CN109666093A - A kind of dynamic aggregation object with hybrid cross-linked network structure - Google Patents

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

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CN109666093A
CN109666093A CN201710967686.5A CN201710967686A CN109666093A CN 109666093 A CN109666093 A CN 109666093A CN 201710967686 A CN201710967686 A CN 201710967686A CN 109666093 A CN109666093 A CN 109666093A
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不公告发明人
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Xiamen iron cloth Mstar Technology Ltd.
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Weng Qiumei
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    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
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    • 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
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    • 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
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    • 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
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    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
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Abstract

The invention discloses a kind of dynamic aggregation objects with hybrid cross-linked network structure, wherein including dynamic covalent cross-linking and supermolecule hydrogen bond action；Wherein, the dynamic covalent cross-linking is based at least one Reversible Addition Fragmentation Chain Transfer dynamic covalent bond, and the supermolecule hydrogen bond action includes to participate in the hydrogen bond action to be formed by the side hydrogen bond group being present in the side group and/or side chain of polymer chain.The dynamic aggregation object has merged dynamic covalent bond and the respective advantage of supermolecule hydrogen bond；Supermolecule hydrogen bond assigns material stimulating responsive, ultra-tough and self-repairability；On the one hand dynamic covalent bond then assigns dynamic aggregation object structural stability and mechanical strength, and due to its dynamic reversibility, so that polymer has the characteristics such as self-repairability, recuperability, repeatable processability.The dynamic aggregation object can be used for making self-repair material, toughness material, sealing material etc. and is widely applied.

Description

A kind of dynamic aggregation object with hybrid cross-linked network structure
Technical field
The present invention relates to intelligent polymer fields, and in particular to a kind of dynamic aggregation with hybrid cross-linked network structure Object.
Background technique
While high molecular material brings tremendous asset to the mankind, the problem of also bringing some severe environments, such as " white Pollution ", the high molecular products such as a large amount of waste plastic and rubber not only bring the great wasting of resources but also influence the life of people It is living.With the exhaustion of fossil energy, environmentally friendly, durable and recyclable high molecular material is recycled by extensive Concern, high molecular material, which will continue development, must walk the road of sustainable development.Simultaneously as the improvement of material life condition, More stringent requirements are proposed for the performance of material by people, and it is impossible to meet people for the high molecular products with general performance Demand, nowadays high molecular material develops to intelligent, high-performance direction.
Conventional thermoplastic's high molecular material has recyclable cycling processability, but its performance often has certain limitation Property；And thermoset macromolecule material has a better heat resistance, inoxidizability and mechanical performance etc., but due to its formed it is three-dimensional Cross-linked network structure does not have cycling processability.It develops a kind of high-performance for having both thermoset macromolecule material and thermoplasticity is high The secondary workability and novel intelligent functional polymer material of molecular material become very it is necessary to.
Supramolecular chemistry is that aggregation chemistry is formed by based on noncovalent intermolecular interactions.Supermolecule is usually Refer to by two or more molecule by the combined complicated composition of intermolecular interaction, the aggregation of regular assembling Body, and certain integrality is kept to make it have specific microstructure and macroscopic properties.Supermolecule have reversible " fracture " and The characteristic of " formation " is widely used in selfreparing, stimulating responsive and recyclable material.However, this noncovalent interaction Compared with traditional covalent bond, general bond energy is weaker, larger by thermodynamic effects, is formed by supramolecular structure to a certain extent For be not a stable system, be easy destroyed.Dynamic chemical includes the oversubscription based on non-covalent interaction Sub- chemistry and the dynamic covalent chemical based on covalent bond.Dynamic covalent chemical has reversible covalent bonds under given conditions " disconnected Split " and " formation " characteristic, the dynamic covalent bond in dynamic covalent chemical belongs to covalent chemical bond, and bond energy is larger, so that dynamic is altogether Valence link is relatively stable, and mechanical performance of dynamic aggregation object etc. is prominent.Dynamic covalent bond combines the invertibity of non-covalent bond and general The high-intensitive advantage of valence link in all, so that it is constructed in functional polymer material, selfreparing and in terms of recycle It obtains and is widely applied.For this purpose, developing in conjunction with the advantages of dynamic covalent bond and supermolecule with high dynamic, high-performance, reaction The controllable crosslinking dynamic aggregation object of mild condition becomes very urgent.
Summary of the invention
The present invention is directed to above-mentioned background, provides a kind of dynamic aggregation object with hybrid cross-linked network structure, it includes Dynamic covalent cross-linking and supermolecule hydrogen bond action；Wherein, the dynamic covalent cross-linking is based at least one reversible addition and is broken chain Shift dynamic covalent bond and its gel point for reaching dynamic covalent cross-linking at least one network structure or more；The supermolecule Hydrogen bond action includes to participate in the hydrogen bond to be formed by the side hydrogen bond group being present in the side group and/or side chain of polymer chain to make With.The dynamic aggregation object also shows good dynamic with good mechanical strength and while certain toughness Invertibity, and reflect the functional characteristics such as self-repairability, stimulating responsive and plasticity.
The present invention is achieved by following technical solution:
A kind of dynamic aggregation object with hybrid cross-linked network, which is characterized in that wherein comprising dynamic covalent cross-linking and super Molecule hydrogen bond action；Wherein, the dynamic covalent cross-linking be based at least one Reversible Addition Fragmentation Chain Transfer dynamic covalent bond and It is more than its gel point for reaching dynamic covalent cross-linking at least one network structure；The supermolecule hydrogen bond action includes to pass through The side hydrogen bond group being present in the side group and/or side chain of polymer chain participates in the hydrogen bond action to be formed.
In the present invention, in addition to the side hydrogen bond, also optionally containing being present in crosslinked polymer network skeleton chain and non- Main chain backbone hydrogen bond group, the end group hydrogen bond group of other polymers chain end, small molecule on cross-linked polymer main chain backbone On hydrogen bond group, the hydrogen bond group on inorganic/organic filler/ingredient, but the present invention is not limited only to this.
In the present invention, the Reversible Addition Fragmentation Chain Transfer dynamic covalent bond has the following structure general formula:
Wherein,Refer to polymer chain, crosslinking link or the connection of any other suitable group；A can be selected from but Not only it is limited to C atom, S atom, Se atom.
When A is the C atomic time, heretofore described Reversible Addition Fragmentation Chain Transfer dynamic covalent bond has following knot Structure general formula:
Wherein, R1、R2、R3、R4Respectively it is individually present；
R1、R2、R3、R4In the presence of, it is each independently selected from hydrogen atom, replaces atom, substituent group；
R1、R2、R3、R4It preferably is selected from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Miscellaneous alkyl, substituted C1-20Alkyl takes The miscellaneous alkyl in generation.
Z2For with C3The divalent linking atom or divalent linking group that carbon atom is connected directly；
Work as Z2When selected from divalent linking group, Z2Structure be not particularly limited, include but are not limited to linear chain structure, contain The branched structure or cyclic structure of side group.
Z2It preferably is selected from C1-20Alkylene, divalent C1-20Miscellaneous alkyl, substituted C1-20Alkylene, substituted divalent C1-20Miscellaneous alkyl In any divalent linker any two or it is wantonly three kinds combination formed divalent linker.
Specifically, Z2N aggressiveness (N >=2) such as trimerization of more preferable divalent acrylic or methacrylic acid and its corresponding esters N aggressiveness (N >=2) such as tripolymer, the tetramer of body, the tetramer, divalent styrene or methyl styrene.
Work as Z2When for above-mentioned divalent linking group, Z1For with double bond C2The divalent linking group that carbon atom is connected directly；Z1's Structure is not particularly limited, and includes but are not limited to singly-bound, linear chain structure, the branched structure containing side group or cyclic structure.
Z1It preferably is selected from C1-20Alkylene, divalent C1-20Miscellaneous alkyl, substituted C1-20Alkylene, substituted divalent C1-20Miscellaneous alkyl In any divalent linker any two or it is wantonly three kinds combination formed divalent linker.
Z1The divalent connection more preferably replaced from the divalent linking group with sucting electronic effect, sucting electronic effect substituent group Group.The divalent linking group of the sucting electronic effect include but are not limited to divalent ester group, divalent amido group, divalent carbonyl, Any divalent linker in divalent aryl such as divalent phenyl group, any two combination, or wantonly three kinds of the divalent formed that combines connect Connect base.The divalent linking group replaced with sucting electronic effect substituent group includes but are not limited to electron-withdrawing group such as carbonyl, aldehyde One of base, nitro, ester group, sulfonic group, acylamino-, aryl, cyano, halogen atom such as fluorine atom or a variety of substituted C1-10It opens Chain alkylidene, C1-10Open chain alkenylene, C1-10Cycloalkylidene, C1-10Sub- cycloalkenyl group, arlydene, sub- aryl, divalent C1-10Rouge Miscellaneous alkyl, divalent C1-10Rouge miscellaneous thiazolinyl, divalent heteroaryl radical, any divalent linker in divalent heteroaryl alkyl, any two group It closes, or wantonly three kinds of the divalent linker for combining formation.
Work as Z2When selected from divalent linking atom, it is selected from S atom, at this time Z1For with double bond C2Carbon atom be connected directly two Valence linking group.Work as Z2When for S atom, heretofore described Reversible Addition Fragmentation Chain Transfer dynamic covalent bond has such as Flowering structure general formula:
Work as Z2When selected from S atom, Z at this time1For with double bond C2The divalent linking group that carbon atom is connected directly；
Z1Structure be not particularly limited, include but are not limited to singly-bound, linear chain structure, branched structure or ring containing side group Shape structure.
Z1It preferably is selected from C1-20Alkylene, divalent C1-20Miscellaneous alkyl, substituted C1-20Alkylene, substituted divalent C1-20Miscellaneous alkyl In any divalent linker any two or it is wantonly three kinds combination formed divalent linker.
Z1More preferably from divalent alkyl, divalent aryl, divalent alkyl ether, divalent aryl ether, divalent alkyl thioether group, Most preferably from divalent alkyl thioether group.
When A is S atom or Se atomic time, R1、R2、R3、R4It is not present；
When A is S atom or Se atomic time, Z1It is former selected from O atom, S atom, Se atom, Si atom, C atom, N atom, P Son.At this point, heretofore described Reversible Addition Fragmentation Chain Transfer dynamic covalent bond, has the following structure in general formula at least It is a kind of:
Work as Z1For O atom, S atom, Se atomic time, R5、R6、R7It is not present；
Work as Z1For N atomic time, R5In the presence of R6、R7It is not present；
Work as Z1For Si atom, C atomic time, R5、R6In the presence of R7It is not present；
Work as Z1For P atomic time, R5、R6、R7、R8In the presence of；
R5、R6、R7、R8In the presence of, it is each independently selected from hydrogen atom, replaces atom, substituent group；
R5、R6、R7、R8Selected from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Miscellaneous alkyl, substituted C1-20Alkyl or substitution Miscellaneous alkyl.
Z2For the divalent linking group being connected directly with S atom or Se atom；
Z2Structure be not particularly limited, include but are not limited to singly-bound, linear chain structure, branched structure or ring containing side group Shape structure.
Z2It preferably is selected from C1-20Alkylene, divalent C1-20Miscellaneous alkyl, substituted C1-20Alkylene, substituted divalent C1-20Miscellaneous alkyl In any divalent linker any two or it is wantonly three kinds combination formed divalent linker.
Z2More preferably from cyano, alkyl, aryl, ester group, acylamino-, urine base, one of carbamate groups or a variety of Substituted alkylidene, substituted C1-10Open chain alkenylene, substituted C1-10Cycloalkylidene, substituted C1-10Sub- cycloalkenyl group, substitution Arlydene, substituted sub- aralkyl, substituted divalent C1-10Rouge miscellaneous alkyl, substituted divalent C1-10Rouge miscellaneous thiazolinyl, two replaced Any divalent linker in valence heteroaryl, substituted divalent heteroaryl alkyl, any two combination, or wantonly three kinds of combination are formed Divalent linker.
Work as Z1For O atom, S atom, Se atom, Si atom, C atom, N atom, P atomic time, Z3For with Z1The direct phase of atom Divalent linking group even；Z3Structure be not particularly limited, include but are not limited to singly-bound, linear chain structure, the branch containing side group Chain structure or cyclic structure.
Z3It preferably is selected from C1-20Alkylene, divalent C1-20Miscellaneous alkyl, substituted C1-20Alkylene, substituted divalent C1-20Miscellaneous alkyl In any divalent linker any two or it is wantonly three kinds combination formed divalent linker.
Z3The divalent connection more preferably replaced from the divalent linking group with sucting electronic effect, sucting electronic effect substituent group Group is so conducive to the activity for improving C=S (Se), makes it easier to the attack by living radical, obtains more quick Addition reaction, to obtain strong dynamic reversibility.The divalent linking group of the sucting electronic effect includes but are not limited to Any divalent linker in divalent ester group, divalent amido group, divalent carbonyl, divalent aryl such as divalent phenyl group, any two group It closes, or wantonly three kinds of the divalent linker for combining formation.With sucting electronic effect substituent group replace divalent linking group include But it is not limited only to electron-withdrawing group such as carbonyl, aldehyde radical, nitro, ester group, sulfonic group, acylamino-, aryl, cyano, halogen atom such as fluorine One of atom or a variety of substituted C1-10Open chain alkylidene, C1-10Open chain alkenylene, C1-10Cycloalkylidene, C1-10Sub- cyclenes Alkyl, arlydene, sub- aryl, divalent C1-10Rouge miscellaneous alkyl, divalent C1-10Rouge miscellaneous thiazolinyl, divalent heteroaryl radical, divalent heteroaryl alkyl In any divalent linker, any two combination, or wantonly three kinds combination formed divalent linker.
In the present invention, the Reversible Addition Fragmentation Chain Transfer dynamic covalent bond includes but are not limited to allyl, alkene Propyl thioether group, double thioester substrates, double selenium ester groups, trithiocarbonic acid ester group, three seleno carbonate groups, two seleno sulfocarbonates Base, two thio seleno carbonate groups, two pairs of thioester substrates, two pairs of selenium ester groups, double trithiocarbonic acid ester groups, double three selenos carbonic esters Base, dithiocarbamate groups, diselenocarbmate base, dithiocarbonic acids ester group, two seleno carbonate groups and its phase The derivatives group answered.
In embodiments of the present invention, at least partly contain following constituent in the side hydrogen bond group:
At least one of further preferably following constituent:
Wherein,Indicate with polymer chain, be crosslinked and link or the company of any other suitable group (including hydrogen atom) It connects.
In the present invention, the hydrogen bond group on the side group/end group, preferably comprises at least one in following constituent Kind:
Wherein, X is O atom or S atom, and M can be selected from O atom, S atom, Si atom, C atom, N atom；
When M is O or S, R9It is not present；
When M is C, Si or N, R9And R10It can be individually present；
R9And R10In the presence of, it is each independently selected from hydrogen atom, replaces atom, substituent group；
When selected from substituent group, R9And R10Structure be not particularly limited, include but are not limited to linear chain structure, containing side group Branched structure or cyclic structure；R9And R10It preferably is selected from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Miscellaneous alkyl, substituted C1-20 Alkyl or substituted miscellaneous alkyl.
Wherein, L1And L2It is divalent linking group, G is terminal end capping group or segment.
L1And L2Structure be not particularly limited, include but are not limited to linear chain structure, the branched structure containing side group or ring-type Structure.L1And L2It preferably is selected from C1-20Alkylene, divalent C1-20Miscellaneous alkyl, substituted C1-20Alkylene, substituted divalent C1-20Miscellaneous hydrocarbon In base any divalent linker any two or it is wantonly three kinds combination formed divalent linker.
The structure of G is not particularly limited, and includes but are not limited to linear chain structure, the branched structure containing side group or cyclic annular knot Structure.G preferably is selected from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Miscellaneous alkyl, substituted C1-20Alkyl or substituted miscellaneous alkyl.
R9、R10、L1、L2, G any two or it is multiple between can cyclization.
In the present invention, the side hydrogen bond group on the side chain skeleton, preferably comprises at least one in following constituent Kind:
Wherein, X is O atom or S atom, and M can be selected from O atom, S atom, Si atom, C atom, N atom；
When M is O atom or S atom, R9It is not present；
When M is C atom, Si atom or N atomic time, R9And R10It can be individually present；
L1And L2It is divalent linking group, G is terminal end capping group or segment；
R9、R10、L1、L2, G any two or it is multiple between can cyclization.
In embodiments of the present invention, also selectively containing aforementioned on side group/end group of the hybrid cross-linked network Other hydrogen bond groups other than the hydrogen bond group of side, include but are not limited to hydroxyl, sulfydryl, carboxyl.
In embodiments of the present invention, a kind of dynamic aggregation object with hybrid cross-linked network structure, which is characterized in that flat The side group and/or side chains number of every 100 backbone repeating units access hydrogen bonds group are 0.1 to 200.
In embodiments of the present invention, it can be selected from for connecting the linker of dynamic covalent bond and/or hydrogen bond group The divalent of hetero atom linker, molecular weight no more than 1000Da or multivalence small molecule alkyl, molecular weight are greater than the divalent of 1000Da Or the divalent of multivalence polymer chain residue, molecular weight no more than 1000Da or polyvalent mineral small molecule chain residue, molecular weight are greater than Any one of the divalent of 1000Da or polyvalent mineral macromolecular chain residue are appointed several.
In an embodiment of the invention, the dynamic aggregation object of the hybrid cross-linked network contains only a network (the first network structure), which is characterized in that contain dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks in this cross-linked network, it is described Dynamic covalent cross-linking reaches its gel point or more.In present embodiment, contain Reversible Addition Fragmentation Chain Transfer dynamic covalent bond Dynamic covalent cross-linking is for providing balanced structure and covalent dynamic；The hydrogen bond crosslinks that side hydrogen bond group is formed provide additional friendship Connection and supermolecule dynamic.Two kinds of crosslinked actions are merged using a network structure, hydridization dynamic is reached with simplest structure Effect.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of two networks (second of network structure), which is characterized in that contain dynamic covalent cross-linking in the 1st network and dynamic covalent cross-linking reaches its gel Or more, wherein not containing any hydrogen bond group；Covalent cross-linking is free of in 2nd network but contains supermolecule hydrogen bond crosslinks；The net In network structure, balanced structure and dynamic covalent bond therein is kept to provide by the dynamic covalent cross-linking in the 1st network covalently dynamic State property provides supermolecule dynamic by the supermolecule hydrogen bond crosslinks in the 2nd network.It is relatively independent between two networks, it can Preferably obtain orthogonal effect.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of two networks (the third network structure), which is characterized in that contain dynamic covalent cross-linking in the 1st network and dynamic covalent cross-linking reaches its gel Or more, wherein not containing any hydrogen bond group；2nd network is the first described network.In the network structure, pass through the 1st net Dynamic covalent cross-linking in network and the 2nd network keeps balanced structure and dynamic covalent bond therein to provide covalent dynamic；Pass through Supermolecule hydrogen bond crosslinks in 2nd network provide supermolecule dynamic.It is preferred that the dynamic covalent bond between two networks can not be sent out Raw mutual exchange.Preferably covalence stablility is provided by two dynamic covalent networks, and orthogonal dynamic covalency is provided, Facilitate the structure and mechanical property for adjusting dynamic covalent networks, can easily be obtained together with hydrogen bond action multifarious Excellent effect.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of two networks (the 4th kind of network structure), which is characterized in that the 1st network is the first described network structure；Covalent cross-linking is free of in 2nd network But containing supermolecule hydrogen bond crosslinks,；Hydrogen bond group between 1st network and the 2nd network can optionally form mutually hydrogen bond.It should In network structure, balanced structure and dynamic covalent bond therein is kept to provide by the dynamic covalent cross-linking in the 1st network covalent Dynamic；Supermolecule dynamic is provided by the supermolecule hydrogen bond crosslinks in the 1st and the 2nd network.Pass through two hydrogen bond crosslinks networks Multifarious supermolecule dynamic can be obtained.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of two networks (the 5th kind of network structure), which is characterized in that the 1st network and the 2nd network are structure described in the first network, but upper described 1st and the 2nd network is not identical.It is this not identical, it can illustrate for example, polymer chain main structure difference, dynamic covalent cross-linking Crosslink density it is different, Reversible Addition Fragmentation Chain Transfer dynamic covalent bond is different, polymer chain side group composition is different, polymer Hydrogen bond group difference in chain side group etc..It, can be with by adjusting the structure of the 1st network and/or the 2nd network in the embodiment Achieve the purpose that accurately to control dynamic aggregation physical performance.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network contains only a network (the 6th kind of network structure), which is characterized in that handed in this cross-linked network containing dynamic covalent cross-linking and optional supermolecule hydrogen bond Connection, the dynamic covalent cross-linking reach its gel point or more, are dispersed with the supermolecule degree of cross linking in dynamic covalent cross-linking network and exist Its gel point supermolecule polymer below.In the network structure, dynamic covalent cross-linking can keep balanced structure, specific Under the conditions of, dynamic covalent cross-linking also can provide dynamic；Supermolecule crosslinking provides dynamic, supermolecule polymerization dispersed therein Object provides supplement dynamic, especially strain-responsive.
In yet another embodiment of the present invention, only one cross-linked network of the dynamic aggregation object of the hybrid cross-linked network Network (the 7th kind of network structure), which is characterized in that this cross-linked network contains dynamic covalent cross-linking and optional supermolecule hydrogen bond is handed over Connection, the dynamic covalent cross-linking reach its gel point or more；The supermolecule degree of cross linking is dispersed in dynamic covalent cross-linking network to exist Supermolecule polymer particle more than its gel point.In the network structure, dynamic covalent cross-linking can keep balanced structure, in spy Under conditions of fixed, dynamic covalent cross-linking also can provide dynamic；Supermolecule crosslinking provides dynamic, and supermolecule polymer particle mentions For filling and supplementing dynamic, and local viscosity and intensity can be obtained in strain-responsive and is increased.
In embodiments of the present invention, a kind of dynamic aggregation object with hybrid cross-linked network structure, which is characterized in that structure Raw material components at dynamic aggregation object further include following any or appoint and several add or object can be used: solvent, auxiliary agent, addition Agent, filler；
Wherein, described to add or workable auxiliary agent, additive are selected from following any or appoint several: catalyst, Initiator, antioxidant, light stabilizer, heat stabilizer, toughener, coupling agent, lubricant, release agent, plasticizer, antistatic agent, Emulsifier, dispersing agent, colorant, fluorescent whitening agent, delustering agent, fire retardant, biocide mildewcide, dehydrating agent, nucleating agent, rheology Agent, thickener, thixotropic agent, levelling agent, foam stabiliser, foaming agent；
Wherein, described to add or workable filler is selected from following any or appoints several: inorganic non-metallic filler, Metal packing, organic filler.
In embodiments of the present invention, the dynamic aggregation object with hybrid cross-linked network structure, raw material components In polymer chain topological structure can be selected from line style, ring-type, branching, cluster, crosslinking and combinations thereof form.
In embodiments of the present invention, the dynamic aggregation object and its raw material group with hybrid cross-linked network structure Point, it can have one or more glass transition temperatures, can also there is no glass transition temperature.For described with miscellaneous Change the glass transition temperature of the dynamic aggregation object of cross-linked network structure, at least one is lower than 0 DEG C or in 0-25 DEG C Between or between 25-100 DEG C or be higher than 100 DEG C.
In embodiments of the present invention, a kind of dynamic aggregation object with hybrid cross-linked network structure, which is characterized in that institute The form for stating dynamic aggregation object or its composition is selected from solid polymer, elastomer, gel, foam.
In embodiments of the present invention, a kind of dynamic aggregation object with hybrid cross-linked network structure, which is characterized in that its Applied to self-repairability coating, self-repairability plate, self-repairability binder, sealing material, toughness material, energy storage device material Material, toy, shape-memory material.
Compared with prior art, the invention has the following advantages:
(1) a kind of dynamic aggregation object with hybrid cross-linked network structure of the invention has merged reversible addition fracture chain and has turned Mobile state covalent bond and two kinds of the supermolecule hydrogen bond elements with dynamic, make full use of and combine respective advantage.It is reversible On the one hand addition fracture chain tra nsfer dynamic covalent bond can be used for providing the covalent cross-linking balanced structure of material, so that dynamic aggregation object Show the excellent properties such as mechanical performance, the stability of general cross-linked polymer；On the other hand introducing in cross-linked polymer can Inverse addition fracture chain tra nsfer dynamic covalent bond makes hybrid cross-linked dynamic aggregation object have good dynamic reversibility, in certain item The dissociation of dynamic covalent bond can occur under part or exchange or re-form, assign the excellent self-repairability of material, can return The dynamic properties such as the property received；In addition, introducing Reversible Addition Fragmentation Chain Transfer dynamic covalent bond in the raw material monomer of free radical polymerization When, material internal stress can be reduced by the reversible chain tra nsfer of dynamic covalent bond, obtain high-mechanical property, low internal flaw High performance material.Simultaneously as side hydrogen bond group is easily formed the hydrogen bond action of good dynamic, it is super based on side hydrogen bond group On the one hand molecule hydrogen bond crosslinks are used to carry out crosslinking supplement to dynamic covalent cross-linking, be on the other hand based on its supermolecule for providing The specific performance of weak bond characteristic and dynamic can assign the excellent toughness of material, self-repairability to improve the toughness of material And shape memory.This cannot achieve in existing polymeric system.
(2) a kind of dynamic aggregation object structure and performance with hybrid cross-linked network structure of the invention have it is good can Control.By controlling the parameters such as molecular structure, molecular weight of raw material, can prepare with different appearance features, performance is adjustable, Widely used dynamic aggregation object；By controlling the type and number of hydrogen bond group on dynamic covalent bond and side group and/or side chain, Dynamic reversibility dynamic aggregation object of different strengths and weaknesses can be prepared；By controlling both dynamic covalent bond and supermolecule hydrogen bond crosslinks The ratio of ingredient can prepare the multifarious dynamic aggregation object such as mechanical strength, self-repairability, ultra-tough.This is traditional It is difficult to inside covalent cross-linking and supermolecule cross-linking system.
(3) a kind of dynamic aggregation object dynamic with hybrid cross-linked network of the invention is strong and has multiple stimulation response Property.On the one hand, Reversible Addition Fragmentation Chain Transfer dynamic covalent bond can be in multiple stimulation (such as temperature, illumination, radiation, plasma And microwave etc.) the lower dynamic reversibility for realizing dynamic aggregation object of effect；On the other hand, the introducing of supermolecule hydrogen bond can be used as dynamic The useful supplement of state property energy, enhances the dynamic property of dynamic aggregation object, to obtain strong dynamic and multiple stimulation responsiveness.This Outside, by optionally control other conditions (as be added initiator, free radical scavenger), can under appropriate environment, Accelerate or be quenched dynamic covalent chemical balance, be at required state, this is total in existing supramolecular chemistry and dynamic It is more difficult inside valence system to accomplish.
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
In the following, the present invention is described in detail.
A kind of dynamic aggregation object with hybrid cross-linked network structure of the present invention, which is characterized in that wherein include Dynamic covalent cross-linking and supermolecule hydrogen bond action；Wherein, the dynamic covalent cross-linking is based at least one reversible addition and is broken chain Shift dynamic covalent bond and its gel point for reaching dynamic covalent cross-linking at least one network structure or more；The supermolecule Hydrogen bond action includes to be joined by the hydrogen bond group (calling " side hydrogen bond " group in the following text) being present in the side group and/or side chain of polymer chain With the hydrogen bond action of formation.
Term " polymerization " reaction/action used in the present invention is propagation process/effect of chain, generally refers to lower point The reactant of son amount has the process of the product of higher molecular weight by the synthesis of the reaction formations such as polycondensation, addition polymerization, ring-opening polymerisation.? Among these, reactant is typically polymerizing power and (can spontaneously be polymerize, or can add energy in initiator or outside Polymerize under effect) the compounds such as monomer, oligomer, prepolymer.Claimed by a kind of product that reactant is polymerize For homopolymer.Copolymer is known as by the product that two or more reactant is polymerize.It should be pointed out that at this " polymerization " described in invention, it includes the linear growth process of reactant molecule chain, the branching comprising reactant molecule chain Journey, the annulation process comprising reactant molecule chain also include the cross-linking process of reactant molecule chain.In embodiments of the present invention In, " polymerization " is also comprising chain growth caused by supermolecule hydrogen bond action.
Heretofore described " crosslinking " reaction/action refers to passing through between reactant molecule and/or in reactant molecule The three-dimensional of physical connection (physical crosslinking) formation for being connected chemically (chemical crosslinking) and/or hydrogen bond action of covalent bond is unlimited netted Process/effect of structure.In cross-linking process, polymer chain is general first constantly to be increased in two-dimensional/three-dimensional direction, the group of gradually forming Cluster (can be two dimension or three-dimensional), and developing deeply is three-dimensional infinite network.In cross-linking process, it is unlimited to reach a three-dimensional for the first time The reflecting point of network is known as gel point (percolation threshold).Unless stated otherwise, the present invention in cross-linked structure refer in particular to gel point with Upper (containing, similarly hereinafter) three-dimensional infinite network structure, non-crosslinking structure include line style, branching, ring-type, two-dimentional cluster and gel point or less Three-dimensional cluster structure isogel point structure below.
Embodiment according to the present invention, the network in a dynamic aggregation object at least containing a dynamic covalent cross-linking, In addition to dynamic covalent cross-linking, there can also be hydrogen bond crosslinks；Dynamic covalent cross-linking and hydrogen bond crosslinks can be in the same cross-linked networks In, it can also be in different cross-linked networks.Therefore, the polymer network is known as " hybrid cross-linked network ".Do not refer in particular to In the case where bright, the present invention in " network ", refer to " cross-linked network ".
In embodiments of the present invention, the dynamic covalent cross-linking in the same dynamic covalent polymer system can have one Kind or more than one, it can using any appropriate dynamic covalent cross-linking topological structure, chemical structure, reactive mode and its Combination etc..In embodiments of the present invention, the cross-linked network in a system at least one, it can be single one net Network can also have the multiple networks being mutually blended, and can also have multiple networks of interpenetrating, can also exist simultaneously blending and mutually Wear, etc..Wherein, two or more networks can be identical or different；Can be subnetwork only includes dynamic covalent cross-linking It only include the combination of hydrogen bond crosslinks with subnetwork, or part only includes dynamic covalent cross-linking and part while including dynamic The combination of state covalent cross-linking and hydrogen bond crosslinks, or part only include dynamic covalent cross-linking comprising hydrogen bond crosslinks and part simultaneously All include simultaneously dynamic covalent cross-linking and hydrogen bond crosslinks in combination or each network with hydrogen bond crosslinks, or contains There is the non-cross-linked polymer of hydrogen bond action to be dispersed in dynamic covalent cross-linking network, or is polymerize with the supermolecule of hydrogen bond crosslinks Object is dispersed in granular form in the network of dynamic covalent cross-linking；Between different non-crosslinked ingredients can with interpenetrating can also part mutually It wears；It can be between any heterogeneity compatible either incompatible；The ingredient of partial dynamic covalent cross-linking can also be with The particle of crosslinking is mutually perhaps incompatibly dispersed in other compositions；But the present invention is not limited only to this；And in reality of the invention It applies in mode, the dynamic covalent cross-linking must reach the gel point of dynamic covalent cross-linking or more at least one network.This Sample can just guarantee that polymer can also be kept even if in the case where only one network for polymer of the invention Balanced structure, namely polymer can be (at least partly) no in the case where can not trigger dynamic covalent bond dissociation Dissolve the cross-linked network not melted.Can there are interaction namely supermolecule hydrogen when there are multiple networks, between heterogeneous networks Key effect, can also be mutually indepedent；And except the dynamic covalent cross-linking of at least one network must reach dynamic covalent cross-linking It is more than gel point outer, the crosslinking of other networks (including dynamic covalently and the sum of supermolecule hydrogen bond crosslinks) can gel point with On can also be in gel point hereinafter, it is preferred that more than gel point.
