross-linked network that split-phase is mutually interted is constituted, and can also be combined and be constituted by three cases above, but the present invention is not limited only to this； Wherein, two or more networks can be identical or different；It can be that subnetwork only contains covalent cross-linking and subnetwork contains only The combination for having metal-ligand to act on, or part are only matched containing covalent cross-linking and metal-containing covalent cross-linking and part simultaneously The combination of body effect, or part are only made containing covalent cross-linking and metal-ligand containing metal-ligand effect and part simultaneously It is all acted on simultaneously containing covalent cross-linking and metal-ligand in combination or each network；But it must satisfy dynamic aggregation It is acted on simultaneously containing the covalent cross-linking and metal-ligand in objects system, and the covalent cross-linking at least one network reaches It is more than the gel point of covalent cross-linking.Optional supermolecule hydrogen bond action can exist in any suitable manner.
For dynamic aggregation object of the invention, covalent cross-linking reaches the solidifying of covalent cross-linking at least one cross-linked network It is more than glue point, it is ensured that even if even if there is only in the case where the covalent cross-linking in the case where only one network, Polymer can also keep balanced structure, namely can have (at least partly) the insoluble structure not melted in the normal state. Can have when there are two or more networks, between heterogeneous networks interaction (including the described metal-ligand effect and/ Or other effects), it can also be mutually indepedent；And except the covalent cross-linking of at least one network must reach the gel of covalent cross-linking Or more it is outer, the crosslinkings of other networks (including the effect of covalent cross-linking, metal-ligand, optional supermolecule hydrogen bond action and its it With) can be more than gel point or in gel point hereinafter, it is preferred that more than gel point.
In embodiments of the present invention, it can be blended in the cross-linked network structure of dynamic aggregation object and/or be interspersed with it It is not crosslinked between the one or more polymer namely those polymer of his non-crosslinked type and its between the cross-linked network Effect.
A preferred embodiment (the first polymer network structure) according to the present invention, the dynamic aggregation object is only Containing a cross-linked network, acted on simultaneously containing covalent cross-linking and metal-ligand in this cross-linked network；Wherein covalent cross-linking The degree of cross linking reaches its gel point or more；Cross-linked network polymer chain contains pendant ligands, forms metal-by this pendant ligands and matches Body effect, the degree of cross linking is in its gel point above and below.The hybrid cross-linked network structure of present embodiment is simple, but extremely has Effect, and convenient for preparation.Metal-ligand is used as the supplement of covalent cross-linking, and the intensity, toughness of material on the one hand can be improved, On the other hand certain self-repairability can be assigned, while can have good shape memory.
Another preferred embodiment (second polymer network structure) according to the present invention, the dynamic aggregation object Only contain a cross-linked network, is acted on simultaneously containing covalent cross-linking and metal-ligand in this cross-linked network；Meanwhile it being crosslinked Also contain supermolecule hydrogen bond action in network；Wherein, the degree of cross linking of covalent cross-linking is more than its gel point；Cross-linked network polymer Chain contains pendant ligands, forms metal-ligand effect by this pendant ligands, the degree of cross linking is in its gel point above and below； The degree of cross linking of supermolecule hydrogen bond action is in its gel point above and below.In this embodiment, covalent cross-linking network is responsible for guarantor Hold balanced structure, metal-ligand effect and supermolecule hydrogen bond action are responsible for providing dynamic crosslinking performance, metal-ligand effect and Supermolecule hydrogen bond action can play collaboration and/or orthogonal effect, further promote the comprehensive performance of material.
A preferred embodiment (the third polymer network structure) according to the present invention, the dynamic aggregation object contain Two cross-linked networks, one of cross-linked network only contain covalent cross-linking, and wherein the degree of cross linking reaches gel point or more；Another net Network only contains metal-ligand effect, forms metal-ligand effect by the pendant ligands on polymer chain, the degree of cross linking exists It is more than its gel point.In this embodiment, covalent cross-linking network is responsible for keeping balanced structure, and metal-ligand effect is responsible for mentioning For dynamic property, covalent cross-linking network and metal-ligand effect network can form interpenetrating or semi-intercrossing network, make full use of two The advantages of person, achieve the effect that collaboration and/or it is orthogonal.
Another preferred embodiment (the 4th kind of polymer network structure) according to the present invention, the dynamic aggregation object Containing there are two cross-linked network, one of cross-linked network contains covalent cross-linking and metal-ligand effect simultaneously, wherein covalently hands over The degree of cross linking of connection reaches its gel point or more；Another cross-linked network only contains-metal-ligand effect.Preferably In, two cross-linked networks can have interaction or without interaction, preferably without interaction.In this embodiment, pass through Second dynamic network provides additional dynamic property, reaches more preferably resultant effect.
Another preferred embodiment (the 5th kind of polymer network structure) according to the present invention, the dynamic aggregation object Containing there are two cross-linked network, one of cross-linked network contains covalent cross-linking and metal-ligand effect simultaneously, wherein covalently hands over The degree of cross linking of connection reaches its gel point or more；Another cross-linked network only contains supermolecule hydrogen bond action.Preferably In, by additionally introducing supermolecular mechanism, makes it possible to and the dynamic of dynamic aggregation object is supplemented, supermolecule hydrogen bond is made Collaboration and/or orthogonal effect are formed with also acting on metal-ligand, reaches better comprehensive performance.
Another preferred embodiment (the 6th kind of polymer network structure) according to the present invention, the dynamic aggregation object Containing there are two cross-linked network, one of cross-linked network only contains covalent cross-linking and its degree of cross linking more than its gel point；In addition One cross-linked network only contains metal-ligand effect；Also contain supermolecule hydrogen bond action at least one cross-linked network simultaneously. In this embodiment, covalent cross-linking network is responsible for keeping balanced structure, and metal-ligand effect is responsible for providing dynamic property, volume Supplement of the outer supermolecule hydrogen bond action as dynamic aggregation object dynamic；Covalent cross-linking network and metal-ligand act on network Interpenetrating or semi-intercrossing network can be formed, the advantages of both making full use of, achievees the effect that collaboration and/or orthogonal.
Another preferred embodiment (the 7th kind of polymer network structure) according to the present invention, the dynamic aggregation object Containing there are three cross-linked network, one of cross-linked network only contains covalent cross-linking and its degree of cross linking more than its gel point, in addition One cross-linked network only contains metal-ligand effect, and third cross-linked network only contains supermolecule hydrogen bond action.In the embodiment party In formula, it can be played more rationally by adjusting parameters such as chemical structure, topological structure, the degrees of cross linking in three cross-linked networks Effectively regulate and control the purpose of polymer performance.
Another preferred embodiment (the 8th kind of polymer network structure) according to the present invention, the dynamic aggregation object Containing there are two cross-linked network, one of cross-linked network contains covalent cross-linking simultaneously and metal-ligand acts on, and covalent cross-linking The degree of cross linking is more than its gel point；Another cross-linked network contains covalent cross-linking and supermolecule hydrogen bond action simultaneously, and covalently The degree of cross linking of crosslinking is more than its gel point.In this embodiment, the network of two covalent cross-linkings can play mutual collaboration Effect, be conducive to regulate and control polymer mechanical property and balanced structure, and by metal-ligand effect and supermolecule hydrogen bond work With responsible offer dynamic property.
Another preferred embodiment (the 9th kind of polymer network structure) according to the present invention, the dynamic aggregation object Containing there are two cross-linked network, one of cross-linked network only contains covalent cross-linking and its degree of cross linking more than its gel point；In addition One cross-linked network contains covalent cross-linking and metal-ligand effect simultaneously, and the degree of cross linking of covalent cross-linking is more than its gel point. In this embodiment, the network of two covalent cross-linkings can play the role of mutually cooperateing with, and be conducive to the power for regulating and controlling polymer Performance and balanced structure are learned, and is acted on by metal-ligand and is responsible for providing dynamic property.
In addition to the embodiment of above-mentioned nine kinds of hybridization network structures, the present invention can also have other diversified hydridization nets Network structural implementation, can contain in an embodiment there are three or its above identical or different network, the same net Can be containing different covalent cross-linkings and/or different metal-ligand effects in network, while also optionally containing identical or different Supermolecule hydrogen bond action, the ingredient containing metal-ligand and/or supermolecule hydrogen bond action is also possible to noncrosslinking ingredient point It dissipates in a network.Those skilled in the art can rationally and effectively be realized with logic according to the present invention and train of thought.
Above-mentioned " covalent cross-linking ", process means can be any appropriate covalent cross-linking and means in principle.Refer generally to Then two ways, the prepolymer of first synthetic linear or branching type carry out interchain linkage reaction；Or from monomer, once Property or reaction reach crosslinking.In the present invention, in order to allow, there are ligand groups in chain side group, can be initially formed pendant ligands and then hand over again Connection.
In embodiments of the present invention, the covalent cross-linking is established by any appropriate by covalent bond Covalent cross-linking link, includes but are not limited to the covalent cross-linking by carbon-carbon bond formation, the covalent friendship formed by carbon-sulfide linkage Connection, the covalent cross-linking formed by carbon-oxygen bond, the covalent cross-linking formed by carbon-nitrogen bond are formed covalent by silicon-oxygen key Crosslinking.Covalent cross-linking in any one cross-linked network structure of dynamic aggregation object can have at least one chemical structure, at least A kind of degree of branching and at least one reaction type and reaction means.
In embodiments of the present invention, the covalent cross-linking is established by any appropriate by covalent bond Covalent cross-linking link, includes but are not limited to the covalent cross-linking by carbon-carbon bond formation, the covalent friendship formed by carbon-sulfide linkage Connection, the covalent cross-linking formed by carbon-oxygen bond, the covalent cross-linking formed by carbon-nitrogen bond are formed covalent by silicon-carbon bond Crosslinking, the covalent cross-linking formed by silicon-oxygen key.Covalent cross-linking in any one cross-linked network structure of dynamic aggregation object can be with There are at least one chemical structure, at least one degree of branching and at least one reaction type and reaction means.
In embodiments of the present invention, the covalent cross-linking can pass through the covalent reaction between any appropriate group It carries out, illustrates such as: passing through carboxyl, acyl halide group, anhydride group, ester group, amide groups, isocyanate groups, epoxy group and hydroxyl Covalent reaction between base is crosslinked；By carboxyl, acyl halide group, anhydride group, ester group, amide groups, isocyanate groups, Covalent reaction between epoxy group and amino is crosslinked；By alkene radical reaction, free radical acrylate react into Row crosslinking；It is reacted by the CuAAC of azido group and alkynyl, the click-reaction of sulfydryl and alkene carries out covalent cross-linking；Pass through silicon Condensation reaction between hydroxyl carries out covalent cross-linking.
In embodiments of the present invention, the generation or introducing of pendant ligands can use any appropriate reaction, including but Be not limited only to Types Below: isocyanates and amino, hydroxyl, sulfydryl, carboxyl react, the electrophilic substitution reaction of heterocycle, heterocycle Nucleophilic substitution, double bond radical reaction, the side chain reaction of heterocycle, nitrine-alkynes click-reaction, sulfydryl-double bond/alkynes clicks Reaction, the reaction of urea-amine, amidation process, tetrazine-norbornene reaction, active ester are reacted with amino；It is preferred that isocyanic acid Ester and amino, hydroxyl, sulfydryl react, nitrine-alkynes click-reaction, the reaction of urea-amine, amidation process, active ester and ammonia The reaction of base；More preferable isocyanates and amino, hydroxyl, sulfydryl react.In any one network structure, pendant ligands Generation or introducing can have the reaction type of one or more, reaction means and structure.
In embodiments of the present invention, the introducing of metal center can carry out on any suitable opportunity.At least with Lower three kinds of methods can introduce before generating ligand, can formerly with ligand formed metal-ligand effect composition again into Row polymerized/cross-linked can also be re-introduced into after completing polymerized/cross-linked.It is preferred that after generating ligand but before covalent cross-linking It introduces.
In embodiments of the present invention, dynamic aggregation object can use the monomer containing pendant ligands and/or can close It is closed at the monomer of pendant ligands, crosslinking agent and/or curing agent and the substance that can provide metal center by chemical reaction At.It is illustrated below for the embodiment of the part preparation method of network structure of the invention.
By taking the first polymer network structure of the invention as an example, described hybrid cross-linked only one net of dynamic aggregation object Network, the covalent cross-linking in network reach covalent gel point or more, exist simultaneously metal-ligand effect.
Using with pendant ligands dithiol monomer and end polyene crosslinking agent direct polymerization/be cross-linked to form this hair The first network structure in bright.By controlling the formula rate of monomer and crosslinking agent, reach the covalent cross-linking in network altogether More than valence gel point, contain pendant ligands simultaneously:
For another example, the unsaturated hydrocarbon monomer with pendant ligands and have active group (including but not limited to hydroxyl, amine Base, carboxyl, isocyano, sulfydryl, epoxy group, double bond, three keys etc.) unsaturated hydrocarbon monomer under the effect of the catalyst altogether It is poly-, then again with double-active group monomer or polymer carry out subsequent crosslinking.As an example but it is not limited to following institute It lifts, for example, the vinyl compound with pendant ligands and the copolymerization of the vinyl compound with epoxy group, and in diamino base class It is crosslinked under the action of conjunction object, forms the first network structure in the present invention using this reaction covalent cross-linking.Pass through control The formula rate of monomer and crosslinking agent makes the covalent cross-linking in network reach covalent gel point or more, contains pendant ligands simultaneously:
In above-mentioned example, pendant ligands can pre-generate before polymerized/cross-linked.
The embodiment of other network structures in the present invention is similar, and those skilled in the art can be according to this hair Bright understanding selects suitable preparation means, reaches ideal purpose.
The dynamic aggregation object of hybrid cross-linked network of the invention, when containing there are two or its above network Multi net voting structure When, in addition to common blending dispersion, entanglement more preferably is intertwined by two or more polymer networks and is formed mutually Wear network.Interpenetrating net polymer structure makes its performance be substantially better than single net of its component due to the synergistic effect between network component Network polymer generates the mechanical properties such as toughness more higher than single network, is based particularly on mentality of designing of the invention and introduces gold In the case where category-ligand effect.
Interpenetrating net polymer preparation method generally includes one-step method interpenetrating and two-step method interpenetrating.One-step method disposably will All the components are added, and then carry out polymerized/cross-linked, prepare target network.Two-step method first prepares first network polymer, immediately Be immersed in the monomer/pre-polymer solution to form the second network, then cause polymerized/cross-linked obtain on-target hybrid net Network.The preparation of hybrid cross-linked dynamic aggregation object in the present invention can also use one-step method interpenetrating and two-step method interpenetrating, specific In the case of must also using three steps and its more than method.
It is illustrated below for the embodiment of the part preparation method of interpenetrating net polymer of the invention.
For example, in the third polymer network structure of the invention, there are two the hybrid cross-linked dynamic aggregation object contains Cross-linked network, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking is more than its gel point, in addition One cross-linked network only contains metal-ligand effect.Firstly, preparing one kind, there is no covalent cross-linkings, but do not contain pendant ligands Linear polymer as the 2nd network.Then, first that the monomer of the 2nd network and the 1st network is (or pre- when preparing 1 network Polymers), crosslinking agent etc. be uniformly mixed, then by above-mentioned covalent cross-linking means progress covalent cross-linking, to obtain the 1st network and the The semi-interpenetrating network polymer of 2 networks namely the 2nd network are scattered in the 1st network.The 1st network can also be initially formed, then 2nd network carries out interpenetrating by swelling (can be by solvent) and the 1st network.After metal center is added, it can be obtained described miscellaneous Change the dynamic aggregation object of cross-linked network.