There is no common covalently cross-linked networks in the present invention, but fractions can be with the particle of common covalent cross-linking It is mutually perhaps incompatibly dispersed in other compositions, the particle of the common covalent cross-linking only forms cross-linked network inside particle Network is not belonging to be developed across the unlimited three-dimensional network of the entire dynamic aggregation object.When in the dynamic covalent cross-linking network Dynamic covalent bond when being disconnected to gel point or less, dynamic covalent cross-linking network is degraded.
Heretofore described " common covalent bond ", what is referred to is traditional covalent in addition to dynamic covalent bond Key is formed by a kind of interaction by share electron pair between atom, (is generally not more than 100 DEG C) under typical temperature With (generally less than 1 day) is more difficult in the usual time is broken comprising but be not limited only to common carbon-carbon bond, carbon-oxygen bond, Carbon-hydrogen link, carbon-nitrogen bond, carbon-sulfide linkage, nitrogen-hydrogen bond, nitrogen-oxygen key, hydrogen-oxygen key, nitrogen-nitrogen key etc..
Heretofore described Reversible Addition Fragmentation Chain Transfer dynamic covalent bond is to make with Reversible Addition Fragmentation Chain Transfer Functional group." Reversible Addition Fragmentation Chain Transfer effect " of the present invention refers to working as a living radical and having The functional group namely Reversible Addition Fragmentation Chain Transfer dynamic covalent bond of the present invention of Reversible Addition Fragmentation Chain Transfer effect Effect forms intermediate, and intermediate, which can break to form a new living radical and be formed, initial has reversible addition disconnected Split the functional group namely Reversible Addition Fragmentation Chain Transfer dynamic covalent bond of the present invention of chain transfer, and this mistake Journey is reversible process.This process similar to the Reversible Addition Fragmentation Chain Transfer process in Invertible ideal, But not fully it is equal to the Reversible Addition Fragmentation Chain Transfer process in Invertible ideal.Firstly, reversible add It is solution polymerization process at fracture chain transfer polymerization, and " Reversible Addition Fragmentation Chain Transfer effect " of the present invention can be molten It is carried out in liquid or solid；Furthermore the activity during Reversible Addition Fragmentation Chain Transfer is participated in Invertible ideal Free radical is usually carbon radicals, and when the Reversible Addition Fragmentation Chain Transfer dynamic covalent bond in the present invention is allyl sulfide ether When, to guarantee to have good dynamic reversibility, the living radical in system preferably is selected from Thiyl Radical.It is of the present invention can Inverse addition fracture chain tra nsfer dynamic covalent bond includes but are not limited to " Polymer Science AComprehensive Reference ", allyl sulfide ether in 2012:181-226 article in the diallyl sulfide of 3.07.2.2 section report and 3.07.3 the Reversible Addition Fragmentation Chain Transfer functional group and double selenium esters in the Reversible Addition Fragmentation Chain Transfer compound of chapter report Base, three seleno carbonate groups, two seleno thiocarbonic acid ester groups, two thio seleno carbonate groups, two pairs of selenium ester groups, double three selenos carbon Perester radical, diselenocarbmate base, two seleno carbonate groups and its corresponding derivatives group, just repeat no more here.
Heretofore described Reversible Addition Fragmentation Chain Transfer dynamic covalent bond, has the following structure general formula:
Wherein,Refer to polymer chain, crosslinking link or the connection of any other suitable group；A can be selected from but Not only it is limited to C atom, S atom, Se atom.
When A is the C atomic time, heretofore described Reversible Addition Fragmentation Chain Transfer dynamic covalent bond has following knot Structure general formula:
Wherein, R1、R2、R3、R4Respectively it is individually present；
R1、R2、R3、R4In the presence of, it is each independently selected from hydrogen atom, replaces atom, substituent group；
Selected from substitution atomic time, R1、R2、R3、R4It is preferred that hydrogen atom；
When selected from substituent group, R1、R2、R3、R4Carbon atom number be not particularly limited, can be polymer chain, preferably carbon is former Subnumber is 1~20, more preferably from 1~10, more preferable 1~5；
When selected from substituent group, R1、R2、R3、R4Structure be not particularly limited, include but are not limited to linear chain structure, containing side The branched structure or cyclic structure of base, preferably linear chain structure；
When selected from substituent group, R1、R2、R3、R4Hetero atom can be contained, hetero atom can also be free of.For simplicity, originally Carbon atom number range in group is labeled in the subscript position of C in invention with the form of subscripts, indicates that the carbon that the group has is former Subnumber, such as C1-10Indicate " there is 1 to 10 carbon atom ", C3-20Indicate " there are 3 to 20 carbon atoms ".It is " unsaturated C3-20Alkyl " refers to C3-20Contain the compound of unsaturated bond in alkyl." substituted C1-20Alkyl " refers to C1-20The hydrogen atom quilt of alkyl Replace obtained compound." the C of hydridization1-20Alkyl " refers to C1-20The compound that carbon atom in alkyl is exchanged for heteroatoms. When a group can be selected from C1-10When alkyl, it can be selected from the alkyl of any carbon atom number in range shown in subscript, i.e., it is optional From C1、C2、C3、C4、C5、C6、C7、C8、C9、C10Any alkyl in alkyl.In the present invention, the case where being not particularly illustrated Under, it indicates to can be selected from any integer within the scope of this with the subscript that range format marks, which includes two endpoints.
R1、R2、R3、R4Selected from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Miscellaneous alkyl, substituted C1-20Alkyl or substitution Miscellaneous alkyl.Wherein, R1、R2、R3、R4In substitution atom or substituent group be not particularly limited, selected from hydrogen atom, halogen atom, Hydrocarbyl substituent, containing any in heteroatomic substituent group.
R1、R2、R3、R4More preferably from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Unsaturated aliphatic hydrocarbyl moiety, aryl, virtue Alkyl, C1-20Miscellaneous alkyl, C1-20Alkyl oxygroup acyl group, C1-20Alkylthio acyl group, C1-20Any atom in hydrocarbylamino acyl group Or the substituted form of group or any group.
R1、R2、R3、R4More preferably from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Alkenyl, aryl, aryl, C1-20Rouge Miscellaneous alkyl, heteroaryl, heteroaryl alkyl, C1-20Alkoxyacyl, aryloxy acyl group, C1-20Alkyl sulfenyl acyl group, artyl sulfo acyl The substituted form of any atom or group or any group in base.
Specifically, R1、R2、R3、R4It is former selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine is included but are not limited to Son, methyl, ethyl, n-propyl, isopropyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecane Base, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, alkene Propyl, acrylic, vinyl, phenyl, aminomethyl phenyl, butyl phenyl, benzyl, methoxycarbonyl, ethoxy carbonyl, phenoxy group carbonyl Base, benzyloxycarbonyl, methyl mercapto carbonyl, ethylmercapto group carbonyl, thiophenyl carbonyl, benzylthio carbonyl, B aminocarbonyl, benzyl amino carbonyl Base, methoxyl group thiocarbonyl, ethyoxyl thiocarbonyl, phenoxythiocarbonyl, benzyloxy thiocarbonyl, the thio carbonyl of methyl mercapto Base, ethylmercapto group thiocarbonyl, phenylthiothiocarbonyl carbonyl, benzylthio thiocarbonyl, ethylamino thiocarbonyl, benzyl aminothio carbonyl Base, substituted C1-20Alkyl, substituted C1-20Alkenyl, substituted aryl, substituted aryl, substituted C1-20Rouge miscellaneous alkyl takes The heteroaryl in generation, substituted heteroaryl alkyl, substituted C1-20Alkoxy carbonyl, substituted aryloxycarbonyl, substituted C1-20Alkane The C that base sulfenyl carbonyl, substituted artyl sulfo carbonyl replace1-20Alkoxy carbonyl, substituted aryloxy thiocarbonyl, Substituted C1-20Any atom or group in alkyl sulfenyl thiocarbonyl, substituted artyl sulfo thiocarbonyl etc..Wherein, fourth Base includes but are not limited to normal-butyl, tert-butyl.Octyl includes but are not limited to n-octyl, 2- ethylhexyl.Wherein, replace former Son or substituent group selected from halogen atom, hydrocarbyl substituent, containing any in heteroatomic substituent group.
Z2For with C3The divalent linking atom or divalent linking group that carbon atom is connected directly；
Work as Z2When selected from divalent linking group, Z2Structure be not particularly limited, include but are not limited to linear chain structure, contain The branched structure or cyclic structure of side group.Wherein, cyclic structure is not particularly limited, and can be selected from aliphatic ring, aromatic ring, sugar Ring, condensed ring；
Z2Hetero atom can be contained, hetero atom can also be free of；
Z2Carbon atom number be not particularly limited, 1~20 preferably is selected from, more preferably from 1~10.
Z2Selected from C1-20Alkylene, divalent C1-20Miscellaneous alkyl, substituted C1-20Alkylene, substituted divalent C1-20In miscellaneous alkyl Any divalent linker or any two or it is wantonly three kinds combination formed divalent linker.Wherein, replace atom or substituent group It is not particularly limited, selected from halogen atom, hydrocarbyl substituent, containing any in heteroatomic substituent group.
Z2It preferably is selected from C1-20Open chain alkylidene, C1-20Open chain alkenylene, C1-20Cycloalkylidene, C1-20Sub- cycloalkenyl group, sub- virtue Base, sub- aryl, divalent C1-20Rouge miscellaneous alkyl, divalent C1-20Rouge miscellaneous thiazolinyl, divalent heteroaryl radical, divalent heteroaryl alkyl, substituted Asia Alkyl, substituted C1-20Open chain alkenylene, substituted C1-20Cycloalkylidene, substituted C1-20Sub- cycloalkenyl group, the Asia virtue replaced Base, substituted sub- aryl, substituted divalent C1-20Rouge miscellaneous alkyl, substituted divalent C1-20Rouge miscellaneous thiazolinyl, substituted divalent heteroaryl Any divalent linker in base, substituted divalent heteroaryl alkyl, any two combination, or wantonly three kinds of the divalent for combining formation Linker.
Z2More preferably from C1-10Open chain alkylidene, C1-10Open chain alkenylene, C1-10Cycloalkylidene, C1-10Sub- cycloalkenyl group, Asia Aryl, sub- aryl, divalent C1-10Rouge miscellaneous alkyl, divalent C1-10Rouge miscellaneous thiazolinyl, divalent heteroaryl radical, divalent heteroaryl alkyl, replace Alkylidene, substituted C1-10Open chain alkenylene, substituted C1-10Cycloalkylidene, substituted C1-10Sub- cycloalkenyl group, the Asia virtue replaced Base, substituted sub- aralkyl, substituted divalent C1-10Rouge miscellaneous alkyl, substituted divalent C1-10Rouge miscellaneous thiazolinyl, substituted divalent heteroaryl Any divalent linker in base, substituted divalent heteroaryl alkyl, any two combination, or wantonly three kinds of the divalent for combining formation Linker.
Specifically, Z2N aggressiveness (N >=2) such as trimerization of more preferable divalent acrylic or methacrylic acid and its corresponding esters N aggressiveness (N >=2) such as tripolymer, the tetramer of body, the tetramer, divalent styrene or methyl styrene.
Work as Z2When for above-mentioned divalent linking group, Z1For with double bond C2The divalent linking group that carbon atom is connected directly；Z1's Structure is not particularly limited, and includes but are not limited to singly-bound, linear chain structure, the branched structure containing side group or cyclic structure.Wherein, Cyclic structure is not particularly limited, and can be selected from aliphatic ring, aromatic ring, saccharide ring, condensed ring, optimization aromatic ring；
Z1Hetero atom can be contained, hetero atom can also be free of；
Z1Carbon atom number be not particularly limited, 1~20 preferably is selected from, more preferably from 1~10.
Z1Selected from C1-20Alkylene, divalent C1-20Miscellaneous alkyl, substituted C1-20Alkylene, substituted divalent C1-20In miscellaneous alkyl Any divalent linker or any two or it is wantonly three kinds combination formed divalent linker.Wherein, replace atom or substituent group It is not particularly limited, selected from halogen atom, hydrocarbyl substituent, containing any in heteroatomic substituent group.
Z1It preferably is selected from C1-20Open chain alkylidene, C1-20Open chain alkenylene, C1-20Cycloalkylidene, C1-20Sub- cycloalkenyl group, sub- virtue Base, sub- aryl, divalent C1-20Rouge miscellaneous alkyl, divalent C1-20Rouge miscellaneous thiazolinyl, divalent heteroaryl radical, divalent heteroaryl alkyl, substituted Asia Alkyl, substituted C1-20Open chain alkenylene, substituted C1-20Cycloalkylidene, substituted C1-20Sub- cycloalkenyl group, the Asia virtue replaced Base, substituted sub- aryl, substituted divalent C1-20Rouge miscellaneous alkyl, substituted divalent C1-20Rouge miscellaneous thiazolinyl, substituted divalent heteroaryl Any divalent linker in base, substituted divalent heteroaryl alkyl, any two combination, or wantonly three kinds of the divalent for combining formation Linker.
Z1More preferably from C1-10Open chain alkylidene, C1-10Open chain alkenylene, C1-10Cycloalkylidene, C1-10Sub- cycloalkenyl group, Asia Aryl, sub- aryl, divalent C1-10Rouge miscellaneous alkyl, divalent C1-10Rouge miscellaneous thiazolinyl, divalent heteroaryl radical, divalent heteroaryl alkyl, replace Alkylidene, substituted C1-10Open chain alkenylene, substituted C1-10Cycloalkylidene, substituted C1-10Sub- cycloalkenyl group, the Asia virtue replaced Base, substituted sub- aralkyl, substituted divalent C1-10Rouge miscellaneous alkyl, substituted divalent C1-10Rouge miscellaneous thiazolinyl, substituted divalent heteroaryl Any divalent linker in base, substituted divalent heteroaryl alkyl, any two combination, or wantonly three kinds of the divalent for combining formation Linker.
Z1The divalent connection more preferably replaced from the divalent linking group with sucting electronic effect, sucting electronic effect substituent group Group is so conducive to the activity for improving C=C, makes it easier to the attack by living radical, obtains more quick add At reaction, to obtain strong dynamic reversibility.The divalent linking group of the sucting electronic effect includes but are not limited to divalent Any divalent linker in ester group, divalent amido group, divalent carbonyl, divalent aryl such as divalent phenyl group, any two combination, or The divalent linker that wantonly three kinds of combination is formed.The divalent linking group replaced with sucting electronic effect substituent group includes but not only It is limited in electron-withdrawing group such as carbonyl, aldehyde radical, nitro, ester group, sulfonic group, acylamino-, aryl, cyano, halogen atom such as fluorine atom One or more substituted C1-10Open chain alkylidene, C1-10Open chain alkenylene, C1-10Cycloalkylidene, C1-10Sub- cycloalkenyl group, Asia Aryl, sub- aryl, divalent C1-10Rouge miscellaneous alkyl, divalent C1-10It is rouge miscellaneous thiazolinyl, divalent heteroaryl radical, any in divalent heteroaryl alkyl Kind divalent linker, any two combination, or wantonly three kinds of the divalent linker for combining formation.
Specifically, Z1Divalent linking group selected from sucting electronic effect includes but are not limited to divalent ester group, divalent acyl ammonia The divalent that base, divalent carbonyl, any divalent linker in divalent phenyl group, any two combination, or wantonly three kinds of combination are formed Linker；The divalent linking group that sucting electronic effect substituent group replaces, includes but are not limited to electron-withdrawing group such as carbonyl, aldehyde One of base, nitro, ester group, sulfonic group, acylamino-, aryl, cyano, halogen atom such as fluorine atom or a variety of substituted penylenes Base, benzal, naphthylene, sub- pyrrole radicals, sub-pyridyl group.
At this point, the Reversible Addition Fragmentation Chain Transfer dynamic covalent bond includes but are not limited to " Polymer Science A Comprehensive Reference ", in 2012:181-226 article in the macromonomer of 3.07.3.1 section report can Inverse addition is broken chain tra nsfer functional group, just repeats no more here.
As an example, it can enumerate such as flowering structure, but the present invention is not limited only to this:
Wherein, n is the quantity of repetitive unit, can be fixed value, is also possible to average value, n >=1.
Work as Z2When selected from divalent linking atom, it is selected from S atom, at this time Z1For with double bond C2Carbon atom be connected directly two Valence linking group.Work as Z2When for S atom, heretofore described Reversible Addition Fragmentation Chain Transfer dynamic covalent bond has such as Flowering structure general formula:
Work as Z2When selected from S atom, Z at this time1For with double bond C2The divalent linking group that carbon atom is connected directly；
Z1Structure be not particularly limited, include but are not limited to singly-bound, linear chain structure, branched structure or ring containing side group Shape structure.Wherein, cyclic structure is not particularly limited, and can be selected from aliphatic ring, aromatic ring, saccharide ring, condensed ring；
Z1Hetero atom can be contained, hetero atom can also be free of；
Z1Carbon atom number be not particularly limited, 1~20 preferably is selected from, more preferably from 1~10.
Z1Selected from C1-20Alkylene, divalent C1-20Miscellaneous alkyl, substituted C1-20Alkylene, substituted divalent C1-20In miscellaneous alkyl Any divalent linker or any two or it is wantonly three kinds combination formed divalent linker.Wherein, replace atom or substituent group It is not particularly limited, selected from halogen atom, hydrocarbyl substituent, containing any in heteroatomic substituent group.
Z1It preferably is selected from C1-20Open chain alkylidene, C1-20Open chain alkenylene, C1-20Cycloalkylidene, C1-20Sub- cycloalkenyl group, sub- virtue Base, sub- aryl, divalent C1-20Rouge miscellaneous alkyl, divalent C1-20Rouge miscellaneous thiazolinyl, divalent heteroaryl radical, divalent heteroaryl alkyl, substituted Asia Alkyl, substituted C1-20Open chain alkenylene, substituted C1-20Cycloalkylidene, substituted C1-20Sub- cycloalkenyl group, the Asia virtue replaced Base, substituted sub- aryl, substituted divalent C1-20Rouge miscellaneous alkyl, substituted divalent C1-20Rouge miscellaneous thiazolinyl, substituted divalent heteroaryl Any divalent linker in base, substituted divalent heteroaryl alkyl, any two combination, or wantonly three kinds of the divalent for combining formation Linker.
Z1More preferably from C1-10Open chain alkylidene, C1-10Open chain alkenylene, C1-10Cycloalkylidene, C1-10Sub- cycloalkenyl group, Asia Aryl, sub- aryl, divalent C1-10Rouge miscellaneous alkyl, divalent C1-10Rouge miscellaneous thiazolinyl, divalent heteroaryl radical, divalent heteroaryl alkyl, replace Alkylidene, substituted C1-10Open chain alkenylene, substituted C1-10Cycloalkylidene, substituted C1-10Sub- cycloalkenyl group, the Asia virtue replaced Base, substituted sub- aralkyl, substituted divalent C1-10Rouge miscellaneous alkyl, substituted divalent C1-10Rouge miscellaneous thiazolinyl, substituted divalent heteroaryl Any divalent linker in base, substituted divalent heteroaryl alkyl, any two combination, or wantonly three kinds of the divalent for combining formation Linker.
Z1More preferably from divalent alkyl, divalent aryl, divalent alkyl ether, divalent aryl ether, divalent alkyl thioether group, Most preferably from divalent alkyl thioether group, better dynamic reversibility can be so obtained.Specifically, Z1It preferably is selected from methylene, Asia Dimethyl sulfide base, ethylidene, propylidene, butylidene, pentylidene, hexylidene, divalent phenyl group, divalent phenyl group ether, divalent benzyl, Divalent ethyoxyl, divalent butoxy, divalent hexyloxy, most preferably from sulfonium methylide ether.
At this point, the Reversible Addition Fragmentation Chain Transfer dynamic covalent bond includes but are not limited to " Polymer Science A Comprehensive Reference ", in 2012:181-226 article in the diallyl sulfide of 3.07.2.2 section report Allyl sulfide ether, just repeats no more here.
As an example, it can enumerate such as flowering structure, but the present invention is not limited only to this:
Wherein, n is the quantity of repetitive unit, can be fixed value, is also possible to average value, n >=1.
When A is S atom or Se atomic time, R1、R2、R3、R4It is not present；
When A is S atom or Se atomic time, Z1It is former selected from O atom, S atom, Se atom, Si atom, C atom, N atom, P Son, preferably S atom, Se atom, C atom, O atom, N atom.At this point, heretofore described Reversible Addition Fragmentation Chain Transfer is dynamic State covalent bond, has the following structure at least one of general formula:
Work as Z1For O atom, S atom, Se atomic time, R5、R6、R7It is not present；
Work as Z1For N atomic time, R5In the presence of R6、R7It is not present；
Work as Z1For Si atom, C atomic time, R5、R6In the presence of R7It is not present；
Work as Z1For P atomic time, R5、R6、R7、R8In the presence of；
R5、R6、R7、R8In the presence of, it is each independently selected from hydrogen atom, replaces atom, substituent group；
Selected from substitution atomic time, R5、R6、R7、R8It is preferred that hydrogen atom；
When selected from substituent group, R5、R6、R7、R8Carbon atom number be not particularly limited, can be polymer chain, preferably carbon is former Subnumber is 1~20, more preferably from 1~10, more preferable 1~5；
When selected from substituent group, R5、R6、R7、R8Structure be not particularly limited, include but are not limited to linear chain structure, containing side The branched structure or cyclic structure of base, preferably linear chain structure；
When selected from substituent group, R5、R6、R7、R8Hetero atom can be contained, hetero atom can also be free of.
R5、R6、R7、R8Selected from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Miscellaneous alkyl, substituted C1-20Alkyl or substitution Miscellaneous alkyl.Wherein, R5、R6、R7、R8In substitution atom or substituent group be not particularly limited, taken selected from halogen atom, alkyl Dai Ji, containing any in heteroatomic substituent group.
R5、R6、R7、R8More preferably from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Unsaturated aliphatic hydrocarbyl moiety, aryl, virtue Alkyl, C1-20Miscellaneous alkyl, C1-20Alkyl oxygroup acyl group, C1-20Alkylthio acyl group, C1-20Any atom in hydrocarbylamino acyl group Or the substituted form of group or any group.
R5、R6、R7、R8More preferably from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Alkenyl, aryl, aryl, C1-20Rouge Miscellaneous alkyl, heteroaryl, heteroaryl alkyl, C1-20Alkoxyacyl, aryloxy acyl group, C1-20Alkyl sulfenyl acyl group, artyl sulfo acyl The substituted form of any atom or group or any group in base.
Specifically, R5、R6、R7、R8It is former selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine is included but are not limited to Son, methyl, ethyl, n-propyl, isopropyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecane Base, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, alkene Propyl, acrylic, vinyl, phenyl, aminomethyl phenyl, butyl phenyl, benzyl, methoxycarbonyl, ethoxy carbonyl, phenoxy group carbonyl Base, benzyloxycarbonyl, methyl mercapto carbonyl, ethylmercapto group carbonyl, thiophenyl carbonyl, benzylthio carbonyl, B aminocarbonyl, benzyl amino carbonyl Base, methoxyl group thiocarbonyl, ethyoxyl thiocarbonyl, phenoxythiocarbonyl, benzyloxy thiocarbonyl, the thio carbonyl of methyl mercapto Base, ethylmercapto group thiocarbonyl, phenylthiothiocarbonyl carbonyl, benzylthio thiocarbonyl, ethylamino thiocarbonyl, benzyl aminothio carbonyl Base, substituted C1-20Alkyl, substituted C1-20Alkenyl, substituted aryl, substituted aryl, substituted C1-20Rouge miscellaneous alkyl takes The heteroaryl in generation, substituted heteroaryl alkyl, substituted C1-20Alkoxy carbonyl, substituted aryloxycarbonyl, substituted C1-20Alkane The C that base sulfenyl carbonyl, substituted artyl sulfo carbonyl replace1-20Alkoxy carbonyl, substituted aryloxy thiocarbonyl, Substituted C1-20Any atom or group in alkyl sulfenyl thiocarbonyl, substituted artyl sulfo thiocarbonyl etc..Wherein, fourth Base includes but are not limited to normal-butyl, tert-butyl.Octyl includes but are not limited to n-octyl, 2- ethylhexyl.Wherein, replace former Son or substituent group selected from halogen atom, hydrocarbyl substituent, containing any in heteroatomic substituent group.
Z2For the divalent linking group being connected directly with S atom or Se atom；
Z2Structure be not particularly limited, include but are not limited to singly-bound, linear chain structure, branched structure or ring containing side group Shape structure.Wherein, cyclic structure is not particularly limited, and can be selected from aliphatic ring, aromatic ring, saccharide ring, condensed ring, preferred fragrance Race's ring；
Z2Hetero atom can be contained, hetero atom can also be free of；
Z2Carbon atom number be not particularly limited, 1~20 preferably is selected from, more preferably from 1~10.
Z2Selected from C1-20Alkylene, divalent C1-20Miscellaneous alkyl, substituted C1-20Alkylene, substituted divalent C1-20In miscellaneous alkyl Any divalent linker or any two or it is wantonly three kinds combination formed divalent linker.Wherein, replace atom or substituent group It is not particularly limited, selected from halogen atom, hydrocarbyl substituent, containing any in heteroatomic substituent group.
Z2It preferably is selected from C1-20Open chain alkylidene, C1-20Open chain alkenylene, C1-20Cycloalkylidene, C1-20Sub- cycloalkenyl group, sub- virtue Base, sub- aryl, divalent C1-20Rouge miscellaneous alkyl, divalent C1-20Rouge miscellaneous thiazolinyl, divalent heteroaryl radical, divalent heteroaryl alkyl, substituted Asia Alkyl, substituted C1-20Open chain alkenylene, substituted C1-20Cycloalkylidene, substituted C1-20Sub- cycloalkenyl group, the Asia virtue replaced Base, substituted sub- aryl, substituted divalent C1-20Rouge miscellaneous alkyl, substituted divalent C1-20Rouge miscellaneous thiazolinyl, substituted divalent heteroaryl Any divalent linker in base, substituted divalent heteroaryl alkyl, any two combination, or wantonly three kinds of the divalent for combining formation Linker.
Z2More preferably from C1-10Open chain alkylidene, C1-10Open chain alkenylene, C1-10Cycloalkylidene, C1-10Sub- cycloalkenyl group, Asia Aryl, sub- aryl, divalent C1-10Rouge miscellaneous alkyl, divalent C1-10Rouge miscellaneous thiazolinyl, divalent heteroaryl radical, divalent heteroaryl alkyl, replace Alkylidene, substituted C1-10Open chain alkenylene, substituted C1-10Cycloalkylidene, substituted C1-10Sub- cycloalkenyl group, the Asia virtue replaced Base, substituted sub- aralkyl, substituted divalent C1-10Rouge miscellaneous alkyl, substituted divalent C1-10Rouge miscellaneous thiazolinyl, substituted divalent heteroaryl Any divalent linker in base, substituted divalent heteroaryl alkyl, any two combination, or wantonly three kinds of the divalent for combining formation Linker.
Z2More preferably from cyano, alkyl, aryl, ester group, acylamino-, urine base, one of carbamate groups or a variety of Substituted alkylidene, substituted C1-10Open chain alkenylene, substituted C1-10Cycloalkylidene, substituted C1-10Sub- cycloalkenyl group, substitution Arlydene, substituted sub- aralkyl, substituted divalent C1-10Rouge miscellaneous alkyl, substituted divalent C1-10Rouge miscellaneous thiazolinyl, two replaced Any divalent linker in valence heteroaryl, substituted divalent heteroaryl alkyl, any two combination, or wantonly three kinds of combination are formed Divalent linker, be so conducive to Z2The dissociation of group and the stronger active free radical of acquisition are consequently facilitating further addition Reaction, obtains more excellent dynamic property.
Specifically, Z2It is selected from but is not limited only to cyano, methyl, ethyl, propyl, isopropyl, phenyl, benzyl, ester group, acyl ammonia One of base, carbamate groups, urine base or a variety of substituted methylene, ethylidene, propylidene, butylidene, pentylidene, Asia Hexyl, heptamethylene, octamethylene, nonylene, decylene, alkylene undecyl, sub-dodecyl, sub- tridecyl, sub- myristyl, Sub- pentadecyl, sub- cetyl, sub- heptadecyl, alkylene octadecyl, sub- nonadecyl, alkylene eicosyl.
Work as Z1For O atom, S atom, Se atom, Si atom, C atom, N atom, P atomic time, Z3For with Z1The direct phase of atom Divalent linking group even；Z3Structure be not particularly limited, include but are not limited to singly-bound, linear chain structure, the branch containing side group Chain structure or cyclic structure.Wherein, cyclic structure is not particularly limited, and can be selected from aliphatic ring, aromatic ring, saccharide ring, condensation Ring, optimization aromatic ring；
Z3Hetero atom can be contained, hetero atom can also be free of；
Z3Carbon atom number be not particularly limited, 1~20 preferably is selected from, more preferably from 1~10.
Z3Selected from C1-20Alkylene, divalent C1-20Miscellaneous alkyl, substituted C1-20Alkylene, substituted divalent C1-20In miscellaneous alkyl Any divalent linker or any two or it is wantonly three kinds combination formed divalent linker.Wherein, replace atom or substituent group It is not particularly limited, selected from halogen atom, hydrocarbyl substituent, containing any in heteroatomic substituent group.
Z3It preferably is selected from C1-20Open chain alkylidene, C1-20Open chain alkenylene, C1-20Cycloalkylidene, C1-20Sub- cycloalkenyl group, sub- virtue Base, sub- aryl, divalent C1-20Rouge miscellaneous alkyl, divalent C1-20Rouge miscellaneous thiazolinyl, divalent heteroaryl radical, divalent heteroaryl alkyl, substituted Asia Alkyl, substituted C1-20Open chain alkenylene, substituted C1-20Cycloalkylidene, substituted C1-20Sub- cycloalkenyl group, the Asia virtue replaced Base, substituted sub- aryl, substituted divalent C1-20Rouge miscellaneous alkyl, substituted divalent C1-20Rouge miscellaneous thiazolinyl, substituted divalent heteroaryl Any divalent linker in base, substituted divalent heteroaryl alkyl, any two combination, or wantonly three kinds of the divalent for combining formation Linker.
Z3More preferably from C1-10Open chain alkylidene, C1-10Open chain alkenylene, C1-10Cycloalkylidene, C1-10Sub- cycloalkenyl group, Asia Aryl, sub- aryl, divalent C1-10Rouge miscellaneous alkyl, divalent C1-10Rouge miscellaneous thiazolinyl, divalent heteroaryl radical, divalent heteroaryl alkyl, replace Alkylidene, substituted C1-10Open chain alkenylene, substituted C1-10Cycloalkylidene, substituted C1-10Sub- cycloalkenyl group, the Asia virtue replaced Base, substituted sub- aralkyl, substituted divalent C1-10Rouge miscellaneous alkyl, substituted divalent C1-10Rouge miscellaneous thiazolinyl, substituted divalent heteroaryl Any divalent linker in base, substituted divalent heteroaryl alkyl, any two combination, or wantonly three kinds of the divalent for combining formation Linker.
Z3The divalent connection more preferably replaced from the divalent linking group with sucting electronic effect, sucting electronic effect substituent group Group is so conducive to the activity for improving C=S (Se), makes it easier to the attack by living radical, obtains more quick Addition reaction, to obtain strong dynamic reversibility.The divalent linking group of the sucting electronic effect includes but are not limited to Any divalent linker in divalent ester group, divalent amido group, divalent carbonyl, divalent aryl such as divalent phenyl group, any two group It closes, or wantonly three kinds of the divalent linker for combining formation.With sucting electronic effect substituent group replace divalent linking group include But it is not limited only to electron-withdrawing group such as carbonyl, aldehyde radical, nitro, ester group, sulfonic group, acylamino-, aryl, cyano, halogen atom such as fluorine One of atom or a variety of substituted C1-10Open chain alkylidene, C1-10Open chain alkenylene, C1-10Cycloalkylidene, C1-10Sub- cyclenes Alkyl, arlydene, sub- aryl, divalent C1-10Rouge miscellaneous alkyl, divalent C1-10Rouge miscellaneous thiazolinyl, divalent heteroaryl radical, divalent heteroaryl alkyl In any divalent linker, any two combination, or wantonly three kinds combination formed divalent linker.
Specifically, Z3Divalent linking group selected from sucting electronic effect includes but are not limited to divalent ester group, divalent acyl ammonia The divalent that base, divalent carbonyl, any divalent linker in divalent phenyl group, any two combination, or wantonly three kinds of combination are formed Linker；The divalent linking group that sucting electronic effect substituent group replaces, includes but are not limited to electron-withdrawing group such as carbonyl, aldehyde One of base, nitro, ester group, sulfonic group, acylamino-, aryl, cyano, halogen atom such as fluorine atom or a variety of substituted penylenes Base, benzal, naphthylene, sub- pyrrole radicals, sub-pyridyl group.
Heretofore described hetero atom is not particularly limited, include but are not limited to O, S, N, P, Si, F, Cl, Br, I, B etc..Wherein, heteroatomic quantity can be one, or two or more.Hetero atom can be used as substitution atom In the presence of；Can also exist independently as divalent linker, citing as-O- (oxygroup or ehter bond) ,-S- (sulfenyl or thioether bond), -N(R7)-(secondary amino group or divalent tertiary amino) etc..
At this point, the Reversible Addition Fragmentation Chain Transfer dynamic covalent bond includes but are not limited to " Polymer Science A Comprehensive Reference ", two thiocarbonyl compounds of 3.07.3.2 section report in 2012:181-226 article And it is double selenium ester groups, three seleno carbonate groups, two seleno thiocarbonic acid ester groups, two thio seleno carbonate groups, two pairs of selenium ester groups, double Three seleno carbonate groups, diselenocarbmate base, two seleno carbonate groups and its corresponding derivatives group.As example Son can be enumerated such as flowering structure, but the present invention is not limited only to this:
In the present invention, it is not limited especially for the compound of Reversible Addition Fragmentation Chain Transfer dynamic covalent bond can be imported System, the preferably dihydric alcohol of the covalent bond of dynamic containing Reversible Addition Fragmentation Chain Transfer, binary isocyanates, binary mercaptan, binary epoxy Dihydric alcohol, the binary isocyanide of compound, alkene, alkynes, amine, carboxylic acid etc., more preferably dynamic containing Reversible Addition Fragmentation Chain Transfer covalent bond Acid esters, alkene, alkynes；Reaction type and the mode etc. that import Reversible Addition Fragmentation Chain Transfer dynamic covalent bond are also limited without special Fixed, preferably following reaction: isocyanates and amino, hydroxyl, sulfydryl, carboxyl react, epoxy and hydroxyl, sulfydryl, amino it is anti- It answers, sulfydryl-double bond/alkynes click-reaction, double bond radical reaction, more preferable isocyanates and amino, hydroxyl, sulfydryl, carboxyl Reaction, sulfydryl-double bond/alkynes click-reaction and double bond radical reaction.
In embodiments of the present invention, it is dynamic to be based at least one Reversible Addition Fragmentation Chain Transfer for the dynamic covalent cross-linking State covalent bond refers to total containing at least one Reversible Addition Fragmentation Chain Transfer dynamic in dynamic covalent cross-linking network skeleton chain Valence link.The Reversible Addition Fragmentation Chain Transfer dynamic covalent bond, which is removed, is present in dynamic aggregation object hydridization as dynamic covalent cross-linking Except in the polymer backbone chains of cross-linked network, be also present in hybrid cross-linked network skeleton chain side group and/or side chain and/ Or on branch and/or bifurcated chain and its on further side group and/or side chain and/or branch and/or bifurcated chain, there may also be In in noncrosslinking polymer chain backbone and/or side group and/or side chain and/or branch and/or bifurcated chain.Wherein only have hydridization to hand over Reversible Addition Fragmentation Chain Transfer dynamic covalent bond on connection network skeleton could constitute dynamic covalent cross-linking.The reversible addition Fracture chain tra nsfer dynamic covalent bond can carry out reversible fracture and regeneration under certain condition；Under suitable conditions, dynamic The Reversible Addition Fragmentation Chain Transfer dynamic covalent bond of any position can participate in dynamic reversible exchange in polymer.Any two Reversible Addition Fragmentation Chain Transfer dynamic between a crosslinking points containing Reversible Addition Fragmentation Chain Transfer dynamic covalent bond on skeleton There is no limit can be one or more, preferably only contain one covalent bond quantity (ratio of Zhan Suoyou key).Only contain one When a, dynamic aggregation object structure is more regular, and dynamic is more controllable.
Wherein, " the hybrid cross-linked network polymer skeletal chain " refers to being present in appointing in cross-linked network skeleton Meaning segment comprising constitute the main chain on the unlimited three-dimensional network skeleton of crosslinking and crosslinking link；Wherein, between polymer chain Crosslinking link can be an atom, a singly-bound, a group, a segment, a cluster etc., therefore between polymer chain Crosslinking link be also considered as polymer backbone chains.Wherein, " side chain ", refer in hybrid cross-linked network structure and The molecular weight that same polymer backbone chains/main chain is connected and is distributed in chain backbone side in non-cross-linked polymer structure is more than The chain structure of 1000Da；Wherein, " branch ", " bifurcated chain " are referred to from polymer backbone chains or any other chain bifurcated Molecular weight out is more than the chain structure of 1000Da；For the sake of simplicity, in the present invention in hybrid cross-linked network structure and non-friendship Side chain, branch, bifurcated chain in linked polymer structure are then collectively referred to as side chain if not otherwise indicated.Wherein, " the side Base " refers to same polymer backbone chains/main chain/side chain in hybrid cross-linked network structure and in non-cross-linked polymer structure It is connected and is distributed in the chemical group of the molecular weight of chain backbone side not higher than 1000Da and molecular weight not higher than 1000Da's Short-side chain.For " side chain " and " side group ", can have multilevel structure namely side chain that can continue with side group and side chain, side The side chain of chain can continue have side group and side chain, and side chain therein also includes branch and bifurcated chain isodesmic structure.Wherein, described " end group " refers in hybrid cross-linked network structure and is connected in non-cross-linked polymer structure with polymer chain and is located at The chemical group of chain end；In the present invention, side group can also have end group under specific condition.In non-cross-linked polymer, skeletal chain As main chain.For the sake of simplicity, cross-linked network skeletal chain and non-cross-linked polymer main chain may be collectively referred to as main chain.For hyperbranched With dendroid chain and its relevant chain structure, polymer chain therein can be considered as branch, can also be considered as main chain, usually outermost The chain enclosed is considered as branch.
In embodiments of the present invention, supermolecule hydrogen bond action includes by band in polymer chain side group and/or side chain Some hydrogen bond groups (" side hydrogen bond " group) participate in the hydrogen bond action formed.The hydrogen bond group having on the side chain includes side chain Hydrogen bond group (" side chain end group hydrogen bond " group) on hydrogen bond group and side chain side group and side chain end group on skeleton.Except described Outside the hydrogen bond of side, also optionally contains in the present invention and be present in crosslinked polymer network skeleton chain and non-cross-linked polymer main chain backbone On hydrogen bond group (" main chain backbone hydrogen bond " group), other polymers chain end hydrogen bond group (" other end group hydrogen bonds " base Group), the hydrogen bond group in small molecule, the hydrogen bond group on inorganic/organic filler/ingredient, but the present invention is not limited only to this.This hair The Drug delivery rate of bright opposite side hydrogen bond group is not particularly limited, average every 100 backbone repeating units access side hydrogen bond group Number preferably is selected from 0.1 to 200, more preferably from 1 to 100, more preferably from 10 to 60.In the present invention, it is preferred to side hydrogen bond group it Between form side hydrogen bond, but the hydrogen bond group for being not excluded for side hydrogen bond group and other positions forms hydrogen bond, be also not excluded for it is any other Hydrogen bond is formed between the hydrogen bond group of position.The usual motility of side hydrogen bond and transfer ability that side hydrogen bond group is formed are strong, can be with Good dynamic property is provided, the performances such as polymer ultra-tough and selfreparing, shape memory are assigned.In the present invention, Ren Heyi Hydrogen bond crosslinks in a network can preferably reach the gel point of hydrogen bond crosslinks or more in any crosslinking degree.Because wherein extremely The degree of cross linking of rare dynamic covalent cross-linking network reaches the gel point of covalent cross-linking or more, and hydrogen bond crosslinks are covalent cross-linkings Supplement, regardless of the degree of cross linking of hydrogen bond crosslinks, as long as the dynamic covalent cross-linking keeps stablizing, the dynamic aggregation object all may be used To keep balanced structure.
In embodiments of the present invention, the preferably described dynamic aggregation object contains side chain skeleton hydrogen bond group, pendant hydrogen At least one of key group, side chain end group hydrogen bond group.As an example, in the preferred embodiment of the present invention, institute It states and only contains side chain skeleton hydrogen bond group in dynamic aggregation object；In another preferred embodiment of the invention, the dynamic Only contain pendant hydrogen key group in polymer；In another preferred embodiment of the invention, in the dynamic aggregation object only Contain side chain end group hydrogen bond group；In another preferred embodiment of the invention, only contain side in the dynamic aggregation object Chain backbone hydrogen bond group and side group hydrogen bond group；In another preferred embodiment of the invention, in the dynamic aggregation object Only contain side chain skeleton hydrogen bond group and side chain end group hydrogen bond group；It is described in another preferred embodiment of the invention Only contain pendant hydrogen key group and side chain end group hydrogen bond group in dynamic aggregation object；In another preferred embodiment of the invention In, side chain skeleton hydrogen bond group, side group hydrogen bond group, side chain end group hydrogen bond group are contained in the dynamic aggregation object；But this hair It is bright to be not limited only to this.
In embodiments of the present invention, since part hydrogen bond does not have directionality and selectivity, under specific circumstances, no With hydrogen bond action can be formed between the hydrogen bond group of position, it is located at identical or different position in identical or different polymer molecule Hydrogen bond group between can form hydrogen bond action between each other, can also with the other compositions in polymer such as it is optional its Hydrogen bond action is formed between hydrogen bond group contained by his polymer molecule, filler, small molecule etc..In the present invention, except formation Outside interchain linkage, chain inner ring can also be formed.It should be pointed out that being not excluded for part in the present invention had been formed by hydrogen bond action both Not the effects of not forming interchain linkage effect, do not form chain inner ring yet, only forming non-crosslinked property polymerization, grafting.In reality of the invention It applies in mode, preferably at least one of side chain skeleton hydrogen bond group, side group hydrogen bond group, side chain end group hydrogen bond group are respective It is formed between same hydrogen bond group between interchain linkage and/or at least two hydrogen bond groups not of the same race and forms interchain linkage. As an example, in one embodiment of the invention, interchain linkage preferably is formed between side chain skeleton hydrogen bond group；In this hair In bright another embodiment, interchain linkage preferably is formed between side group hydrogen bond group；In another embodiment party of the invention In formula, interchain linkage preferably is formed between side chain end group hydrogen bond group；In another embodiment of the invention, preferred side chain Interchain linkage is formed between skeleton hydrogen bond group and side group hydrogen bond group；In another embodiment of the invention, preferred side Interchain linkage is formed between chain backbone hydrogen bond group and side chain end group hydrogen bond group；In another embodiment of the invention, It is preferred that forming interchain linkage between side group hydrogen bond group and side chain end group hydrogen bond group；In another embodiment of the invention In, preferably interchain linkage is formed between side chain skeleton hydrogen bond group, side group hydrogen bond group and side chain end group hydrogen bond group；But this hair It is bright to be not limited only to this.
In the present invention, the supermolecule hydrogen bond action is covalently attached to generally by the atom Z big with electronegativity Hydrogen atom and electronegativity is big, radius is small atom Y between Z and Y using hydrogen as medium, generate the hydrogen bond chain of Z-H ... Y shape formula It connects, wherein described Z, the Y is the atom that any appropriate electronegativity is big and radius is small, can may be not for same element Same element can be selected from the atoms such as F, N, O, C, S, Cl, P, Br, I, more preferably from F, N, O atom, more preferably from O, N atom； Z, Y is selected from O, N atomic time, and contained compound abundance, hydrogen bond are easily formed and dynamic is strong.Wherein, the supermolecule Hydrogen bond action preferably as supermolecule polymerize and/or be crosslinked and/or chain in ring formation exist namely hydrogen bond can the only company of playing It connects two or more chain segment units and plays and increase polymer chain dimensions but do not play supermolecule crosslinked action or hydrogen bond only rises It is crosslinked to interchain supermolecule, or only plays in chain in combination of any two or more in ring formation or three of the above. When cyclic in chain, if generating grommet and/or torus, crosslinking can produce.It is not excluded for hydrogen bond action in the present invention and plays to connect The effect of branch.
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 hydrogen bond action is just weak, is conducive to Auxiliary is provided for covalent cross-linking, plays and dynamic aggregation object is promoted to keep balanced structure and improve mechanical property (modulus and intensity) Effect.If the number of teeth of hydrogen bond is few, intensity is low, and the dynamic of hydrogen bond action, can be with Reversible Addition Fragmentation Chain Transfer with regard to strong Dynamic covalent bond provides dynamic property, such as self-repairability together.In embodiments of the present invention, preferably more than four teeth Hydrogen bond action, such readily available required dynamic and required intensity.
In embodiments of the present invention, at least partly the side hydrogen bond group contains following constituent:
At least one of further preferably following constituent:
Wherein,Indicate with polymer chain, be crosslinked and link or the company of any other suitable group (including hydrogen atom) It connects.Other hydrogen bond groups can be the group of any suitable architecture.
In the present invention, the hydrogen bond group on the side group/end group, preferably comprises at least one in following constituent Kind:
Wherein, X is O atom or S atom, and M can be selected from O atom, S atom, Si atom, C atom, N atom；
When M is O or S, R9It is not present；
When M is C, Si or N, R9And R10It can be individually present；
R9And R10In the presence of, it is each independently selected from hydrogen atom, replaces atom, substituent group；
Selected from substitution atomic time, R9And R10Selected from any halogen atom, preferably fluorine atom；
When selected from substituent group, R9And R10Carbon atom number be not particularly limited, can be polymer chain, preferably carbon atom number It is 1~20, more preferably from 1~10；
When selected from substituent group, R9And R10Structure be not particularly limited, include but are not limited to linear chain structure, containing side group Branched structure or cyclic structure, preferably linear chain structure or cycloaliphatic ring structure promote hydrogen bond shape to reduce space steric effect At；
When selected from substituent group, R9And R10Hetero atom can be contained, hetero atom can also be free of.
R9And R10Selected from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Miscellaneous alkyl, substituted C1-20Alkyl is substituted miscellaneous Alkyl.Wherein, R9And R10In substitution atom or substituent group be not particularly limited, selected from halogen atom, hydrocarbyl substituent, containing miscellaneous It is any in the substituent group of atom.
R9And R10More preferably from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Unsaturated aliphatic hydrocarbyl moiety, aryl, aryl, C1-20Miscellaneous alkyl, C1-20Alkyl oxygroup acyl group, C1-20Alkylthio acyl group, C1-20Any atom or base in hydrocarbylamino acyl group The substituted form of group or any group.Wherein, R9And R10In acyl group be not particularly limited.R9And R10In acyl group more It preferably is selected from carbonic acyl radical or thio carbonic acyl radical.
R9And R10More preferably from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Alkenyl, aryl, aryl, C1-20The miscellaneous hydrocarbon of rouge Base, heteroaryl, heteroaryl alkyl, C1-20Alkoxyacyl, aryloxy acyl group, C1-20In alkyl sulfenyl acyl group, artyl sulfo acyl group The substituted form of any atom or group or any group.
Specifically, R9And R10Selected from including but are not limited to hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, first Base, ethyl, n-propyl, isopropyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, ten Trialkyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, allyl, Acrylic, vinyl, phenyl, aminomethyl phenyl, butyl phenyl, benzyl, methoxycarbonyl, ethoxy carbonyl, phenyloxycarbonyl, benzyl Epoxide carbonyl, methyl mercapto carbonyl, ethylmercapto group carbonyl, thiophenyl carbonyl, benzylthio carbonyl, B aminocarbonyl, benzylaminocarbonyl, first Oxygroup thiocarbonyl, ethyoxyl thiocarbonyl, phenoxythiocarbonyl, benzyloxy thiocarbonyl, methyl mercapto thiocarbonyl, second sulphur Base thiocarbonyl, phenylthiothiocarbonyl carbonyl, benzylthio thiocarbonyl, ethylamino thiocarbonyl, benzyl aminothiocarbonyl, replace C1-20Alkyl, substituted C1-20Alkenyl, substituted aryl, substituted aryl, substituted C1-20Rouge miscellaneous alkyl, substituted heteroaryl Base, substituted heteroaryl alkyl, substituted C1-20Alkoxy carbonyl, substituted aryloxycarbonyl, substituted C1-20Alkyl sulfenyl carbonyl The C that base, substituted artyl sulfo carbonyl replace1-20Alkoxy carbonyl, substituted aryloxy thiocarbonyl, replace C1-20Any atom or group in alkyl sulfenyl thiocarbonyl, substituted artyl sulfo thiocarbonyl etc..Wherein, butyl includes But it is not limited only to normal-butyl, tert-butyl.Octyl includes but are not limited to n-octyl, 2- ethylhexyl.Wherein, replace atom or Substituent group selected from halogen atom, hydrocarbyl substituent, containing any in heteroatomic substituent group.
Wherein, L1And L2It is divalent linking group, G is terminal end capping group or segment.
L1And L2Structure be not particularly limited, include but are not limited to linear chain structure, the branched structure containing side group or ring-type Structure.Wherein, cyclic structure is not particularly limited, and can be selected from aliphatic ring, aromatic ring, saccharide ring, condensed ring, preferred aliphat Ring；
L1And L2Hetero atom can be contained, hetero atom can also be free of；
L1And L2Carbon atom number be not particularly limited, 1~20 preferably is selected from, more preferably from 1~10.
L1And L2Selected from C1-20Alkylene, divalent C1-20Miscellaneous alkyl, substituted C1-20Alkylene, substituted divalent C1-20Miscellaneous hydrocarbon In base any divalent linker any two or it is wantonly three kinds combination formed divalent linker.Wherein, replace atom or take Dai Ji is not particularly limited, selected from halogen atom, hydrocarbyl substituent, containing any in heteroatomic substituent group.
L1And L2It preferably is selected from C1-20Open chain alkylidene, C1-20Open chain alkenylene, C1-20Cycloalkylidene, C1-20Sub- cycloalkenyl group, Arlydene, sub- aryl, divalent C1-20Rouge miscellaneous alkyl, divalent C1-20Rouge miscellaneous thiazolinyl, divalent heteroaryl alkyl, replaces divalent heteroaryl radical Alkylidene, substituted C1-20Open chain alkenylene, substituted C1-20Cycloalkylidene, substituted C1-20Sub- cycloalkenyl group, substituted Asia Aryl, substituted sub- aryl, substituted divalent C1-20Rouge miscellaneous alkyl, substituted divalent C1-20Rouge miscellaneous thiazolinyl, substituted divalent are miscellaneous Any divalent linker in aryl, substituted divalent heteroaryl alkyl, any two combination, or wantonly three kinds of combine formation two Valence linker.
L1And L2More preferably from C1-10Open chain alkylidene, C1-10Open chain alkenylene, C3-10Cycloalkylidene, C1-10Sub- cycloolefin Base, arlydene, sub- aryl, divalent C1-10Rouge miscellaneous alkyl, divalent C1-10Rouge miscellaneous thiazolinyl, divalent heteroaryl radical, divalent heteroaryl alkyl, Substituted alkylidene, substituted C1-10Open chain alkenylene, substituted C1-10Cycloalkylidene, substituted C1-10Sub- cycloalkenyl group, substitution Arlydene, substituted sub- aralkyl, substituted divalent C1-10Rouge miscellaneous alkyl, substituted divalent C1-10Rouge miscellaneous thiazolinyl, two replaced Any divalent linker in valence heteroaryl, substituted divalent heteroaryl alkyl, any two combination, or wantonly three kinds of combination are formed Divalent linker.
Specifically, L1And L2Selected from methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, heptamethylene, Ya Xin Base, nonylene, decylene, 1,2- phenylene, benzal, C1-20Oxaalkylene, C1-20Thia alkylene, C1-20Azepine alkylene The substituted form of any group, any group in base, azepine aryl, any two or any two it is above identical or different Group or its be substituted form combination.Wherein, atom or substituent group is replaced to be selected from halogen atom, hydrocarbyl substituent, containing miscellaneous It is any in the substituent group of atom.
L1And L2More preferable singly-bound, methylene, 1,2- ethylidene, 1,3- propylidene.
The structure of G is not particularly limited, and includes but are not limited to linear chain structure, the branched structure containing side group or cyclic annular knot Structure.Wherein, cyclic structure is not particularly limited, and can be selected from aliphatic ring, aromatic ring, saccharide ring, condensed ring, preferred aliphat Ring.
G can contain hetero atom, can also be free of hetero atom.
The carbon atom number of G is not particularly limited, and preferably is selected from 1~20, more preferably from 1~10.
G is selected from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Miscellaneous alkyl, substituted C1-20Alkyl or substituted miscellaneous alkyl. Wherein, the substitution atom in G or substituent group are not particularly limited, and selected from halogen atom, hydrocarbyl substituent, contain heteroatomic substitution It is any in base.
G is more preferably from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Unsaturated aliphatic hydrocarbyl moiety, aryl, aryl, C1-20 Miscellaneous alkyl, C1-20Alkyl oxygroup acyl group, C1-20Any atom or group or any group is taken in alkylthio acyl group For form.
G is more preferably from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Alkenyl, aryl, aryl, C1-20It is rouge miscellaneous alkyl, miscellaneous Aryl, heteroaryl alkyl, C1-20Alkoxyacyl, aryloxy acyl group, C1-20It is any in alkyl sulfenyl acyl group, artyl sulfo acyl group The substituted form of kind atom or group or any group.
G is more preferably from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Alkenyl, aryl, aryl, C1-20It is rouge miscellaneous alkyl, miscellaneous Aryl, heteroaryl alkyl, C1-20Alkoxy carbonyl, aryloxycarbonyl, C1-20Alkyl sulfenyl carbonyl, artyl sulfo carbonyl, C1-20 Alkoxy carbonyl, aryloxy thiocarbonyl, C1-20It is any in alkyl sulfenyl thiocarbonyl, artyl sulfo thiocarbonyl The substituted form of atom or group or any group.
Specifically, G is selected from and includes but are not limited to hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl, second Base, n-propyl, isopropyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecane Base, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, allyl, propylene Base, vinyl, phenyl, aminomethyl phenyl, butyl phenyl, benzyl, methoxycarbonyl, ethoxy carbonyl, phenyloxycarbonyl, benzyloxy Carbonyl, methyl mercapto carbonyl, ethylmercapto group carbonyl, thiophenyl carbonyl, benzylthio carbonyl, B aminocarbonyl, benzylaminocarbonyl, methoxyl group Thiocarbonyl, ethyoxyl thiocarbonyl, phenoxythiocarbonyl, benzyloxy thiocarbonyl, methyl mercapto thiocarbonyl, ethylmercapto group sulphur For carbonyl, phenylthiothiocarbonyl carbonyl, benzylthio thiocarbonyl, substituted C1-20Alkyl, substituted C1-20Alkenyl, substituted aryl, Substituted aryl, substituted C1-20Rouge miscellaneous alkyl, substituted heteroaryl, substituted heteroaryl alkyl, substituted C1-20Alkoxy carbonyl Base, substituted aryloxycarbonyl, substituted C1-20Alkyl sulfenyl carbonyl, substituted artyl sulfo carbonyl, substituted C1-20Alcoxyl Base thiocarbonyl, substituted aryloxy thiocarbonyl, substituted C1-20Alkyl sulfenyl thiocarbonyl, substituted artyl sulfo sulphur For any atom or group in carbonyl etc..Wherein, butyl includes but are not limited to normal-butyl, tert-butyl.Octyl includes but not It is only limitted to n-octyl, 2- ethylhexyl.Wherein, atom or substituent group is replaced to be selected from halogen atom, hydrocarbyl substituent, contain hetero atom Substituent group in it is any.
G further preferably from hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, amyl, hexyl, Heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, ten Seven alkyl, octadecyl, nonadecyl, eicosyl, allyl, benzyl, trityl, phenyl, benzyl, methylbenzyl, nitre Base benzyl, tert. butyl-sulphenyl, benzyl sulfenyl, 2- pyridinylthio, acetyl group, benzoyl, methoxycarbonyl, ethyoxyl carbonyl Base, t-butyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, methyl mercapto carbonyl, ethylmercapto group carbonyl, tert. butyl-sulphenyl carbonyl, Thiophenyl carbonyl, benzylthio carbonyl, ethylenebis dithiocarbamate carbonyl, phenyl first thiocarbonyl, methoxyl group thiocarbonyl, the thio carbonyl of ethyoxyl Base, tert-butyl oxygroup thiocarbonyl, phenoxythiocarbonyl, benzyloxy thiocarbonyl, methyl mercapto thiocarbonyl, ethylmercapto group are thio Carbonyl, tert. butyl-sulphenyl thiocarbonyl, phenylthiothiocarbonyl carbonyl, benzylthio thiocarbonyl, C1-10Halohydrocarbyl, trifluoroacetyl The substituted form of any group or any group in base, halogenophenyl, halogeno-benzyl, nitrobenzophenone, nitrobenzyl etc.. Wherein, atom or substituent group is replaced preferably to be selected from fluorine atom, alkoxy or nitro.
G more preferably from hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, benzyl, trityl, Phenyl, benzyl, methylbenzyl, tert. butyl-sulphenyl, benzyl sulfenyl, 2- pyridinylthio, 2- pyridylcarbonyl, tert-butyl oxygroup carbonyl Base, phenyloxycarbonyl, benzyloxycarbonyl, tert-butyl oxygroup thiocarbonyl, phenoxythiocarbonyl, benzyloxy thiocarbonyl, uncle Any group in butyl alkylthio carbonyl, phenylthiothiocarbonyl carbonyl, benzylthio thiocarbonyl, trifluoroacetyl group etc..
G more preferably from hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, benzyl, trityl, Any group in phenyl, benzyl, methylbenzyl, tert. butyl-sulphenyl, benzyl sulfenyl, 2- pyridinylthio etc..
G is most preferably from hydrogen atom, methyl, ethyl, n-propyl, normal-butyl.
R9、R10、L1、L2, G any two or it is multiple between can cyclization.
More specifically, hydrogen bond group citing such as (but the present invention is not limited only to this) in suitable side group and end group:
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.
In the present invention, the side hydrogen bond group on the polymer chain side chain skeleton, preferably has such as general structure (6), at least one of (7), wherein G is end-capping group or segment at this time.Side hydrogen bond group and end group hydrogen bond group are usually empty Between freedom degree it is higher, transfer ability is stronger, be more conducive to obtain supermolecule dynamic.
In the present invention, the skeleton hydrogen bond group (including the hydrogen bond group on side chain/branch/bifurcated chain backbone), In at least partly atom be polymer chain skeleton component part.Suitable skeleton hydrogen bond group citing is as (but the present invention is not only It is limited to this):
In embodiments of the present invention, the hydrogen bond group of hydrogen bond action is formed either mutual between different hydrogen bond groups Apotype combination is also possible to combining between hydrogen bond group of the same race from complementary type, makees as long as being capable of forming suitable hydrogen bond between group With.The combination of some hydrogen bond groups can be exemplified below, but the present invention is not limited only to this:
It in the present invention, can be same containing one or more kinds of hydrogen bond groups in same dynamic aggregation object It can also can contain a kind of hydrogen bond in hydrogen bond group namely dynamic aggregation object containing one or more in cross-linked network The combination of group or a variety of hydrogen bond groups.The hydrogen bond group can be formed by any appropriate chemical reaction, such as 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；By succinimide ester groups and amino, Covalent reaction between hydroxyl, sulfydryl is formed.
In the present invention, the skeleton hydrogen bond group can be generates in polymer polymerizing/cross-linking process, namely passes through It forms the hydrogen bond group and generates polymerized/cross-linked；It is also possible to pre-generate and carries out polymerized/cross-linked again；It is preferred that in polymer It is generated during polymerized/cross-linked, skeleton hydrogen bond group is generated during polymerized/cross-linked can simplify synthesis technology, have more Good operability.The side hydrogen bond group can before polymerized/cross-linked, later or in the process generate, before or after The quantity of generation can be than relatively freely controlling.
In embodiments of the present invention, also selectively containing aforementioned on side group/end group of the hybrid cross-linked network Other hydrogen bond groups other than preferred hydrogen bond group, include but are not limited to hydroxyl, sulfydryl, carboxyl.In the present invention, this The content of other hydrogen bond groups of class is preferably shorter than the 50mol% of hydrogen bond group total content, more preferably less than 20mol%, further Preferably shorter than 5mol%.
In embodiments of the present invention, supermolecule hydrogen bond action is except through the side hydrogen bond group on dynamic crosslinking network Between formed hydrogen bond action outside, can also by the side hydrogen bond group with as other groups in additive introducing crosslinked network Hydrogen bond group on point forms hydrogen bond action.Such other components that can participate in being formed hydrogen bond action include but are not limited to small Molecule, polymer, inorganic material, hydrogen bond group contained therein, which can be arbitrarily be formed with the side hydrogen bond group, not to be surpassed Cross the group of four tooth hydrogen bonds.As an example, may include but be not limited only to the aforementioned hydrogen bond group and sulfydryl, amino, Carboxyl and its derivative base.Hydrogen bond can also be formed between such other components, but is preferably formed as being no more than four tooth hydrogen bonds.It is such Material can be the particle or cluster of covalent cross-linking, but not with the dynamic covalent cross-linking shape in hybrid cross-linked network of the invention At covalent cross-linking interpenetrating networks.Polymer therein can be the structures such as line style, ring-type, dendroid, hyperbranched, cluster.
In embodiments of the present invention, it can be selected from for connecting the linker of dynamic covalent bond and/or hydrogen bond group The divalent of hetero atom linker, molecular weight no more than 1000Da or multivalence small molecule alkyl, molecular weight are greater than the divalent of 1000Da Or the divalent of multivalence polymer chain residue, molecular weight no more than 1000Da or polyvalent mineral small molecule chain residue, molecular weight are greater than Any one of the divalent of 1000Da or polyvalent mineral macromolecular chain residue are appointed several.