For another example, in the 9th kind of polymer network structure of the invention, the hybrid cross-linked dynamic aggregation object contains two A cross-linked network, the degree of cross linking of one of cross-linked network only containing covalent cross-linking and covalent cross-linking is more than its gel point, separately An outer cross-linked network contains the degree of cross linking of metal-ligand effect and covalent cross-linking and covalent cross-linking more than its gel point. Firstly, preparing one kind, there is no covalent cross-linkings, but contain the linear polymer of pendant ligands as the 2nd network.Then, it is preparing When 1 network, first the monomer (or prepolymer) of the 2nd network and the 1st network, crosslinking agent etc. are uniformly mixed, then by above-mentioned total Valence is crosslinked means and carries out covalent cross-linking, to obtain the semi-interpenetrating network polymer namely the 2nd network of the 1st network and the 2nd network It is scattered in the 1st network.It can also be initially formed the 1st network, the 2nd network is then passed through swelling (can be by solvent) and the 1st net Network carries out interpenetrating.After metal center is added, the dynamic aggregation object of the hybrid cross-linked network can be obtained.
The relative molecular mass of term " molecular weight " used representative species in the present invention, for small molecule compound, small Molecular radical and certain macromolecular compounds with fixed structure, for macro-radical, molecular weight generally has single point Property is dissipated, namely there is fixed member amount；And there is polydispersion for oligomer, high polymer, oligomer residue, high polymer residue etc. The substance of property molecular weight, molecular weight generally refer to average molecular weight.Wherein, the small molecule compound in the present invention, small molecule Group refers in particular to the compound or group that molecular weight is no more than 1000Da；Macromolecular compound, that macro-radical refers in particular to molecular weight is big In the compound or group of 1000 Da.
Term " hetero atom " used refers to nitrogen-atoms, oxygen atom, sulphur atom, phosphorus atoms, silicon atom, boron atom in the present invention Etc. common non-carbon.
Term " alkyl " used refers to the saturated hydrocarbyl with straight or branched structure in the present invention.In appropriate situation Under, alkyl can have specified carbon atom number, for example, C1-4Alkyl, the alkyl be included in linear chain or branched chain arrangement in have 1, 2, the alkyl of 3 or 4 carbon atoms.The example of suitable alkyl includes but is not limited to methyl, ethyl, propyl, normal-butyl, isobutyl Base, tert-butyl, n-pentyl, 2- methyl butyl, 3- methyl butyl, 4- methyl butyl, n-hexyl, 2- methyl amyl, 3- methylpent Base, 4- methyl amyl, 5- methyl amyl, 2- ethyl-butyl, 3- ethyl-butyl, heptyl, octyl, nonyl, decyl.
It, all can be in the case where not specifying when the structure being related in the present invention has isomer Any one of them isomers comprising position isomery, conformational isomerism, chiral photo-isomerisation, cis-trans isomerism etc..
In the present invention " substituted ", by taking " substituted alkyl " as an example, refer to any of any position in substituted " alkyl " A or more than one hydrogen atom can be replaced any substituent group.In the case where being not particularly limited, substituent group therein It is not particularly limited.
For a compound, a group or an atom, can be substituted simultaneously and by hydridization, such as nitrobenzophenone Replace hydrogen atom, for another example-CH2-CH2-CH2It is replaced by-CH2-S-CH(CH3)-。
In order to illustrate simplicity the term is indicated using conjunction "and/or" in the description of the invention The option selected from the conjunction "and/or" foregoing description, or described option after conjunction "and/or" can be contained, Or it is simultaneously selected from described these three situations of option before and after conjunction "and/or".
In embodiments of the present invention, the form of the dynamic aggregation object or its composition is selected from ordinary solid, oligomerisation Object swell gel, plasticizer swell gel, ionic liquid swell gel, elastomer, foamed material, wherein ordinary solid and bubble The dissolvable small-molecular-weight component content contained in foam material is generally not more than 10wt%, and the small-molecular-weight contained in gel/ Oligomer component content is generally not less than 50wt%.The shape and volume of ordinary solid are relatively more fixed, have preferably mechanical strong Degree, can not be by the constraint of sweller.Elastomer has the general properties of ordinary solid, but has preferable elasticity simultaneously, and And it is softer.Gel then has good flexibility, can embody preferable resilience；Using oligomer, plasticizer and Ionic liquid prepares gel, and it is volatile scattered can effectively to solve water and organic solvent low boiling point in hydrogel and common organogel The defect of mistake.Foamed material then has the advantages that density is low, light, can also overcome the brittleness and gel of part ordinary solid The relatively low problem of mechanical strength, soft foam material also have the characteristic of good elasticity and soft comfortable.The material of different shape There can be suitable purposes in different fields.
In embodiments of the present invention, dynamic aggregation object gel can by sweller (including oligomer, plasticising One of agent, ionic liquid or combinations thereof) in carry out crosslinking acquisition, can also dynamic aggregation object prepare after the completion of recycle it is molten Swollen dose carries out swelling acquisition.Certainly, the present invention not only limit and this, those skilled in the art can be with logic according to the present invention and arteries and veins Network is rationally and effectively realized.
In the preparation process of dynamic aggregation object, mechanical foaming method, physical blowing method, three kinds of chemical blowing process are mainly used Method foams to dynamic aggregation object.
Wherein, the mechanical foaming method is by strong stirring in the preparation process of dynamic aggregation object a large amount of empty Gas or other gases are introduced into lotion, suspension or the solution of polymer and make uniform foams, then pass through physics Or chemical change is allowed to be molded with as foamed material.To shorten, molding cycle can be passed through air and addition emulsifier or surface is living Property agent.
Wherein, the physical blowing method, be realized in the preparation process of dynamic aggregation object using physical principle it is poly- The foaming for closing object, generally includes but are not limited to following methods: (1) inert gas blown method, i.e., lazy under pressurized condition Property gas indentation molten polymer or pasty material in, then decompression heating, make dissolution gas expansion and foam；(2) it utilizes Low-boiling point liquid evaporation gasification foaming makes that is, in low-boiling point liquid indentation polymer or under certain pressure, temperature regime Liquid dissolves in polymer beads, then heats and softens polymer, and liquid also gasifies therewith evaporation and foamed；(3) leaching, It is immersed in polymer with liquid medium and dissolves added solid matter in advance, make to occur a large amount of holes in polymer and be in Foam shape, such as by solable matter salt elder generation and mixed with polymers, puts in water instead after being shaped to product, then by product Multiple processing dissolves out solable matter to get open-celled foam product is arrived；(4) hollow microsphere method is added hollow in the material It is combined after microballoon as obturator-type foamed polymer；(5) expandable particles method is filled, first mixing filling expandable particles, Expandable particles are made to foam in molding or mixed process with the polymer material of activity foaming；Wherein, preferably by polymerizeing The method that inert gas and low-boiling point liquid are dissolved in object foams.Using physical blowing method, have operation Poisoning smaller, The advantages that cost is relatively low for foaming raw material, foaming agent noresidue body.Further, it is also possible to be prepared using freeze-drying.
Wherein, the chemical blowing process is to generate gas along with chemical reaction in dynamic aggregation object foaming process And the method to foam, generally include but are not limited to following two method: (1) thermal decomposable foaming agent foaming utilizes The gas decomposed to give off after chemical foaming agent heating foams.(2) it interacts between polymers compositions and generates the foaming of gas Method generates inert gas (such as carbon dioxide that is, using the chemical reaction occurred between two or more components in foaming system Or nitrogen) polymer is caused to expand and foam.It is carried out in foaming process for control polymerization reaction and foamable reaction balance, to protect Card product has preferable quality, and a small amount of catalyst and foam stabiliser (or surfactant) is generally added.Wherein, preferably by The method for adding chemical foaming agent in the polymer foams.
In the preparation process of dynamic aggregation object, mainly using moulded from foam molding, injection-expansion molded and extrusion hair Three kinds of methods of type are soaked to form dynamic aggregation object foamed material.
Wherein, moulded from foam molding, technical process is simpler, is easy to control, and can be divided into one-step method and two Two kinds of footwork.One step processing refers to that mixed material, which is direct plungeed into die cavity, carries out foaming；Two-step method, which refers to, first will The material prefoam processing mixed, is then placed in die cavity and carries out foaming.Wherein, since one-step method moulded from foam forms ratio Two-step method is easy to operate and high production efficiency, therefore it is preferred that one-step method carries out moulded from foam molding.
Wherein, described injection-expansion molded, technique and equipment are similar with common injection moulding, bubble nucleating rank Section is after screw rod is added in material, by heating and friction is made material become melt state, the control that foaming agent is passed through metering valve Then foaming agent is uniformly mixed by the hybrid element of screw head, in nucleating agent in certain flow rate injecting material melt Under the action of form nuclei of bubbles.Expansion stage and solidifying and setting stage all occur after full of die cavity, when under cavity pressure When drop, the expansion process of gassing core, while so that foam is formed with the cooling of mold.
Wherein, the foam shaping by extrusion, technique and equipment are similar with common extrusion molding, before extrusion or Foaming agent is added in extruder in extrusion process, melt flows through pressure at head and declines, and foaming agent volatilizees and forms requirement Foaming structure.
In the preparation process of dynamic aggregation object, those skilled in the art can be poly- according to practical preparation situation and target Closing physical performance selects suitable foaming method and foamed material forming method to prepare dynamic aggregation object foamed material.
In embodiments of the present invention, the structure of dynamic aggregation object foamed material is related to open-celled structure, hole-closing structure, half Open three kinds of semi-closure structure.It in open-celled structure, is interconnected between abscess and abscess, or connection completely, one-dimensional or three-dimensional can lead to Gas or liquid are crossed, abscess diameter is that 0.01-3mm is differed.Hole-closing structure, has an individual blisters structure, inner cell and abscess it Between there is wall film to separate, the overwhelming majority be not interconnected, abscess diameter be 0.01-3mm differ.The existing phase interconnection of contained abscess It is then half open-celled structure that leading to again, which has mutual disconnected structure,.It, can also be by mechanical compression for having formed the foaming structure of closed pore Or chemical method becomes open-celled structure, those skilled in the art can select according to actual needs.
In embodiments of the present invention, dynamic aggregation object foamed material can be divided into soft, hard according to its softness With semi-rigid three classes: (1) flexible foam, 23 DEG C and 50% relative humidity under, the elasticity modulus of foamed plastics is less than 70MPa；(2) rigid foam, 23 DEG C and 50% relative humidity under, elasticity modulus be greater than 700MPa；(3) semi-rigid (or half It is soft) foam, the foams between above two class, elasticity modulus is between 70MPa and 700MPa.
In embodiments of the present invention, dynamic aggregation object foamed material can be divided into low ratio foamed, middle hair according to its density again Bubble and high-foaming.The foamed material of low ratio foamed, density are greater than 0.4g/cm3, expansion ratio is less than 1.5；The foam material of middle foaming Material, density are 0.1~0.4g/cm3, expansion ratio is 1.5~9；And the foamed material of high-foaming, density are less than 0.1g/ cm3, expansion ratio is greater than 9.
During the preparation process, certain addible other polymers, auxiliary agent, filler can also be added to be total in dynamic aggregation object With composition dynamic aggregation object material, but these additives it is not necessary to.
It is new can to play improvement material property, imparting material as additive in system for the other polymers Performance improves materials'use and economic benefit, has the function that material comprehensively utilizes.Addible other polymers, it is optional From natural polymer, synthetic macromolecular compound.The present invention is to the character of added polymer and possessed Molecular weight can be that oligomer or high polymer can according to the difference of polymeric species according to the difference of molecular weight without limitation Think homopolymer or copolymer, it in the specific use process should be according to the performance of target material and actual fabrication process It needs and is 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 Amide, polyacrylonitrile, polybenzimidazoles, polyethylene terephthalate, polybutylene terephthalate (PBT), polycarbonate, Dimethyl silicone polymer, polyethylene glycol, polyester, polyether sulfone, polyarylsulfone (PAS), polyether-ether-ketone, tetrafluoroethylene-perfluoro propane copolymer, Polyimides, polyacrylate, polyacrylonitrile, polyphenylene oxide, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high impact poly Styrene, polysulfones, polytetrafluoroethylene (PTFE), polyurethane, polyureas, polyvinyl acetate, ethylene-propylene copolymer, ethylene-acetic acid second Enoate copolymer, AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, vinyl chloride-second Vinyl acetate copolymer, polyvinylpyrrolidone, epoxy resin, phenolic resin, Lauxite, unsaturated polyester (UP), poly- isoamyl two Alkene, poly- suitable butadiene, styrene-butadiene copolymer, hycar, polychlorobutadiene, isobutene-isoamyl Diene copolymers, polysiloxane, vinylidene-chlorotrifluoroethylene, epichlorohydrin ethylene oxide copoymer Deng.
In the preparation process of dynamic aggregation object material, the certain addible auxiliary agents being added can improve material Preparation process improves product quality and yield, reduces product cost or assign certain distinctive application performance of product.Described Addible auxiliary agent is selected from following any or several auxiliary agents: additive synthesis, including catalyst, initiator；Stabilizing additive, Including antioxidant, light stabilizer, heat stabilizer；Improve the auxiliary agent of mechanical property, including toughener；Improve helping for processing performance Agent, including lubricant, release agent；The auxiliary agent of softness and lighting, including plasticizer, foaming agent；Change helping for surface property Agent, including antistatic agent, emulsifier, dispersing agent；Change the auxiliary agent of coloured light, including colorant, fluorescent whitening agent, delustering agent；It is difficult Burning and suppression cigarette auxiliary agent, including fire retardant；Other auxiliary agents, including nucleating agent, rheological agent, thickener, levelling agent, antibacterial agent.
Catalyst in the addible auxiliary agent can reduce reaction activity by changing reaction path Accelerate the reaction rate of reactant during the reaction.It includes but are not limited to following any or appoints several catalyst: 1. Polyurethane catalyst for synthesizing: amines catalyst, such as triethylamine, triethylenediamine, bis- (dimethylaminoethyl) ethers, 2- (2- Dimethylamino-ethoxy) ethyl alcohol, N, bis- (dimethylamine propyl) isopropanolamines of N-, N- (dimethylamino-propyl) diisopropanolamine (DIPA), four Methyl dipropylenetriamine, N, N- dimethyl cyclohexyl amine, N, N, N ', N '-tetramethyl Alkylenediamine, N, N, N ', N ', N '-five Methyl diethylenetriamines, N, N- dimethylethanolamine, 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 octanoic acid are sub- Tin, dibutyltin dilaurate, dioctyl tin dilaurate, zinc Isoocatanoate, isooctyl acid lead, potassium oleate, zinc naphthenate, ring Alkanoic acid cobalt, ferric acetyl acetonade, phenylmercuric acetate, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octanoate, potassium oleate, calcium carbonate etc.；② Polyolefin catalyst for synthesizing: such as Ziegler-Natta catalyst, π-allyl nickel, alkyl lithium catalyst, metallocene catalysis Agent, aluminium diethyl monochloride, titanium tetrachloride, titanium trichloride, boron trifluoride etherate, magnesia, dimethylamine, stannous chloride, Triethylamine, tetraphenylboron sodium, antimony oxide, sesquialter ethylmercury chloride aluminium, vanadium oxytrichloride, triisobutyl aluminium, nickel naphthenate, aphthenic acids Rare earth etc.；3. CuAAC catalysts: sharing concerted catalysis by monovalence copper compound and amine ligand；Monovalence copper compound is optional From Cu (I) salt, such as CuCl, CuBr, CuI, CuCN, CuOAc；Also selected from Cu (I) complex compound, such as [Cu (CH3CN)4]PF6、 [Cu(CH3CN)4]OTf、CuBr(PPh3)3Deng；Amine ligand can be selected from three [(1- benzyl -1H-1,2,3- triazole-4-yl) methyl] Amine (TBTA), three [(1- tert-butyl -1H-1,2,3- triazole-4-yl) methyl] amine (TTTA), three (2- benzimidazole methyl) amine (TBIA), it is hydrated bathophenanthroline disulfonic acid sodium etc.；4. thiol-ene catalysts: photochemical catalyst, as dimethoxybenzoin, 2- hydroxy-2-methyl phenylacetone, 2,2- dimethoxy -2- phenyl acetophenone etc.；Nucleopilic reagent catalyst, such as ethylenediamine, three Ethanol amine, triethylamine, pyridine, 4-dimethylaminopyridine, imidazoles, diisopropyl ethyl amine etc..Catalyst amount used does not have It is particularly limited to, generally 0.01-0.5wt%.
Initiator in the addible auxiliary agent, can cause in polymerization process monomer molecule activate and Free radical is generated, reaction rate is improved, reaction is promoted to carry out, include but are not limited to following any or appoints several initiators: 1. radical polymerization shares initiator: organic peroxide, such as lauroyl peroxide, benzoyl peroxide (BPO), two carbon of peroxidating Sour diisopropyl ester, di-cyclohexylperoxy di-carbonate, dicetyl peroxydicarbonate bis- (4- tert-butylcyclohexyl) esters, tert-butyl hydroperoxide Benzoic ether, tert-butyl hydroperoxide pivalate, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide；Azo-compound, such as Azodiisobutyronitrile (AIBN), azobisisoheptonitrile；Inorganic peroxide, such as ammonium persulfate, potassium peroxydisulfate；2. living polymerization With initiator: such as 2,2,6,6- tetramethyl -1- oxygroup piperidines, 1- chloro-1-phenyl ethane/stannous chloride/bis- pyridines ternary system Deng；3. ionic polymerization initiator: such as butyl lithium, sodium/naphthalene system, boron trifluoride/aqueous systems, tin tetrachloride/alkyl halide system Deng；4. coordination polymerization initiator: such as titanium tetrachloride/triethyl aluminum system, two zirconium cyclopentadienyl of dichloro/methylaluminoxane system；⑤ Ring-opening polymerisation initiator: such as sodium methoxide, potassium methoxide, ethylenediamine, hexamethylene diisocyanate, stannous octoate.Wherein, cause The preferred lauroyl peroxide of agent, benzoyl peroxide, azodiisobutyronitrile, potassium peroxydisulfate.Initiator amount used is without spy It does not limit, generally 0.1-1wt%.