Wherein, the hetero atom linker can be any appropriate heteroatomic linking group that contains, optional From following any or appoint several combination: ether, sulfenyl, carbonyl, sulfuryl, amide groups, carbonate group, carbamate groups, Urea groups, divalent amido, trivalent amido, divalent silicon substrate, trivalent silicon substrate, tetravalence silicon substrate, divalent phosphorus base, three valent phosphors base, divalent boryl, Trivalent boryl.
Wherein, the molecular weight is no more than the small molecule alkyl of 1000Da, typically contains 1 to 71 carbon atoms, Heteroatom group can be contained, can be free of has heteroatom group.Generally, the small molecule alkyl can be selected from the following group It is any, any unsaturated form, any substituted form, any by hydridization form and combinations thereof: C1-71 Alkyl, ring C3-71Alkyl, phenyl, benzyl, aryl；Small molecule alkyl is preferably methyl, ethyl, propyl, propylene, butyl, fourth Alkene, amyl, hexyl, heptyl, octyl, nonyl, decyl, cyclohexyl, phenyl；More preferably methyl, ethyl, propyl, phenyl.Its In, small molecule alkyl is also selected from liquid crystal segment.
Wherein, the molecular weight is greater than the polymer chain residue of 1000Da, can be residual for any appropriate polymer chain Base includes but are not limited to carbochain polymer residue, carbon heterochain polymer residue, elemento-organic polymer residue and combinations thereof. Wherein, polymer can be homopolymer, can also be the copolymer of a several monomers, oligomer or polymer composition；Polymer chain can It can also be rigid chain for flexible chain.
Wherein, the carbochain polymer residue can be any appropriate macromolecular main chain mainly by carbon atom structure At polymer residue, can be selected from by it is any in the following group, any it is unsaturated in the form of, any substituted form, It is any by hydridization form and combinations thereof: polyolefins chain residue, such as Polyethylene Chain residue, polypropylene chains residue, poly- isobutyl Alkene chain residue, polystyrene chain residue, polyvinyl chloride chain residue, Vingon chain residue, polyvinyl fluoride chain residue, polytetrafluoro Ethylene chain residue, polytrifluorochloroethylene chain residue, polyvinyl acetate chain residue, Polyvinylalkylethers chain residue, polybutadiene Alkene chain residue, polyisoprene chain residue, polychlorobutadiene chain residue, polynorbornene chain residue, polyvinyl alcohol residue etc.；It is poly- Acrylic compounds chain residue, such as polyacrylic acid chain residue, polyacrylamide chain residue, polymethyl acrylate chain residue, poly- methyl-prop E pioic acid methyl ester chain residue etc.；Polypropylene nitrile chain residue, such as polyacrylonitrile chain residue；It is preferred that Polyethylene Chain residue, polypropylene Chain residue, polystyrene chain residue, polyvinyl chloride chain residue, polybutadiene chain residue, polyisoprene chain residue, polyacrylic acid Chain residue, polyacrylamide chain residue, polyacrylonitrile chain residue.
The carbon heterochain polymer residue, can be any appropriate macromolecular main chain mainly by carbon atom and nitrogen, The polymer residue that the hetero atoms such as oxygen, sulphur are constituted, can be selected from by it is any in the following group, any it is unsaturated in the form of, it is any Kind substituted form, any by hydridization form and combinations thereof: polyethers chain residue, such as polyethylene oxide chain residue, poly- Propylene oxide chain residue, polytetrahydrofuran chain residue, asphalt mixtures modified by epoxy resin fat chain residue, phenolic resin chain residue, polyphenylene oxide chain residue etc.； Polyesters chain residue, such as polycaprolactone chain residue, poly- valerolactone chain residue, polylactide chain residue, poly terephthalic acid second two Alcohol ester chain residue, unsaturated polyester (UP) chain residue, alkyd resin chain residue, polycarbonate chain residue, Biopolvester chain residue, liquid crystal Polyester chain residue etc.；Polyamines chain residue, as polyamide chains residue, polyimides chain residue, polyurethane chain residue, polyureas chain are residual Base, polysulfide are for carbamic acid ester chain residue, Lauxite chain residue, melamine resin chain residue, liquid crystal polymer chain residue etc.；It is poly- Sulphur class chain residue, such as polysulfones chain residue, polyphenylene sulfide chain residue；It is preferred that polyethylene oxide chain residue, polytetrahydrofuran chain are residual Base, polycaprolactone chain residue, polylactide chain residue, polyamide chains residue, polyurethane chain residue, gathers asphalt mixtures modified by epoxy resin fat chain residue Urea chain residue.
The elemento-organic polymer residue can be any appropriate macromolecular main chain mainly by silicon, boron, aluminium etc. The polymer residue that the hetero atoms such as inorganic elements hetero atom and optional nitrogen, oxygen, sulphur, phosphorus are constituted can be selected to appoint in the following group It is a kind of, any unsaturated form, any substituted form, any by hydridization form and combinations thereof: organosilicon Quasi polymer chain residue such as poly-organosilicon alkane chain residue, polysiloxane chain residue, poly-organosilicon borine chain residue, poly- has Machine silazane chain residue, poly-organosilicon sulfane chain residue, to gather organic phosphorus siloxane chain residue, poly- organic metal siloxane chain residual Base；Organic boron quasi polymer chain residue, such as poly- organo-borane chain residue, poly- organic boron azane chain residue, poly- organic boron sulfane chain Residue, poly- organic boron phosphine chain residue etc.；Organic phosphates polymer chain residue；Organic leadP quasi polymer chain residue；Organic tin Polymer chain residue；Organo-arsenic quasi polymer chain residue；Antimony organic quasi polymer chain residue；It is preferred that poly-organosilicon alkane chain residue, Polysiloxane chain residue, poly- organo-borane chain residue.
The molecular weight is no more than the inorganic molecules chain residue of 1000Da, can be any appropriate molecular backbone The inorganic molecules chain being mainly made of the hetero atoms such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus with side chain Residue, generally, the inorganic molecules chain residue can be selected from by it is any in the following group, any it is unsaturated in the form of, It is any substituted form, any by hydridization form: silane chain residue, silicon oxide compound chain residue, sulphur silicon compound Chain residue, sulfur-nitrogen compound chain residue, phosphazene compound chain residue, phosphoric-oxygenic compound chain residue, borine chain residue, boron oxidation are closed Object chain residue；It is preferred that silane chain residue, silicon oxide compound chain residue, phosphazene compound chain residue, borine chain residue.
The molecular weight is greater than the inorganic macromolecular chain residue of 1000Da, can be any appropriate macromolecular main chain The inorganic macromolecular chain being mainly made of the hetero atoms such as the inorganic elements such as silicon, boron, aluminium hetero atom and nitrogen, oxygen, sulphur, phosphorus with side chain Residue, can be selected from by it is any in the following group, any it is unsaturated in the form of, any substituted form, any quilt Hydridization form and combinations thereof: polysilane chain residue, polysiloxane chain residue, polysulfide silicon chain residue, polysulfide nitrogen chain residue, polyphosphoric acid Chain residue, polyphosphazene chain residue, polychlorostyrene are for phosphonitrile chain residue, polyborane chain residue；It is preferred that polysilane chain residue, polysiloxane chain Residue, polyphosphazene chain residue, polyborane chain residue.
The topological structure of linker for connecting dynamic covalent bond and/or hydrogen bond group is not particularly limited, It can be straight chain type, branched chain type, multi-arm structural type, star-like, H-type, combed, dendritic, mononuclear type, polycyclic type, loop coil type, thick Ring-like, bridged ring type, the chain with cyclic structure, two and three dimensions cluster type and combinations thereof.In the present invention, it or even is not excluded for making The reaction such as further polymerized/cross-linked and connection are carried out with the polymer beads of crosslinking.The topological structure of linker is preferably straight chain Type, branched chain type, star-like, combed, dendritic, two and three dimensions cluster type, more preferably straight chain type, branched chain type.For straight chain type, The linker of branched chain type structure, molecular chain movement energy barrier is low, and molecular chain movement ability is strong, is conducive to machine-shaping, and can So that polymeric acceptor reveals quick self-repairability and sensitive strain-responsive ability, it can obtain with quick selfreparing, can return Receive the dynamic aggregation object for reusing characteristic and good processing performance.Connection for two and three dimensions cluster type structure Base, topological structure is relatively stable, can provide better mechanical property, thermal stability, solvent resistant for dynamic aggregation object Property and creep resistance.
In the present invention, the dynamic aggregation object has good structural stability under normal circumstances, in certain spies It can promote the dissociation of Reversible Addition Fragmentation Chain Transfer dynamic covalent bond under conditions of fixed or exchange or re-form, show Good dynamic reversibility out has the dynamic properties such as excellent selfreparing.These specified conditions include temperature control, illumination, Radiation, plasma and microwave etc..The dynamic aggregation object can directly pass through heating, illumination, radiation, plasma and micro- Wave promotes the dissociation and exchange of Reversible Addition Fragmentation Chain Transfer dynamic covalent bond, to obtain the dynamic characteristics such as self-repairability；Example As directly promoted the exchange of trithiocarbonic acid ester bond to obtain self-repairability by UV illumination；And it is faster dynamic in order to obtain State property is not excluded for that the combination of two or more of these specified conditions can be used, and such as heating and illumination act on acquisition more simultaneously Fast self-healing properties etc..Can also by the way that initiator is added in system, then heating, illumination, radiation, plasma and It is generated free radicals under microwave, promotes the dissociation and exchange of Reversible Addition Fragmentation Chain Transfer dynamic covalent bond, obtain self-repairability etc. Dynamic characteristic.Illumination type of the present invention is unrestricted, preferably ultraviolet light (UV), infrared light, visible light, laser, chemistry Fluorescence, more preferable ultraviolet light.Radiation of the present invention includes but are not limited to high energy ionizing ray such as alpha ray, β ray, γ Ray, x-ray, electron beam.Plasma of the present invention refers to atom and atomic group after being deprived of by part electronics The ionized gas shape substance of the negative ions composition generated after being ionized.Microwave of the present invention refers to that frequency is 300MHz The electromagnetic wave of~300GHz.
In an embodiment of the invention, the dynamic aggregation object of the hybrid cross-linked network contains only a network (the first network structure), which is characterized in that contain dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks in this cross-linked network, it is described Dynamic covalent cross-linking reaches its gel point or more.In present embodiment, contain Reversible Addition Fragmentation Chain Transfer dynamic covalent bond Dynamic covalent cross-linking is for providing balanced structure and covalent dynamic；The hydrogen bond crosslinks that side hydrogen bond group is formed provide additional friendship Connection and supermolecule dynamic.Two kinds of crosslinked actions are merged using a network structure, hydridization dynamic is reached with simplest structure Effect.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of two networks (second of network structure), which is characterized in that contain dynamic covalent cross-linking in the 1st network and dynamic covalent cross-linking reaches its gel Or more, wherein not containing any hydrogen bond group；Covalent cross-linking is free of in 2nd network but contains supermolecule hydrogen bond crosslinks；The net In network structure, balanced structure and dynamic covalent bond therein is kept to provide by the dynamic covalent cross-linking in the 1st network covalently dynamic State property provides supermolecule dynamic by the supermolecule hydrogen bond crosslinks in the 2nd network.It is relatively independent between two networks, it can Preferably obtain orthogonal effect.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of two networks (the third network structure), which is characterized in that contain dynamic covalent cross-linking in the 1st network and dynamic covalent cross-linking reaches its gel Or more, wherein not containing any hydrogen bond group；2nd network is the first described network.In the network structure, pass through the 1st net Dynamic covalent cross-linking in network and the 2nd network keeps balanced structure and dynamic covalent bond therein to provide covalent dynamic；Pass through Supermolecule hydrogen bond crosslinks in 2nd network provide supermolecule dynamic.It is preferred that the dynamic covalent bond between two networks can not be sent out Raw mutual exchange.Preferably covalence stablility is provided by two dynamic covalent networks, and orthogonal dynamic covalency is provided, Facilitate the structure and mechanical property for adjusting dynamic covalent networks, can easily be obtained together with hydrogen bond action multifarious Excellent effect.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of two networks (the 4th kind of network structure), which is characterized in that the 1st network is the first described network structure；Covalent cross-linking is free of in 2nd network But contain supermolecule hydrogen bond crosslinks；Hydrogen bond group between 1st network and the 2nd network can optionally form mutually hydrogen bond.It should In network structure, balanced structure and dynamic covalent bond therein is kept to provide by the dynamic covalent cross-linking in the 1st network covalent Dynamic；Supermolecule dynamic is provided by the supermolecule hydrogen bond crosslinks in the 1st and the 2nd network.Pass through two hydrogen bond crosslinks networks Multifarious supermolecule dynamic can be obtained.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network is made of two networks (the 5th kind of network structure), which is characterized in that the 1st network and the 2nd network are structure described in the first network, but upper described 1st and the 2nd network is not identical.It is this not identical, it can illustrate for example, polymer chain main structure difference, dynamic covalent cross-linking Crosslink density it is different, Reversible Addition Fragmentation Chain Transfer dynamic covalent bond is different, polymer chain side group composition is different, polymer Hydrogen bond group difference in chain side group etc..It, can be with by adjusting the structure of the 1st network and/or the 2nd network in the embodiment Achieve the purpose that accurately to control dynamic aggregation physical performance.
In yet another embodiment of the present invention, the dynamic aggregation object of the hybrid cross-linked network contains only a network (the 6th kind of network structure), which is characterized in that handed in this cross-linked network containing dynamic covalent cross-linking and optional supermolecule hydrogen bond Connection, the dynamic covalent cross-linking reach its gel point or more, are dispersed with the supermolecule degree of cross linking in dynamic covalent cross-linking network and exist Its gel point supermolecule polymer below.In the network structure, dynamic covalent cross-linking can keep balanced structure, specific Under the conditions of, dynamic covalent cross-linking also can provide dynamic；Supermolecule crosslinking provides dynamic, supermolecule polymerization dispersed therein Object provides supplement dynamic, especially strain-responsive.
In yet another embodiment of the present invention, the dynamic aggregation object dynamic aggregation object of the hybrid cross-linked network only has One cross-linked network (the 7th kind of network structure), which is characterized in that this cross-linked network contains dynamic covalent cross-linking and optionally surpasses Molecule hydrogen bond crosslinks, the dynamic covalent cross-linking reach its gel point or more；Oversubscription is dispersed in dynamic covalent cross-linking network Supermolecule polymer particle of the sub- degree of cross linking more than its gel point.In the network structure, dynamic covalent cross-linking can keep flat Weigh structure, and under given conditions, dynamic covalent cross-linking also can provide dynamic；Supermolecule crosslinking provides dynamic, supermolecule Polymer beads provide filling and supplement dynamic, and can obtain local viscosity and intensity in strain-responsive and increase.
In addition to the embodiment of above-mentioned seven kinds of hybridization network structures, the present invention can also have other diversified hydridization nets Network structural implementation may include three or its above identical or different network, the same net in one embodiment It may include different dynamic covalent cross-linkings and/or different supermolecule hydrogen bond actions in network, including optional skeleton hydrogen The hydrogen bond action that key group participates in.In special circumstances, side hydrogen bond group in dynamic covalent cross-linking network itself cannot mutual shape At hydrogen bond, need to form hydrogen bond with the other compositions being additionally added into.Reversible Addition Fragmentation Chain Transfer dynamic covalent bond is for mentioning For covalent dynamic property, so that dynamic aggregation object reveals the dynamics such as selfreparing, plasticity；Side hydrogen bond group and optional On the one hand the hydrogen bond action that skeleton hydrogen bond group is formed provides additional intensity, a side for polymer as reversible physical crosslinking Face can use its good dynamic property again, assign the performances such as ultra-tough, selfreparing, shape memory.Those skilled in the art Member can rationally and effectively be realized with logic according to the present invention and train of thought.
In embodiments of the present invention, it is preferably initially formed the dynamic covalent bond, then by common covalently cross-linked Reaction forms the dynamic covalent cross-linking network.The common covalent cross-linking reacts, and can be in technological principle any appropriate Common covalent cross-linking means.Refer generally to two ways, then the prepolymer of first synthetic linear or branching type carries out interchain linkage Reaction；Or from monomer, disposably reach crosslinking with the monomer molecule of low molecular weight.In embodiments of the present invention, institute The common covalent cross-linking reaction stated can be included but are not limited to Types Below using any appropriate reaction: isocyanates with The reaction of amino, hydroxyl, sulfydryl, carboxyl, epoxy group, free radical acrylate reaction, double bond radical reaction, epoxy and ammonia Base, hydroxyl, phenol-formaldehyde reaction, nitrine-alkynes click-reaction, sulfydryl-double bond/alkynes click-reaction, tetrazine-norbornene reaction, activity Ester and amino, hydroxyl, sulfydryl react, silicone hydroxyl condensation reaction；Preferred isocyanate and amino, hydroxyl, sulfydryl react, and third Olefin(e) acid ester radical reaction, double bond radical reaction, epoxy group and amino, hydroxyl react, sulfydryl-double bond/alkynes click-reaction. In any one dynamic covalent cross-linking network structure, the reaction of common covalent cross-linking can have one or more reaction type, Reaction means and structure.
In embodiments of the present invention, the generation or introducing of hydrogen bond group, can before covalent cross-linking, later or mistake It is carried out in journey.It is preferred that carrying out before crosslinking or in the process, carried out more preferably before crosslinking.Because covalent cross-linking is laggard It if row, must will be generally added by way of swelling in relation to reagent, complex process and ineffective.When pre- using polymer When aggressiveness or first the crosslinking regeneration hydrogen bond group, the activity that can introduce the hydrogen bond group must be contained on polymer chain Point includes but is not limited to amino, hydroxyl, carboxyl, aldehyde radical, sulfydryl, isocyanate group, epoxy group, acid anhydrides, carbon carbon pair as example Key, maleimide, triple carbon-carbon bonds, azido, itrile group, hydrazine, tetrazine, succinimide ester.The generation or introducing of hydrogen bond group It any appropriate reaction can be used, include but are not limited to Types Below: isocyanates and amino, hydroxyl, sulfydryl, carboxyl Reaction, free radical acrylate reaction, double bond radical reaction, epoxy and amino, hydroxyl, sulfydryl react, nitrine-alkynes point Hit reaction, sulfydryl-double bond/alkynes click-reaction, the reaction of urea-amine, amidation process, tetrazine-norbornene reaction, active ester It is reacted with amino, hydroxyl, sulfydryl, silicone hydroxyl condensation reaction；Preferred isocyanate and amino, hydroxyl, sulfydryl react, and urinate The reaction of element-amine, amidation process, active ester and amino, hydroxyl, sulfydryl react；More preferable isocyanates and amino, hydroxyl The reaction of base, sulfydryl.The supermolecule crosslinking of polymer chain side group can have reaction type, reaction means and the knot of one or more Structure.
It is illustrated below for the embodiment of the part preparation method of network structure of the invention.
In the first network structure of the invention, dynamic covalent cross-linking and supermolecule are contained in the hybrid cross-linked network Hydrogen bond crosslinks, the dynamic covalent cross-linking reach its gel point or more.
In embodiments of the present invention, a kind of preparation method of hybrid cross-linked network dynamic polymer is using first synthesizing side Base contains the monomer of hydrogen bond group, and side group is then contained the monomer of hydrogen bond group and contains the Reversible Addition Fragmentation Chain Transfer The activated monomer of dynamic covalent bond and/or other activated monomers and/or crosslinking agent direct polymerization become the first described network Hybrid cross-linked dynamic aggregation object.As an example but be not limited to it is following lifted, for example, contain side hydrogen bond group (following structural formula In be denoted as RH, RHThe hydrogen bond of formation be no more than four teeth) diene monomers and structure in Reversible Addition Fragmentation Chain Transfer dynamic altogether Valence link (is denoted as R in following structural formulaF) diene activated monomer and crosslinking action can be formed in the present invention with polymerized/cross-linked The first network structure.By having Reversible Addition Fragmentation Chain Transfer in diene monomers and structure of the control containing side hydrogen bond group The diene activated monomer of dynamic covalent bond and the formula rate of crosslinking agent make the dynamic covalent cross-linking in network reach covalent gel Or more, hydrogen bond group is had in side group.
For another example, be initially formed skeleton and side group contain hydrogen bond base because prepolymer, then again by being broken containing the reversible addition The cross-linking agents of chain tra nsfer dynamic covalent bond form the hybrid cross-linked dynamic aggregation object of the first network.
For another example, the monoene activated monomer that side group has hydrogen bond group is first synthesized, is then turned with the fracture chain containing reversible addition The diene activated monomer of mobile state covalent bond directly forms the first network by free radical polymerization under the action of initiator Hybrid cross-linked dynamic aggregation object.
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.
Dynamic aggregation object with hybrid cross-linked network structure of the invention, when network structure be containing there are two or two with When the Multi net voting structure of upper network, in addition to common blending dispersion, more preferably by two or more polymer networks It is intertwined the interpenetrating networks for tangling and being formed.Interpenetrating net polymer structure makes its performance due to the synergistic effect between network component It is substantially better than single network polymer of its component, generates the mechanical properties such as toughness more higher than single network, is based particularly on this In the case that the mentality of designing of invention introduces hydrogen bond crosslinks.
In the present invention, two classes can be classified as according to polymers compositions crosslinking situation in composition interpenetrating networks, it is Semi-IPN With full interpenetrating.Only a kind of component is covalent cross-linking in Semi-IPN, and another component is worn in the form of non-covalent strand It inserts and becomes entangled in covalent cross-linking component.
Traditional interpenetrating net polymer preparation method generally includes one-step method interpenetrating and two-step method interpenetrating.One-step method i.e. one All the components are added secondary property, then carry out polymerized/cross-linked, prepare target network.Two-step method first prepares first network polymerization And then object is immersed in the monomer/pre-polymer solution to form the second network, then cause polymerized/cross-linked and obtain target Hybridization network.The preparation with hybrid cross-linked network dynamic polymer in the present invention can also use one-step method interpenetrating and two steps Method interpenetrating, under specific circumstances 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, the dynamic aggregation object of the hybrid cross-linked network is by two nets in second of network structure of the invention Network is constituted.Contain dynamic covalent cross-linking in 1st network and dynamic covalent cross-linking reaches covalent gel point or more, wherein without containing appointing What hydrogen bond group；Covalent cross-linking is free of in 2nd network but contains supermolecule hydrogen bond crosslinks.It can described in a kind of be free of firstly, preparing Inverse addition is broken chain tra nsfer dynamic covalent bond, but contains the linear polymerization of hydrogen bond group on the side group of polymer chain and/or side chain Object is as the 2nd network.Then, first that the mixing such as monomer, the crosslinking agent of the 2nd network and the 1st network are equal when preparing 1 network It is even, then covalent cross-linking is carried out by above-mentioned covalent cross-linking means, so that the semi-intercrossing network for obtaining the 1st network and the 2nd network is poly- It closes object namely the 2nd network is scattered in the 1st network.It can also be initially formed the 1st network, it then (can by swelling the 2nd network By solvent) it is compound with the progress of the 1st network.
For example, the dynamic aggregation object of the hybrid cross-linked network is by two nets in the 5th kind of network structure of the invention Network is constituted.Contain dynamic covalent cross-linking and supermolecule hydrogen bond crosslinks, the dynamic covalent cross-linking in 1st network and the 2nd network Reach its gel point or more.Firstly, preparing the prepolymer of the 1st network or the 1st network by above-mentioned covalent cross-linking means.So Afterwards, first that the mixing such as monomer, the crosslinking agent of prepolymer and the 2nd network of the 1st network or the 1st network are equal when preparing 2 network It is even, then covalent cross-linking is carried out by above-mentioned covalent cross-linking means, so that the full interpenetrating networks for obtaining the 1st network and the 2nd network are poly- Close object.In this preparation method, preferably the covalent gel point of the 1st network is the lightly crosslinked of gel point or more, is conducive to the 2nd in this way The interpenetrating effect of network.
In embodiments of the present invention, the dynamic aggregation object of the hybrid cross-linked network, the polymerization in raw material components Object chain topological structure can be selected from line style, ring-type, branching, cluster, crosslinking and combinations thereof form.
In embodiments of the present invention, the dynamic aggregation object of the hybrid cross-linked network, can have one or Multiple glass transition temperatures can also not have glass transition temperature.For the dynamic aggregation object of the hybrid cross-linked network Glass transition temperature, at least one lower than 0 DEG C or between 0-25 DEG C or between 25-100 DEG C, Or it is higher than 100 DEG C；Wherein, dynamic aggregation object of the glass transition temperature lower than 0 DEG C has preferable low temperature service performance, side Just as sealant, elastomer, gel etc. carry out using；Glass transition temperature is in the dynamic aggregation object energy between 0-25 DEG C Enough be conducive to carry out at normal temperature using can also facilitate as elastomer, sealant, gel, foam and common solid Body uses；Glass transition temperature be in 25-100 DEG C between dynamic aggregation object be convenient for room temperature ordinary solid achieved above, Foam and gel；Glass transition temperature is higher than 100 DEG C of dynamic aggregation object, dimensional stability, mechanical strength, temperature tolerance It is good, advantageous as stress loading material carry out using.It is lower than 25 DEG C of dynamic aggregation object, energy for glass transition temperature Enough embody excellent dynamic, self-repairability, recuperability；It is higher than 25 DEG C of dynamic aggregation for glass transition temperature Object can embody good shape memory, stress bearing capacity；In addition, the presence of supermolecule hydrogen bond, it can be to dynamic The glass transition temperature of state polymer is further regulated and controled, to the dynamic, the degree of cross linking, mechanical strength of dynamic aggregation object It is supplemented.For the dynamic aggregation object in the present invention, preferably at least have a glass transition temperature not higher than 50 DEG C, more into One step preferably at least has a glass transition temperature not higher than 25 DEG C, and most preferably each glass transition temperature is not higher than 25 ℃.The system that each glass transition temperature is not higher than 25 DEG C is good flexible and flowable due to having at a temperature of routine use Property/creep properties, thus particularly suitable as self-repair material carry out using.For the glass transition temperature of dynamic aggregation object, It can be measured by the measuring method of glass transition temperature general in this fields such as DSC, DMA.
In embodiments of the present invention, each raw material component of hybrid cross-linked dynamic aggregation object also can have one or more A glass transition temperature, can also not have glass transition temperature, glass transition temperature, at least one lower than 0 DEG C, Or between 0-25 DEG C or between 25-100 DEG C or higher than 100 DEG C, wherein glass transition temperature is lower than 0 DEG C of raw materials of compound is convenient for low temperature preparation and processing when preparing dynamic aggregation object；Glass transition temperature is in 0- Raw materials of compound between 25 DEG C can carry out preparation machine-shaping at normal temperature；Glass transition temperature be in 25-100 DEG C it Between raw materials of compound using conventional heating equipment, that is, plastic, manufacturing cost is low；Glass transition temperature is higher than 100 DEG C of change Closing raw material can be used for preparing the heat-resisting material of good stability of the dimension, good mechanical performance.There is different glass using a variety of The raw materials of compound for changing transition temperature prepares dynamic aggregation object, and can obtain has different glassization transformation temperature in different range The dynamic aggregation object of degree, can embody multiple comprehensive performance, have both dynamic and stability.
In embodiments of the present invention, the form of the dynamic aggregation object of the hybrid cross-linked network or its composition can be Ordinary solid, elastomer, gel (including organogel, oligomer swell gel, plasticizer swell gel, ionic liquid swelling Gel), foam etc., wherein the dissolvable small-molecular-weight component content contained in ordinary solid and foam is generally not more than 10wt%, and the small-molecular-weight component content contained in gel is generally not less than 50wt%.When as ordinary solid, usually have There are the performances such as more excellent structural stability, mechanical performance, ageing-resistant, the structure to the dynamic aggregation object can also be passed through The dynamic aggregation object for obtaining a series of mechanical properties adjustable (from softness to firm) is adjusted, has wide range of applications.As bullet Property body, usually more general solid is more soft, and more significant deformation can occur under lesser stress, this is conducive to It obtains preferable self-repairability, is based particularly on Reversible Addition Fragmentation Chain Transfer dynamic covalent bond of the invention in certain condition Under strong dynamic.Usually very soft as gel, this makes it have advantageous advantage in terms of selfreparing, It is based particularly on the strong dynamic of Reversible Addition Fragmentation Chain Transfer dynamic covalent bond of the invention under certain condition.As foam When material, one side advantageously reduces the apparent density of material, on the other hand can obtain the performances such as insulation.Based on On feature, the preferred ordinary solid of form, elastomer, the gel of dynamic aggregation object of the present invention or its composition be (including neat Polymers swell gel, plasticizer swell gel, ionic liquid swell gel) and foam.
In embodiments of the present invention, when using organic solvent to prepare gel, prepared gel is organic solidifying Glue.The gel of ionic liquid, oligomer and plasticising solvent swell is also referred to as organogel.
In embodiments of the present invention, the foaming method of dynamic aggregation object foamed material is prepared according to foaming agent used Difference can be divided into physical blowing method and chemical blowing process two major classes.
Wherein, the physical blowing method, be realized in the preparation process of dynamic aggregation object using physical principle it is poly- Close the foaming of object comprising but it is not limited only to following methods: (1) inert gas blown method, i.e., indifferent gas under pressurized condition Body is pressed into molten polymer or pasty material, then decompression heating, is made the gas expansion of dissolution and is foamed；(2) low boiling is utilized Point liquid evaporation gasification foaming makes liquid that is, in low-boiling point liquid indentation polymer or under certain pressure, temperature regime It dissolves in polymer (particle), then heats and softens polymer, liquid also gasifies therewith evaporation and foamed；(3) leaching, i.e., 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 hair Blister, such as by solable matter salt elder generation and mixed with polymers, put in water repeatedly after being shaped to product, then by product Processing dissolves out solable matter to get open-celled foam product is arrived；(4) hollow microsphere method is added hollow micro- in the material It is combined after ball 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 polymer In dissolve in inert gas and the method for low-boiling point liquid foams.Using physical blowing method, have operation Poisoning smaller, hair The advantages that bubble cost of material is lower, 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 comprising but it is not limited only to following two method: (1) thermal decomposable foaming agent foaming utilizes chemistry The gas decomposed to give off after foaming agent heating foams.(2) it interacts between polymers compositions and generates the foaming of gas, i.e., Using the chemical reaction occurred between two or more components in foaming system, inert gas (such as carbon dioxide or nitrogen are generated Gas) cause polymer to expand and foam.It is carried out in foaming process for control polymerization reaction and foamable reaction balance, to guarantee product There is preferable quality, a small amount of catalyst and foam stabiliser (or surfactant) is generally added.Wherein, preferably by polymerizeing The method for adding chemical foaming agent in object foams.
In embodiments of the present invention, the structure of dynamic aggregation object foamed material is related to open-celled structure, hole-closing structure, half Open three kinds of semi-closure structure etc..It in open-celled structure, is interconnected between abscess and abscess, or connection completely, one-dimensional or three-dimensional can By gas or liquid, abscess diameter is that 0.01~3mm is differed.Hole-closing structure has individual blisters structure, inner cell and abscess Between there is wall film to separate, the overwhelming majority be not interconnected, abscess diameter be 0.01~3mm differ.The existing phase of contained abscess It is intercommunicated and to have mutual disconnected structure be then half open-celled structure.
In embodiments of the present invention, foam dynamic aggregation object can be divided into soft, hard and half according to its softness Hard 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 soft) foam, the foams between above two class, elasticity modulus is between 70MPa Between 700MPa.
A kind of dynamic aggregation object with hybrid cross-linked network structure provided by the present invention, can be used for preparing a variety of friendships Link state polymer material, includes but are not limited to polyurethane, poly- urine, polyolefin, polyacrylate, epoxy resin, alkyd tree Rouge, polyamide, phenolic resin and amino resins etc..In view of the excellent performance of polyurethane and easy preparation process, this hair The bright polyurethane dynamic aggregation object preferably with hybrid cross-linked network, particularly preferably steeps as polyurethane dynamic aggregation object The matrix of foam material.
In embodiments of the present invention, polyurethane dynamic aggregation object preferably uses polyol compound, polynary amine compounds It is prepared by object, polynary sulfhydryl compound.
In the present invention, polyol compound includes small molecule, oligomer and macromolecule polyol.For connecting multiple alcohol radicals The group of member is not particularly limited.
In embodiments of the present invention, sub as its concrete example, can enumerate small molecule polyol includes but not only It is limited to, ethylene glycol (EG), propylene glycol (PG), diglycol, Diethylene Glycol, 1,4-butanediol, neopentyl glycol, 1,6- Hexylene glycol, trimethylolpropane (TMP), glycerol, pentaerythrite, xylitol, sorbierite etc..
It is sub as its concrete example in embodiments of the present invention, oligomer can be enumerated and macromolecule polyol includes But be not limited only to, polyester polyol, polyether polyol, polyolefin polyhydric alcohol, polycarbonate polyol, poly-organosilicon polyalcohol, Polysulfones polyalcohol, vegetable oil polyol and other polymers polyalcohol etc. further include its copolymer and modifier form.Oligomer It is outer except being synthesized using known polymerization with macromolecule polyol, can also by nitrine-alkynes addition of copper catalysis, The reactions preparations such as the addition or condensations such as sulfydryl-alkene addition, sulfydryl-alkynes addition, tetrazine-norbornene reaction.
As polyester polyol, it can be and be condensed by Dicarboxylic Acids (acid anhydrides or ester) and polyalcohol (including dihydric alcohol) It (or transesterification) or is formed by lactone and polymerization.
For the present invention, synthesize polyester polyol used in flexible polyurethane foam, preferably be selected from relative molecular mass compared with Low linear or Slight branching terminal hydroxy group saturated polyol polyester.Synthesize polyester polyols used in rigid polyurethane foam Alcohol preferably then is selected from aromatic polyester polyol.Aromatic polyester polyol be by phthalic anhydride and dihydric alcohol or trihydroxylic alcohol (EG, PG, DEG, DPG, TMP, NPG, MPD, BDO, HDO) it polymerize obtained polyester polyol, due to containing phenyl ring rigid radical in molecule, Humidification can be played.
It is with epoxides by the compound containing active hydrogen group in the presence of a catalyst through addition polymerization as polyether polyol Reaction is made.Compound containing active hydrogen group can be enumerated for example, propylene glycol, glycerol, trimethylolpropane, ethylenediamine season Penta tetrol, xylitol, triethylene diamine, sorbierite, sucrose, bisphenol-A, bisphenol S, three (2- ethoxy) isocyanates, toluene two Amine etc..Epoxides can be enumerated for example, ethylene oxide (EO), propylene oxide (PO), epoxy butane (BO), epoxychloropropane (ECH), tetrahydrofuran (THF) etc..
As polyolefin polyhydric alcohol, can enumerate for example, terminal hydroxy group polyethylene, hydroxy terminated polypropylene, polybutadiene polyol Alcohol, end hydroxy butadiene-acrylonitrile, liquid end hydroxy styrene-butadiene rubber, hydrogenation end hydroxy butadiene, the poly- isoamyl two of terminal hydroxy group Alkene, hydrogenation hydroxyl terminated polyisoprene, styrene-co-allyl alcohol copolymer polyols etc..
As polycarbonate polyol (abbreviation PCDL), generally it is being catalyzed using small molecule dihydric alcohol and small molecule carbonic ester Ester exchange reaction is carried out in the presence of agent, finally decompression extracts small-molecule substance out to get polycarbonate glycol is arrived.Small molecule binary Alcohol can be enumerated for example, 1,6- hexylene glycol, 1,4-butanediol, 1,4-CHDM, 1,5-PD, 3- methylpent two Alcohol etc..Small molecule carbonic ester can be enumerated for example, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diphenyl carbonate, carbon Sour ethyl, propylene carbonate etc..
Polysiloxane is one kind using Si-O-Si as main chain, and the high-molecular compound of organic group is connected on Si atom. Its general structure are as follows: (RnSO(4-n)/2)m.Wherein, R is organic group, such as methyl, ethyl, phenyl, vinyl etc.；N is silicon atom The organic group number (1~3) of upper connection；M is the degree of polymerization.Poly-organosilicon polyalcohol can be enumerated for example, dichlorosilane hydrolysis life At silanol, then hydroxy-end capped line style poly-organosilicon dihydric alcohol is can be obtained in dehydrating polycondensation.For the present invention, selected poly-organosilicon Polyalcohol can be hydroxy-end capped polysiloxane or hydroxyl in the polysiloxane of side group, be also possible to hydroxyl alkane Base is located at the polysiloxane of end or side group.
Polysulfones is to contain alkyl-SO in molecular backbone2The high-molecular compound of alkyl chain link.Polysulfones is usually by aromatics The aromatic polymer that two alkali metal salts and activated aromatic dihalide of dihydroxy compounds are polymerized.Aromatic dihydroxy chemical combination Object can illustrate for example, bisphenol-A, bisphenol S, 4,4 '-dihydroxybiphenyls.Activated aromatic dihalide can illustrate for example, right Phthalyl chloride, 4,4-dichlorodiphenyl sulfone.For the present invention, selected polysulfones polyalcohol can be hydroxy-end capped polysulfones, or Polysulfones of the hydroxyl in side group.
As vegetable oil polyol, can enumerate for example, castor oil, castor oil derivative polyalcohol, soybean oil polyol, Palm oil polyalcohol etc..For the present invention, selected vegetable oil polyol is mainly used for the raw material of rigid poly urethanes foamed material.
It is the styrene-acrylonitrile graft polyether polyols based on PO-EO copolyether triol as polymer polyatomic alcohol Alcohol, also known as graft polyether, abbreviation POP.
Polyethylene glycol (PEG), polytrimethylene ether glycol, polytetrahydrofuran, polyoxypropyleneglycol, polyoxygenated can be enumerated Propylene triol, bisphenol-A polyethylene glycol oxide ether, poly- phthalic acid diglycol esterdiol, polybutadiene polyol, end hydroxyl Base Polybutadiene-acrylonitrile, poly dimethyl silicon polyalcohol, castor oil polyhydric alcohol, styrene-acrylonitrile graft polyether polyol Chemical structural formula is as follows:
For the present invention, prepare soft polyurethane foam and rigid foam material to the relative molecular mass of above-mentioned polyol compound or Hydroxyl value requires different.Soft bubble, the degree of functionality of preferred polyol compound are 2~3, and relative molecular mass is 2000~7000 ranges It is interior, hydroxyl value about 50~80mg KOH/g；Hard bubble, the degree of functionality of preferred polyol compound are 3~8, and relative molecular mass is 300 In~500 ranges, hydroxyl value about 450~550mg KOH/g.Semi-rigid foam, hard bubble, the degree of functionality of preferred polyol compound It is 3~8, relative molecular mass is in 600~2000 ranges, hydroxyl value about 100~200mg KOH/g.
In embodiments of the present invention, the polyhydric amine compounds that polyurethane (polyureas) dynamic aggregation object preferably uses, packet Include but be not limited only to small molecule polyamine, oligomer and macromolecular multi-component amine.As long as the change with 2 or 2 or more amino Closing object can enumerate then its molecular weight and skeleton etc. are just not particularly limited e.g., including but be not limited only to as shown below Aromatic polyamine and aliphatic polyamine etc..
As small molecule aromatic polyamine, specific examples thereof include for example, diaminotoluene, diamino dimethylbenzene, tetramethyl It is base xylylene amine, m-phenylene diamine (MPD), three (dimethylaminomethyl) phenol, diaminodiphenyl-methane, 3,3 '-two chloro- 4,4 '-diphenylmethanediamiands (MOCA), 3,5- dimethythiotoluene diamine (DMTDA), 3,5- diethyl toluene diamine (DETDA)。
As small molecule aliphatic polyamine, specific examples thereof include for example, methylene diamine, 1,2- ethylenediamine, the third neighbour two Amine, 1,2- diaminopropanes, 1,3-diaminopentane, hexamethylene diamine, diaminoheptane, diamino dodecane, diethyl Aminopropyl amine, diethylenetriamines, N- aminoethylpiperazine, trien, N, N '-dimethyl ethylene diamine, N, N '-diethylethylenediamine, N, N '-diisopropylethylened,amine, N, N '-dimethyl -1,3- propane diamine, N, N '-diethyl Base -1,3- propane diamine, N, N '-diisopropyl -1,3- propane diamine, N, N '-dimethyl -1,6- hexamethylene diamine, N, diethyl -1 N ' -, 6- hexamethylene diamine, N, bis- (hexa-methylene) triamines of N ', N "-trimethyl etc..
As oligomer and macromolecular multi-component amine, it may include but be not limited only to based on polyester, polyethers, polyolefin, gather Carbonic ester, poly-organosilicon, vegetable oil and polyamine of other polymers etc..It can specifically illustrate for example, being copolymerized ether diamine, end Amine terminated polyether, Amino End Group methyl-silicone oil for fragrant amino.Its chemical structural formula is as follows,
In embodiments of the present invention, it is preferably used in and prepares the polynary of polyurethane (polysulfide is for amine ester) dynamic aggregation object Sulfhydryl compound includes but are not limited to the polynary sulfydryl of small molecule, oligomer and macromolecular multi-component sulfhydryl compound.As long as tool There is the compound of 2 or 2 or more sulfydryls, then its molecular weight and skeleton etc. are just not particularly limited, can specifically arrange It enumerates e.g., including but it is not limited only to compound shown below.
As the polynary sulfhydryl compound of small molecule, specific examples thereof include for example, the third two sulphur of 1,2- dithioglycol, 1,3- Alcohol, 1,4- succinimide mercaptans, 1,2- succinimide mercaptans, 1,3- succinimide mercaptans, 1,5- pentane disulfide thioalcohol, 1,6- ethanthiol, 1,8- pungent two Mercaptan, two mercaptan of 1,9- nonyl, two mercaptan of the 1,10- last of the ten Heavenly stems, 2,3- succinimide mercaptans, double mercapto ethyl thioethers, 3,7- dithia -1,9- nonyl Two mercaptan, 3- sulfydryl-β -4- dimethyleyelohexane ethyl mercaptan, 1,4- dimercaptobenzene, adjacent dimercaptobenzene, 3,4- first dimercaptobenzene, 1, 5- naphthyl disulfide alcohol, Lu's succinimide mercaptans, 4,4 '-dimercapto diphenyl sulfides, dimercapto -3,6- dioxy octane, 1,5- sulfydryl -3- are thio Pentane, three mercaptan of 1,3,5- triazine -2,4,6- etc..
As oligomer and macromolecular multi-component sulfhydryl compound, it may include but be not limited only to based on polyester, polyethers, gather Alkene, polycarbonate, poly-organosilicon, vegetable oil and multi-thiol of other polymers etc..
In above-mentioned polyalcohol, polyamine and polynary sulfhydryl compound, it can also contain simultaneously in the same compound Two in alcoholic extract hydroxyl group, amino and sulfydryl can contain carbamate, sulfo-amino perhaps on three its skeletons or in side group Formic acid esters, urea, amide, ester, ether, thioether group；Preferably comprise the bases such as carbamate, thiocarbamate, urea, amide Group；Most preferably carbamate groups and urea groups.
In addition, above-mentioned polyalcohol, polyamine and polynary sulfhydryl compound can be used alone, it is also combinable to use 2 kinds Or 2 kinds or more.Merge using 2 kinds or two or more when mixing ratio, according to the present invention a kind of can have hybrid cross-linked network Purposes used in the dynamic aggregation object (or composition) of structure, a kind of dynamic with hybrid cross-linked network structure of the invention The adjustment of the progress proper ratio such as physical property required by polymer (or composition).
In embodiments of the present invention, polyurethane dynamic aggregation object preferably uses isocyanate compound to be prepared. The isocyanate compound includes but are not limited to small molecule, oligomer and macromolecular multi-component isocyanate compound.As long as It is the compound of the isocyanates with 2 or 2 or more, then its molecular weight and skeleton etc. are just not particularly limited, has Body can enumerate e.g., including but it is not limited only to compound shown below.
It as small molecule isocyanates, includes but are not limited to, toluene di-isocyanate(TDI) (TDI), diphenyl methane two are different Cyanate (MDI), isoflurane chalcone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), polymethylene polyphenyl are different It is cyanate (PAPI), liquefied mdi, dicyclohexyl methyl hydride diisocyanate (HMDI), naphthalene diisocyanate (NDI), different to benzene two Cyanate (PPDI), benzene dimethylene diisocyanate (XDI), dimethyl diphenyl diisocyanate (TODI), 1,4- hexamethylene Diisocyanate (CHDI), tetramethyl m-xylylene diisocyanate (m-TMXDI), trimethyl -1,6- hexa-methylene two Isocyanates (TMHDI), cyclohexanedimethyleterephthalate diisocyanate (HXDI), norbornene alkyl diisocyanate (NBDI), TDI bis- Aggressiveness, triphenylmethane triisocyanate (TTI), 4,4 ', 4 "-thiophosphoric acid triphenyl triisocyanates (TPTI), HDI trimerization Body, IPDI tripolymer, TDI tripolymer, MDI tripolymer, TDI-TMP addition product etc..
It as oligomerisation and polymer isocyanic ester compound, includes but are not limited to, based on polyester, polyethers, polyolefin, gathers Carbonic ester, poly-organosilicon, vegetable oil and polyhydric isocyanate compound of other polymers etc..
Above-mentioned various polyisocyanate compounds can be used alone a kind in them, or merge and use 2 kinds or 2 kinds More than.Merge using 2 kinds or two or more when mixing ratio, can be according to the present invention a kind of with hybrid cross-linked network structure Purposes used in dynamic aggregation object (or composition), a kind of dynamic aggregation object with hybrid cross-linked network structure of the invention The adjustment of the progress proper ratio such as physical property required by (or composition).
In polyurethane-based material preparation process, it is also necessary to chain extender, catalyst be added according to the actual situation；For poly- ammonia For ester foam, it is also necessary to foaming agent and foam stabiliser etc. be added.
In embodiments of the present invention, the chain extender of polyurethane material can be the oligomer with active hydrogen, can also be with It is the small molecule compound with active hydrogen.The present invention is under normal circumstances preferably with the small molecule compound of active hydrogen.It can illustrate E.g., including but be not limited only to, polyamine, polyalcohol, multi-thiol, hydramine and water of small molecule etc..
The upper chain extender, it is specific enumerable out for example, ethylene glycol, propylene glycol, diglycol, glycerol, three hydroxyl first Base propane, pentaerythrite, 1,4- butanediol, 1,6-HD, hydroquinone two hydroxy ethyl ether (HQEE), the double hydroxyl second of resorcinol Base ether (HER), to bis-hydroxyethyl bisphenol A, triethanolamine, triisopropanolamine, diaminotoluene, diamino dimethylbenzene, tetramethyl Xylylene amine, tetraethyl diphenyl methylene diamines, tetra isopropyl hexichol subunit diamines, m-phenylene diamine (MPD), three (dimethylaminos Ylmethyl) phenol, diaminodiphenyl-methane, 3,3 '-two chloro- 4,4 '-diphenylmethanediamiands (MOCA), 3,5- dimethyl sulphur-based Toluenediamine (DMTDA), 3,5- diethyl toluene diamine (DETDA), 1,3,5- triethyl group -2,6- diaminobenzene (TEMPDA). Chain extender dosage used is not particularly limited, generally 0.1-25wt.%.
In embodiments of the present invention, the catalyst of polyurethane material can enumerate amines catalyst below and have Machine metal compound as catalyst etc..
It is specific enumerable out for example, triethylamine, triethylenediamine, bis- (dimethylaminoethyls) as amines catalyst Ether, 2- (2- Dimethylamino-ethoxy) ethyl alcohol, trimethyl hydroxyethylammonium propane diamine, N, bis- (dimethylamine propyl) isopropanolamines of N-, N- (dimethylamino-propyl) diisopropanolamine (DIPA), N, N, N '-trimethyl-N '-ethoxy diamine ethylether, tetramethyl dipropylene Triamine, N, N- dimethyl cyclohexyl amine, N, N, N ', N '-tetramethyl Alkylenediamine, N, N, N ', N ', N '-pentamethyl diethylidene Triamine, 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..
It is specific enumerable out for example, organo-tin compound such as stannous octoate, dibutyl tin as organometallic catalysts Dilaurate, dioctyl tin dilaurate, zinc Isoocatanoate, isooctyl acid lead, potassium oleate, zinc naphthenate, cobalt naphthenate, acetyl Acetone iron, phenylmercuric acetate, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octanoate, potassium oleate, calcium carbonate etc..
In embodiments of the present invention, the foaming agent of polyurethane material, can be physical blowing agent, be also possible to chemistry Foaming agent.Its surface-active with higher can be effectively reduced the surface tension of liquid, and arrange in liquid film surface electric double layer And air is surrounded, bubble is formed, then form foam by single isolated bubbles.Above-mentioned physical blowing agent includes but are not limited to following any Kind or appoint several foaming agents: air, carbon dioxide, nitrogen, freon (such as HCFC-141b, HCFC-123, HCFC-22, HCFC-365mfc, HCFC-245fa etc.), methylene chloride, trichlorofluoromethane, dicholorodifluoromethane, dichlorotetra-fluoroethane, positive penta Alkane, pentamethylene, isopentane, physical microballoon/granule foaming agent.Above-mentioned chemical foaming agent includes but are not limited to following any Or appoint several foaming agents: water, calcium carbonate, magnesium carbonate, sodium bicarbonate, sodium metasilicate, carbon black, azo-compound (such as two formyl of azo Amine (ADC), azodiisobutyronitrile, azoformic acid isopropyl ester, diethyl azodiformate, two azoaminobenzenes, azo diformazan Sour barium), sulfonyl hydrazines compound (such as 4,4- disulfonyl hydrazide diphenyl ether (OBSH), benzene sulfonyl hydrazide, unifor, 2,4- first Benzene disulfohydrazide, 3,3- disulfonyl hydrazide diphenyl sulphone (DPS), to (N- methoxy methyl acylamino-) benzene sulfonyl hydrazide), nitroso compound (such as N, N- dinitrosopentamethlyene tetramine (DPT), N, the sub- terephthalamide (NTA) of N- dimethyl-N, N- bis-) etc..Above-mentioned foaming Agent can be used alone or be used with the mixture of two or more.The amount of foaming agent used is usual amounts, that is, is using water In the case where for 0.1 arrive 10php, preferably 0.1 arrives 5php, using halogenated hydrocarbons, aliphatic alkanes and in the case where alicyclic alkanes It is about 0.1 to 20php, wherein php indicates the number of foaming agent in polymer polyatomic alcohol per hundred parts.
In embodiments of the present invention, the foam stabiliser of polyurethane material is organopolysiloxane surfactant. This organosiloxane surfactant is usually the block copolymer of dimethyl silicone polymer Yu polyoxygenated alkene.Bubble used Foam stabilizers dosage is not particularly limited, generally 0.1-5wt.%.
In embodiments of the present invention, in addition to polyurethane chain extender above-mentioned, catalyst, foaming agent, foam stabiliser, In the range of not interfering the object of the invention, can also according to circumstances select to be added or used to other polymers, filler, solvent, Auxiliary agent etc. or plays improvement processability collectively as the recipe ingredient of dynamic aggregation object in the preparation process of dynamic aggregation object The effect of energy.
Wherein, the other polymers can play in system as additive and improve material property, assign material Material new capability improves materials'use and economic benefit, has the function that material comprehensively utilizes.Addible other polymers, It can be selected from natural polymer, synthetic macromolecular compound.The present invention is to the character of added polymer and is had Some molecular weight can be oligomer or high polymer according to the difference of molecular weight, not according to polymeric species without limitation Together, it can be homopolymer or copolymer, should be prepared in the specific use process according to the performance of target material and actually The needs of journey and selected.
When the other polymers are selected from natural polymer, it can be selected from following any or appoint several days Right high-molecular compound: natural rubber, chitosan, chitin, native protein, polysaccharide etc..
When the other polymers are selected from synthetic macromolecular compound, it can be selected from following any or appoint several: Polytrifluorochloroethylene, haloflex, chliorinated polyvinyl chloride, polyvinyl chloride, Vingon, low density polyethylene (LDPE), middle density Polyethylene, high density polyethylene (HDPE), ultra-high molecular weight polyethylene, melamine formaldehyde resin, polyamide, polyacrylic acid, polypropylene Acid esters, polyacrylamide, polyacrylonitrile, polybenzimidazoles, polyethylene terephthalate, polybutylene terephthalate Ester, polycarbonate, polyethylene glycol, polyester, polyether sulfone, polyarylsulfone (PAS), polyether-ether-ketone, tetrafluoroethylene-perfluoro propane copolymer, polyamides Imines, polyacrylate, polyacrylonitrile, polyphenylene oxide, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high-impact polyphenyl second Alkene, polysulfones, polytetrafluoroethylene (PTFE), polyurethane, polyureas, polyvinyl acetate, ethylene-propylene copolymer, ethane-acetic acid ethyenyl ester are total Polymers, AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, vinyl chloride-vinyl acetate Ester copolymer, polyvinylpyrrolidone, epoxy resin, phenolic resin, Lauxite, unsaturated polyester (UP), polyisoprene, gather it is suitable Butadiene, styrene-butadiene copolymer, hycar, poly- (the chloro- 1,3- butadiene of 2-), isobutene-are different Pentadiene copolymer, ethylene-propylene-Isosorbide-5-Nitrae-hexadiene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene- Ethylidene norbornene copolymer, dimethyl silicone polymer, Polymethyl methacrylate, polymethylphenylsiloxane, poly- methyl Vinyl benzene radical siloxane, poly- methyl ethylene trifluoropropyl siloxane, vinylidene-chlorotrifluoroethylene, inclined fluorine second Alkene-hexafluoropropylene copolymer, vinylidene-tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene propylene copolymer, polycyclic oxygen Chloropropane, epichlorohydrin ethylene oxide copoymer, epoxychloropropane-ethylene oxide-propylene oxide copolymer etc..
The upper filler that can be added/use, primarily serves following effect in polymer samples: 1. reducing molding system The shrinking percentage of part improves dimensional stability, surface smoothness, flatness and the zero diopter of product or without photosensitiveness etc.；2. adjusting The viscosity of material；3. meeting different performance requirement, such as improves material impact intensity and compressive strength, hardness, rigidity and modulus, mentions High-wearing feature improves heat distortion temperature, improves electric conductivity and thermal conductivity etc.；4. improving the coloring effect of pigment；5. it is steady to assign light Qualitative and chemical corrosion resistance；6. playing compatibilization, cost can be reduced, improves product competitiveness in the market.
The upper filler that can be added/use, selected from following any or several fillers: inorganic non-metallic filler, gold Belong to filler, organic filler.
The inorganic non-metallic filler for adding/using includes but is not limited to any of the following or appoints several: carbonic acid Calcium, clay, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, asbestos, asbestos fibre, Orthoclase, chalk, lime stone, blanc fixe, gypsum, graphite, carbon black, graphene, graphene oxide, carbon nanotube, curing Molybdenum, slag, flue dust, wood powder and shell powder, diatomite, red mud, wollastonite, silica-alumina carbon black, aluminium hydroxide, magnesium hydroxide, fine coal Ash, oil shale powder, swelling perlite powder, aluminum nitride powder, boron nitride powder, vermiculite, iron cement, white clay, alkali mud, (hollow) glass are micro- Pearl, foam microspheres, expandable particles, glass powder, cement, glass fibre, carbon fiber, quartz fibre, charcoal core boron fibre, two boronations Titanium fiber, calcium titanium fiber, silicon carbide fibre, ceramic fibre, whisker etc..In an embodiment of the invention, preferably have Conductive inorganic non-metallic filler includes but are not limited to graphite, carbon black, graphene, carbon nanotube, carbon fiber, convenient Obtain composite material conductive and/or with electric heating function.In yet another embodiment of the present invention, preferably have The non-metallic fillers with heating function under the effect of infrared and/or near infrared light include but are not limited to graphene, oxidation stone Black alkene, carbon nanotube, the composite material for facilitating acquisition that can be heated using infrared and/or near infrared light.Good heat generation Energy, the especially heating property of remote control property, advantageously allow polymer and obtain the performances such as controllable shape memory, selfreparing.? In another embodiment of the invention, preferably with the inorganic non-metallic filler of thermal conductivity, graphite, stone are included but are not limited to Black alkene, carbon nanotube, aluminium nitride, boron nitride, silicon carbide facilitate the composite material for obtaining thermally conductive function.
The metal packing added/used, including metallic compound, include but are not limited to it is following any or Appoint several: metal powder, fiber comprising but it is not limited only to copper, silver, nickel, iron, gold etc. and its powder, the fiber of alloy；Nanometer Metallic particles comprising but it is not limited only to nanogold particle, nano-Ag particles, nanoparticle palladium, nano iron particles, nanometer cobalt Grain, nano nickle granules, nanometer Fe3O4Particle, nanometer γ-Fe2O3Particle, nanometer MgFe2O4Particle, nanometer MnFe2O4Particle is received Rice CoFe2O4Particle, nano Co Pt3Particle, nanometer Fe Pt particle, nanometer Fe Pd particle, ferronickel bimetallic magnetic nanoparticle with And other are in infrared, near-infrared, ultraviolet, the nano-metal particle that can be generated heat under at least one effect of electromagnetism etc.；Liquid metal, It includes but are not limited to mercury, gallium, gallium indium liquid alloy, gallium indium tin liquid alloy, other gallium base liquid metal alloys；Metal has Machine compound molecule, crystal and other in infrared, near-infrared, the ultraviolet, substance that can generate heat under at least one effect of electromagnetism Deng.In an embodiment of the invention, the filler of electromagnetism and/or near-infrared heating can be preferably carried out, including but not only It is limited to nanogold, nano silver, Technique of Nano Pd, nanometer Fe3O4, to carry out remote sensing heating.In another embodiment of the invention In, preferred liquid metal filler facilitates acquisition to have Thermal conductivity, electric conductivity and to be able to maintain substrate flexible and prolong The composite material of malleability.In yet another embodiment of the present invention, preferably in infrared, near-infrared, ultraviolet, electromagnetism is at least one On the one hand lower organo-metallic compound molecule, the crystal that can be generated heat of effect facilitates compound, the effect of another side raising induction fever Rate and promotion heating effect.
The organic filler added/used includes but are not limited to following any or appoints several: 1. natural organic Filler, such as fur, natural rubber, cotton, velveteen, fiber crops, jute, flax, asbestos, cellulose, cellulose acetate, shellac, crust Element, chitosan, lignin, starch, protein, enzyme, hormone, raw lacquer, timber, wood powder, shell powder, glycogen, xylose, silk etc.；② Synthetic resin filler, as AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, acetic acid are fine Tie up element, polytrifluorochloroethylene, haloflex, chliorinated polyvinyl chloride, epoxy resin, ethylene-propylene copolymer, ethylene-acetate Vinyl ester copolymers, high density polyethylene (HDPE), high impact polystyrene, low density polyethylene (LDPE), medium density polyethylene, melamine- Formaldehyde resin, polyamide, polyacrylic acid, polyacrylamide, polyacrylonitrile, polyarylsulfone (PAS), polybenzimidazoles, poly terephthalic acid fourth Diol ester, polycarbonate, dimethyl silicone polymer, polyethylene glycol, polyester, polysulfones, polyether sulfone, polyethylene terephthalate Ester, phenolic resin, tetrafluoroethylene-perfluoro propane copolymer, polyimides, polymethyl acrylate, polymethacrylonitrile, poly- methyl Methyl acrylate, polyphenylene oxide, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, polytetrafluoroethylene (PTFE), polyurethane, polyvinyl alcohol, Polyvinyl acetate, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, Vingon, polyvinylpyrrolidone, ureaformaldehyde Resin, ultra-high molecular weight polyethylene, unsaturated polyester (UP), polyether-ether-ketone etc.；3. synthetic rubber filler, such as isoprene rubber, along fourth rubber Glue, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, EP rubbers, silicon rubber, fluorubber, lactoprene, Polyurethane rubber, epichlorohydrin rubber, thermoplastic elastomer (TPE) etc.；4. synthetic fibers filler, such as viscose fiber, copper ammonia fiber, diethylester Fiber, triethyl fiber, Fypro, polycarbonate, vinal, polyester fiber, polyurethane fiber, poly- third Alkene nitrile fiber, vinylon, polyvinyl chloride fibre, polyolefine fiber, fluorofibre, polytetrafluoroethylene fibre, virtue Fragrant polyamide fiber, aramid fiber or aramid fiber etc.；5. metallo-organic compound, including its molecule and crystal grain Deng, the effects of can preferably carrying out illumination, electromagnetism and the material heated.
Wherein, the wire feeding that can be added/use does not limit, mainly depending on required material property, preferred carbon Sour calcium, barium sulfate, talcum powder, carbon black, graphene, glass microballoon, foam microspheres, expandable particles, glass fibre, carbon fiber, Natural rubber, chitosan, starch, protein, polyethylene, polypropylene, polyvinyl chloride, vinyl-vinyl acetate copolymer, poly- second Enol, isoprene rubber, butadiene rubber, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, EP rubbers, silicon rubber, heat Thermoplastic elastic, Fypro, polycarbonate, vinal, polyester fiber, polyacrylonitrile fibre.Used Amount of filler is not particularly limited, generally 1-30wt.%.
The upper solvent that can be added/use, adjustable viscosity are convenient for technological operation, in product preparation process or are matched It is used in system.Its include but are not limited to it is following any or appoint it is several: hydro carbons (such as hexane), halogenated hydrocarbon (such as tetrachloromethane), Aromatic hydrocarbons (such as toluene, dimethylbenzene), ketone (such as acetone, methyl ethyl ketone), ethers (such as ether, tetrahydrofuran, dioxane), Esters (such as ethyl acetate, butyl acetate), glycol ether-ether (such as ethylene glycol ether acetate, propylene glycol monomethyl ether acetate), two The intensive polar solvents such as methylformamide (DMF), N-Methyl pyrrolidone (NMP).Solvent usage used is not particularly limited, and one As be 1-200wt.%.
The auxiliary agent may include but be not limited to the combination of following one or more, such as additive synthesis, including other catalysis Agent, initiator；Stabilizing additive, including antioxidant, light stabilizer, heat stabilizer, dispersing agent, emulsifier, fire retardant；Improve The auxiliary agent of mechanical property, including toughener, coupling agent；Improve processing performance auxiliary agent, including lubricant, release agent, plasticizer, Thickener, thixotropic agent, levelling agent；Change the auxiliary agent of coloured light, including colorant, fluorescent whitening agent, delustering agent；Other auxiliary agents, packet Include antistatic agent, biocide mildewcide, foaming agent, nucleating agent, rheological agent etc..