Antioxidant in the addible auxiliary agent can delay the oxidation process of polymer material, guarantee material Successfully it can be processed and be prolonged its service life, include but are not limited to following any or appoint several antioxidant: by Hinder phenols, such as 2,6- di-tert-butyl-4-methy 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 butyl benzene Phenol)；Sulfur-bearing Hinered 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]-hexahydros equal three Piperazine；Isocyanuric acid ester Hinered phenols, such as three (3,5- di-tert-butyl-4-hydroxyl benzyl)-triisocyanates；Amine, such as N, N '-two (betanaphthyl) p-phenylenediamine, N, N '-diphenyl-para-phenylene diamine, N- phenyl-N '-cyclohexyl p-phenylenediamine；Sulfur-bearing class, such as Dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, Asia Tricresyl phosphate nonyl phenyl ester, three [2.4- di-tert-butyl-phenyl] phosphite esters etc., wherein the preferred tea polyphenols of antioxidant (TP), butyl Hydroxyanisole (BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), three [2.4- di-tert-butyl-phenyls] Phosphite ester (irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010).Antioxidant dosage used is not particularly limited, generally 0.01-1wt%.
Light stabilizer in the addible auxiliary agent can prevent polymer material from light aging occurs, and extending it makes With the service life comprising but be not limited only to following any or appoint several light stabilizers: photomask agent, such as carbon black, titanium dioxide, oxygen Change zinc, calcium sulfite；Ultraviolet absorbing agent, such as ESCALOL 567,2- hydroxyl -4- n-octyloxy hexichol first Ketone, 2- (2- hydroxyl -3,5- di-tert-butyl-phenyl) -5- chlorobenzotriazole, 2- (2- hydroxy-5-methyl base phenyl) benzotriazole, 2, 4,6- tri- (2- hydroxyl -4- n-butoxyphenyl) -1,3,5- s-triazine, 2- cyano -3,3- diphenylacrylate 2- ethylhexyl； Pioneer's type ultraviolet absorbing agent, such as the p- tert-butyl phenyl ester of salicylic acid, double acid double phenol A ester；UV quenchers, such as bis- (3, 5- di-t-butyl -4- benzylphosphonic acid mono ethyl ester), 2,2 '-thiobis (4- spy's octyl phenol oxygroup) nickel；Hindered amine light stabilizer Agent, as bis- (2,2,6, the 6- tetramethyl piperidine) esters of decanedioic acid, benzoic acid (2,2,6,6- tetramethyl piperidine) ester, three (1,2,2,6, 6- pentamethvl base) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acid (2,4- bis- tertiary fourths Base benzene) ester, alkyl phosphoric acid amide, N, N '-zinc dibutyl dithiocaarbamate, N, the positive fourth positive group dithiocarbamates of N '-two Nickel formate etc..Wherein, bis- (2,2,6, the 6- tetramethyl piperidine) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid, institute Light stabilizer dosage is not particularly limited, generally 0.01-0.5wt%.
Heat stabilizer in the addible auxiliary agent, enable to polymer material in processing or use process not Chemical change occurs because heated, or delays these variations to achieve the purpose that prolong the service life comprising but not only limit In following any or several heat stabilizers: lead salts, as lead sulfate tribasic, dibasic lead phosphite, dibasic are stearic Lead plumbate, dibasic phthalic acid lead, tribasic Malaysia lead plumbate, lead stearate, lead salicylate, Dythal, alkali Formula ceruse；Metal soap: such as cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate；Organo-tin compound Class, such as di-n-butyltin dilaurate, Bis(lauroyloxy)dioctyltin, maleic acid two (just) butyl tin, double single-ethylhexyl maleates Dioctyltin, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital tin C-102, dimercapto acetic acid isooctyl stannous methide, two sulphur Alcohol stannous methide and its compound；Antimony stabilizer, such as mercaptan antimonic salt, mercaptoacetate mercaptans type, mercapto-carboxylic ester antimony, carboxylate Antimony；Epoxy compound species, such as epoxidized oil, epoxy aliphatic ester, epoxy resin；Phosphorous acid esters, such as three aromatic ester of phosphorous acid, Asia Tricresyl phosphate alkyl ester, three aralkyl ester of phosphorous acid, alkane virtue mixed ester, aggretion type phosphite ester；Polyalcohols, such as pentaerythrite, xylose Alcohol, mannitol, D-sorbite, trimethylolpropane；It is compound steady to be such as co-precipitated metallic soap, liquid metal soap for composite thermal stabilizer Determine agent, organotin compound stabilizer etc..Wherein, the preferred barium stearate of heat stabilizer, calcium stearate, tin dilaurate di-n-butyl Tin, maleic acid two (just) butyl tin, heat stabilizer dosage used are not particularly limited, generally 0.1-0.5wt%.
Toughener in the addible auxiliary agent can reduce polymer material brittleness, increase toughness, improve material Bearing strength comprising but be not limited only to following any or appoint several toughener: methyl methacrylate-butadiene-benzene second Alkene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modifier, acrylic nitrile-butadiene two Alkene-styrol copolymer, acrylonitrile-butadiene copolymer, the third glue of second, ethylene-propylene diene copolymer, cis-butadiene cement, butadiene-styrene rubber, styrene-fourth Styrene block copolymer etc..Wherein, preferred the third glue of second of toughener, acrylonitrile-butadiene-styrene copolymer (ABS), Styrene-Butadiene-Styrene Block Copolymer (SBS), Methyl Methacrylate-Butadiene-Styrene Copolymer Resin (MBS), chlorinated polyethylene resin (CPE), toughener dosage used are not particularly limited, generally 5-10wt%.
Lubricant in the addible auxiliary agent can be improved material lubricity, reduce friction, reduce Interface Adhesion Performance comprising but be not limited only to following any or appoint several lubricants: saturated hydrocarbons and halogenated hydrocarbon, such as solid paraffin, micro- Spar wax, atoleine, low molecular weight polyethylene, oxidized polyethylene wax；Fatty acid, such as stearic acid；Fatty acid ester, such as rouge Fat acid low-carbon-ester, polyol esters of fatty acids, native paraffin, ester type waxes and saponified wax；Aliphatic amide type, such as stearmide or tristearin Sour amide, oleamide or oleamide, erucyl amide, N, N '-ethylene bis stearamide；Fatty alcohol and polyalcohols, it is such as stearic Alcohol, cetanol, pentaerythrite；Metal soap, such as lead stearate, calcium stearate, barium stearate, magnesium stearate, zinc stearate. Wherein, the preferred solid paraffin of lubricant, atoleine, stearic acid, low molecular weight polyethylene, lubricant quantity used is without spy It does not limit, generally 0.5-1wt%.
Release agent in the addible auxiliary agent, it can make polymer samples be easy to demould, and surface is smooth, clean, It includes but are not limited to following any or appoints several release agents: paraffin hydrocarbon, soaps, dimethicone, ethyl silicon oil, methyl Phenyl silicone oil, castor oil, used oil, mineral oil, molybdenum disulfide, vinyl chloride resin, polystyrene, silicon rubber, polyvinyl alcohol etc.. Wherein, the preferred dimethicone of release agent, remover dosage used are not particularly limited, generally 0.5-2wt%.
Plasticizer in the addible auxiliary agent, can increase the plasticity of polymer material, so that polymer Hardness, modulus, softening temperature and brittle temperature decline, elongation, flexibility and flexibility improve comprising but be not limited only to Under it is any or appoint several plasticizer: Phthalates: dibutyl phthalate, dioctyl phthalate, adjacent benzene two Formic acid di-isooctyl, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, O-phthalic It is bis- (13) esters of sour butyl benzyl, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid, right Phthalic acid two (2- ethyl) own ester；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyl) own ester；Aliphatic ester Class, 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, ring Oxygen 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, Dihydric alcohol lipid, such as C5~9Sour glycol ester, C5~9Sour Triethylene Glycol；Class containing chlorine such as afforests paraffin class, chloro fat Acid esters；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester；Phenyl alkylsulfonate, inclined benzene three Acid esters, citrate, pentaerythrite and pentaerythritol fatty acid ester etc..Wherein, plasticizer pref-erable dioctyl phthalate (DOP), Dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), adjacent benzene Dioctyl phthalate diisodecyl ester (DIDP), tricresyl phosphate (TCP), plasticizer consumption used are not particularly limited, generally 5- 20wt%.
Foaming agent in the addible auxiliary agent can make polymer samples foaming pore-forming, to obtain light, soft Soft or firm polymer material comprising but be not limited only to following any or appoint several foaming agents: physical blowing agent, such as third Alkane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, butane, ether, chlorine Methane, methylene chloride, dichloroethylene, dicholorodifluoromethane, trifluorochloromethane；Inorganic foaming agent, as sodium bicarbonate, ammonium carbonate, Ammonium hydrogen carbonate；Organic foaming agent, such as N, five methine tetramine of N '-dinitro, N, N '-dimethyl-N, N '-dinitroso is to benzene two Formamide, azodicarbonamide, barium azo-biscarbonate, two diisopropyl carbonate of azo, azodicarbonamide potassium formate, azo two are different Butyronitrile, 4,4 '-oxobenzenesulfonyl hydrazide, benzene sulfonyl hydrazide, trihydrazinotriazine, p-toluene sulfonylsemicarbazide,-two sulphur of biphenyl -4,4 ' Acyl azide；Physical microballoon/granule foaming agent, such as the expandable microballoon of Akzo Nobel company production；Foamed promoter, As urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, dibasic lead phosphite, lead stearate, cadmium stearate, Zinc stearate, zinc oxide；Frothing inhibitor, such as maleic acid, fumaric acid, stearyl chloride, phthalyl chloride, maleic anhydride, benzene two Formic anhydride, hydroquinone, naphthalenediol, aliphatic amine, amide, oxime, isocyanates, mercaptan, thiophenol, thiocarbamide, sulfide, sulfone, ring Hexanone, acetylacetone,2,4-pentanedione, hexacholorocyclopentadiene, dibutyl maleic acid tin etc..Wherein, the preferred sodium bicarbonate of foaming agent, ammonium carbonate, idol Nitrogen diformamide (blowing agent AC), N, five methine tetramine (blowing agent H) of N '-dinitro, N, N '-dimethyl-N, N '-two are sub- Nitro terephthalamide (foaming agent NTA), physical microballoon foaming agent, foaming agent consumption used are not particularly limited, and one As be 0.1-30wt%.
The deleterious charge assembled in polymer samples can be guided or be disappeared by the antistatic agent in the addible auxiliary agent It removes, it is made production and life not brought inconvenience or be endangered comprising but be not limited only to following any or appoint several antistatic Agent: anionic antistatic agent, as alkylsulfonate, to Sodium Nonylphenoxypropane Sulfonate, alkyl phosphate diethanolamine salt, To nonyl diphenyl ether potassium sulfonate, phosphate derivative, phosphate, phosphoric acid polyethylene oxide alkyl ethers alcohol ester, phosphate derivative, Fatty amine sulfonate, butyrate sodium sulfonate；Cationic antistatic agent, as aliphatic ammonium salt hydrochlorate, lauryl trimethyl ammonium chloride, Dodecyl trimethylamine bromide；Amphoteric ion type antistatic agent, as alkyl dicarboxyl methyl ammonium second inner salt, lauryl betaine, N, N, N- trialkyl ammonium acetyl (N '-alkyl) amine second inner salt, bis- polyethylene oxide base-N- ethylphosphonic acid of N- lauryl-N, N- Sodium, N- alkylaminoacid salts；Non-ionic antistatic agent, such as fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide addition Object, alkyl phenol ethylene oxide addition product, tricresyl phosphate polyoxyethylene groups ether-ether, fatty acid glyceride；Polymer Antistatic Agent, such as Polyene propionamide N- quaternary ammonium salt substituent, poly- 4- vinyl -1- acetone yl pyridines phosphoric acid-are to butyl phenyl ester salt etc.；Wherein, resist quiet The preferred lauryl trimethyl ammonium chloride of electric agent, alkyl phosphate diethanolamine salt (antistatic agent P), antistatic agent dosage used It is not particularly limited, generally 0.3-3wt%.
Emulsifier in the addible auxiliary agent can improve various compositions in the mixed with polymers liquid containing auxiliary agent Surface tension between phase is allowed to form uniform and stable dispersion or emulsion comprising but be not limited only to following any Kind appoints several emulsifiers: anionic, such as higher fatty acid salt, alkylsulfonate, alkylbenzene sulfonate, alkyl naphthalene sulfonic acid Sodium, sulphosuccinates, petroleum sulfonate, aliphatic alcohol sulfate, castor oil salt, sulphation butyl ricinoleate salt, Phosphate ester salt, fatty acyl-peptide condensation product；Cationic, such as alkylammonium salt, alkyl quaternary ammonium salts, Fixanol；Amphoteric ion Type, such as carboxylic acid ester type, sulfonic acid ester type, sulfuric acid ester type, phosphate type；It is non-ionic, as fatty alcohol polyoxyethylene ether, alkyl phenol are poly- Ethylene oxide ether, polyoxyethylene carboxylate, polypropylene oxide-ethylene oxide adduct, fatty acid glyceride, pentaerythrite fat Acid esters, sorbierite and sorbitan fatty acid ester, sucrose fatty ester, hydramine fatty acid amide etc..Wherein, preferred dodecyl Benzene sulfonic acid sodium salt, sorbitan fatty acid ester, triethanolamine stearate (Emulphor FM), emulsifier used is without spy It does not limit, generally 1-5wt%.
Dispersing agent in the addible auxiliary agent enables to solid flocculation group in mixed with polymers liquid to be separated into carefully Small particle and be suspended in liquid, those are poorly soluble the solid and liquid particles in liquid for uniform dispersion, while can also prevent The only sedimentation and cohesion of particle forms stable suspension comprising but be not limited only to following any or appoint several dispersing agents: yin Ionic, such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate；Cationic；It is non-ionic, such as poly alkyl alcohol Ethylene oxide ether, sorbitol anhydride fatty acid polyoxyethylene ether；Inorganic type, such as silicate, condensed phosphate；Polymer electrolyte, it is such as bright Glue, water-soluble glue, lecithin, sodium alginate, lignosulfonates, polyvinyl alcohol etc..Wherein, the preferred detergent alkylate of dispersing agent Sodium sulfonate, naphthalene system methylene sulfonate (dispersing agent N), fatty alcohol polyoxyethylene ether, dispersant dosage used do not limit especially It is fixed, generally 0.3-0.8wt%.
Colorant in the addible auxiliary agent can make polymeric articles show required color, increase Surface color and polish comprising but be not limited only to it is following any or appoint several colorants: inorganic pigment, as titanium white, chrome yellow, cadmium red, Iron oxide red, molybdate red, ultramarine, chrome green, carbon black；Organic pigment, such as lithol red BK directions, lake red C, red, good base R is red, phthalocyanine Red, fast carmine HF3C, the bright red R of plastics and the not red BR of Crow, forever solid orange HL, Fast Yellow G, vapour bar plastics Huang R, permanent yellow 3G, Permanent yellow H2G, phthalocyanine blue B, dark green, plastics purple RL, nigrosine；Organic dyestuff, such as thioindigo red, vat yellow 4GF, indanthrene blue RSN, slag rhodamine toner, Oil Yellow etc..Wherein, the selection of colorant does not need especially to limit depending on color sample demand Fixed, colorant concentrations used are not particularly limited, generally 0.3-0.8wt%.
Fluorescent whitening agent in the addible auxiliary agent can make contaminated substance obtain the sparkling of similar fluorite Effect comprising but be not limited only to following any or appoint several fluorescent whitening agents: Stilbene-based, coumarin type, pyrazoline Type, benzo oxygen nitrogen type, phthalimide type etc..Wherein, (fluorescence increases the preferred stilbene biphenyl sodium disulfonate of fluorescent whitening agent White dose of CBS), bis- (5 methyl -2- benzoxazolyl) talan (fluorescent whitening agent KSN) of 4,4-, 2,2- (4,4 '-hexichol second Alkenyl) 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 addible auxiliary agent when incident light being enabled to reach polymer surfaces, occurs unrestrained anti- It penetrates, generates the matt and delustring appearance of low gloss comprising but be not limited only to following any or appoint several delustering agents: sedimentation sulphur Sour barium, silica, aqueous gypsum powder, talcum powder, titanium dioxide, poly- methyl carbamide resin etc..Wherein, the preferred titanium dioxide of delustering agent Silicon, delustering agent dosage used are not particularly limited, generally 2-5wt%.
Fire retardant in the addible auxiliary agent, can increase the flame resistance of material comprising but be not limited only to Under it is any or appoint several fire retardants: phosphorus system, such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, phosphoric acid Toluene diphenyl ester；Halogen phosphoric acid ester, such as three (2,3- dibromopropyl) phosphates, tricresyl phosphate (2,3- dichloro the third) ester；Organic halogen Compound, such as high chlorine contents chlorinated paraffin, 1,1,2,2- tetrabromoethane, deca-BDE, penta decane of perchloro- ring；Inorganic fire retardants, Such as antimony oxide, aluminium hydroxide, magnesium hydroxide, zinc borate；Reactive flame retardant, such as chlorendic anhydride, bis- (2,3- dibromos third Base) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride etc..Wherein, the preferred deca-BDE of fire retardant, phosphoric acid Triphenylmethyl methacrylate, tricresyl phosphate, phosphate toluene diphenyl ester, antimony oxide, amount of flame-retardant agent used are not particularly limited, and one As be 1-20wt%.
Nucleating agent in the addible auxiliary agent can accelerate crystallization speed by the crystallization behavior of change polymer Rate increases crystal density and promotes fine grain size, reaches and shortens material molding cycle, improves the product transparency, surface The purpose of the physical mechanical properties such as gloss, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance comprising but Be not limited only to it is following any or appoint several nucleating agents: benzoic acid, adipic acid, sodium benzoate, talcum powder, p-phenolsulfonic acid's sodium, Silica, benzylidene sorbitol and its derivative, EP rubbers, ethylene propylene diene rubber etc..Wherein, the preferred dioxy of nucleating agent SiClx, benzylidene sorbitol (DBS), ethylene propylene diene rubber, nucleating agent dosage used are not particularly limited, generally 0.1-1wt%.
Rheological agent in the addible auxiliary agent can guarantee that polymer has good brushing during film Property and coating thickness appropriate, the sedimentation of solid particle when preventing storage, can be improved its redispersibility comprising but not only limit In following any or several rheological agents: inorganic, such as barium sulfate, zinc oxide, alkaline earth oxide, calcium carbonate, chlorination Lithium, sodium sulphate, magnesium silicate, fumed silica, waterglass, colloidal silicon dioxide；Organo-metallic compound, as aluminum stearate, Aluminium alkoxide, titanium chelate, aluminium chelate compound；Organic, such as organobentonite, castor oil derivative, isocyanate derivates, propylene Yogurt liquid, acrylic copolymer, polyvinyl alcohol, polyethylene wax etc..Wherein, preferably organobentonite, polyethylene wax, hydrophobically modified Alkali-swellable emulsions (HASE), alkali-swellable emulsions (ASE), rheological agent dosage used are not particularly limited, generally 0.1-1wt%.
Thickener in the addible auxiliary agent can assign the good thixotropy of mixed with polymers liquid and appropriate Consistency is wrapped to meet various demands such as its stability and application performance in production, storage and use process It includes but is not limited only to following any or appoints several thickeners: lower-molecular substance, such as fatty acid salt, fatty alcohol polyoxyethylene ether sulphur Hydrochlorate, alkyldimethylamine oxide, fatty monoethanol amide, fatty diglycollic amide, fatty acid Isopropamide, dehydration mountain Pears alcohol tricarboxylic ester, glycerol trioleate, coamidopropyl glycine betaine；Polymer substance, such as bentonite, artificial hectorite, micro- Powder silica, colloidal aluminum, plant polyose class, microbial polysaccharide class, animal protein, seaweed acids, poly-methyl acrylate, first Base acrylic copolymer, cis-butenedioic anhydride copolymer, polyacrylamide, polyvinyl pyrrolidone, polyvinyl alcohol, polyethers, polyvinyl methyl ether urea Alkane polymer etc..Wherein, the preferred coconut oil diethanol amide of thickener, acrylic acid-methacrylic acid copolymer, thickening used Agent dosage is not particularly limited, generally 0.1-1.5wt%.
Levelling agent in the addible auxiliary agent can guarantee the flat and smooth uniform of polymer coating film, improve and apply Film surface quality improves dicoration comprising but be not limited only to following any or appoint several levelling agents: polyacrylate, Organic siliconresin etc..Wherein, the preferred polyacrylate of levelling agent, levelling agent dosage used are not particularly limited, generally 0.5-1.5wt%.
Antibacterial agent in the addible auxiliary agent, can within a certain period of time, make certain micro-organisms (bacterium, fungi, Saccharomycete, algae and virus etc.) growth or breeding be maintained at necessary below horizontal, be generally divided into inorganic antiseptic, You Jikang Microbial inoculum and natural antibacterial agent.Wherein, inorganic antiseptic include but are not limited to silver, copper, zinc, nickel, cadmium, lead, mercury, zinc oxide, Copper oxide, ammonium dihydrogen phosphate, lithium carbonate etc.；Organic antibacterial agent includes but are not limited to vanilla aldehydes, ethyl vanillin aldehydes, acyl group The organic compounds such as phenyl amines, imidazoles, thiazoles, isothiazolone derivative, quaternary ammonium salt, double croak classes, phenols；Natural antibacterial Agent includes but are not limited to chitin, mustard, castor oil, horseradish etc..Wherein, antibacterial agent preferably silver, zinc, vanilla aldehydes chemical combination Object, ethyl vanillin aldehydes compound, antibacterial agent dosage used are not particularly limited, generally 0.05-0.5wt%.
The addible filler, primarily serves following effect in the polymeric material: 1. reducing molded article Shrinking percentage improves dimensional stability, surface smoothness, flatness and the zero diopter of product or without photosensitiveness etc.；2. adjusting material Viscosity；3. meeting different performance requirement, such as raising material impact intensity and compressive strength, hardness, rigidity and modulus, raising are resistance to Mill property improves heat distortion temperature, improves electric conductivity and thermal conductivity etc.；4. improving the coloring effect of pigment；5. assigning photostability And chemical corrosion resistance；6. playing compatibilization, cost can be reduced, improves product competitiveness in the market.
The addible filler, selected from following any or several fillers: inorganic non-metallic filler, metal are filled out Material, organic filler.
The addible inorganic non-metallic filler includes but are not limited to following any or appoints several: calcium carbonate, Clay, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, asbestos, asbestos fibre, just Feldspar, chalk, lime stone, blanc fixe, gypsum, graphite, carbon black, graphene, graphene oxide, carbon nanotube, fullerene, two Molybdenum sulfide, slag, flue dust, wood powder and shell powder, diatomite, red mud, wollastonite, silica-alumina carbon black, aluminium hydroxide, magnesium hydroxide, Flyash, oil shale powder, swelling perlite powder, conductive black, vermiculite, iron cement, white clay, alkali mud, boron mud, (hollow) glass are micro- Pearl, foam microspheres, expandable particles, glass powder, cement, synthesis inorganic rubber, synthetic inorganic fiber, glass fibre, carbon fiber, Quartz fibre, charcoal core boron fibre, titanium diboride fiber, calcium titanium fiber, carbon silica fibre, ceramic fibre, whisker etc..
The addible metal packing, including metal simple-substance, metal alloy, metal oxide, metal inorganic chemical combination Object, metallo-organic compound etc. comprising but be not limited only to following any or appoint several: copper, silver, nickel, iron, gold etc. and its conjunction Powder, nano particle and the fiber of gold；Wherein, nano particle includes but are not limited to nanogold particle, nano-Ag particles, nanometer Palladium particle, nano cobalt granule, nano nickle granules, nano magnetic particle (such as γ-Fe2O3、CoFe2O4、NiFe2O4、MnFe2O4、 Fe3O4、FeN、Fe2N、ε-Fe3N、Fe16N etc.)；It additionally include liquid metal comprising but it is not limited only to mercury, gallium, gallium indium liquid State alloy, gallium indium tin liquid alloy, other gallium base liquid metal alloys；Wherein, metallo-organic compound includes some ultraviolet The metallo-organic compound molecule or crystal that can be generated heat under line, infrared ray or electromagnetic action.
The addible organic filler includes but are not limited to following any or appoints several: fur, natural rubber Glue, synthesis organic rubber, synthetic organic fibre, cotton, velveteen, fiber crops, jute, flax, asbestos, shellac, lignin, protein, Enzyme, hormone, raw lacquer, wood powder, shell powder, xylose, silk, artificial silk, vinylon, phenolic aldehyde microballon, resin microbeads etc..
Wherein, the wire feeding of addition does not limit, mainly depending on required material property, preferably calcium carbonate, sulphur Sour barium, talcum powder, carbon black, graphene, (hollow) glass microballoon, foam microspheres, expandable particles, glass fibre, carbon fiber, gold Belong to powder, natural rubber, protein, resin microbeads, amount of filler used is not particularly limited, generally 1-30wt%.
In the preparation process of dynamic aggregation object material, the preferred antioxidant of addible auxiliary agent, light stabilizer, thermostabilization Agent, toughener, plasticizer, foaming agent, fire retardant.The preferred calcium carbonate of addible filler, barium sulfate, talcum powder, carbon black, glass Microballon, expandable particles, graphene, glass fibre, carbon fiber.
In the preparation process of dynamic aggregation object, special limit is not done to the additive amount of dynamic aggregation object each component raw material Fixed, those skilled in the art can be adjusted according to practical preparation situation and target polymerization physical performance.
The manufacturing method of composition of the invention is not particularly limited, for example, roller, kneader, extruder, ten thousand can be passed through Can blender etc. additive the subsequent operations such as be blended to prepolymer as needed, then be crosslinked, foamed.
Dynamic aggregation object elastomer of the invention is obtained due to the metal-ligand effect containing good dynamic characteristics Dynamic aggregation object has certain modulus, toughness, self-healing properties simultaneously, can be widely used in adhesive, coating, film And elastic component in structural composite material etc..
A kind of hybrid cross-linked dynamic aggregation object gel provided by the present invention, preferably oligomer swell gel, plasticizer are molten Swollen gel, ionic liquid swell gel, more preferable plasticizer swell gel.
A kind of dynamic aggregation object plasticizer swell gel preparation method of the invention, including the following steps: will be hybrid cross-linked The raw material of dynamic aggregation object is added in suitable plasticizer, makes the quality of the dynamic aggregation object of prepared hybrid cross-linked network Score is 0.5~50%, carries out covalent cross-linking by suitable method, after reaction, a kind of dynamic is made in natural cooling The gel of polymeric plasticizer swelling, that is, one-step method prepare gel；The polymer chain containing ligand can also first be prepared Metal center is added after being swollen it in suitable plasticizer in network, takes out after its gelation reaction and removes extra increasing Mould agent.Upper the plasticizer is selected from following any or appoints several: Phthalates: dibutyl phthalate, adjacent benzene two Formic acid dioctyl ester, diisooctyl phthalate, dibutyl phthalate (DHP), diisooctyl phthalate, phthalic acid Dinonyl, BBP(Butyl Benzyl Phthalate, butyl phthalate butyl glycolate, dicyclohexyl phthalate, adjacent benzene two Bis- (13) esters of formic acid, terephthalic acid (TPA) two (2- ethyl) own ester；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；Epoxide Class, as epoxy glycerite esters, epoxy fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, epoxy are stearic Sour (2- ethyl) own ester, epoxy soybean oleic acid 2- ethylhexyl, the own ester of 4,5- epoxy tetrahydrophthalic acid two (2- ethyl), Chinese littleleaf box methyl acetylricinolate, dihydric alcohol lipid, such as C5~9Sour glycol ester, C5~9Sour Triethylene Glycol；Class containing chlorine, Such as afforest paraffin class, chloro fat acid esters；Polyesters, as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD are poly- Ester；Phenyl alkylsulfonate, trimellitate, citrate, pentaerythrite and pentaerythritol fatty acid ester etc..Wherein, epoxidation soybean Epoxidation reaction preparation occurs for a kind of Environment-friendlyplastic plastic plasticizer of function admirable of oil, refined soybean oil and peroxide.? It is resistance in polrvinyl chloride product to volatilize, is not easy to migrate, not easy to lose.This is to holding product light, thermal stability and prolongs the service life It is highly beneficial.Epoxidised soybean oil toxicity is minimum, is allowed for the packaging material of food and medicine by many countries, is The epoxy plasticiser that uniquely can be used for packaging material for food of Food and Drug Adminstration of the US's approval.It is dynamic in one kind of the invention In the gel preparation of state polymeric plasticizer swelling, the preferred epoxidized soybean oil of plasticizer.
In embodiments of the present invention, the oligomer is included but are not limited to: epoxy acrylate, modified epoxy third Olefin(e) acid ester, epoxy linseed oil triacrylate, polyester acrylic ester prepolymer, polyether acrylate, urethane acrylate Prepolymer, tripropylene glycol methoxy-ether mono acrylic ester, methoxy-ether neopentyl glycol propoxyl group mono acrylic ester, methoxy-ether three Hydroxymethyl-propane ethyoxyl diacrylate, the polymerization of amine modification acrylate, atoleine, number-average molecular weight less than 10000 Object；It is preferred that epoxy acrylate, polyester acrylate, polyether acrylate prepolymer, number-average molecular weight are poly- less than 10000 Urea, polycarbonate, polyester, polyethers or polyamide.
In embodiments of the present invention, the ionic liquid is included but are not limited to: glyoxaline ion liquid, pyridines Ionic liquid, quaternary ammonium ionic liquid, quaternary phosphine class ionic liquid, pyrrolidines ionic liquid, piperidines ionic liquid, alkenyl function Ionic liquid, Hydroxyl-functionalized Ionic Liquids, ether functionalized ion liquid, ester group functionalized ion liquid, carboxyl function can be changed Ionic liquid, itrile group functionalized ion liquid, amino functional ionic liquid, sulfonic acid funtionalized ionic liquid, benzyl function can be changed Ionic liquid, guanidine ionic liquid can be changed；It preferably specifically is selected from: 1- ethyl-3-methylimidazole tetrafluoroborate, 1- hexyl -2,3- Methylimidazole hexafluorophosphate, 1- ethyl-3-methylimidazole bromide, N- octylpyridinium bromide, tributyhnethylammonium chloride, four Butyl bromide phosphine, N- butyl-N- crassitude bromide, N- butyl-N- methyl piperidine bromide, 1- vinyl -3- butyl imidazole Hexafluorophosphate, 1,2- dimethyl -3- hydroxyethyl imidazole toluenesulfonate, 1- ethyl diethyldithiocarbamate ether -3- methylimidazole hexafluoro Phosphate, 1- ethyl acetate base -3- methylimidazole hexafluorophosphate, 1- carboxyethyl -3- methylimidazole bromide, 1- nitrile propyl -3- Methylimidazole hexafluorophosphate, 1- amine propyl -3- methylimidazole hexafluorophosphate, N- sulfonic acid butyl-pyridinium fluoroform sulphonate, 1- benzyl -3- methyl imidazolium tetrafluoroborate, tetramethylguanidine trifluoro-methanyl sulfonate.
A kind of hybrid cross-linked dynamic aggregation object foamed material provided by the present invention can be soft, semi-rigid or hard Matter foam.Foam can have water or it is anhydrous under the conditions of prepare, foaming method can be physical blowing, chemical blowing, machine One of tool foaming is a variety of.Further, the non-reacted foaming of suitable auxiliary type known in the art can be used in foam Agent.
A kind of preparation method of dynamic aggregation object foamed material of the invention can be selected from following steps: single in preparation When one network dynamic polymer foams, reaction mass component A and reaction mass component B is first independently made；Reactant Material component A is by 8 parts~20 parts of polyol compound, 0.05 part~1.0 parts of chain extender, 0.05 part~1.0 parts of crosslinking agent, has 0.01-0.5 parts of machine metal-based catalysts, 0.01-0.5 parts of amines catalyst, in 5-35 DEG C of material temperature, mixing speed 50-200r/ It is stirred evenly under conditions of min obtained；Reaction mass component B is by 10 parts~20 parts of polyisocyanate compound, foaming agent 0.5 Part~3.5 parts, 0.05 part~0.2 part of foam stabiliser, it is stirred under conditions of 5-35 DEG C of mixing speed 50-200r/min of material temperature It mixes and is uniformly made；Then reaction mass component A is mixed with reaction mass component B according to 1.0~1.5:1 mass ratio, through profession Equipment quickly stirs to get the single network dynamic aggregation object of foaming.Finally, the single network dynamic aggregation object after foaming is added Enter into mold, solidify 30min~60min at room temperature, then solidifies at high temperature to get the dynamic based on single network is arrived Polymer foams.At least one component contains pendant ligands in the component A and component B.It is solid at a high temperature of described Turn to be 60 DEG C in temperature at solidify 6h, or in temperature be 80 DEG C of solidification 4h, or in temperature be 120 DEG C of solidification 2h.It is above-mentioned polynary Hydroxyl (OH) group and the molar ratio of isocyanates (NCO) group in polyisocyanate compound in alcoholic compound may make Final polyurethane foam is free of free-end NCO group.The molar ratio of NCO/OH is preferably 0.9/1 to 1.2/1.NCO/ It is 100 that the molar ratio that OH is 1/1, which corresponds to isocyanate index,.In the case where water is used as foaming agent, the isocyanates refers to Number preferably greater than 100, such isocyanate groups can be reacted with water.
In dynamic aggregation object foamed material preparation method of the invention, in the dynamic aggregation for preparing binary hybrid cross-linked network When object foamed material, the step of according to above-mentioned preparation single network dynamic aggregation object, the 1st network is first prepared；Then in preparation the 2nd In network development process, the 1st network is added in reaction mass A ', i.e., reaction mass component A ' at this time is 8 parts of polyol compound ~20 parts, 0.05 part~1 part of chain extender, 0.05 part~0.4 part of crosslinking agent, 0.01~0.5 part of organometallic catalysts, amine 0.01~0.5 part of class catalyst, the 1st 0.1 part of network polymer~15 parts, in 5-35 DEG C of mixing speed 50-200r/min of material temperature Under conditions of stir evenly it is obtained；Reaction mass component B ' be 10 parts~20 parts of polyisocyanate compound, 2 parts of foaming agent~ 3.5 0.05 part~0.2 part of part, foam stabiliser stir evenly under conditions of 5-50 DEG C of mixing speed 50-200r/min of material temperature It is made.Then reaction mass component A ' is mixed with reaction mass component B ' according to 1.0~1.5:1 mass ratio, through professional equipment Quickly stir to get the dynamic aggregation object of the hybrid cross-linked network of foaming.Finally, by the dynamic of the hybrid cross-linked network after foaming Polymer is added in mold, solidifies 30min~60min at room temperature, is then solidified at high temperature and is handed over to get to based on hydridization The dynamic aggregation object foamed material of networking network.At least one component contains pendant ligands in the component A ' and component B '. Be cured as at a high temperature of described be 60 DEG C in temperature at solidify 6h, or in temperature be 80 DEG C of solidification 4h, or be 120 DEG C in temperature and consolidate Change 2h.And so on, when preparing the dynamic aggregation object foamed material of ternary hybrid cross-linked network, first prepare the 1st network and the 2nd Network, then when preparing 3 network, the 1st network is added and the 2nd network is sufficiently mixed and foams.
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.
Dynamic aggregation object of the invention is made due to the metal-ligand of the good dynamic characteristics formed with pendant ligands group With dynamic aggregation object obtained all has certain self-healing properties.Simultaneously because the presence of dynamic key, can be used as can be sacrificial The toughness of domestic animal key increase material.For example, being designed by suitable component selection and formula, can prepare with good plasticity Polymer block glue；Based on the dynamic reversibility of metal-ligand effect, it can design and prepare with shape memory and review one's lessons by oneself The material and toughness of multiple function splendid thin polymer film, fiber or plate, in bio-medical material, military affairs, aviation boat It, the fields such as the energy, building tool has been widely used；In addition, the sensor to stress sensitive can be prepared using its dynamic Deng.
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
The acrylamide of the 5- vinyl pyrimidine of 21g and 35g are mixed, No. 1 reactor is added after being dissolved in the toluene of 200mL In, the azodiisobutyronitrile (AIBN) of 2g is added, 6h is stirred to react after being warming up to 95 DEG C, 30g toluene diisocyanate is then added Acid esters continues after being stirred to react 1h, removes excess of solvent, reactant is transferred in No. 2 reactors of wide-mouth, toward No. 2 reactions The copper chloride solution of certain 100mL dibutyl phthalate and 2mL 0.2mol/L is added in device, continues to stir 5min mixing After uniformly, stop stirring, maintains after state 12h to get to dynamic aggregation object plasticizer swell gel.Performance test: 90% Compressive strength (MPa): 1.35 ± 0.22；Tensile strength (MPa): 2.14 ± 0.37；Elongation at break (%): 245.15 ± 23.44.Under the action of pulling force, the synergistic action effect between hydrogen bond and metal-ligand effect makes the drawing of the dynamic aggregation object Stretch intensity and elongation at break obtained certain promotion, the product can make as a kind of toughness adhesive carry out using. When the gel is in polar solvent, hydrogen bond action weakens, the mechanical properties decrease of gel, in polar solvent environment In, metal-ligand effect and hydrogen bond show orthogonal mechanics effect.