Other catalyst in the auxiliary agent can reduce reaction activity by changing reaction path to accelerate The reaction rate of reactant during the reaction.It includes but are not limited to following any or appoints several catalyst: 1. polyene Hydrocarbon catalyst for synthesizing: such as Ziegler-Natta catalyst, π-allyl nickel, alkyl lithium catalyst, metallocene catalyst, one Chlorodiethyl aluminium, titanium tetrachloride, titanium trichloride, boron trifluoride etherate, magnesia, dimethylamine, stannous chloride, three second Amine, tetraphenylboron sodium, antimony oxide, sesquialter ethylmercury chloride aluminium, vanadium oxytrichloride, triisobutyl aluminium, nickel naphthenate, naphthenic acid rare earth Deng；2. CuAAC catalysts: sharing concerted catalysis by monovalence copper compound and amine ligand；Monovalence copper compound can be selected from Cu (I) salt, such as CuCl, CuBr, CuI, CuCN, CuOAc；Also selected from Cu (I) complex compound, such as [Cu (CH3CN)4]PF6、 [Cu (CH3CN)4]OTf、CuBr(PPh3)3Deng；Amine ligand can be selected from three [(1- benzyl -1H-1,2,3- triazole-4-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.；3. thiol-ene catalysts: photochemical catalyst, as dimethoxybenzoin, 2- hydroxy-2-methyl phenylacetone, 2,2- dimethoxy -2- phenyl acetophenone etc..Catalyst amount used does not limit especially It is fixed, generally 0.01-0.5wt%.
In embodiments of the present invention, some characteristic reactions need initiator, such as sulfydryl-double bond click-reaction, propylene In acid esters radical reaction, double bond-double bond coupling process, radical initiator is needed, can be drawn in polymerization process It plays monomer molecule activation and generates free radical, improve reaction rate, reaction is promoted to carry out.It can also add in dynamic polymer systems Enter initiator, decomposition of initiator at living radical can promote the dissociation and exchange of dynamic covalent bond, to obtain excellent Dynamic property.The initiator includes but are not limited to following any or appoints several initiators: photoinitiator, such as 2,2- bis- Methoxyl group -2- phenyl acetophenone (DMPA), 2- hydroxy-2-methyl -1- phenylacetone, 1- hydroxycyclohexyl phenyl ketone, 2,4, 6- trimethylbenzoyl-diphenyl phosphine oxide (TPO), benzophenone, 2- hydroxyl -4- (2- hydroxy ethoxy) -2- methylbenzene third Ketone, 2- hydroxy-2-methyl -1- [4- (2- hydroxyl-oxethyl) phenyl] -1- acetone and α-ketoglutaric acid.Organic peroxide, such as Lauroyl peroxide, benzoyl peroxide (BPO), di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate, peroxide Change bis- (4- tert-butylcyclohexyl) esters of two carbonic acid, tert butyl peroxy benzoate, tert-butyl hydroperoxide pivalate, two tertiary fourths Base peroxide, di-isopropylbenzene hydroperoxide；Azo-compound, such as azodiisobutyronitrile (AIBN), azobisisoheptonitrile；It is inorganic Peroxide, such as ammonium persulfate, potassium peroxydisulfate；Wherein, initiator preferably 2,2- dimethoxy -2- phenyl acetophenone, azo Bis-isobutyronitrile, lauroyl peroxide, benzoyl peroxide, potassium peroxydisulfate.Double bond-double bond coupling reaction can also be using radiation The mode of polymerization, using high energy ionizing ray (such as alpha ray, β ray, gamma-rays, x-ray, electron beam) radiation monomer generate from Son or free radical form activated centre and polymerize.In embodiments of the present invention, it is suitable according to circumstances to select Initiator and polymerization methods.
Antioxidant in the upper auxiliary agent that can be added/use, can delay the oxidation process of polymer samples, guarantee Material successfully can be processed and be prolonged its service life, and included but are not limited to following any or appointed several antioxygens Agent: Hinered phenols, such as 2,6- di-tert-butyl-4-methy phenol, 1,1,3- tri- (- 4 hydroxyl -5- tert-butyl-phenyl of 2- methyl) fourth Alkane, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butyl Base phenol)；Sulfur-bearing Hinered phenols, such as 4,4 '-thiobis-[3 methy 6 tert butyl phenol], 2,2 '-thiobis-[4- methyl- 6- tert-butyl phenol]；Triazine system hindered phenol, such as 1,3,5- bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl]-hexahydros are equal Triazine；Isocyanuric acid ester Hinered phenols, such as three (3,5- di-tert-butyl-4-hydroxyl benzyl)-triisocyanates；Amine, such as N, N '-two (betanaphthyl) p-phenylenediamine, N, N '-diphenyl-para-phenylene diamine, N- phenyl-N '-cyclohexyl p-phenylenediamine；Sulfur-bearing class, such as Dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, Asia Tricresyl phosphate nonyl phenyl ester, three [2.4- di-tert-butyl-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 upper auxiliary agent that can be added/use, can prevent polymer samples from light aging occurs, extend Its service life, include but are not limited to it is following any or appoint it is several: photomask agent, as carbon black, titanium dioxide, zinc oxide, Calcium sulfite；Ultraviolet absorbing agent, such as ESCALOL 567,2-hydroxy-4-n-octoxybenzophenone, 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 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- bis- Tertiary butyl-4-hydroxy benzylphosphonic acid mono ethyl ester), 2,2 '-thiobis (4- spy's octyl phenol oxygroup) nickel；Hindered amine light stabilizer, such as Bis- (2,2,6,6- tetramethyl piperidine) esters of decanedioic acid, benzoic acid (2,2,6,6- tetramethyl piperidine) ester, three (1,2,2,6,6- five Methyl piperidine base) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acid (2,4- di-tert-butyl) Ester, alkyl phosphoric acid amide, N, N '-zinc dibutyl dithiocaarbamate, N, N '-second, n-butyl dithiocarbamate nickel Deng；Wherein, bis- (2,2,6, the 6- tetramethyl piperidine) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid.Light used Stabilizing agent dosage is not particularly limited, generally 0.01-0.5wt.%.
Heat stabilizer in the upper auxiliary agent that can be added/use, enables to polymer material processing or using Chemical change does not occur because heated in journey, or delays these variations to achieve the purpose that prolong the service life comprising but It is not limited only to following any or appoints several heat stabilizers: lead salts, such as lead sulfate tribasic, dibasic lead phosphite, disalt Base lead stearate, dibasic phthalic acid lead, tribasic Malaysia lead plumbate, lead stearate, lead salicylate, dibasic phthalic acid Lead, basic lead carbonate；Metal soap: such as cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate；Organotin Compounds, such as di-n-butyltin dilaurate, Bis(lauroyloxy)dioctyltin, maleic acid two (just) butyl tin, double maleic acids Mono octyl ester dioctyltin, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital tin C-102, dimercapto acetic acid isooctyl dimethyl Tin, two mercaptan stannous methides and its compound；Antimony stabilizer, such as mercaptan antimonic salt, mercaptoacetate mercaptans type, mercapto-carboxylic ester Antimony, carboxylate antimony；Epoxy compound species, such as epoxidized oil, epoxy aliphatic ester, epoxy resin；Phosphorous acid esters, such as phosphorous acid Three aromatic ester, three alkyl ester of phosphorous acid, three aralkyl ester of phosphorous acid, alkane virtue mixed ester, aggretion type phosphite ester；Polyalcohols, such as season penta Tetrol, xylitol, mannitol, D-sorbite, trimethylolpropane；Composite thermal stabilizer is such as co-precipitated metallic soap, liquid metals Soap compound stabilizer, organotin compound stabilizer etc..Wherein, the preferred barium stearate of heat stabilizer, calcium stearate, tin dilaurate two Normal-butyl tin, maleic acid two (just) butyl tin, heat stabilizer dosage used are not particularly limited, generally 0.1-0.5 Wt%.
Dispersing agent in the upper auxiliary agent that can be added/use enables to solid flocculation group point in mixed with polymers liquid It dissipates for tiny particle and is suspended in liquid, those are poorly soluble the solid and liquid particles in liquid for uniform dispersion, simultaneously Also it can prevent the sedimentation and cohesion of particle, form stable suspension comprising but be not limited only to following any or appoint several points Powder: anionic, such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate；Cationic；It is non-ionic, such as rouge Fat alcohol polyoxyethylene ether, sorbitol anhydride fatty acid polyoxyethylene ether；Inorganic type, such as silicate, condensed phosphate；Macromolecule Type, such as starch, gelatin, water-soluble glue, lecithin, carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, lignin sulfonic acid Salt, polyvinyl alcohol etc..Wherein, the preferred neopelex of dispersing agent, naphthalene system methylene sulfonate (dispersing agent N), fat Alcohol polyoxyethylene ether, dispersant dosage used are not particularly limited, generally 0.3-0.8wt%.
Emulsifier in the upper auxiliary agent that can be added/use can improve each in the mixed with polymers liquid comprising auxiliary agent Kind constitute phase between surface tension, be allowed to form uniform and stable dispersion or emulsion comprising but be not limited only to Under it is any or appoint several emulsifiers: anionic, such as higher fatty acid salt, alkylsulfonate, alkylbenzene sulfonate, alkylnaphthalene Sodium sulfonate, sulphosuccinates, petroleum sulfonate, aliphatic alcohol sulfate, castor oil salt, sulphation butyl ricinoleate Salt, phosphate ester salt, fatty acyl-peptide condensation product；Cationic, such as alkylammonium salt, alkyl quaternary ammonium salts, Fixanol；Both sexes from Subtype, such as carboxylic acid ester type, sulfonic acid ester type, sulfuric acid ester type, phosphate type；It is non-ionic, such as fatty alcohol polyoxyethylene ether, alkyl phenol Polyoxyethylene ether, polyoxyethylene carboxylate, polypropylene oxide-ethylene oxide adduct, fatty acid glyceride, pentaerythritol resin Fat acid esters, sorbierite and sorbitan fatty acid ester, sucrose fatty ester, hydramine fatty acid amide etc..Wherein, preferred dodecane Base benzene sulfonic acid sodium salt, sorbitan fatty acid ester, triethanolamine stearate (Emulphor FM), emulsifier used do not have It is particularly limited to, generally 1-5wt%.
Fire retardant in the upper auxiliary agent that can be added/use, can increase the flame resistance of material comprising but not only limit In it is following any or appoint it is several: phosphorus system, such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, phosphoric acid first Benzene diphenyl ester；Halogen phosphoric acid ester, such as three (2,3- dibromopropyl) phosphates, tricresyl phosphate (2,3- dichloro the third) ester；Organic halogenation Object, 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- dibromopropyls) Fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride etc.；Wherein, the preferred deca-BDE of fire retardant, phosphoric acid triphen Ester, tricresyl phosphate, phosphate toluene diphenyl ester, antimony oxide.Amount of flame-retardant agent used is not particularly limited, generally 1-20wt.%.
Toughener in the upper auxiliary agent that can be added/use, can reduce polymer material brittleness, increases toughness, mention High material bearing strength comprising but be not limited only to following any or appoint several toughener: methyl methacrylate-fourth two Alkene-styrene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modifier, propylene Nitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, the third glue of second, ethylene-propylene diene copolymer, cis-butadiene cement, butadiene-styrene rubber, benzene Ethylene-butadiene-styrene block copolymer etc..Wherein, preferred the third glue of second of toughener, acrylonitrile-butadiene-styrene (ABS) copolymerization Object (ABS), Styrene-Butadiene-Styrene Block Copolymer (SBS), methyl methacrylate-butadiene-styrene copolymerization Resin (MBS), chlorinated polyethylene resin (CPE), toughener dosage used are not particularly limited, generally 5-10wt%.
Coupling agent in the upper auxiliary agent that can be added/use, can improve the dynamic aggregation object and inorganic filler of synthesis Interface performance.It includes but are not limited to following any or appoints several: silane coupling agent, with alkoxysilyl Silane compound, titanium coupling agent, zirconium coupling agent etc..More specifically, can enumerate for example, trimethoxyvinyl silane, ethylene Ethyl triethoxy silicane alkane, vinyl three (2- methoxy ethoxy) silane, gamma-methyl allyl acyloxypropyl trimethoxysilane, 3- glycidoxy-propyltrimethoxy silane etc..Coupling agent dosage used is not particularly limited, generally 0.01-2wt.%.
Lubricant in the upper auxiliary agent that can be added/use can be improved the lubricity of polymer samples, reduce and rub It wipes, reduce Interface Adhesion performance comprising but be not limited only to following any or appoint several lubricants: saturated hydrocarbons and halogenated hydrocarbons Class, such as solid paraffin, microcrystalline wax, atoleine, low molecular weight polyethylene, oxidized polyethylene wax；Fatty acid, it is such as stearic Acid, hydroxy stearic acid；Fatty acid ester, such as fatty acid low-carbon-ester, polyol esters of fatty acids, native paraffin, ester type waxes and saponified wax； Aliphatic amide type, such as stearmide or stearic amide, oleamide or oleamide, erucyl amide, N, N '-ethylene is double stearic Amide；Fatty alcohol and polyalcohols, such as stearyl alcohol, cetanol, pentaerythrite；Metal soap, as lead stearate, calcium stearate, Barium stearate, magnesium stearate, zinc stearate etc.；Wherein, the preferred solid paraffin of lubricant, atoleine, stearic acid, low molecular weight Polyethylene.Lubricant quantity used is not particularly limited, generally 0.5-1wt.%.
Release agent in the upper auxiliary agent that can be added/use, can make polymer samples be easy to demould, surface is smooth, clean Only comprising but be not limited only to following any or appoint several: paraffin hydrocarbon, soaps, dimethicone, ethyl silicon oil, methylbenzene Base silicone oil, castor oil, used oil, mineral oil, molybdenum disulfide, polyethylene glycol, vinyl chloride resin, polystyrene, silicon rubber, poly- second Enol etc..Wherein, the preferred dimethicone of release agent, polyethylene glycol, release agent dosage used are not particularly limited, generally 0.5-2wt.%.
Plasticizer in the upper auxiliary agent that can be added/use, can increase the plasticity of polymer samples, so that polymerization Hardness, modulus, softening temperature and the brittle temperature decline of object, elongation, flexibility and flexibility raising comprising but not only limit In it is following any or appoint it is several: Phthalates, dibutyl phthalate, dioctyl phthalate, O-phthalic Sour di-isooctyl, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, phthalic acid Bis- (13) esters of butyl benzyl, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid, to benzene Dioctyl phthalate 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), epoxidized soybean oil.Plasticizer consumption used does not limit especially It is fixed, generally 5-50wt.%.
Thickener in the auxiliary agent that can be added/use, can assign the good thixotropy of mixed with polymers liquid and Consistency appropriate, to meet various need such as its stability and application performance in production, storage and use process It asks comprising but be not limited only to following any or appoint several thickeners: lower-molecular substance, such as fatty acid salt, fatty alcohol polyoxy Ethylene ether sulfate, alkyldimethylamine oxide, fatty monoethanol amide, fatty diglycollic amide, fatty acid isopropyl acyl Amine, anhydro sorbitol tricarboxylic ester, glycerol trioleate, coamidopropyl glycine betaine, 2- alkyl-N- carboxymethyl-N- hydroxyl second Base imidazoline, titanate coupling agent；Polymer substance, as bentonite, artificial hectorite, fine particle silica, colloidal aluminum, plant are more Carbohydrate, microbial polysaccharide class, animal protein, cellulose family, starch, seaweed acids, poly-methyl acrylate, methacrylic acid Copolymer, cis-butenedioic anhydride copolymer, crotonic acid-copolymers, polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol, polyethers, polyethylene Methyl ether urethane polymer etc.；Wherein, the preferred hydroxyethyl cellulose of thickener, coconut oil diethanol amide, acrylic acid-metering system Acid copolymer.Thickener dosage used is not particularly limited, generally 0.1-1.5wt.%.
Thixotropic agent in the auxiliary agent that can be added/use, is added in dynamic polymer systems, by hydrogen bond with polymerize Object molecule forms three-dimensional net structure, so that dynamic aggregation object viscosity is increased several times to manyfold, or even lose flowability.Including but It is not limited only to following any or appoints several: gas-phase silica, rilanit special, bentonite, silicic acid anhydride, silica derivative, urine Plain derivative etc..Thixotropic agent dosage used is not particularly limited, generally 0.5-2wt.%.
Levelling agent in the upper auxiliary agent that can be added/use can guarantee the flat and smooth uniform of polymer coating film, change Kind film coated surface quality improves dicoration comprising but be not limited only to following any or appoint several levelling agents: poly dimethyl silicon Oxygen alkane, polymethylphenylsiloxane, cellulose acetate butyrate, polyacrylate, organic siliconresin etc.；Wherein, levelling agent is excellent Select dimethyl silicone polymer, polyacrylate.Levelling agent dosage used is not particularly limited, generally 0.5-1.5wt.%.
Colorant in the upper auxiliary agent that can be added/use, can make polymeric articles show required color, Increase surface color and polish comprising but be not limited only to following any or appoint several: inorganic pigment, such as titanium white, chrome yellow, cadmium red, iron 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 is red, The bright red R of fast carmine HF3C, the plastics and not red BR of Crow, forever solid orange HL, Fast Yellow G, vapour bar plastics Huang R, permanent yellow 3G, forever Gu Huang H2G, phthalocyanine blue B, dark green, plastics purple RL, nigrosine；Organic dyestuff, as thioindigo red, vat yellow 4GF, indanthrene blue RSN, Slag rhodamine toner, Oil Yellow etc.；Wherein, the selection of colorant does not need to be particularly limited to depending on color sample demand.Institute Colorant concentrations are not particularly limited, generally 0.3-0.8wt.%.
Fluorescent whitening agent in the upper auxiliary agent that can be added/use, can make contaminated substance obtain the glittering of similar fluorite Luminous effect comprising but be not limited only to it is following any or appoint several fluorescent whitening agents: Stilbene-based, coumarin type, Pyrazoline type, benzo oxygen nitrogen type, phthalimide type etc..Wherein, the preferred stilbene biphenyl sodium disulfonate of fluorescent whitening agent (fluorescent brightener CBS), 4,4- bis- (5 methyl -2- benzoxazolyl) talan (fluorescent whitening agent KSN), 2,2- (4,4 ' - Diphenylethyllene) double benzoxazoles (fluorescent whitening agent OB -1), fluorescent whitening agent dosage used is not particularly limited, generally For 0.002-0.03wt%.
Delustering agent in the upper auxiliary agent that can be added/use, when incident light being enabled to reach polymer surfaces, occurs Diffusing reflection generates the matt and delustring appearance of low gloss comprising but be not limited only to following any or appoint several delustering agents: it is heavy Barium sulfate, silica, aqueous gypsum powder, talcum powder, titanium dioxide, poly- methyl carbamide resin etc. drop.Wherein, the preferred dioxy of delustering agent SiClx, delustering agent dosage used are not particularly limited, generally 2-5wt%.
Antistatic agent in the upper auxiliary agent that can be added/use, can prevent the static charge accumulation generated by friction.Its It includes but are not limited to following any or appoints several: conductive black, quaternary ammonium salt (such as N- alkyl dimethyl ethamine ethyl-sulfate Salt, (3- dodecanamide propyl) Trimethylamine Methylsulfate salt) or be the hydrophilic of polyethylene glycol, epoxyethane derivative etc. Property compound.Antistatic agent dosage used is not particularly limited, generally 0.01-2wt.%.
Biocide mildewcide in the auxiliary agent that can be added/use, can inhibit the growth of mould, keep product clean and tidy Appearance prolongs the service life.It includes but are not limited to following any or appoints several: isothiazolinone derivatives, such as 5- are chloro- 2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, N- normal-butyl -1,2- benzisothiazole -3- Ketone, octylisothiazolinone；The chloro- 2- hydroxyl-diphenyl ethers of 2,4,4- tri-；2- (4- thiazolyl) benzimidazole；8-hydroxyquinoline Copper or bis- (8-hydroxyquinoline base) copper；Organo-tin compound such as tributyl-tin fumarate, tributyltin acetate, bis- (tributyl tins) Sulfide, bis- (tributyl tin) tin oxide；N, N- dimethyl-N '-phenyl (fluorine dichloromethyl is thio) sulfonamide.Sterilization used Mould inhibitor dosage is not particularly limited, generally 0.5-2wt.%.
Foaming agent in the upper auxiliary agent that can be added/use can make polymer samples foaming pore-forming, to obtain matter Gently, polymer material heat-insulated, with certain elasticity comprising but be not limited only to following any or appoint several foaming agents: object Get a haircut infusion, as propane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, Butane, ether, chloromethanes, methylene chloride, dichloroethylene, dicholorodifluoromethane, trifluorochloromethane；Inorganic foaming agent, such as carbonic acid Hydrogen sodium, ammonium carbonate, ammonium hydrogen carbonate；Organic foaming agent, such as N, five methine tetramine of N '-dinitro, N, N '-dimethyl-N, N '- Dinitrosoterephthalamine, azodicarbonamide, barium azo-biscarbonate, two diisopropyl carbonate of azo, azodicarbonamide Potassium formate, azodiisobutyronitrile, 4,4 '-oxobenzenesulfonyl hydrazide, benzene sulfonyl hydrazide, trihydrazinotriazine, p-toluene sulfonylsemicarbazide, Biphenyl -4,4 '-disulfonyl nitrine；Foamed promoter, such as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, two Alkali lead phosphite, lead stearate, cadmium stearate, zinc stearate, zinc oxide；Frothing inhibitor, such as maleic acid, fumaric acid, hard Acyl chlorine, phthalyl chloride, maleic anhydride, phthalate anhydride, hydroquinone, naphthalenediol, aliphatic amine, amide, oxime, isocyanic acid Ester, mercaptan, thiophenol, thiocarbamide, sulfide, sulfone, cyclohexanone, acetylacetone,2,4-pentanedione, hexacholorocyclopentadiene, dibutyl maleic acid tin etc..Its In, the preferred sodium bicarbonate of foaming agent, ammonium carbonate, azodicarbonamide (blowing agent AC), N, five methine tetramine of N '-dinitro (blowing agent H), N, N '-dimethyl-N, N '-dinitrosoterephthalamine (foaming agent NTA), physical microballoon foaming agent, Foaming agent consumption used is not particularly limited, generally 0.1-30wt%.
Nucleating agent in the upper auxiliary agent that can be added/use can accelerate knot by the crystallization behavior of change polymer Brilliant rate increases crystal density and promotes fine grain size, reach shorten material molding cycle, improve product the transparency, The purpose of the physical mechanical properties such as lustrous surface, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance, packet It includes but is not limited only to following any or appoints several nucleating agents: benzoic acid, adipic acid, sodium benzoate, talcum powder, p-phenolsulfonic acid Sodium, silica, benzylidene sorbitol and its derivative, EP rubbers, ethylene propylene diene rubber etc..Wherein, nucleating agent is preferred Silica, benzylidene sorbitol (DBS), ethylene propylene diene rubber, nucleating agent dosage used are not particularly limited, generally 0.1-1wt%.
It is good can to guarantee that polymer has during film for rheological agent in the upper auxiliary agent that can be added/use Brushability and coating thickness appropriate, prevent storage when solid particle sedimentation, can be improved its redispersibility comprising but It is not limited only to following any or appoints several rheological agents: inorganic, such as barium sulfate, zinc oxide, alkaline earth oxide, carbonic acid Calcium, lithium chloride, sodium sulphate, magnesium silicate, fumed silica, waterglass, colloidal silicon dioxide；Organo-metallic compound is such as hard Resin acid aluminium, aluminium alkoxide, titanium chelate, aluminium chelate compound；Organic, as organobentonite, castor oil derivative, cellulose are derivative Object, isocyanate derivates, acrylic emulsion, acrylic copolymer, polyvinyl alcohol, polyethylene wax, cellulose esters etc..Wherein, It is preferred that organobentonite, polyethylene wax, hydrophobically modified alkalinity swellable emulsions (HASE), alkali-swellable emulsions (ASE), used Rheological agent dosage be not particularly limited, generally 0.1-1wt%.
A kind of preparation method of dynamic aggregation object ionic liquid gel of the invention, includes the following steps: that hydridization will be prepared The raw material of the dynamic aggregation object of cross-linked network is added in ionic liquid, makes the dynamic aggregation object of prepared hybrid cross-linked network Mass fraction be 0.3~75%, by the appropriate means carry out covalent cross-linking a kind of dynamic is made after reaction Polymer ions liquid gel.The preparation method of another dynamic aggregation object ionic liquid gel of the invention, including walk as follows It is rapid: the dynamic aggregation object with hybrid cross-linked network structure being swollen in the solvent containing ionic liquid, prepared hydridization is made The mass fraction of the dynamic aggregation object of cross-linked network is 0.3~75%, sufficiently removes solvent after swelling, that is, a kind of dynamic aggregation is made Object ionic liquid gel.The upper ionic liquid is generally made of organic cation and inorganic anion, as an example, cation Selected from include but are not limited to alkyl quaternary ammonium ion, alkyl quaternary see imidazol ion that ion, 1,3- dialkyl group replace, N- alkyl takes The pyridinium ion etc. in generation；Anion be selected from include but are not limited to for halide ion, tetrafluoroborate ion, hexafluoro-phosphate radical from Son also has CF3SO3 -、 (CF3SO2)2N-、C3F7COO-、C4F9SO3 -、CF3COO-、(CF3SO2)3C-、(C2F5SO2)3C-、 (C2F5SO2)2N-、 SbF6 -、AsF6 -Deng.In ionic liquid used in the present invention, the preferred glyoxaline cation of cation, anion It is preferred that hexafluorophosphoricacid acid ions and tetrafluoroborate ion.Prepare the preferably self-contained esters of acrylic acid of polymer precursor of ionic liquid Polymer, the fluorine of monomer replace saturation of olefins, the polymer containing acrylonitrile.
A kind of gel process for preparing of dynamic aggregation object oligomer swelling of the invention, includes the following steps: to have miscellaneous The raw material for changing the dynamic aggregation object of cross-linked network structure is added in oligomer, keeps the dynamic of prepared hybrid cross-linked network poly- The mass fraction for closing object is 0.3~75%, carries out covalent cross-linking by the appropriate means and one kind is made after reaction The gel of dynamic aggregation object oligomer swelling.The gel process for preparing of another dynamic aggregation object oligomer swelling of the invention, Include the following steps: that will there is the dynamic aggregation object of hybrid cross-linked network structure to swell in the solvent containing oligomer, makes institute The mass fraction of the dynamic aggregation object of the hybrid cross-linked network of preparation is 0.3~75%, sufficiently removes solvent after swelling, that is, is made one The gel of kind dynamic aggregation object oligomer swelling.The upper oligomer includes but are not limited to polyethylene glycol oligomer, polyethylene Alcohol oligomer, polyvinyl acetate ester oligomer, polyacrylic acid N-butyl oligomer, atoleine etc..
A kind of gel process for preparing of dynamic aggregation object plasticising solvent swell of the invention, includes the following steps: to have miscellaneous The raw material for changing the dynamic aggregation object of cross-linked network structure is added in plasticizer, keeps the dynamic of prepared hybrid cross-linked network poly- The mass fraction for closing object is 0.3~75%, carries out covalent cross-linking by the appropriate means and one kind is made after reaction The gel of dynamic aggregation object plasticising solvent swell.The gel process for preparing of another dynamic aggregation object plasticising solvent swell of the invention, Include the following steps: that will there is the dynamic aggregation object of hybrid cross-linked network structure to swell in the solvent containing plasticizer, makes institute The mass fraction of the dynamic aggregation object of the hybrid cross-linked network of preparation is 0.3~75%, sufficiently removes solvent after swelling, that is, is made one The gel of kind dynamic aggregation object plasticising solvent swell.Upper the plasticizer, which is selected from, to be included but are not limited to following any or appoints several Kind: Phthalates: dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, O-phthalic Sour two heptyl esters, diisooctyl phthalate, diisononyl phthalate, BBP(Butyl Benzyl Phthalate, phthalic acid fourth Bis- (13) esters of ester butyl glycolate, dicyclohexyl phthalate, phthalic acid, terephthalic acid (TPA) two (2- ethyl) oneself Ester；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyl) own ester；Fatty acid ester, such as (the 2- second of adipic acid two Base) own ester, decanedioic acid two (2- ethyl) own ester；Epoxy compound species, such as epoxy glycerite esters, epoxy fatty acid monoester class, ring Oxygen tetrahydrophthalic acid esters, epoxidized soybean oil, the own ester of epoxystearic acid (2- ethyl), epoxy soybean oleic acid 2- ethyl hexyl Ester, the own ester of 4,5- epoxy tetrahydrophthalic acid two (2- ethyl), Chinese littleleaf box methyl acetylricinolate, dihydric alcohol lipid, such as C5~9 Sour glycol ester, C5~9Sour Triethylene Glycol；Class containing chlorine such as afforests paraffin class, chloro fat acid esters；Polyesters, such as second Diacid 1,2- propylene glycol system polyester, decanedioic acid 1,2- propanediol polyester；Phenyl alkylsulfonate, trimellitate, citrate, season Penta 4 pure and mild pentaerythritol fatty acid esters etc..Wherein, epoxidised soybean oil is a kind of Environment-friendlyplastic plastic plasticizer of function admirable, through essence It refines soybean oil and epoxidation reaction preparation occurs for peroxide.It is resistance in polrvinyl chloride product to volatilize, is not easy to migrate, not fugitive It loses.This is to keeping product light, thermal stability and to prolong the service life be highly beneficial.Epoxidised soybean oil toxicity is minimum, It is allowed for the packaging material of food and medicine by many countries, is that the unique of Food and Drug Adminstration of the US's approval can be used for eating The epoxy plasticiser of product packaging material.In a kind of gel preparation of dynamic aggregation object plasticising solvent swell of the invention, plasticising The preferred epoxidized soybean oil of agent.Preparation plasticising solvent swell gel polymer precursor preferably be selected from vinyl-chloride-containing monomer polymer, The polymer of polymer containing norbornene monomer, the monomer containing saturation of olefins.
A kind of preparation method of dynamic aggregation object foam of the invention includes the following steps: in preparation single network dynamic When foam of polymers, reaction mass A and reaction mass B is first independently made；Reaction mass A is by side group hydrogen bonds group The friendship of 8 parts~20 parts of polyol compound, 0.05 part~1.0 parts of chain extender, the covalent bond of dynamic containing Reversible Addition Fragmentation Chain Transfer Connection 0.05 part~1.0 parts of agent, 0.01-0.5 parts of organometallic catalysts, 0.01-0.5 parts of amines catalyst, in material temperature 5-35 DEG C, stir evenly under conditions of mixing speed 50-200r/min it is obtained；Reaction mass B is by 10 parts of polyisocyanate compound ~20 parts, 0.5 part~3.5 parts of foaming agent, 0.05 part~0.2 part of foam stabiliser, in 5-35 DEG C of mixing speed 50- of material temperature It is stirred evenly under conditions of 200r/min obtained；Then by reaction mass A and reaction mass B according to 1.0~1.5:1 mass ratio Mixing, the single network dynamic aggregation object of foaming is quickly stirred to get through professional equipment.Finally, the single network after foaming is moved State polymer is added in mold, solidifies 30min~60min at room temperature, is then solidified at high temperature to get to based on single The dynamic aggregation object foamed material of network.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 solidification 4h, or temperature be 120 DEG C of solidification 2h.Hydroxyl (OH) group and polyisocyanic acid in above-mentioned polyol compound are esterified The molar ratio for closing isocyanates (NCO) group in object may make final polyurethane foam without free-end NCO group. The molar ratio of NCO/OH preferably is selected from 0.9/1 to 1.2/1.The molar ratio that NCO/OH is 1/1 is corresponding to isocyanate index 100.In the case where water is used as foaming agent, the isocyanate index is preferably greater than 100, and such isocyanate groups can be with Water reaction.
In dynamic aggregation object foam preparation processes of the invention, in the dynamic aggregation object bubble for preparing binary hybrid cross-linked network When foam, the step of according to above-mentioned preparation single network dynamic aggregation object, the 1st network is first prepared；Then the 2nd network development process is being prepared In, the 1st network is added in reaction mass A (or reaction mass B), i.e., reaction mass A at this time is side group hydrogen bonds group The crosslinking of 8 parts~20 parts of polyol compound, 0.05 part~1 part of chain extender, the covalent bond of dynamic containing Reversible Addition Fragmentation Chain Transfer 0.05 part~0.4 part of agent, 0.01~0.5 part of organometallic catalysts, 0.01~0.5 part of amines catalyst, the 1st network polymerization It 0.1 part~15 parts of object, is stirred evenly under conditions of 5-35 DEG C of mixing speed 50-200r/min of material temperature obtained；Reaction mass B For 10 parts~20 parts of polyisocyanate compound, 2 parts~3.5 parts of foaming agent, 0.05 part~0.2 part of foam stabiliser, in material temperature It is stirred evenly under conditions of 5-50 DEG C of mixing speed 50-200r/min obtained.Or first network is added in reaction mass B, other The same above process.Then reaction mass A is mixed with reaction mass B according to 1.0~1.5:1 mass ratio, it is quick through professional equipment Stir to get the dynamic aggregation object of the hybrid cross-linked network of foaming.Finally, by the dynamic aggregation of the hybrid cross-linked network after foaming Object is added in mold, solidifies 30min~60min at room temperature, is then solidified at high temperature to get to based on hybrid cross-linked net The dynamic aggregation object foamed material of network.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 Solidify 4h, or temperature be 120 DEG C of solidification 2h.And so on, in the dynamic aggregation object foam of preparation ternary hybrid cross-linked network When, the 1st network and the 2nd network are first prepared, then when preparing 3 network, the 1st network is added and the 2nd network is sufficiently mixed progress Foaming.
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 such as 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.
A kind of dynamic aggregation physical performance with hybrid cross-linked network structure provided by the present invention is adjustable on a large scale, can answer It for every field, has broad application prospects, is especially embodied in military aerospace equipment, functional paint and coating, biology doctor The fields such as medicine, bio-medical material, the energy, building, bionical will have the application effect to attract people's attention.For example, anti-by polymerization Chain tra nsfer during answering reduces reaction rate, so that reaction more stably occurs, reduces internal stress and reduces material internal defect To obtain the material of superelevation mechanical performance；For example, being designed by suitable component selection and formula, can prepare with good Good self-repairability and recuperable polymer closure glue；For example, self-repair function is introduced polymer material, so that material Inside can independently repair after generating damage, help to obtain that the service life is longer, more reliable performance and more economical structural wood Material；For example, the sealing material with self-repairability can be prepared into, for the sealing and waterproof of electronic apparatus, as earphone stopple, Charge stopple etc..Such as in microelectronics polymer device and adhesive in use, since the microcrack that heat and mechanics fatigue generate is led The problem of performance forfeiture of cause is long-term existence, introduces these materials for self-repair function, can greatly improve microelectronic product Reliability and service life.As sealing elements such as the plug of self-repairability and sealing rings, in electronic apparatus, food, drug etc. Field is widely used, such as charger interface, data line interface as mobile phone, tablet computer, notebook, camera etc. etc. The plug at place, the aperture generated in connector swapping process carry out repairing reach the purpose of waterproof.As self-repair material Additionally aid to obtain the material with bionical effect, also have wide practical use in biologic medical field, it is available more resistant to Long human synovial.The material of exploitation specific use is also contributed to as self-repair material, can such as be restored under certain condition The material of interface performance, conduction and the performances such as thermally conductive, such as play and subtract as battery/electrode of super capacitor binder, diaphragm The breakage of few electrode, the effect for increasing the electrode material service life.In addition, the dynamic of supermolecule hydrogen bond, can further enhance poly- The toughness for closing object, can be prepared into as the splendid film of performance, fiber or plate, can be widely applied to military affairs, space flight, The fields such as movement, the energy, building.In addition, the self-repairability polymer of shape memory can be prepared using its dynamic reversibility Material prepares the toy with visco-elastic magic conversion effect.
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
Suitable 3,3 '-dipropionic acid trithiocarbonates and triphenyl phosphorus are first added into reactor, under anaerobic The anhydrous tetrahydrofuran solution of hydroxy-ethyl acrylate is added, the toluene solution of azo-dicarboxylate is then added dropwise, controls The molar ratio of 3,3 '-dipropionic acid trithiocarbonates and hydroxy-ethyl acrylate is 1:2, and whole process controls reaction temperature 10 DEG C, reaction terminates after being added dropwise to complete, and obtains the bifunctional vinyl compound containing three thioester substrates.
The n-isopropyl acrylamide that molar ratio is 15:1 is added in the reactor and contains three thioester substrates with obtained above Bifunctional vinyl compound, using methyl phenyl ethers anisole as solvent, two isobutyl of azo fine (AIBN) is initiator, under anaerobic, anti-in 65 DEG C 12h is answered, the polymer fluid with certain viscosity is obtained；Then the polymeric liquid for taking 100 mass parts, is swollen in 75 In the epoxidized soybean oil of mass parts and the tricresyl phosphate mixed liquor of 75 mass parts, it is molten that removing residual solvent obtains plasticizer Swollen polymer gel.
The material has light stimulus responsiveness, has certain self-repairability and plasticity under the action of light.Polymer Sample also shows certain shape memory, can be used for intelligent bionic gel.
Embodiment 2
Using methanol as solvent, sodium methoxide is catalyst, by mercaptoethanol and the chloro- 2- chloromethyl -1- propylene of 3- with molar ratio For the mixing of 2:1 ratio, 16h is reacted in a heated condition, obtains the dihydric alcohol containing allyl sulfide ether；It is molten with tetrahydrofuran Agent, triethylamine are catalyst, and the dihydric alcohol containing allyl sulfide ether is reacted with acryloyl chloride, control reaction temperature 0~ 25 DEG C, synthesize the bifunctional vinyl compound containing allyl sulfide ether.
Under anaerobic, using 1- hydroxycyclohexylphenylketone as photoinitiator, toluene is solvent, under UV light action, It with the ratio of the amount of substance is that 200:16 is crosslinked by acrylamide and the bifunctional vinyl compound obtained above containing allyl sulfide ether Copolymerization becomes the hybrid cross-linked dynamic aggregation object organogel with first network.
The material has light stimulus responsiveness, has certain self-repairability and plasticity under the action of light, can be by it It is used for the thin-film material with self-healing properties.
Embodiment 3
Using methanol as solvent, sodium methoxide is catalyst, by sulfydryl Pyrogentisinic Acid and the chloro- 2- chloromethyl -1- propylene of 3- with mole Than being mixed for 2:1 ratio, 16h is reacted in a heated condition, obtains the dihydric alcohol containing allyl sulfide ether；With tetrahydrofuran For solvent, triethylamine is catalyst, and the dihydric alcohol containing allyl sulfide ether is reacted with acryloyl chloride, and control reaction temperature exists 0~25 DEG C, synthesize the bifunctional vinyl compound containing allyl sulfide ether.
Under anaerobic, using 1- hydroxycyclohexylphenylketone as photoinitiator, toluene is solvent, under UV light action, By styrene, N- methyl -2- acrylamide, the bifunctional vinyl compound obtained above containing allyl sulfide ether with the amount of substance Than mixing for 100:20:15, polystyrene-based blocky dynamic aggregation object is obtained by free-radical polymerized.It is with superelevation Mechanical performance, while also there is light stimulus responsiveness, there is certain self-repairability under the action of light.Utilize the polymeric material High-intensitive, lightweight performance possessed by material can use the material as the sheathing material with certain self-healing properties, such as Casing of domestic electrical equipment, telephone outer shell, instrument and meter etc..
Embodiment 4
The present embodiment prepares a kind of polyurethane foamed material, and specific step is as follows:
Using methanol as solvent, sodium methoxide is catalyst, is by mercaptoethanol and the chloro- 2- chloromethyl -1- propylene molar ratio of 3- The mixing of 2:1 ratio reacts 16h in a heated condition and 2,2 '-[(2- methylene -1,3- propane diyl) two (sulphur)] diethyls is made Alcohol.
35.2g2,2 '-[(2- methylene -1,3- propane diyl) two (sulphur)] two are added into BUSS formula outer circulation reactor Ethyl alcohol, catalyst KOH 2.25g are separately added into ethylene oxide 220g, (S)-(oxiranylmethyl) ammonia after being heated to 120 DEG C Base t-butyl formate 172g is reacted, controlled at 140~150 DEG C.Under constant temperature conditions, slaking reaction 40 is carried out to divide Clock starts when reactor pressure no longer declines as reactor content cooling.It is added when temperature is reduced to 72 DEG C in acetic acid progress And reaction obtains that a kind of main chain contains allyl sulfide ether, side group contains carbamate groups until the pH of reaction system is 6.8 Polyether Glycols compound.
Reaction mass A is weighed by weight: the polyethers two that main chain contains allyl sulfide ether, side group contains carbamate groups 10 parts of first alcoholic compound, 0.4 part of 1,4- chain expansion of succinic acid agent, 0.4 part of triethanolamine crosslinking agent, organometallic catalysts February 0.1 part of dilaurylate, 0.15 part of Triethylamine catalyst, are added in No. 1 mold, in 30 DEG C of material temperature, mixing speed 180r/ It is stirred evenly under conditions of min obtained；Reaction mass B: 10 parts of hexamethylene diisocyanate (HDI), 2.2 parts of foaming agent, bubble 0.1 part of foam stabilizers, 0.2 part of benzoin ethyl ether photoinitiator (BEE), are added in No. 2 molds, in 30 DEG C of mixing speeds of material temperature It is stirred evenly under conditions of 180r/min；Then reaction mass A is mixed with reaction mass B according to 1.2:1 mass ratio, through profession Equipment is quickly stirred to bubble is generated, and stands 72h, the dynamic aggregation object of the hybrid cross-linked network after being foamed.After foaming The dynamic aggregation object of hybrid cross-linked network be added in No. 3 molds, solidify 30min at room temperature, then solidify at 120 DEG C 2h to get arrive a kind of flexibel polyurethane base foamed material.
Mechanics Performance Testing: tensile strength (MPa): 3.6；Elongation (%): 680；
The material has excellent flexibility and wearability, can be used in preparing automotive interior material.The material also has Light stimulus responsiveness has certain self-repairability under the action of light.
Embodiment 5
The present embodiment is prepared into ionic liquid gel, and specific step is as follows:
By Isosorbide-5-Nitrae-pentadiene -3- alcohol 84g and methyl isocyanate 57g, using 2g triethylamine as catalyst, in 250ml bis- It is reacted in chloromethanes, the bifunctional vinyl compound that side group has carbamate groups is made.
By the two -2- propylene base ester of trithiocarbonic acid and diallyl sulfone relative to 15~25wt% of ionic liquid, it is added To 1- butyl -3- methylimidazole hexafluorophosphate ([C4MIM]PF6) in ionic liquid, add relative to monomer 0.1~ (3- mercaptopropionic acid) ester of crosslinking agent pentaerythrite four of 20wt% and a small amount of BHT antioxidant and relative to monomer 0.05~ The photoinitiator benzoin dimethylether (DMPA) of 0.55wt% pours into the glass plate for accompanying silica gel pad after stirring is sufficiently mixed In mold 1, ultraviolet radioactive 4 hours in UV crosslinking instrument are placed on, the 1st network polymer can be obtained.
Again carbamic acid will be had relative to the 1,4- succinimide mercaptans of 15~25wt% of ionic liquid, side group obtained above The bifunctional vinyl compound of ester group and a small amount of BHT antioxidant and relative to the 1st network polymer of 25~50wt% of ionic liquid, are added To 1- butyl -3- methylimidazole hexafluorophosphate ([C4MIM]PF6) in ionic liquid, add relative to monomer 0.05~ The photoinitiator benzoin dimethylether (DMPA) of 0.55wt% pours into the glass plate for accompanying silica gel pad after stirring is sufficiently mixed In mold 2, ultraviolet radioactive in UV crosslinking instrument is placed on 10 hours to get a kind of ion of the adjustable binary interpenetrating networks of performance is arrived Liquid dynamic aggregation object gel.
For the modulus of the ionic liquid gel of example preparation in 15-30kPa, elongation at break can achieve 6-10 times, break Stress is split in 30-75kPa.The material has light stimulus responsiveness, has certain self-repairability and plasticity under the action of light.
Embodiment 6
It is as follows that the present embodiment is prepared into foamed material method:
Suitable 3,3 '-dipropionic acid trithiocarbonates and triphenyl phosphorus are first added into reactor, under anaerobic The anhydrous tetrahydrofuran solution of propenyl is added, the toluene solution of azo-dicarboxylate, control 3,3 '-two is then added dropwise The molar ratio of propionic acid trithiocarbonate and propenyl is 1:2, and whole process controls reaction temperature at 10 DEG C, after being added dropwise to complete instead It should terminate, obtain the bifunctional vinyl compound containing three thioester substrates.
2- isocyanate group -2- methylpropane and 2- methyl -3- butine-diamines are reacted according to molar ratio for 1:1, N- is made (1,1- dimethyl ethyl)-N '-(1,1- dimethyl -2- propine -1- base) urea.
By N- (1,1- dimethyl ethyl)-N '-(1,1- dimethyl -2- propine -1- base) urea, 11 moles of 10 molar equivalents The 4 of equivalent, 4 '-dimercapto diphenyl sulfides, a small amount of BHT antioxidant, suitable benzoin dimethylether (DMPA), stirring are abundant It after mixing, pours into the glass board mould 1 for accompanying silica gel pad, is placed on ultraviolet radioactive 4h in UV crosslinking instrument, obtains the 2nd network Polymer.
By the 1,6- ethanthiol of 20 molar equivalents, the diene obtained above containing three thioester substrates of 14 molar equivalents Close object, the iso-cyanuric acid triallyl ester of 4 molar equivalents, a small amount of BHT antioxidant, suitable expandable polymer microballoon And the 2nd network polymer of gross mass 45%, suitable benzoin dimethylether (DMPA) are accounted for, after stirring is sufficiently mixed, pour into folder Have in the glass board mould 2 of silica gel pad, is placed in UV crosslinking instrument ultraviolet radioactive 10h to get to a kind of binary interpenetrating networks Composite foam material.
The material can be used for heat preserving and insulating material etc., which also has light stimulus responsiveness, have under the action of light Certain self-repairability.
Embodiment 7
Being prepared into ionic liquid gel, specific step is as follows:
By the two -2- propylene base ester of trithiocarbonic acid and 3- sulfydryl -2- (sulfydryl first relative to 15~25wt% of ionic liquid Base)-N- methyl propanamide, a small amount of BHT antioxidant, it is added to 1- butyl -3- methylimidazole hexafluorophosphate ([C4MIM] PF6) in ionic liquid, add relative to 0.1~20wt% of monomer (3- mercaptopropionic acid) ester of crosslinking agent pentaerythrite four and It pours into and accompanies after stirring is sufficiently mixed relative to the photoinitiator benzoin dimethylether (DMPA) of 0.05~0.55wt% of monomer In the glass board mould 1 of silica gel pad, ultraviolet radioactive 4 hours in UV crosslinking instrument are placed on, the polymerization of the 2nd network dynamic can be obtained Object.
It again will be relative to the trithiocarbonic acid two of 15~25wt% of ionic liquid (2- methyl -2- acrylic) ester, diene Propylbenzene and relative to the 2nd network polymer of 25~50wt% of ionic liquid and a small amount of BHT antioxidant, is added to 1- butyl- 3- methylimidazole hexafluorophosphate ([C4MIM]PF6) in ionic liquid, add the crosslinking agent relative to 0.1~20wt% of monomer (3- mercaptopropionic acid) ester of pentaerythrite four and the photoinitiator benzoin dimethylether relative to 0.05~0.55wt% of monomer (DMPA), it after stirring is sufficiently mixed, pours into the glass board mould 2 for accompanying silica gel pad, is placed on ultraviolet spoke in UV crosslinking instrument 8 hours are penetrated to get the ionic liquid dynamic aggregation object gel for arriving a kind of adjustable binary interpenetrating networks of performance.
The modulus of the ionic liquid gel of example preparation is in 16kPa, and elongation at break can achieve 8 times, fracture strength In 40kPa.In the present embodiment, polymer battery can be applied to using dynamic aggregation object gel obtained as polymer dielectric Material, while there is certain self-repairability under the action of light.
Embodiment 8
The present embodiment it is specific the preparation method is as follows:
Using methanol as solvent, sodium methoxide is catalyst, by dithioglycol and the chloro- 2- chloromethyl -1- propylene of 3- with molar ratio For the mixing of 2:1 ratio, 16h is reacted in a heated condition, obtains 2,2 '-[(2- methylene -1,3- propane diyl) two (sulphur)] two Ethyl mercaptan.
By the Isosorbide-5-Nitrae of 1 molar equivalent-pentadiene -3- amine and 1 molar equivalent ethyl isocyanate, using triethylamine as urging Agent, methylene chloride are solvent, react and N- ethyl-N '-(1,3-pentadiene base) urea is made.
By N- ethyl-N '-(1,3- pentadienyl) urea of 15 molar equivalents, the ethanthiol, a small amount of of 14 molar equivalents BHT antioxidant, suitable benzoin dimethylether (DMPA) pour into the glass template die for accompanying silica gel pad after stirring is sufficiently mixed In tool 1, it is placed on ultraviolet radioactive 4h in UV crosslinking instrument, obtains the 2nd network polymer.
By 2,2 '-[(2- methylene -1,3- propane diyl) two (sulphur)] diethyl mercaptan, 18 molar equivalents of 15 molar equivalents Diallyl adipate, the trithiocyanuric acids of 2 molar equivalents, a small amount of BHT antioxidant and 35% total mass fraction the 2nd net Network polymer, suitable benzoin dimethylether (DMPA) pour into the glass board mould for accompanying silica gel pad after stirring is sufficiently mixed In 2, ultraviolet radioactive 10h is placed in UV crosslinking instrument to get to a kind of binary interpenetrating networks dynamic aggregation object material.
Resulting polymers tensile strength is 5.8MPa, elongation at break 244%.In addition, product obtained also have it is good Good plasticity, can be placed in mold of different shapes, and apply a level pressure under the conditions of certain temperature according to actual needs Power can be shaped to polymeric articles of different shapes according to mold, can be used for preparing mobile phone protecting case material.
Embodiment 9
The present embodiment it is specific the preparation method is as follows:
It is in molar ratio 1:1 reaction synthesis N- by 1,3-pentadiene based isocyanate and propyl alcohol using triethylamine as catalyst 1,3- pentadienyl carbamic acid propyl ester.
By the N-1,3- pentadienyl carbamic acid propyl ester of 10 molar equivalents, the ethanthiol, a small amount of of 11 molar equivalents BHT antioxidant, suitable benzoin dimethylether (DMPA) pour into the glass template die for accompanying silica gel pad after stirring is sufficiently mixed In tool 1, it is placed on ultraviolet radioactive 4h in UV crosslinking instrument, obtains the 2nd network polymer.
By the N-1,3- pentadienyl carbamic acid propyl ester of 12 molar equivalents, the two (2- of trithiocarbonic acid of 20 molar equivalents Cyclobutenyl) ester, 15 molar equivalents pentaerythrite four (3- mercaptopropionic acid) ester, a small amount of BHT antioxidant and 40% mass fraction The 2nd network polymer, 0.5 part of benzoin dimethylether (DMPA), stirring be sufficiently mixed after, pour into the glass for accompanying silica gel pad In board mold 2, ultraviolet radioactive 10h is placed in UV crosslinking instrument to get to a kind of binary interpenetrating networks dynamic aggregation object material.
Resulting polymers can be used as anti-tear adhesive, block glue, have certain self-repairability under the action of light.
Embodiment 10
The present embodiment it is specific the preparation method is as follows:
Cyclohexyl -1,4- the dimethanol monovinyl ether of 6 molar equivalents is added in the round-bottomed flask of dried and clean, 6 rubs Two -2- propylene the base ester of trithiocarbonic acid of your equivalent leads to nitrogen protection, be added 60mL dichloromethane solvent be stirred it is molten Solution, adds a small amount of photoinitiator DMPA and a small amount of antioxidant BHT, stirs evenly；In addition the 3- of 9 molar equivalents is taken respectively Thio (2- the sulfydryl) -1- propane mercaptan of 2, the 3- bis- of sulfydryl -2- (mercapto methyl)-N- methyl propanamide and 2 molar equivalents, point It is not dissolved in after 20 mL dichloromethane solvents are configured to solution, round-bottomed flask is injected separately by injection under stirring In, with ultraviolet light 1h, obtain the 1st network dynamic polymer.
The round-bottomed flask of a dried and clean is taken again, and the bisphenol a diallyl ether of 10 molar equivalents is added and accounts for gross mass 1st network dynamic polymer of number 45% leads to nitrogen protection, and the dichloromethane solvent that 50mL is added is stirred dissolution, then A small amount of photoinitiator DMPA and a small amount of antioxidant BHT is added, stirs evenly；In addition the 3- sulfydryl -2- of 9 molar equivalents is taken (mercapto methyl)-N- methyl propanamide is dissolved in after 20mL dichloromethane solvent is configured to solution, passes through note under stirring It penetrates in agent injection round-bottomed flask, with ultraviolet light 1h, obtains hybrid cross-linked network dynamic polymer.
The coating material that the dynamic aggregation object can be used for having self-repair function can be repaired tiny under the action of light Crackle.
Embodiment 11
It is as follows that present embodiment prepares a kind of epoxy resin method:
Using anhydrous tetrahydro furan as solvent, sodium hydride is catalyst, epoxychloropropane and 3- sulfydryl -2- thiopurine methyltransferase -1- third Alkene is 2:1 mixing with molar ratio, and reaction obtains 2,2 '-[(2- methylene -1,3- propyls) two (sulphur methylene)] at normal temperature Diepoxide for example.
2,2 '-[(2- methylene -1,3- propyl) two (sulphur methylene)] diepoxide for example of 10 molar equivalents, 10 are rubbed Two (2,3- glycidyl) terephthalates, 3- sulfydryl -2- (mercapto methyl)-N- methyl-prop of 17 molar equivalents of your equivalent Amide dissolves in methylene chloride, and epoxy terminated prepolymer is generated as catalyst reaction using potassium hydroxide；Then 2 moles are added The Toluene-2,4-diisocyanate of equivalent, 4,6- triamines, stirring react 1h under room temperature after being sufficiently mixed, obtain the 1st network dynamic polymer.
First by 2,2 '-[(2- methylene -1,3- propyl) two (sulphur methylene)] diepoxide for example of 10 molar equivalents with (2- the ethoxy)-N '-of the N of 8.5 molar equivalents, N- bis- propyl-urine dissolves in methylene chloride, using potassium hydroxide as catalyst, Heating reaction obtains epoxy terminated prepolymer, and the crosslinking agent Isosorbide-5-Nitrae of 1 molar equivalent, 7- azophenlyene triamine, suitable light is then added The 1st network dynamic polymer of initiator DMPA and 55% total mass fraction are heating and curing after stirring is sufficiently mixed to obtain the final product To a kind of binary interpenetrating networks epoxy resin.
Mechanics Performance Testing: tensile strength (MPa): 30.5；Elongation (%): 115；
The material has good mechanical properties and wear-resisting, can be used for auto parts, noise reduction gear, chemical industry equipment pipeline valve Corrosion-proof wear-resistant material etc. in part.The material also has light stimulus responsiveness, has certain self-repairability under the action of light.
Embodiment 12
Specific step is as follows for the present embodiment:
The potassium carbonate of the carbon diselenide of 3 molar equivalents, the benzyl chloride of 4 molar equivalents, 5 molar equivalents is dissolved at normal temperature In suitable DMSO/H2O (volume ratio 4/1) in the mixed solvent, after be stirred to react 30min in 0 DEG C under nitrogen protection.Reaction After the completion, through ether extraction, washing, organic phase is dry with anhydrous sodium sulfate, filtering, after in vacuum drying, then with n-hexane Column is crossed for eluent, finally obtains product selenium, three seleno carbonic ester of selenium '-dibenzyl.
Under anaerobic, using anhydrous tetrahydro furan as solvent, AIBN is initiator, and it is 100:16:5's that molar ratio, which is added, N-isopropylacrylamide, diallyl azelate and selenium, three seleno carbonic ester of selenium '-dibenzyl, reaction 12h is obtained at 65 DEG C 1st network dynamic polymer.
120mL THF solvent is added in the flask of dried and clean, leads to nitrogen and removes water deoxygenation 1h, be then added 12 moles and work as Two -2- propylene the base ester of trithiocarbonic acid of amount, 3- sulfydryl -2- (mercapto methyl)-N- methyl propanamide of 6 molar equivalents, 9 moles It is molten to be heated to 60 DEG C of stirrings for two (2- mercaptoethyl) succinates of equivalent, the 1st network dynamic polymer of 30% mass fraction Xie Hou, adds a small amount of BHT antioxidant, the triallyl phosphite of 2 molar equivalents, suitable AIBN, suitable triethylamine, 4h is reacted under the conditions of nitrogen protection；After the reaction was completed, reaction solution filter and obtains head product except solvent, using n-hexane/ Methylene chloride (2:1) elutes decontamination, then obtains the dynamic aggregation object with larger viscosity after dry 12h under the conditions of 60 DEG C Sample, can be as a kind of thermoplastic adhesive for rubber, the bonding of plastic or other material.
Embodiment 13
Specific step is as follows for the present embodiment:
Using methanol as solvent, sodium methoxide is catalyst, is by mercaptoethanol and the chloro- 2- chloromethyl -1- propylene molar ratio of 3- The mixing of 2:1 ratio reacts 16h in a heated condition and 2,2 '-[(2- methylene -1,3- propane diyl) two (sulphur)] diethyls is made Alcohol.
The hydroxypropyl terminated dimethyl silicone polymer dihydric alcohol that 12 molar equivalents are weighed in the flask of dried and clean (divides About 1000) son amount, is heated to 110 DEG C of water removal 1h, the hexamethylene diisocyanate (HDI) of 8.8 molar equivalents is then added, In 85 DEG C of reaction 1.5h under the conditions of nitrogen protection；Then 60 DEG C are cooled to, the N of 0.5 molar equivalent, (the 2- hydroxyl second of N- bis- is added Base)-N '-propyl-urine, the 2 of 1.8 molar equivalents, 2 '-[(2- methylene -1,3- propane diyl) two (sulphur)] diethanols, 150mL Acetone, 3 drop stannous octoates, is warming up to 85 DEG C of back flow reaction 2h after mixing evenly；After be cooled to 60 DEG C, add 0.2 mole and work as The triethanolamine of amount continues to be stirred to react 1h as crosslinking agent, obtains the polymer fluid with certain viscosity.Then it is added The Graphene powder of 7.5% mass fraction, suitable neopelex after being dispersed with stirring 30min, carry out ultrasound 15min, It is stirred for 30min, so that Graphene powder is uniformly dispersed in a polymer matrix；Acetone is removed in vacuum, is cooled to room temperature, final Enhance polyurethane nanocomposite to elastomeric graphene, resulting dynamic aggregation object has excellent conduction Property, the minimal stress acted on dynamic aggregation object can be showed in the form of curent change, be passed with sensitive stress Feel function.In the present embodiment, dynamic aggregation object obtained can be applied to medical instrument stress sensing device, and available Infrared remote sensing heating carries out selfreparing.
Embodiment 14
Specific preparation process is as follows:
The carbon disulfide and 3- bromopropyl tert-butyldimethyl silyl ether that molar ratio is 2.1:1 are added in the reactor, with N, Dinethylformamide is solvent, obtains intermediate product 1 for 24 hours in 40 DEG C of reactions under potassium carbonate effect.Intermediate product 1 is in the tetrabutyl Ammonium fluoride and the lower deprotection of acetic acid effect, obtain trithiocarbonic acid two (3- hydroxypropyl) ester.
The addition 65g polytetrahydrofuran diol first into BUSS formula outer circulation reactor, catalyst KOH 1.25g, then into The displacement of row nitrogen, is separately added into propylene oxide 900g, the tertiary fourth of (S)-(oxiranylmethyl) carbamic acid after being heated to 120 DEG C Ester 256g is reacted, and reaction temperature controls 140~150 DEG C.Under constant temperature conditions, it carries out slaking reaction 40 minutes, wait react When device pressure no longer declines, start as reactor content cooling.Acetic acid is added when temperature is reduced to 70 DEG C and carries out neutralization reaction, until The pH of reaction system is 6.8, obtains a kind of polyether polyol that side group contains carbamate groups.
The polyether polyols that 25.34g side group obtained above contains carbamate groups are weighed in the flask of dried and clean Alcohol is heated to 110 DEG C of water removal 1h, 12.32g hexamethylene diisocyanate is then added, in 85 DEG C under the conditions of nitrogen protection 1.5h is reacted, then cools to 60 DEG C, 1.45g trithiocarbonic acid two (3- hydroxypropyl) ester, 75mL acetone, 3 drop octanoic acids are added Stannous is warming up to 85 DEG C of back flow reaction 2h after mixing evenly, is cooled to 60 DEG C, adds 1.65g triethanolamine and continues stirring instead 1h is answered, the polymer fluid with certain viscosity is obtained, obtains a kind of dynamic aggregation object elastomer material flexible after except solvent Material, can use as the toy with visco-elastic magic conversion effect.
Embodiment 15
Present embodiment prepares polyurethane flexible foam material, and specific step is as follows:
Cytimidine is reacted under the catalysis of triethylamine with the polyethylene glycol that both ends are succinimidyl succinate base, is obtained It is the polyethylene glycol of cytimidine base to both ends.
By end hydroxy butadiene (HTPB) and 2- t-butoxycarbonyl amino ethyl mercaptan with HTPB side group double bond molal quantity: 2- The sulfydryl molal quantity of t-butoxycarbonyl amino ethyl mercaptan is 1:1.2 mixing, is then added relative to 2- t-butoxycarbonyl amino second The photoinitiator benzoin dimethylether (DMPA) of mercaptan 0.2wt% is placed on ultraviolet radioactive 4 in UV crosslinking instrument after stirring sufficiently Hour, obtain the HTPB that side group has carbamate groups.
Weigh reaction mass A in parts by weight: (synthesis process is shown in embodiment to ester to trithiocarbonic acid two (3- hydroxypropyl) 14) 2 parts, side group with 0.4 part of 12 parts of HTPB, the 1,4- butanediol of carbamate groups, both ends be the poly- of cytimidine base 8 parts of ethylene glycol, 0.2 part of dibutyl tin dilaurate, 0.2 part of diethylenetriamines, 0.2 part of organic silicone oil, 2 parts of methylene chloride, It is added in No. 1 mold, is stirred evenly under conditions of 30 DEG C of material temperature, mixing speed 180r/min；Reaction mass B:HDI trimerization 10 parts of body, 2.5 parts of foaming agent, 0.1 part of foam stabiliser, are added in No. 2 molds, in 30 DEG C of mixing speed 180r/ of material temperature It is stirred evenly under conditions of min；Then reaction mass A is mixed with reaction mass B according to 1.2:1 mass ratio, through professional equipment Quickly stirring stands 72h to bubble is generated, and obtains the soft poly- of the single network dynamic aggregation object for being dispersed with supermolecule polymer Urethane foam.The dynamic aggregation object of hybrid cross-linked network after foaming is added in No. 3 molds, is solidified at room temperature Then 30min solidifies 2h at 120 DEG C to get a kind of flexibel polyurethane base foamed material is arrived.