Embodiment 2
3- isocyanate group -1- the propylene of 40g is added in dry No. 1 reactor, 0.5g potassium peroxydisulfate is added while stirring (KPS) 80 DEG C are warming up to, 4h is stirred to react, maintains this temperature, while stirring 5- (amino methyl) -2- (1- pyrrole that 40g is added Oxazolyl) pyridine, after the reaction was continued 2h, the 1,4-Diaminobutane of 11g is added, after the reaction was continued 1h, reactant is transferred to extensively Mouthful No. 2 reactors in, into No. 2 reactors addition 100mL 1- butyl -3- methylimidazole hexafluorophosphoric acid ionic liquid, Nickel chloride solution, the 1g graphene of 2mL 0.2mol/L continues to stir 5min, ultrasound 20min, after mixing, stops stirring, It maintains after state 12h to get to dynamic aggregation object ionic liquid swell gel.After being pressed with finger sample surfaces, Sample can show good elasticity, and can carry out stretching extension in a big way.It is made into 80.0 × 10.0 × The dumbbell shape batten of 2.0mm size carries out extension test using cupping machine, and rate of extension 50mm/min measures sample Tensile strength is 2.73 ± 0.45MPa, and elongation at break is 361 ± 62%.Polymer samples in the present embodiment embody Good self-repairability, cut with a knife it is disconnected after, section part is slightly applied pressure be bonded it is (optional during this Section is slightly soaked), section can bond again after 90min.Dynamic aggregation object sample in the present embodiment, can be made It carries out for a kind of graphene composite intelligent Heat Conduction Material using further, since the high conductivity of graphene, makes in the present embodiment Dynamic aggregation object has different conductivity under different stress states, which, which can be used as strain gauge, is made With.
Embodiment 3
Polyacrylic resin, 100mL N, the N- dimethyl methyl that 50g relative molecular weight is 3000 are added in No. 1 reactor Amide, 2mL condensing agent I-hydroxybenzotriazole (HOBT) and 3mL activator 1- (3- dimethylamino-propyl) -3- ethyl carbon two are sub- After being uniformly mixed, 4- amino -2,6-diacetylpyridine of 50g is added (with chloro- 2, the 6- bis- of 4- in amine hydrochlorate (EDC) Acetylpyridine is reacted with the hydrazine hydrate solution of potassium phthalimide to be made), continue after being stirred to react 12h at room temperature, The polyacrylic resin that 50g relative molecular weight is 3000 is added, after being stirred, addition 28g 1,6- diamino hexane, after Continuous reaction 12h, removes excess of solvent, reactant is transferred in No. 2 reactors of wide-mouth, is added 100 into No. 2 reactors ML polyacrylic acid N-butyl oligomer, the liquor zinci chloridi of 3mL 0.2mol/L, 3g Cellulose nanocrystal body, continue to stir 10min, ultrasound 20min stop stirring after mixing, maintain after state 12h to get molten to dynamic aggregation object oligomer Swollen gel.It is made into the dumbbell shape batten of 80.0 × 10.0 × 0.02mm size, carries out extension test using cupping machine, Rate of extension is 50mm/min, and measuring sample tensile strength is 3.32 ± 0.34MPa, and fracture percentage of elongation is 432 ± 45%.Polymerization Object is soft, has good intensity and toughness, can extend in a certain range, and has good tear resistance Energy.After the polymer samples broken recycling, applying good pressure and be placed in and place 1-2h at room temperature, section can be bonded voluntarily, Again it forms.The product can be prepared to a kind of self-adhesion love toys, with intensity and toughness while can also realize from It repairs.
Embodiment 4
Polyethers ketone powder, 200mL toluene, 3mL condensing agent 1- that 100g side group contains carboxyl are added in No. 1 reactor Hydroxybenzotriazole (HOBT) and 5mL activator 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDC), are stirred It mixes to dissolution after mixing, the N of 46g is added, N- lutidines -2,6- diimine continues to be stirred to react at room temperature 12h, it is spare；Polyacrylic resin, 100mL toluene, the 3mL contracting that 100g relative molecular weight is 3000 are added in No. 2 reactors Mixture I-hydroxybenzotriazole (HOBT) and 4mL activator 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDC), after being uniformly mixed, 5- amino -1,10- phenanthroline of 34g is added, continues after being stirred to react 12h at room temperature, Reactant in No. 1, No. 2 reactors is mixed and is transferred in No. 3 reactors of wide-mouth, 2g carbon fiber is added, after mixing, It is sub- to add 1mL condensing agent I-hydroxybenzotriazole (HOBT), 2mL activator 1- (3- dimethylamino-propyl) -3- ethyl carbon two Amine hydrochlorate (EDC), the 1,5- 1,5-DAP of 47g, 3mL 0.2mol/L ferric chloride solution and 2mL0.2mol/L chlorination Cadmium solution after reacting 12h, removes excess of solvent to get dynamic aggregation object ordinary solid is arrived.It is made into 80.0 × 10.0 × The dumbbell shape batten of 2.0mm size carries out extension test using cupping machine, and rate of extension 10mm/min measures sample Tensile strength is 41.23 ± 3.41MPa, and elongation at break is 54.39 ± 12.12%, using its surface hardness and High intensity, can be made into tool housing use, and surface scratch can be automatically repaired healing.
Embodiment 5
Hydrogeneous methyl-silicone oil and a certain amount of propenyl are mixed, is put into No. 1 reactor and stirs evenly, in control reaction Double bond molal quantity in the molal quantity and propenyl of active hydrogen atom (hydrogen atom being directly connected with Si) in hydrogeneous methyl-silicone oil Ratio is about 1:1.2, and addition reaction occurs using chloroplatinic acid as catalyst, obtains the methyl-silicone oil that side group contains polyhydroxy group, I.e. a kind of poly-organosilicon polyalcohol (molecular weight is about 7000).Poly-organosilicon obtained by a part is added in No. 2 reactors Polyalcohol, (5- amino -5H- tetrazolium reacts system with thricarbonate di tert butyl carbonate to 5- isocyanate group -5H- tetrazolium in methylene chloride ) and a certain amount of dry toluene, controlling hydroxyl and isocyanate group the mass ratio of the material example is 2:1, is warming up to 80 DEG C and is stirred to react After 2h, a certain amount of 1,6- diisocyanate root hexane is added, the reaction was continued 2h removes extra solvent, by obtained modification Silicone oil dries spare；Remaining poly-organosilicon polyalcohol, a certain amount of dry toluene and a certain amount of methyl isocyanate are added Enter into No. 3 reactors, the amount ratio for controlling isocyano and hydroxylated material is 1:1, be warming up to 80 DEG C be stirred to react 2h after, remove Extra solvent is removed, product and modified silicon oil is added to after carrying out mixing 30min in small-sized internal mixer, is added in parts by weight 2 parts of white carbon blacks, 1 part of titanium dioxide, 0.5 part of di-iron trioxide, 0.2 part of carbon nanotube, 0.05 part of organic silicone oil, 0.3 part containing crystallization The copper sulphate of water continues to be kneaded 6h, after being sufficiently mixed additive and sizing material uniformly, sizing material is taken out, suitable mold is placed in In, it is cooled to is placed at room temperature for 30min later, be removed from the molds sample, dynamic aggregation object elastomer is finally obtained, with good Good plasticity, product of different shapes can be prepared into according to die size, while possessing excellent toughness, measures this material Possess different conductivity under unused pulling force or pressure effect, illustrates that it also has stress response.This elastomer is cut It has no progeny, applies good pressure 1-2h in section part, section can be bonded voluntarily, be formed again.It is special using its function Property, the fields such as strain gauge, electric, medical instrument, auto industry can be applied to.
Embodiment 6
Polyacrylic resin, 100mL N, the N- dimethyl methyl that 20g relative molecular weight is 2000 are added in No. 1 reactor Amide, 2mL condensing agent I-hydroxybenzotriazole (HOBT) and 3mL activator 1- (3- dimethylamino-propyl) -3- ethyl carbon two are sub- Amine hydrochlorate (EDC) after being uniformly mixed, is added 2, the 6- dimethoxy-pyridine -4- amine of 42g, continues to stir at room temperature After reacting 12h, adds the polyvinyl alcohol that 20g relative molecular weight is 20000 and reactant is transferred to wide-mouth after mixing In container, 55g methyl diphenylene diisocyanate, 1g nanoscale ferroso-ferric oxide, 5g expandable particles, 2g gallium indium liquid is added State alloy is warming up to 80 DEG C after mixing, is allowed to be crosslinked and foam, and then product is put into 60 DEG C of baking ovens and cures 6h, i.e., Dynamic aggregation object foamed material is made.Performance test: density (kg/m3): 68.64 ± 9.43；70% compressive strength (MPa): 2.32±0.23；Tensile strength (MPa): 4.22 ± 0.73；Elongation at break (%): 313.24 ± 42.35.The product can be by Being prepared into antistatic flexible foam can heal automatically in cracking.
Embodiment 7
Take 20g modified polyorganosiloxane (with methyl hydrogen polysiloxanes, (bis- (dimethylamino) pyridin-4-yls of 2,6-) first Base acrylate is raw material, carries out hydrosilylation under the catalysis of chloroplatinic acid and is made), 25g modified polyorganosiloxane is (with first Base hydrogen containing siloxane, equimolar amounts isocyanates ethyl acrylate react product obtained at room temperature with ethamine for original Material, under the catalysis of chloroplatinic acid carry out hydrosilylation and be made), 20g side group polysiloxanes containing double bonds, 12g 1, 3- dimercaptopropane, 7g AC foaming agent, 5g foam microspheres, 0.1g Metal Organic Molecular cage (MOC-16), 8g calcium carbonate, 0.5g Stearic acid, 0.1g irgasfos 168,0.3g antioxidant 1010,0.5g di-n-butyltin dilaurate are added to after mixing Mixing blending is carried out in small-sized internal mixer, wherein blending temperature is 100 DEG C, and the blending time is 30min, after mixing, by sample Product take out, and are put into twin-roll machine and suppress flakiness, and 6h is placed in 80 DEG C of vacuum drying ovens and is further reacted and is dried, it After be cooled to and be placed at room temperature for 30min.It takes out and is kneaded print, place it in suitable mold, sent out using vulcanizing press Soak type, wherein molding temperature is 130-140 DEG C, clamp time 10-15min, pressure 10MPa, and it is poly- to finally obtain dynamic Polymer foam, with good pliability and elasticity.It is made into the blocky sample of 20.0 × 20.0 × 20.0mm size Product carry out compression performance test using universal testing machine, and compression speed 2mm/min, measuring 50% compressive strength of sample is 4.21±0.48MPa.After polymer material is cut off, after polymer material is cut off, applying pressure in its section part can Again it forms, the self-healing properties having using it can be reused.In the present embodiment, had using material obtained Have can selfreparing characteristic, can be used for production stationery material carry out using.
Embodiment 8
5- acrylamido -7- azepine -1H- indoles (5- amino -7- azepine -1H- the Yin of 33g is added in No. 1 reactor The product of diindyl and acrylic acid reaction), 36g acrylamide, 52g styrene and 200mL DMF, be uniformly mixed, be added while stirring 1g ammonium persulfate (APS) is warming up to 80 DEG C, after being stirred to react 4h, and product is transferred in No. 2 reactors of wide-mouth, is stirred simultaneously It mixes and 45g toluene di-isocyanate(TDI) is added, after the reaction was continued 2h, remove solvent, product 1 is taken out spare；Add in No. 3 reactors Enter 2- (3- ethyl urea groups) ethyl acrylate, 36g acrylamide, 52g styrene and 200mL DMF of 100g, is uniformly mixed, side Stirring side is added 1g ammonium persulfate (APS) and is warming up to 80 DEG C, after being stirred to react 4h, and product is transferred to No. 2 reactors of wide-mouth In, while stirring and 45g toluene di-isocyanate(TDI) is added, after the reaction was continued 2h, solvent is removed, product 2 is taken out.By product 1, produce The N of object 2,20g, N '-dimethyl-N, N '-dinitrosoterephthalamine (foaming agent NTA), 3g hollow glass microballoon, The Zn of 0.2g4O(BTB)2(MOF-177), 10g calcium carbonate, 1.5g stearic acid, 0.5g irgasfos 168,0.5g tin dilaurate two be just Butyl tin is added in small-sized internal mixer progress mixing blending after mixing, wherein blending temperature is 100 DEG C, when blending Between be 30min, after mixing, sample is taken out, is put into twin-roll machine and suppresses flakiness, is cooled to is placed at room temperature for later 30min.It takes out and is kneaded print, place it in suitable mold, carry out foaming using vulcanizing press, wherein molding Temperature is 90-105 DEG C, clamp time 10-15min, pressure 10MPa, finally obtains dynamic aggregation object foamed material, is had There are good rigidity and intensity.Be made into the bulk sample of 20.0 × 20.0 × 20.0mm size, using universal testing machine into The test of row compression performance, compression speed 2mm/min, measuring 10% compressive strength of sample is 2.42 ± 0.83MPa.What is obtained is poly- It is polymer foam light specific gravity, easily molded, it can be automatically repaired, can be used as thermal insulation material after damaged.
Embodiment 9
(3- amino -1,8- naphthyridines and acrylic acid are anti-for the 3- acrylamido -1,8- naphthyridines of addition 36g in No. 1 reactor The product answered), 36g acrylamide, 40g methyl acrylate and 200mL toluene, be uniformly mixed, 1g persulfuric acid be added while stirring Potassium (KPS) is warming up to 80 DEG C, after being stirred to react 4h, and product is transferred in No. 2 reactors of wide-mouth, while stirring and 45g is added Isosorbide-5-Nitrae-diisocyanate ester group butane, after the reaction was continued 2h, remove solvent, product 1 taken out spare；Product 1,100g are gathered 1,2- butadiene, 10g triphenyl phosphate, 2g azodiisobutyronitrile, 1g glass fibre, 2g nanoscale talcum powder, 0.4g antioxidant 1010, the chiral pincer ligand of the Isosorbide-5-Nitrae of 10g-dimercapto butane and 1g double-core Pd after mixing, are added in small-sized internal mixer Carry out mixing blending, wherein blending temperature is 100 DEG C, and the blending time is 30min, takes out mixture after mixing, will mix Object is put into suitable grinding tool, is continued after curing 6h in 80 DEG C of baking ovens, and it is common to obtain a kind of dynamic aggregation object for cooling sample Solid.Its surface is smooth, there is certain glossiness, and hardness and mechanical strength are higher.It is made into 80.0 × 10.0 × 2.0mm ruler Very little dumbbell shape batten carries out extension test using cupping machine, and rate of extension 10mm/min measures sample tensile strength For 7.32 ± 1.13MPa, stretch modulus is that sample is placed in often by 24.42 ± 2.53MPa with blade after its surface scratch The lower 3-4h scratch of placing of temperature can heal automatically, can be made into the plate use with self-healing properties.
Embodiment 10
2- amino -6- ethoxy pyridine, the 100mL N,N-dimethylformamide, 2mL of 34g are added in No. 1 reactor Condensing agent I-hydroxybenzotriazole (HOBT) and 3mL activator 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDC), after being uniformly mixed, bis- (methylol) propionic acid of 2,2- of 33g is added, continue after being stirred to react 12h at room temperature, Product 1 is taken out spare；Product 1, MDI, 20g water of 120g, 10g methylene chloride, 10g crosslinking agent are added in No. 2 reactors Glycerine, 1g di-n-butyltin dilaurate, 3g trifluoromethanesulfonic acid europium after mixing with professional blender are warming up to 80 DEG C, So that it is reacted and is foamed, foam is obtained into a kind of dynamic aggregation object as curing 6h is continued in 60 DEG C of baking ovens after the completion of foaming Foamed material is made into the bulk sample of 20.0 × 20.0 × 20.0mm size, carries out compression performance using universal testing machine Test, compression speed 2mm/min, measuring 50% compressive strength of sample is 3.13 ± 0.52MPa.Obtained foam of polymers material Expect light specific gravity, easily molded, can be automatically repaired, can be used as thermal insulation material after breakage cracking.
Embodiment 11
The 1,5- glutaryl of bis- (2- the amino-ethyl) -1- hydroxyethyl benzene of 50g 3,5-, 42g are added in No. 1 reactor Chlorine, 200mL dry methylene chloride is heated to 70 DEG C of beginning polymerization reactions, and after reacting 4h, 5- (the 1- isocyanic acid of 14g is added Root closes ethyl) pyrimidine, the reaction was continued 2h removes solvent, product 1 is made.Product 1,12g chain extender are added in No. 3 reactors 1,4- butanediol, 100mL toluene, 0.5g dibutyl tin dilaurate, 0.3g triethylenediamine, 1g organic silicone oil, 4mL The manganese chloride solution of 0.2mol/L stirs evenly under conditions of 35 DEG C of material temperature, mixing speed 200r/min, 38g is then added TDI is warming up to 80 DEG C, and is stirred, and after reacting 2h, reactant is transferred in No. 4 reactors of wide-mouth, stops stirring, After maintaining temperature 6h, residual solvent is removed to get a kind of dynamic aggregation object elastomer is arrived.Obtained elastomer has good Resilience, be made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm size, carry out stretching survey using cupping machine Examination, rate of extension 50mm/min, measure sample tensile strength be 4.23 ± 0.45MPa, elongation at break be 482.12 ± 83.12%.The product can be prepared into a kind of elasticity hammer, and adjustment level can be beaten when installation floor or wallboard, It can heal automatically when cracking.
Embodiment 12
57g (bis- (dimethylamino) pyridin-4-yls of 2,6-) methacrylate, 18g 3- is added in No. 1 reactor Butene-1-ol, 5g azodiisobutyronitrile are warming up to 90 DEG C after mixing evenly, the reaction was continued 4h, and product 1 is made；It is anti-at No. 2 Answer in device be added product 1,10g dicyclopentadienyl nickel polymer, 80mL 1,2- dimethyl -3- hydroxyethyl imidazole toluenesulfonate from Sub- liquid, 10mL pyridine, the trifluoromethanesulfonic acid zinc solution of 5mL 0.2mol/L, 0.5g carbon nanotube are warming up to after mixing 80 DEG C, it is added dropwise to 22g isophorone diisocyanate while stirring, after reacting 1h, stops stirring, maintains state 12h, i.e., Obtain dynamic aggregation object ionic liquid swell gel.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm size, is utilized Cupping machine carries out extension test, and rate of extension 50mm/min, measuring sample tensile strength is 3.12 ± 0.53MPa, breaks Splitting elongation is 342.42 ± 43.44.Dynamic aggregation object gel in this embodiment can be used as energy storage material device, It can heal automatically when cracking failure.
Embodiment 13
2- propylene tetrazole radical -1,10- phenanthroline (2- cyano -1,10- phenanthroline and the 3- of 30g are added in No. 1 reactor Azido -1- propylene carries out click-reaction under triethylamine hydrochloride and toluene catalytically and is made), 50g methyl acrylate, 100mL deionized water, 1g potassium peroxydisulfate, are uniformly mixed, and are warming up to 80 DEG C, after reacting 4h, remove excess of solvent, will produce Object is mixed with the uncured bisphenol A type epoxy resin of 100g, and the cobalt chloride solution of 5mL 0.2mol/L is added, and is added after stirring 20g hexamethylene diamine curing agent, stirring is warming up to 50 DEG C in suitable mold, after system forms completely, is cooled to room temperature, i.e., A kind of dynamic aggregation object ordinary solid is made.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm size, utilizes stretching Testing machine carries out extension test, and rate of extension 10mm/min, measuring sample tensile strength is 23.14 ± 3.32MPa, and fracture is stretched Long rate is 15.32 ± 0.72%, and polymer samples obtained have biggish surface hardness and intensity.It can be made in the product For at a kind of self-repair material, can heal automatically in impaired scraped.
Embodiment 14
Polyacrylic resin, 100mL toluene, the 3mL condensation that 100g relative molecular weight is 3000 are added in No. 1 reactor Agent I-hydroxybenzotriazole (HOBT) and 4mL activator 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride (EDC), after being uniformly mixed, 4- amino -2,6- dichloropyridine of 40g is added, continues after being stirred to react 12h at room temperature, 1mL condensing agent I-hydroxybenzotriazole (HOBT), 2mL activator 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide is added Hydrochloride (EDC), 1, the 6- diamino hexane of 52g, 3mL 0.2mol/L silver nitrate solution, continue to stir, react 12h after, Excess of solvent is removed, by obtained product and 6 particle mixing extruding pelletization of 100g nylon, and 20 g glass fibres, 2g are added Nanoscale talcum powder, 2g dibasic lead stearate, 2g molybdenum disulfide, 3g lauryl trimethyl ammonium chloride, extrusion temperature 240 DEG C, dry particle after be molded, injection temperature be 220 DEG C to get arrive dynamic aggregation object ordinary solid.Injection molding is obtained mute Bell pattern item carries out extension test using cupping machine, and rate of extension 10mm/min, measuring sample tensile strength is 42.21 ± 4.47MPa, elongation at break are 45.69 ± 4.21%, and polymer samples obtained have lustrous surface and intensity, can will make It carries out at the smooth plate in surface using with self-healing properties.
Embodiment 14
Polyacrylic resin, 100mL N, the N- dimethyl methyl that 20g relative molecular weight is 2000 are added in No. 1 reactor Amide, 2mL condensing agent I-hydroxybenzotriazole (HOBT) and 3mL activator 1- (3- dimethylamino-propyl) -3- ethyl carbon two are sub- Amine hydrochlorate (EDC) after being uniformly mixed, is added 1- (imidazolidine -2- base) urea of 31g, continues to be stirred to react at room temperature After 12h, reactant is transferred in large container by 4- allyl -1, the 6- heptadiene for adding 34g after mixing, is added 1,3- dimercaptopropane, 0.5g antioxidant butylated hydroxy anisole (BHA), Fe of the 0.5g Jing Guo surface modification of 40g3O4Particle, 0.3g bentonite, the chromium chloride solution of 5mL 0.2mol/L, 100mL dioctyl phthalate are uniformly mixed and are placed on 300W purple 30min is irradiated under outer lamp, takes out after cooling, obtains a kind of dynamic aggregation object plasticizer swell gel, and there is certain glue Elasticity.Under the action of pulling force, the synergistic action effect between hydrogen bond and metal-ligand effect makes the stretching of the dynamic aggregation object Intensity and elongation at break have obtained certain promotion.The plasticizer swell gel can also be shown under the action of an external magnetic field Certain shape memory characteristic, can be made a kind of shape-memory material carry out using.
Embodiment 15
3- isocyanate group -1- the propylene of 20g is added in dry No. 1 reactor, while stirring the 5- hydroxyl -1H- Yin of 34g Azoles is warming up to 80 DEG C, after being stirred to react 1h, and 100mL dry toluene is added, and maintains 80 DEG C, is added 0.5g potassium peroxydisulfate (KPS), It is stirred to react 4h, obtained product 1 is spare；Cyanuric acid and the chloro- 1- hexene of 6- are kept into molar ratio in No. 3 reactors 4:1 is dissolved in anhydrous dimethyl sulphoxide, is stirred to react 15 hours at 80 DEG C under potassium carbonate catalysis, obtains hydrogen bonds group Product 2；By product 1, product 2,34g 4- allyl -1,6- heptadiene, the 1,3- dimercaptopropane of 40g, 0.5g antioxidant 168, polyethers of the 100mL number-average molecular weight less than 10000, the copper chloride solution of 5mL 0.2mol/L, 5g hollow glass micro-ball mix It after closing uniformly, is placed under 300W ultraviolet lamp and irradiates 30min, taken out after cooling, obtain a kind of dynamic aggregation object oligomer swelling The modulus of gel, the prepared oligomer swell gel containing tiny balloon is about 8.3MPa, and strain can achieve 5 times, fracture Stress is about 5.5MPa.The product can be used as the use of the sealing material with self-repair function.
Embodiment 16
3- isocyanate group -1- the propylene of 20g is added in dry No. 1 reactor, while stirring the 2- methylpyrazole-of 24g 3- amine is warming up to 80 DEG C, after being stirred to react 1h, and 100mL dry toluene is added, and maintains 80 DEG C, is added 0.7g potassium peroxydisulfate (KPS) With 40g propenyl, it is stirred to react 4h, obtained product 1 is taken out spare；50g polypropylene oxide is added in No. 2 reactors Triol, 100mL DMF, it is warming up to 80 DEG C after being completely dissolved, 4, the 4- diisocyanate dicyclohexyl first of 14g is added while stirring Alkane after reacting 2h, removes excess of solvent, product 2 is made.Product 1, product 2,10g water, 20mL methylene chloride, 0.1g ruthenium is miscellaneous Benzene, the manganous chloride solution of 3mL 0.2mol/L, 0.5g modified triethylene diamine solution (DY-8154), 2g conductive black, 1g Graphene and 5g foam microspheres are uniformly mixed, and 15g MDI is added, and are continuesd to mix uniformly, are moved on in suitable mold, be warming up to It 80 DEG C, after foaming, puts it in 60 DEG C of baking oven and continues to cure 6h, it is cooling later to take out sample, it obtains a kind of dynamic State polymer foams.It is made into the bulk sample of 20.0 × 20.0 × 20.0mm size, is carried out using universal testing machine Compression performance test, compression speed 2mm/min, measuring 50% compressive strength of sample is 4.42 ± 0.71MPa.What is obtained is poly- Polymer foam light specific gravity, resilience are good, easily molded, breakage cracking after can be automatically repaired, resistivity with its by Stress and change, can be used as strain gauge.
Embodiment 17
The 5- acrylamide yl pyridines -2- methyl formate (5- aminopyridine -2- formic acid first of 31g is added in No. 1 reactor The product of ester and acrylic acid reaction), 26g acrylamide, 40g methyl acrylate and 200mL toluene, be uniformly mixed, while stirring 1g potassium peroxydisulfate (KPS) is added and is warming up to 80 DEG C, after being stirred to react 4h, product is transferred in No. 2 reactors of wide-mouth, simultaneously Stirring is added Isosorbide-5-Nitrae-diisocyanate ester group butane of 45g, after the reaction was continued 2h, removes solvent, product 1 is taken out spare；It will produce The uncured phenolic resin of object 1,100g, the expandable microballoon of 20g, 10g diisopropyl azodiformate, 5g quartz fibre, 20g Hexa, 5g tetra- be hydrated nickel acetate place it in suitable mold after mixing, using vulcanizing press into Row foaming, wherein molding temperature is 100-130 DEG C, clamp time 10-15min, pressure 10MPa, will after molding Foam, which is placed in 60 DEG C of baking ovens, continues to cure 4h, obtains dynamic aggregation object foamed material after cooling, with good rigidity and Intensity.It is made into the bulk sample of 20.0 × 20.0 × 20.0mm size, carries out compression performance test using universal testing machine, Compression speed is 2mm/min, and measuring 10% compressive strength of sample is 4.23 ± 0.56MPa.Obtained polymer foams ratio It is heavy and light, easily molded, it can be automatically repaired after damaged, it can be as toy material.
Embodiment 18
3- isocyanate group -1- the propylene of 40g is added in dry No. 1 reactor, the 4- hydroxyl that 50g is added while stirring is rattled away Piperazine and 0.5g triethylamine, are warming up to 80 DEG C, are stirred to react 1h, and 100mL toluene is added, maintains this temperature, adds the 1- of 17g 0.5g is added after mixing in allyl -2,4- dioxo -1,2, the 3- butene-1-ol of 3,4- tetrahydro -5- pyrimidines and 36g After potassium peroxydisulfate (KPS) the reaction was continued 4h, extra solvent is removed, product 1 is obtained；By product 1, the 1,4- butanediol of 5g (BDO), TDI, 5g p-methyl benzenesulfonic acid zinc salt hydrate, the 10mL water of the N-ethylmorpholine of 0.5g, the AC foaming agent of 3g, 20g mixes It being put into suitable mold after closing uniformly, carries out foaming using vulcanizing press, wherein molding temperature is 110-140 DEG C, Clamp time is 10-15min, pressure 10MPa, and foam is placed in 60 DEG C of baking ovens after molding and continues to cure 4h, is obtained after cooling To dynamic aggregation object foamed material, quality is relatively soft and high resilience.It is made into 20.0 × 20.0 × 20.0mm size Bulk sample carries out compression performance test using universal testing machine, and compression speed is 2 mm/min, measures sample 50% and compresses by force Degree is 2.43 ± 0.36MPa.Obtained polymer foams light specific gravity, resilience are good, can be automatically repaired after damaged, can will Its as toy material carry out using.
Embodiment 19
3- methyl -2- propylene tetrazole radical-pyridine (3- methyl -2- cyanopyridine and 3- of 20g is added in No. 1 reactor Azido -1- propylene carries out click-reaction under triethylamine hydrochloride and toluene catalytically and is made), 50g methyl acrylate, 20g 1,2- butadiene monoxide, 100mL toluene, 1g potassium peroxydisulfate, be uniformly mixed, and be warming up to 80 DEG C, react 4h after, remove Product 1 is made in excess of solvent；By product 1, diethyl toluene diamine (DETDA), the 0.5g dibutyl tin dilaurate of 10g (DY-12), TDI, 5g palladium (II) propionate, the 10mL water of 4g diethyl azodiformate, 20g, it is suitable to be put into after mixing Mold in, utilize vulcanizing press carry out foaming, wherein molding temperature be 110-120 DEG C, clamp time 10- Foam is placed in 60 DEG C of baking ovens after molding and continues to cure 4h by 15min, pressure 10MPa, and dynamic aggregation object bubble is obtained after cooling Foam material.It is made into the bulk sample of 20.0 × 20.0 × 20.0mm size, carries out compression performance survey using universal testing machine Examination, compression speed 2mm/min, measuring 10% compressive strength of sample is 5.13 ± 0.66MPa.Obtained polymer foams Light specific gravity, intensity are high, can be automatically repaired after cracking, can be carried out as stationery material using.
Embodiment 20
In No. 1 reactor, 20g nitrile rubber is dissolved in 100mL butanone, after being completely dissolved, 8 are added into reactor G ethyl azidoacetate, 1g triethylamine hydrochloride and 5mL deionized water, stirring are reacted for 24 hours, will remove solvent, obtain production Object 1；23g glycerine, 0.2g triethylenediamine are added in No. 2 reactors, stirring is warming up to 80 DEG C, the 1,6- of 42g is added After being stirred to react 2h, product 2 is made in hexamethylene diisocyanate；By product 1, product 2,3g carbon black, 3g white carbon black, 5g titanium dioxide, 0.5g di-iron trioxide, 3g carbon nanotube, 0.05 part of organic silicone oil, 0.3 part of copper sulphate containing the crystallization water are kneaded 6h, make to add After agent and sizing material are sufficiently mixed uniformly, sizing material is taken out, is placed in suitable mold, is cooled to is placed at room temperature for 30min later, from Sample is taken out in mold, finally obtains dynamic aggregation object elastomer, with good plasticity, can be prepared according to die size At product of different shapes, while possessing excellent toughness, measures this material and possess under unused pulling force or pressure effect Different conductivity illustrates that it also has stress response.After this polymer cutting, apply good pressure 1- in section part 2h, section can be bonded voluntarily, be formed again.Using its functional characteristic, strain gauge can be made into.
Embodiment 21
2- acrylamido-purine (production of 2-aminopurine and acrylic acid reaction of 36g is added in No. 1 reactor Object), 2- hydroxyethyl -2- methyl -2- acrylate, 40g methyl methacrylate and the 200mL toluene of 76g, be uniformly mixed, 1.5g potassium peroxydisulfate (KPS) is added while stirring and is warming up to 80 DEG C, after being stirred to react 4h, by product be transferred to No. 2 of wide-mouth it is anti- Answer in device, at the same stir be added TDI, 40mL deionized water of 90g, 1g cupric sulfate pentahydrate powder, 0.5g N, N- diformazan basic ring Hexylamine and 2g sorbierite, are warming up to 80 DEG C, are quickly stirred to react with the blender of profession, by foam as 60 DEG C after foaming Continue to cure 6h in baking oven, obtains a kind of dynamic aggregation object foamed material after cooling.It is made into 20.0 × 20.0 × 20.0 The bulk sample of mm size carries out compression performance test using universal testing machine, and compression speed 2mm/min measures sample 50% compressive strength is 1.63 ± 0.26MPa.Obtained polymer foams light specific gravity, resilience are good, can after damaged from It is dynamic to repair, can be made into shape memory foam carry out using.
Embodiment 22
50g polyvinyl alcohol is added in parts by weight in No. 1 reactor, and 100mL methylene chloride is added, stirring keeps its molten Solution, side stirs the 9- isothiocyanato acridine for being slowly dropped into 10g, is warming up to 60 DEG C, after reacting it sufficiently, removes extra molten Agent, obtained product 1 take out spare；Product 1 is transferred in No. 2 reactors of wide-mouth, while stirring and 62g triphenyl methane is added Triisocyanate, 30mL deionized water, 3g tetrafluoro boric acid silver powder, 1g carbon fiber, 3g glass fibre, 0.5g N, N- diformazan Base benzylamine and 3g trimethylolpropane, are warming up to 80 DEG C, are quickly stirred to react with the blender of profession, by foam after foaming As for curing 6h is continued in 60 DEG C of baking ovens, a kind of dynamic aggregation object foamed material is obtained after cooling.It is made into 20.0 × The bulk sample of 20.0 × 20.0mm size carries out compression performance test using universal testing machine, and compression speed is 2 mm/min, Measuring 10% compressive strength of sample is 5.15 ± 0.42MPa.Obtained polymer foams light specific gravity, intensity height, cracks it After can be automatically repaired, can be made into thermal insulation material carry out using.
Embodiment 23
N-Methyl pyrrolidone, the 3g graphene oxide of 150mL are added in No. 1 reactor, after ultrasonic wave is uniformly dispersed, 4, the 4- diamino-diphenyl ether (ODA) of 4.6g, 2- amino -4,5- dihydro -1,3-thiazoles -4- ketone of 2.3g is added, and heats up To 80 DEG C, after being uniformly mixed, reactant is moved into hydro-thermal reaction container, is placed under 80 DEG C of baking ovens and reacts for 24 hours, instead N-Methyl pyrrolidone should be dispersed using ultrasonic wave by modified graphene oxide obtained after the completion, be configured to 3.5mg/mL's Solution, it is spare；The N-Methyl pyrrolidone of 72mL, the 4,4- diamino-diphenyl ether of 3.2g are added in No. 2 reactors (ODA), the modified graphene oxide solution of 6.3mL after being uniformly dispersed using ultrasonic wave, is added the 3 of 4.8g in a nitrogen atmosphere, 3', 4,4'- biphenyltetracarboxylic dianhydrides (BPDA) are stirred to after being completely dissolved, and 13mL acetic anhydride, 10.5mL pyridine, 3mL is added The AC foaming agent of the trifluoromethanesulfonic acid europium solution of 0.2mol/L, 0.5g after being stirred to react for 24 hours, removes excess of solvent, by product It is put into suitable mold, carries out foaming using vulcanizing press, wherein molding temperature is 120-140 DEG C, clamp time For 10-15min, pressure 10MPa, foam is placed in 60 DEG C of baking ovens after molding and continues to cure 4h, it is poly- that dynamic is obtained after cooling Polymer foam.It is made into the bulk sample of 20.0 × 20.0 × 20.0mm size, is compressed using universal testing machine Performance test, compression speed 2mm/min, measuring 10% compressive strength of sample is 7.33 ± 0.86MPa.Obtained polymer bubble Foam material proportion is light, intensity is high, can be automatically repaired after cracking, can be carried out as relay skeleton resistant to high temperature using.
Embodiment 24
N-Methyl pyrrolidone, the 5g graphene oxide of 150mL are added in No. 1 reactor, after ultrasonic wave is uniformly dispersed, 1,8- diamino -3,6- dioxaoctane of 7.5g, the 7- aminoisoquinoline of 7g is added, and is warming up to 80 DEG C, is stirred After even, reactant is moved into hydro-thermal reaction container, is placed under 80 DEG C of baking ovens and reacts for 24 hours, change after the reaction was completed by obtained Property graphene oxide is scattered in N-Methyl pyrrolidone using ultrasonic wave, is configured to the solution of 3.5mg/mL, spare；It is anti-at No. 2 Answer in device be added the N-Methyl pyrrolidone of 80mL, the 1,8- diamino -3,6- dioxaoctane of 6.2g, 10mL it is modified oxidized After being uniformly dispersed using ultrasonic wave, pentamethylene -1,2 of 8.4g, 3,4- tetrabasic carboxylic acids two are added in graphene solution in a nitrogen atmosphere Acid anhydride is stirred to after being completely dissolved, and the silver trifluoromethanesulfonate solution of 20mL acetic anhydride, 15mL pyridine, 5mL 0.2mol/L is added, and is mixed After closing uniformly, reactant is transferred to immediately in the mold of production film, after reaction for 24 hours, it is thin to obtain a kind of dynamic aggregation object Film.It is cut into the dumbbell shape batten of 80.0 × 10.0 × (0.08 ± 0.02) mm sizes, is stretched using cupping machine Test, rate of extension 50mm/min, measure sample tensile strength be 8.61 ± 1.88MPa, elongation at break be 756 ± 121%.It is thin without the progress of scarfing type standard sample that right angle is produced according to QB/T 1130-91 plastic quarter tear resistance test method Film tear resistance test, measure sample cross direction tear strength be 27.34 ± 5.23MPa, machine direction tear be 27.68 ± 5.44MPa.Obtained thin polymer film quality is softer, has very high intensity and toughness, can extend in a certain range, And there is certain tear resistance.Sample break after recycle, place it in mold be bonded 2-4h after, can again at Film is reused, and can be used as a kind of recuperability antistatic film using its property.
Embodiment 25
In No. 1 reactor, poly- 1, the 2- isoprene rubber of 30g is dissolved in 100mL butanone, after being completely dissolved, to anti- 2,2':6', 2 "-terpyridyl -4'- mercaptan, the 4- mercaptopyridine of 8g, 1g antioxidant 1010 that 4g is added in device are answered, stirring is mixed After closing uniformly, reactant is moved on in suitable mold, is placed under 300W ultraviolet lamp and irradiates 30min, removes solvent after cooling, i.e., Product 1 is made；By product 1,1g irgasfos 168,20g polyurethane resin, 0.5g the organic clathrate compound of Ce-TBMN metal, 5g Isosorbide-5-Nitrae-dimercapto butane, 3g titanium dioxide, 5g white carbon black, 2g AIBN, mixing completely after, be added in small-sized internal mixer and carry out Mixing is blended, wherein blending temperature is 100 DEG C, and the blending time is 30min, and after mixing, sample is taken out, is cooled down later To being placed at room temperature for 30min.It takes out and is kneaded print, place it in suitable mold, finally obtain dynamic aggregation object elastomer, With good resilience, intensity, toughness and good plasticity, product of different shapes can be prepared into according to die size. After this polymer cutting, apply good pressure 1-2h in section part, section can be bonded voluntarily, be formed again.Using its institute The functional characteristic having, can be made into deceleration driven carry out using.
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 (13)