Mechanics Performance Testing: tensile strength (MPa): 3.2；Elongation (%): 620；
The material can be used for the materials such as pillow, also have certain self-healing properties under the action of light.
Embodiment 16
It is in molar ratio that 1:1 reacts obtained N- ethyl-by ethyl isocyanate and propargylamine using triethylamine as catalyst N ' -2- propinyl urea.
Again by 10 parts of N- ethyl-N ' -2-propynyl ureas, 18 parts of two -2- propylene base esters of trithiocarbonic acid and 18 parts of crosslinking agents 1,2,6- hexane, three base three (mercaptoacetate), a small amount of BHT antioxidant and 1.2 parts of foamable polymer microballoons, stirring It after being sufficiently mixed, pours into the glass board mould for accompanying silica gel pad, is placed on ultraviolet radioactive 4h in UV crosslinking instrument, generate gas Bubble, the dynamic aggregation object after foaming is added in mold, solidifies 2h at room temperature, solidifies 2h at 80 DEG C then to get arriving A kind of foamed material.
Mechanics Performance Testing: tensile strength (MPa): 4.6；Elongation (%): 480；
The foamed material has good flexibility, can be used as everyday articles etc..Meanwhile also there is the material light stimulus to ring Ying Xing has certain self-repairability under the action of light.
Embodiment 17
8.34g is hydrogenated into the p-aminophenyl bi-end-blocking that methylenebis phenyl isocyanate and 16.64g molecular weight are 2000 Polytetrahydrofuran is added in the three-necked flask of dried and clean, leads to nitrogen protection, in 70 DEG C of reaction 1h；60mL is added afterwards to be dissolved with 1.86 g aminodithioformic acid N- amino-ethyl-S- amino-ethyl esters and 0.48g 5,6- diamino -2- methyl -4 (3H)-are phonetic The dimethylacetamide solution of pyridine ketone starts to react after mixing evenly, and reaction temperature controls between 60~75 DEG C, reacts 1.5h Afterwards, 10mL is added dissolved with the dimethylacetamide solution and a small amount of DMPA photoinitiator of 1.24g diethylenetriamines, The reaction was continued 2 h, obtain thick polyureas fluid.Certain thickness liquid film is made in 15% polyureas solution on a glass, Dry 4h removal solvent is placed in 60 DEG C of baking ovens.It is soaked in water, rinses rear demoulding, colorless and transparent polyurea film is obtained after drying.
The thin-film material has fabulous water resistance, can be used for polyureas base waterproof material, while having light stimulus responsiveness, There is certain self-repairability under the action of light, subtle crackle can be repaired.
Embodiment 18
The present embodiment prepares a kind of foamed urethane material, and specific step is as follows:
Using isocyanates ethyl acrylate as monomer, AIBN is initiator, is heated to 65 DEG C of reaction 4h, passes through radical polymerization It closes and polyisocyanate ethyl acrylate is made；Polyisocyanate ethyl acrylate obtained and a certain amount of propyl alcohol are mixed, with Triethylamine reacts in methylene chloride as catalyst, the isocyano in control reaction in polyisocyanate ethyl acrylate Molal quantity n and propyl alcohol in the ratio of molal quantity x of hydroxyl be about 10:6 so that polyisocyanate ethyl acrylate side group has Carbamate groups.
Reaction mass A: 1 part of trithiocarbonic acid two (3- hydroxypropyl) ester, phthalic anhydride-butanediol polyester two is weighed in parts by weight 14 parts of first alcohol, 0.4 part of chain extender 1,4- butanediol, 0.2 part of dibutyl tin dilaurate, 0.2 part of diethylenetriamines, organosilicon 0.2 part of oil, is added in No. 1 mold, stirs evenly under conditions of 30 DEG C of material temperature, mixing speed 180r/min；Reaction mass B: 8 parts of dicyclohexyl methyl hydride diisocyanate (HMDI), side group obtained above contain the polyisocyanate 4 of carbamate groups Part, 2.5 parts of foaming agent, 0.1 part of foam stabiliser, 0.5 part of photoinitiator benzoin dimethylether (DMPA), are added to No. 2 molds In, it is stirred evenly under conditions of 30 DEG C of mixing speed 180r/min of material temperature；Then by reaction mass A and reaction mass B according to The mixing of 1.2:1 mass ratio quickly stirs to bubble is generated through professional equipment, stands 72h, obtains based on single network dynamic aggregation The polyurethane-based foam plastics of object.The dynamic aggregation object of hybrid cross-linked network after foaming is added in No. 3 molds, in room temperature Then lower solidification 30min solidifies 2h at 120 DEG C to get a kind of polyurethane-based foam material is arrived.
Mechanics Performance Testing: tensile strength (MPa): 6.6；Elongation (%): 420；
The material has lightweight, high-strength, high tenacity characteristic, can be with being widely used in building and upholstery.The material also has There is light stimulus responsiveness, there is certain self-repairability under the action of light.
Embodiment 19
Being prepared into ionic liquid gel, specific step is as follows:
It is in molar ratio that 1:1 reacts obtained N- ethyl-by ethyl isocyanate and propargylamine using triethylamine as catalyst N ' -2- propinyl urea.
By the succinic acid diacrylamine of 10 molar equivalents (being made by succinic acid and allylamine by amidation process), It is N- ethyl-N ' -2-propynyl urea of 3 molar equivalents, the 1,4- succinimide mercaptans of 12 molar equivalents, a small amount of BHT antioxidant, appropriate Benzoin dimethylether photoinitiator (DMPA), stirring be sufficiently mixed after, pour into the glass board mould 1 for accompanying silica gel pad, It is placed on ultraviolet radioactive 4h in UV crosslinking instrument, supermolecule polymer is obtained, is broken into little particle.
By the bisphenol a diallyl ether of 12 molar equivalents, the trithiocarbonic acid two-(2- methyl -2- propylene of 20 molar equivalents Base) ester, 21 molar equivalents three base three (mercaptoacetate) of 1,2,6- hexane, a small amount of BHT antioxidant and 5% mass fraction Supermolecule polymer particle, suitable benzoin dimethylether (DMPA), stirring be sufficiently mixed after, pour into and accompany silica gel pad In glass board mould 2, it is placed on ultraviolet radioactive 6h in UV crosslinking instrument, obtains thick dynamic aggregation object；Then 100 mass are taken The dynamic aggregation object of part, is swollen in the polyethylene glycol oligomer of 200 mass parts, obtains having the dynamic of hybrid cross-linked network State polymer oligomer swell gel.
The oligomer swell gel has good flexibility, can be used as the orthopaedics health with certain self-healing properties Gel rubber material is multiplexed to use.
Embodiment 20
Suitable 3,3 '-dipropionic acid trithiocarbonates and triphenyl phosphorus are first added into reactor, under anaerobic The anhydrous tetrahydrofuran solution of 4- azido -2- iodophenol is added, the toluene solution of azo-dicarboxylate is then added dropwise, The molar ratio for controlling 3,3 '-dipropionic acid trithiocarbonates and 4- azido -2- iodophenol is 1:2, whole process control reaction Temperature is at 10 DEG C, and reaction terminates after being added dropwise to complete, and obtains two azido compounds containing three thioester substrates.
By Isosorbide-5-Nitrae-pentadiene -3- alcohol 84g and methyl isocyanate 57g, using 2g triethylamine as catalyst, in 250ml bis- It is reacted in chloromethanes, the bifunctional vinyl compound that side group has carbamate groups is made.
Suitable tetrahydrofuran/DMF mixed solvent is added in the round-bottomed flask of dried and clean, after sealing, utilizes argon gas It is bubbled deoxygenation 1h, two azido compounds containing three thioester substrates of 8 molar equivalents, 11 molar equivalents are then added using syringe Adipic acid dipropargyl ester, the 2 of 2 molar equivalents, 4,6- triazido-S- triazines, suitable n,N-diisopropylethylamine, so Using syringe, by configured monovalence copper-tetrahydrofuran solution, (cuprous iodide of 0.01 molar equivalent is dissolved in suitable afterwards In tetrahydrofuran solvent) it is added in reaction flask.Reaction flask is heated to 55 DEG C, reacts 60h while stirring, obtains 1 network.
The 1,3- diallyl of bifunctional vinyl compound, 6 molar equivalents by the side group of 6 molar equivalents with carbamate groups Urea, the ethanthiol of 12 molar equivalents, a small amount of BHT antioxidant and 35% mass fraction the 1st network polymer, suitable Benzoin dimethylether (DMPA) pours into the glass board mould 2 for accompanying silica gel pad after stirring is sufficiently mixed, is placed on ultraviolet friendship Join ultraviolet radioactive 6h in instrument, obtain the dynamic aggregation object of block-like hybrid cross-linked network, using hot-forming, can be used as has The plastic plate of selfreparing and re-workability uses.
Embodiment 21
Cytimidine is reacted under the catalysis of triethylamine with the polyethylene glycol that both ends are succinimidyl succinate base, is obtained It is the polyethylene glycol of cytimidine base to both ends.
Suitable 3,3 '-dipropionic acid trithiocarbonates and triphenyl phosphorus are first added into reactor, under anaerobic The anhydrous tetrahydrofuran solution of hydroxy-ethyl acrylate is added, the toluene solution of azo-dicarboxylate is then added dropwise, controls The molar ratio of 3,3 '-dipropionic acid trithiocarbonates and hydroxy-ethyl acrylate is 1:2, and whole process controls reaction temperature 10 DEG C, reaction terminates after being added dropwise to complete, and obtains the bifunctional vinyl compound containing three thioester substrates.
Using AIBN as initiator, tetrahydrofuran is solvent, the bifunctional vinyl compound obtained above containing three thioester substrates, methyl Butyl acrylate is monomer, and the ratio of the amount of both control substance is 16:100, obtains dynamic by free radical polymerization at 70 DEG C Polymer network.
By 10 parts of both ends be cytimidine base polyethylene glycol, 20 parts of dynamic aggregation object networks, a small amount of BHT antioxidant and 1.2 parts of foamable polymer microballoons pour into mold after stirring is sufficiently mixed, and heating generates bubble, will be dynamic after foaming State polymer is added in mold, solidifies 2h at room temperature, is then solidified 2h at 80 DEG C and is steeped to get to a kind of dynamic aggregation object Foam material.
Mechanics Performance Testing: tensile strength (MPa): 3.6；Elongation (%): 440；
The foamed material can be used as heat-insulated, pipe insulation of heat preservation of refrigeration storage etc..Meanwhile the material also has light stimulus response Property, there is certain self-repairability under the action of light.
Embodiment 22
It is as follows that present embodiment prepares a kind of foamed material method:
50g polyethylene glycol, catalyst KOH 1.25g are added first into BUSS formula outer circulation reactor, then carries out nitrogen Displacement, be heated to being separately added into after 120 DEG C ethylene oxide 680g, (S)-(oxiranylmethyl) butyl carbamate 256g into Row reaction, reaction temperature control 140~150 DEG C.Under constant temperature conditions, progress slaking reaction 40 minutes, not to reactor pressure When declining again, start as reactor content cooling.Acetic acid is added when temperature is reduced to 70 DEG C and carries out neutralization reaction, until reaction system PH be 6.8, obtain a kind of polyether Glycols that side group contains carbamate groups.
The carbon disulfide and p- bromomethyl tert-butyldimethyl silyl ether that molar ratio is 2.1:1 is added, in the reactor with second Cyanogen is solvent, obtains intermediate product 1 for 24 hours in 40 DEG C of reactions under potassium carbonate effect；Intermediate product 1 is in tetrabutyl ammonium fluoride and acetic acid The lower deprotection of effect, obtains trithiocarbonic acid two (4- (methylol) benzyl) ester.
Reaction mass A is weighed in parts by weight: 12 parts of polyether Glycols that side group contains carbamate groups, three thio carbon Sour two (4- (methylol) benzyl) 1.4 parts of esters, 0.2 part of chain extender 1,4- butanediol, 0.2 part of dibutyl tin dilaurate, three second 0.4 part of hydramine, 0.1 part of organic silicone oil, are added in No. 1 mold, stir under conditions of 30 DEG C of material temperature, mixing speed 180r/min It mixes uniformly；13 parts of reaction mass B:2,4- toluene di-isocyanate(TDI), 2.5 parts of foaming agent, 0.1 part of foam stabiliser, are added to No. 2 In mold, stirred evenly under conditions of 30 DEG C of mixing speed 180r/min of material temperature；Then by reaction mass A and reaction mass B It is mixed according to 1.2:1 mass ratio, is quickly stirred through professional equipment to bubble is generated, stand 72h, obtain the 1st network polymerization Object.
1- level Four butyl -3,3 '-two (2- ethoxy) is urinated into 6 parts, 0.4 part of expandable polymer microballoon, 1,4- butanediol 0.2 part, 0.2 part of dibutyl tin dilaurate, 0.1 part of organic silicone oil is added in No. 3 molds, then is added 10 into No. 3 molds The 1st network polymer of part, 7wt% carbon nanotube, 5wt% graphene stir evenly, obtain mixture C；Then by 8 parts of 2,4- Toluene di-isocyanate(TDI) is added in No. 4 molds, then mixture C is added in No. 4 molds, quickly stirred through professional equipment to Bubble is generated, 72h, the dynamic aggregation object of the hybrid cross-linked network after being foamed are stood.By the hybrid cross-linked network after foaming Dynamic aggregation object be added in No. 5 molds, solidify 30min at room temperature, then 80 DEG C of solidification 4h to get arrive a kind of binary Semi-intercrossing network composite foam material.
Mechanics Performance Testing: tensile strength (MPa): 5.8；Elongation (%): 880；
The material has the characteristics that lightweight, high-strength, conductive and heat-conductive, heat insulation effect are good, also has under the action of light certain Self-healing properties, can be used for automobile structure, thermal insulation material etc..
Embodiment 23
(1) the carbamate compounds reaction by end hydroxy butadiene (HTPB) and end with sulfydryl, so that HTPB Side group on have carbamate groups；
It reacts to obtain the 2nd network with hexamethylene diisocyanate by having the HTPB of carbamate groups in side group again.
It is as follows that present embodiment prepares a kind of foamed material method:
The addition 150g polypropylene oxide triol first into BUSS formula outer circulation reactor, catalyst KOH 1.25g, then into The displacement of row nitrogen is added (S)-(oxiranylmethyl) t-butyl carbamate 250g after being heated to 120 DEG C and is reacted, instead Temperature is answered to control 140~150 DEG C.Under constant temperature conditions, it carries out slaking reaction 40 minutes, when reactor pressure no longer declines, Start as reactor content cooling.Acetic acid is added when temperature is reduced to 70 DEG C and carries out neutralization reaction, until the pH of reaction system is 6.8, obtain a kind of polyether polyol that side group contains carbamate groups.
By end hydroxy butadiene (HTPB) and 2- t-butoxycarbonyl amino ethyl mercaptan with HTPB side group double bond molal quantity: 2- The sulfydryl molal quantity of t-butoxycarbonyl amino ethyl mercaptan is 1:1.2 mixing, is then added relative to 2- t-butoxycarbonyl amino second The photoinitiator benzoin dimethylether (DMPA) of mercaptan 0.2wt% is placed on ultraviolet radioactive 4 in UV crosslinking instrument after stirring sufficiently Hour, obtain the HTPB that side group has carbamate groups.
Weigh reaction mass A in parts by weight: 2 parts of trithiocarbonic acid two (3- hydroxypropyl) ester, side group obtained above contain There are 12 parts of polyether polyol, 0.2 part of the 1,4- butanediol, 0.2 part of dibutyl tin dilaurate, triethanolamine of carbamate groups 0.4 part, 0.1 part of organic silicone oil, are added in No. 1 mold, stir under conditions of 30 DEG C of material temperature, mixing speed 180r/min equal It is even；Reaction mass B:2,4,6- 13 parts of toluene triisocyanates, 2.5 parts of foaming agent, 0.1 part of foam stabiliser are added to No. 2 moulds In tool, stirred evenly under conditions of 30 DEG C of material temperature, mixing speed 180r/min；Then reaction mass A and reaction mass B are pressed It is mixed according to 1.2:1 mass ratio, is quickly stirred through professional equipment to bubble is generated, stand 72h, obtain the 1st network polymer.
Side group is had to 1.5 parts of 14 parts of HTPB, expandable polymer microballoon, the 1,4- butanediol 0.4 of carbamate groups Part, 0.2 part of dibutyl tin dilaurate, 0.1 part of organic silicone oil, are added in No. 3 molds, then 16 parts are added into No. 3 molds 1st network polymer, stirs evenly, and obtains mixture C；Then No. 4 molds are added to by 12 parts of hexamethylene diisocyanate In, then mixture C is added in No. 4 molds, it is quickly stirred through professional equipment to bubble is generated, 72h is stood, after obtaining foaming Hybrid cross-linked network dynamic aggregation object.The dynamic aggregation object of hybrid cross-linked network after foaming is added in No. 5 molds, Solidify 30min at room temperature, then 80 DEG C of solidification 4h to get arrive a kind of binary interpenetrating networks composite foam material.
Mechanics Performance Testing: tensile strength (MPa): 4.2；Elongation (%): 580；
The material can be used for manufacturing gasket material, heat preserving and insulating material, insulating materials.Also there is the material light stimulus to ring Ying Xing has certain self-repairability under the action of light.
Embodiment 24
It is as follows that the present embodiment is prepared into foamed material method:
Using methanol as solvent, sodium methoxide is catalyst, by dithioglycol and the chloro- 2- chloromethyl -1- propylene of 3- with molar ratio For the mixing of 2:1 ratio, 16h is reacted in a heated condition, obtains 2,2 '-[(2- methylene -1,3- propane diyl) two (sulphur)] two Ethyl mercaptan.
By 2,2 '-[(2- methylene -1,3- propane diyl) two (sulphur)] diethyl mercaptan of 8 molar equivalents, 9 molar equivalents 3- sulfydryl -2- (mercapto methyl)-N- methyl propanamide, the 1,3- diallyl urea of 14 molar equivalents, 2 molar equivalents triolefin Propyl amine, a small amount of BHT antioxidant, suitable photoinitiator DMPA pour into the glass for accompanying silica gel pad after stirring is sufficiently mixed In glass plate mold 1, it is placed on ultraviolet radioactive 4h in UV crosslinking instrument, obtains the 1st network dynamic polymer.
By the acrylic aminodithioformic acid acrylic ester of 12 molar equivalents, 18 molar equivalent level Four butyl (bis- mercaptos of 1,3- Base propane -2- base) carbamate, the diallyl sulfone of 15 molar equivalents, 6 molar equivalents trithiocyanuric acid, a small amount of BHT antioxidant and the 1st network dynamic polymer of 45% total mass fraction, suitable photoinitiator DMPA stir sufficiently mixed It after conjunction, pours into the glass board mould 2 for accompanying silica gel pad, it is described to get arriving to be placed on ultraviolet radioactive 6h in UV crosslinking instrument Hybrid cross-linked network dynamic polymer.The material has good flexibility, can be made as stretchable packing film With.
Embodiment 25
The polytetrahydrofuran diol 1000 that 25.32g is weighed in the flask of dried and clean is heated to 110 DEG C of water removal 1h, so 12.5g isoflurane chalcone diisocyanate is added afterwards and then cools to 60 DEG C in 85 DEG C of reaction 1.5h under the conditions of nitrogen protection, 3.2gN is added, (2- the ethoxy)-N '-of N- bis- propyl-urine, 25g acetone, 3 drip stannous octoates, are warming up to 85 DEG C after mixing evenly Back flow reaction 2h obtains the 2nd network polymer.
The round-bottomed flask for separately taking a dried and clean, weighs 25.32g polytetrahydrofuran diol 1000, is heated to 110 DEG C and removes Then 12.5g isoflurane chalcone diisocyanate is added, in 85 DEG C of reaction 1.5h under the conditions of nitrogen protection in water 1h；Then cool down To 60 DEG C, it is added 2.24g trithiocarbonic acid two (methylol) ester, 0.44g 1,4-butanediol, 25g acetone, the organic illiteracy of 3.2g is de- Soil is scattered in the solution of 20mLDMF, and 3 drop stannous octoates stir 15min, ultrasonic 15min is stirred for 15min, is warming up to 85 DEG C Back flow reaction 2h；After be cooled to 60 DEG C, be added the 1st network polymer 20g, dipropylenetriamine 1.44g the reaction was continued 1h is obtained miscellaneous Change cross-linked network dynamic aggregation logistics body, through obtaining the modified dynamic aggregation object of thick montmorillonite intercalation except solvent.The dynamic Polymer material can be prepared into the sealing material with self-repairability, for the sealing and waterproof of electronic apparatus, such as earpiece holes Plug, charging stopple etc. have excellent caking property and air-tightness, while the dynamic aggregation object also has centainly under the action of light Self-repairability, tiny crackle can be repaired.
Embodiment 26
Using the N,N-DMAA of equimolar amounts and N- carbamyl acrylamide as raw material, potassium peroxydisulfate is added As initiator, the acrylamide copolymer containing side hydrogen bond group is prepared by free radical polymerization, is broken into small Particle.
Suitable 3,3 '-dipropionic acid trithiocarbonates and triphenyl phosphorus are first added into reactor, under anaerobic The anhydrous tetrahydrofuran solution of N- hydroxyethyl acrylamide is added, the toluene solution of azo-dicarboxylate is then added dropwise, The molar ratio for controlling 3,3 '-dipropionic acid trithiocarbonates and N- hydroxyethyl acrylamide is 1:2, whole process control reaction Temperature is at 10 DEG C, and reaction terminates after being added dropwise to complete, and obtains the bifunctional vinyl compound on chain containing amide groups and three thioester substrates.
Using AIBN as initiator, tetrahydrofuran is solvent, pair on chain obtained above containing amide groups and three thioester substrates Ene compound, N-isopropylacrylamide, butyl acrylate are monomer, and the ratio for controlling the amount of three's substance is 16:25:100,70 The random copolymer of three, i.e. dynamic aggregation object network are obtained by free radical polymerization at DEG C.
120mL THF solvent is added in the flask of dried and clean, leads to nitrogen and removes water deoxygenation 1h, 100 weight are then added The dynamic aggregation object network of part, 2wt% acrylamide copolymer particle add a small amount of after being heated to 60 DEG C of stirring and dissolvings BHT antioxidant, 5wt% gallium indium liquid alloy after being mixed evenly, react 4h under the conditions of nitrogen protection；Reaction is completed Afterwards, reaction solution filter except solvent obtains head product, decontamination is eluted using n-hexane/methylene chloride (2:1), then 60 Dynamic aggregation object sample is obtained after dry 12h under the conditions of DEG C.It in the present embodiment, can be using polymeric articles as conduction heat sealable Glue, applied to the sealing of building filleting, the encapsulation process of electronic component, while having good sealing property and thermal conductivity also With certain self-repairability.
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 (12)

1. a kind of dynamic aggregation object with hybrid cross-linked network structure, which is characterized in that wherein comprising dynamic covalent cross-linking and Supermolecule hydrogen bond action；Wherein, it is covalent to be based at least one Reversible Addition Fragmentation Chain Transfer dynamic for the dynamic covalent cross-linking More than key and its gel point for reaching dynamic covalent cross-linking at least one network structure, the supermolecule hydrogen bond action includes The hydrogen bond to be formed is participated in by the side hydrogen bond group being present in the side group or side chain or side group and side chain of polymer chain to make With wherein including the group containing following constituent in the side hydrogen bond group:
2. a kind of dynamic aggregation object with hybrid cross-linked network structure according to claim 1, which is characterized in that described Reversible Addition Fragmentation Chain Transfer dynamic covalent bond, have the following structure general formula:
Wherein,Refer to polymer chain, crosslinking link or the connection of any other suitable group；A is selected from C atom, S Atom, Se atom；
When A is the C atomic time, the Reversible Addition Fragmentation Chain Transfer dynamic covalent bond has the following structure general formula:
Wherein, R1、R2、R3、R4Respectively it is individually present；Z2For with C3Divalent linking atom or the divalent connection that carbon atom is connected directly Group；
Work as Z2When selected from divalent linking group, Z1For with double bond C2The divalent linking group that carbon atom is connected directly；
Work as Z2When selected from divalent linking atom, it is selected from S atom, at this time Z1For with double bond C2The divalent that carbon atom is connected directly connects Connect group；Work as Z2When for S atom, the Reversible Addition Fragmentation Chain Transfer dynamic covalent bond has the following structure general formula:
When A is S atom or Se atomic time, R1、R2、R3、R4It is not present；
When A is S atom or Se atomic time, Z1Selected from O atom, S atom, Se atom, Si atom, C atom, N atom, P atom；This When, the Reversible Addition Fragmentation Chain Transfer dynamic covalent bond has the following structure at least one of general formula:
Work as Z1For O atom, S atom, Se atomic time, R5、R6、R7It is not present；
Work as Z1For N atomic time, R5In the presence of R6、R7It is not present；
Work as Z1For Si atom, C atomic time, R5、R6In the presence of R7It is not present；
Work as Z1For P atomic time, R5、R6、R7、R8In the presence of；
Z2For the divalent linking group being connected directly with S atom or Se atom；Z3For with Z1The divalent linker that atom is connected directly Group.
3. a kind of dynamic aggregation object with hybrid cross-linked network structure according to claim 2, which is characterized in that R1、 R2、R3、R4、R5、R6、R7、R8It is each independently selected from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Miscellaneous alkyl, substituted C1-20 Alkyl, substituted miscellaneous alkyl.
4. a kind of dynamic aggregation object with hybrid cross-linked network structure according to any one of claim 1 or 2, special Sign is that the Reversible Addition Fragmentation Chain Transfer dynamic covalent bond is selected from allyl, allyl sulfide ether, double thioester substrates, double selenium Ester group, trithiocarbonic acid ester group, three seleno carbonate groups, two seleno thiocarbonic acid ester groups, two thio seleno carbonate groups, two pairs Thioester substrate, two pairs of selenium ester groups, double trithiocarbonic acid ester groups, double three selenos carbonate groups, dithiocarbamate groups, two selenos Carbamate groups, dithiocarbonic acids ester group, two seleno carbonate groups and its corresponding derivatives group.
5. a kind of dynamic aggregation object with hybrid cross-linked network structure according to claim 1, which is characterized in that described The end group hydrogen bond group on side hydrogen bond group and end group in polymer chain side group, side chain skeleton, has the following structure general formula At least one of:
Wherein, X is O atom or S atom, and M is selected from O atom, S atom, Si atom, C atom, N atom；
When M is O atom or S atom, R9It is not present；
When M is C atom, Si atom or N atomic time, R9And R10Respectively it is individually present；
L1And L2It is divalent linking group, G is terminal end capping group or segment；
R9、R10、L1、L2, G any two or it is multiple between it is cyclic or not cyclic.
6. a kind of dynamic aggregation object with hybrid cross-linked network structure according to claim 1, which is characterized in that described Also selectively contain hydroxyl, sulfydryl, carboxyl in the side group or end group of hybrid cross-linked network dynamic polymer.
7. a kind of dynamic aggregation object with hybrid cross-linked network structure according to claim 1, which is characterized in that average The number of every side group or side chain or side group and side chain of the access of 100 main chain backbone repetitive units containing the side hydrogen bond group It is 0.1 to 200.
8. a kind of dynamic aggregation object with hybrid cross-linked network structure according to claim 1, which is characterized in that described Also contain at least one of main chain backbone hydrogen bond group and other end group hydrogen bond groups in dynamic aggregation object.
9. a kind of dynamic aggregation object with hybrid cross-linked network structure according to claim 1, which is characterized in that it has Just like one of lower network structure:
The first: only one cross-linked network of dynamic aggregation object, this cross-linked network contain dynamic covalent cross-linking and supermolecule hydrogen bond Crosslinking, the dynamic covalent cross-linking reach its gel point or more；
Second: dynamic aggregation object is made of two cross-linked networks, wherein contains dynamic covalent cross-linking and dynamic in the 1st network Covalent cross-linking reaches its gel point or more, wherein not containing any hydrogen bond group；Without covalent cross-linking but containing super in 2nd network Molecule hydrogen bond crosslinks；
The third: dynamic aggregation object is made of two networks, wherein containing dynamic covalent cross-linking and dynamically covalent in the 1st network Crosslinking reaches its gel point or more, wherein not containing any hydrogen bond group；Contain dynamic covalent cross-linking and supermolecule in 2nd network Hydrogen bond crosslinks, the dynamic covalent cross-linking reach its gel point or more；
4th kind: dynamic aggregation object is made of two networks, wherein contains dynamic covalent cross-linking and supermolecule hydrogen in the 1st network Key crosslinking, the dynamic covalent cross-linking reach its gel point or more；Covalent cross-linking is free of in 2nd network but contains supermolecule hydrogen bond Crosslinking；
5th kind: dynamic aggregation object is made of two networks, wherein contains dynamic covalent cross-linking in the 1st network and the 2nd network With supermolecule hydrogen bond crosslinks, the dynamic covalent cross-linking reaches its gel point or more, but upper 1st and the 2nd network is not identical；
6th kind: only one cross-linked network of dynamic aggregation object, this cross-linked network contain dynamic covalent cross-linking and optional oversubscription Sub- hydrogen bond crosslinks, the dynamic covalent cross-linking reach its gel point or more；Supermolecule is dispersed in dynamic covalent cross-linking network The degree of cross linking is in its gel point supermolecule polymer below；
7th kind: only one cross-linked network of dynamic aggregation object, this cross-linked network contain dynamic covalent cross-linking and optional oversubscription Sub- hydrogen bond crosslinks, the dynamic covalent cross-linking reach its gel point or more；Supermolecule is dispersed in dynamic covalent cross-linking network Supermolecule polymer particle of the degree of cross linking more than its gel point.
10. a kind of dynamic aggregation object with hybrid cross-linked network structure according to claim 1, which is characterized in that structure Raw material components at dynamic aggregation object further include following any or appoint and several add or object can be used: solvent, auxiliary agent, addition Agent, filler；
Wherein, described to add or workable auxiliary agent, additive are selected from following any or appoint several: catalyst, initiation Agent, antioxidant, light stabilizer, heat stabilizer, toughener, coupling agent, lubricant, release agent, plasticizer, antistatic agent, emulsification Agent, dispersing agent, colorant, fluorescent whitening agent, delustering agent, fire retardant, biocide mildewcide, dehydrating agent, nucleating agent, rheological agent, increasing Thick dose, thixotropic agent, levelling agent, foam stabiliser, foaming agent；
Wherein, described to add or workable filler is selected from following any or appoints several: inorganic non-metallic filler, metal Filler, organic filler.
11. a kind of dynamic aggregation object with hybrid cross-linked network structure according to claim 1, which is characterized in that institute The form for stating dynamic aggregation object or its composition is selected from ordinary solid polymer, elastomer, gel, foam.
12. a kind of according to claim 1, dynamic aggregation with hybrid cross-linked network structure described in any one of 9,10,11 Object, which is characterized in that it is applied to self-repairability coating, self-repairability binder, sealing material, toughness material, energy storage device Material, toy, shape-memory material.
CN201710967686.5A 2017-10-17 2017-10-17 A kind of dynamic aggregation object with hybrid cross-linked network structure Pending CN109666093A (en)

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