1. a kind of hybrid cross-linked dynamic aggregation object, which is characterized in that provide a kind of hybrid cross-linked dynamic aggregation object or its composition；Its The covalent cross-linking for acting on containing metal-ligand and being formed by covalent bond, wherein covalent cross-linking is at least one cross-linked network Reach the gel point of covalent cross-linking or more；Wherein, the metal-ligand acts through the ligand groups in polymer chain side group It interacts and realizes with introduced metal center；Wherein, the form of the hybrid cross-linked dynamic aggregation object is selected from oligomer Swell gel, plasticizer swell gel, ionic liquid swell gel, elastomer, ordinary solid, foamed material.
2. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that in the dynamic aggregation object structure also Contain supermolecule hydrogen bond action.
3. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the dynamic aggregation object only contains One cross-linked network is acted on containing covalent cross-linking and metal-ligand simultaneously in this cross-linked network；The wherein crosslinking of covalent cross-linking Degree reaches its gel point or more；Cross-linked network polymer chain contains pendant ligands, forms metal-ligand by this pendant ligands and makees With the degree of cross linking is in its gel point above and below.
4. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the dynamic aggregation object only contains One cross-linked network is acted on containing covalent cross-linking and metal-ligand simultaneously in this cross-linked network；Meanwhile in cross-linked network Also contain supermolecule hydrogen bond action；Wherein, the degree of cross linking of covalent cross-linking is more than its gel point；Cross-linked network polymer chain contains Pendant ligands form metal-ligand effect by this pendant ligands, and the degree of cross linking is in its gel point above and below；Supermolecule The degree of cross linking of hydrogen bond action is in its gel point above and below.
5. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that there are two the dynamic aggregation object contains Cross-linked network, one of cross-linked network only contain covalent cross-linking, and wherein the degree of cross linking reaches gel point or more；Another network is only It is acted on containing metal-ligand, forms metal-ligand effect by the pendant ligands on polymer chain, the degree of cross linking is solidifying at it It is more than glue point.
6. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the dynamic aggregation object contains two A cross-linked network, one of cross-linked network contain covalent cross-linking and metal-ligand effect simultaneously, wherein the friendship of covalent cross-linking Connection degree reaches its gel point or more；Another cross-linked network only contains-metal-ligand effect.
7. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the dynamic aggregation object contains two A cross-linked network, one of cross-linked network contain covalent cross-linking and metal-ligand effect simultaneously, wherein the friendship of covalent cross-linking Connection degree reaches its gel point or more；Another cross-linked network only contains supermolecule hydrogen bond action.
8. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the dynamic aggregation object contains two A cross-linked network, one of cross-linked network only contain covalent cross-linking and its degree of cross linking more than its gel point；Another is handed over Networking network only contains metal-ligand effect；Also contain supermolecule hydrogen bond action at least one cross-linked network simultaneously.
9. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the dynamic aggregation object contains three A cross-linked network, one of cross-linked network only contain covalent cross-linking and its degree of cross linking more than its gel point, another friendship Networking network only contains metal-ligand effect, and third cross-linked network only contains supermolecule hydrogen bond action.
10. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the dynamic aggregation object contains Two cross-linked networks, one of cross-linked network contain covalent cross-linking and metal-ligand effect, and the crosslinking of covalent cross-linking simultaneously Degree is more than its gel point；Another cross-linked network contains covalent cross-linking and supermolecule hydrogen bond action, and covalent cross-linking simultaneously The degree of cross linking more than its gel point.
11. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that the dynamic aggregation object contains Two cross-linked networks, one of cross-linked network only contain covalent cross-linking and its degree of cross linking more than its gel point；Another Cross-linked network contains covalent cross-linking and metal-ligand effect simultaneously, and the degree of cross linking of covalent cross-linking is more than its gel point.
12. hybrid cross-linked dynamic aggregation object according to claim 1, which is characterized in that constitute the formula of dynamic aggregation object Component further include it is following any or appoint it is several can additive: other polymers, auxiliary agent, filler；
Wherein, addible other polymers are selected from following any or appoint several: natural polymer, synthesis macromolecule Compound；
Wherein, addible auxiliary agent is selected from following any or appoints several: catalyst, initiator, antioxidant, light stabilizer, heat Stabilizer, chain extender, toughener, coupling agent, lubricant, release agent, plasticizer, foaming agent, antistatic agent, emulsifier, dispersion Agent, colorant, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, rheological agent, thickener, levelling agent, antibacterial agent；
Wherein, addible filler is selected from following any or appoints several: inorganic non-metallic filler, metal packing, organic filler.
13. according to claim 1 to hybrid cross-linked dynamic aggregation object described in any one of 12, which is characterized in that it is applied to Self-repairability material, sealing material, toughness material, adhesive, toy material, shape-memory material, force snesor material, energy storage Device material.
CN201710524150.6A 2017-06-30 2017-06-30 Hybrid cross-linked dynamic polymer Active CN109207110B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710524150.6A CN109207110B (en) 2017-06-30 2017-06-30 Hybrid cross-linked dynamic polymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710524150.6A CN109207110B (en) 2017-06-30 2017-06-30 Hybrid cross-linked dynamic polymer

Publications (2)

Publication Number Publication Date
CN109207110A true CN109207110A (en) 2019-01-15
CN109207110B CN109207110B (en) 2022-08-12

Family

ID=64961051

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710524150.6A Active CN109207110B (en) 2017-06-30 2017-06-30 Hybrid cross-linked dynamic polymer

Country Status (1)

Country Link
CN (1) CN109207110B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110052172A (en) * 2019-03-17 2019-07-26 浙江工业大学 A kind of preparation method and correlation block copolymer of the heat-resisting solvent resistant homopore membrane of cross-linking type
CN112128116A (en) * 2020-09-23 2020-12-25 泗县金皖泵业有限公司 Gear speed changing disk type water pump
CN113603844A (en) * 2021-07-13 2021-11-05 浙江大学 Method for preparing shape memory polymer device with complex permanent shape by utilizing secondary crosslinking and application
CN114340819A (en) * 2019-08-30 2022-04-12 苏黎世联邦理工学院 Light gold
CN115975212A (en) * 2023-01-18 2023-04-18 韩山师范学院 Zinc-copper biological metal organic framework with cage-shaped pore cavity and preparation and application thereof
WO2023166036A1 (en) * 2022-03-04 2023-09-07 Basf Se Polyurethane (pu) composition and method of producing pu composition

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1962710A (en) * 2005-11-10 2007-05-16 拜尔材料科学股份公司 Hydrophilic polyisocyanate mixtures
CN101541890A (en) * 2006-09-26 2009-09-23 克里斯凯德太阳能有限公司 Organic compound, photovoltaic layer and organic photovoltaic device
CN101589085A (en) * 2007-01-18 2009-11-25 拜尔材料科学股份公司 Hydrogel of hydrophilic polyurethane (meth) acrylate
CN103013014A (en) * 2012-12-26 2013-04-03 东南大学 Super-strong hydrogel with plurality of networks and preparation method thereof
CN104961881A (en) * 2015-06-03 2015-10-07 四川大学 Dynamic bond-containing polyurethane material for 3D printing and its preparation method and use
CN104968712A (en) * 2013-01-30 2015-10-07 剑桥实业有限公司 Nested supramolecular capsules
CN105008326A (en) * 2013-02-25 2015-10-28 株式会社自动网络技术研究所 Highly sensitive (meth)acrylate and radically curable material

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1962710A (en) * 2005-11-10 2007-05-16 拜尔材料科学股份公司 Hydrophilic polyisocyanate mixtures
CN101541890A (en) * 2006-09-26 2009-09-23 克里斯凯德太阳能有限公司 Organic compound, photovoltaic layer and organic photovoltaic device
CN101589085A (en) * 2007-01-18 2009-11-25 拜尔材料科学股份公司 Hydrogel of hydrophilic polyurethane (meth) acrylate
CN103013014A (en) * 2012-12-26 2013-04-03 东南大学 Super-strong hydrogel with plurality of networks and preparation method thereof
CN104968712A (en) * 2013-01-30 2015-10-07 剑桥实业有限公司 Nested supramolecular capsules
CN105008326A (en) * 2013-02-25 2015-10-28 株式会社自动网络技术研究所 Highly sensitive (meth)acrylate and radically curable material
CN104961881A (en) * 2015-06-03 2015-10-07 四川大学 Dynamic bond-containing polyurethane material for 3D printing and its preparation method and use

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ABDELKRIM EL-GHAYOURY等: ""Combining Covalent and Noncovalent Cross-Linking: A Novel Terpolymer for Two-Step Curing Applications"", 《MACROMOLECULES》 *
JY SUN等: ""Highly stretchable and tough hydrogels"", 《NATURE》 *
XUECHEN LIANG等: ""Tough, rapid-recovery composite hydrogels fabricated via synergistic core–shell microgel covalent bonding and Fe3+ coordination cross-linking"", 《SOFT MATTER》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110052172A (en) * 2019-03-17 2019-07-26 浙江工业大学 A kind of preparation method and correlation block copolymer of the heat-resisting solvent resistant homopore membrane of cross-linking type
CN110052172B (en) * 2019-03-17 2021-08-24 浙江工业大学 Preparation method of cross-linked heat-resistant solvent-resistant homogeneous pore membrane and related block copolymer
CN114340819A (en) * 2019-08-30 2022-04-12 苏黎世联邦理工学院 Light gold
CN112128116A (en) * 2020-09-23 2020-12-25 泗县金皖泵业有限公司 Gear speed changing disk type water pump
CN112128116B (en) * 2020-09-23 2022-01-14 泗县金皖泵业有限公司 Gear speed changing disk type water pump
CN113603844A (en) * 2021-07-13 2021-11-05 浙江大学 Method for preparing shape memory polymer device with complex permanent shape by utilizing secondary crosslinking and application
WO2023166036A1 (en) * 2022-03-04 2023-09-07 Basf Se Polyurethane (pu) composition and method of producing pu composition
CN115975212A (en) * 2023-01-18 2023-04-18 韩山师范学院 Zinc-copper biological metal organic framework with cage-shaped pore cavity and preparation and application thereof
CN115975212B (en) * 2023-01-18 2023-11-28 韩山师范学院 Zinc-copper biological metal organic frame with cage-shaped hole cavities and preparation and application thereof

Also Published As

Publication number Publication date
CN109207110B (en) 2022-08-12

Similar Documents

Publication Publication Date Title
CN109207110A (en) A kind of hybrid cross-linked dynamic aggregation object
CN107805308A (en) A kind of dynamic aggregation thing and its application with hybrid cross-linked network
CN109206627A (en) A kind of hybrid cross-linked dynamic aggregation object
CN107698748A (en) A kind of dynamic aggregation thing of hybrid cross-linked network and its application
CN109206576A (en) A kind of hybrid cross-linked dynamic aggregation object
CN108342072A (en) A kind of dynamic aggregation object and its application with hybrid cross-linked structure
CN109422835A (en) A kind of dynamic aggregation object containing combination supermolecular mechanism
CN109666168A (en) A kind of self-repairability solid-state hydridization dynamic aggregation object and its application
CN109666178A (en) A kind of hydridization dynamic aggregation compositions and its application
CN109206625A (en) A kind of physics split-phase supermolecule dynamic aggregation object and its application
CN108342002A (en) A kind of dynamic aggregation object and its application with hybrid cross-linked network
CN108341951A (en) A kind of dynamic aggregation object and its application with hybrid cross-linked structure
CN108341965A (en) A kind of crosslinking dynamic aggregation object and its application
CN108341943A (en) A kind of hydridization dynamic aggregation object and its application
CN109666093A (en) A kind of dynamic aggregation object with hybrid cross-linked network structure
CN108342037A (en) A kind of energy-absorbing method based on hybrid cross-linked network dynamic polymer
CN109666153A (en) A kind of hydridization dynamic aggregation compositions and its application
CN109206825A (en) A kind of assembly energy-absorbing method based on physics split-phase supermolecule dynamic aggregation object
CN109666167A (en) A kind of hydridization dynamic aggregation compositions
CN109206570A (en) A kind of compliant physical split-phase supermolecule dynamic aggregation object and its application
CN109666159A (en) A kind of method of energy-absorbing and application thereof
CN109206580A (en) A kind of hybrid cross-linked dynamic aggregation object
CN109423148A (en) A kind of energy-absorbing method based on dynamic aggregation object
CN109666156A (en) A kind of energy-absorbing method based on hydridization dynamic aggregation compositions
CN109666160A (en) A kind of dynamic aggregation object with hybrid cross-linked network

Legal Events

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

Effective date of registration: 20220111

Address after: Room 3179, Xuanye building, Pioneer Park, torch hi tech Zone, Xiamen, Fujian, 361000

Applicant after: Xiamen iron cloth Mstar Technology Ltd.

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

Applicant before: Weng Qiumei

CB02 Change of applicant information
CB02 Change of applicant information

Address after: 361000 chuangkehui-219, Chuangye building, No. 11-1, torch East Road, entrepreneurship Park, Xiamen Torch High tech Zone, Xiamen, Fujian

Applicant after: Xiamen Tiance Material Technology Co.,Ltd.

Address before: Room 3179, Xuanye building, Pioneer Park, torch hi tech Zone, Xiamen, Fujian, 361000

Applicant before: Xiamen iron cloth Mstar Technology Ltd.

GR01 Patent grant
GR01 Patent grant