Specific embodiment
The present invention relates to a kind of hydridization dynamic aggregation compositions comprising at least two component of A, B, wherein component A is packet
Containing at least one cross-linked network and at the same time containing can occur olefin cross metathesis metathesis reaction unsaturated carbon-carbon double bond and
The hydridization dynamic aggregation object of the hydrogen bond group of supermolecule hydrogen bond action can be formed;Component B is the unsaturated carbon carbon in catalyst component A
The catalyst and/or its compound of double bond generation olefin cross metathesis metathesis reaction.
In order to illustrate simplicity the term is indicated using conjunction "and/or" in the description of the invention
It may include the option selected from the conjunction "and/or" foregoing description, or described option after conjunction "and/or",
Or it is simultaneously selected from described these three situations of option before and after conjunction "and/or".
In the following, first the polymers compositions A in the present invention is described in detail.
Heretofore described " polymerization " reaction/action be chain propagation process/effect, namely by intermolecular reaction/
Effect (including covalent chemical reaction and supermolecule hydrogen bond action) formation straight chain, branching, ring, two-dimensional/three-dimensional cluster, three-dimensional are unlimited
The polymer of network structure.
Term " crosslinking " reaction/action used in the present invention, refer to intermolecular and/or intramolecular by covalent bond and/
Or supermolecule hydrogen bond action forms the process with three-dimensional unlimited reticular pattern product.In cross-linking process, polymer chain is generally first
Constantly increase in two-dimensional/three-dimensional direction, gradually form cluster (can be two dimension or three-dimensional), developing deeply is three-dimensional infinite net
Network.Therefore, crosslinking can be considered as a kind of special shape of polymerization.In cross-linking process, just reach a three-dimensional infinite network
When the degree of cross linking, referred to as gel point, also referred to as percolation threshold.The cross-linking products (contained, similarly hereinafter) more than gel point, have
Three-dimensional infinite network structure, cross-linked network constitute an entirety and across entire polymer architectures;In gel point friendship below
Co-product, is only lax interchain link structure, and not formed three-dimensional infinite network structure, and is not belonging to across entire polymerization
The cross-linked network that can constitute an entirety of object structure.Unless stated otherwise, the present invention in cross-linked structure be gel point with
On three-dimensional infinite network structure, non-crosslinking structure includes the line style that the degree of cross linking is zero and non-linearity structure and gel point or less
Two-dimensional/three-dimensional cluster structure.
In the present invention, " skeleton " refers to structure on the chain length direction of polymer chain.It is described for cross-linked polymer
" main chain ", refer to any segment being present in cross-linked network skeleton.It is described for the polymer of non-crosslinking structure
" main chain " refers to the most chain of chain link if not otherwise indicated.Wherein, " side chain " refers to same main polymer chain phase
Connect and be distributed in the chain structure of main chain side;Wherein, " branch "/" bifurcated chain " can be side chain and be also possible to other
The chain structure come out from any chain bifurcated.Wherein, " side group " refers to that any chain of same polymer is connected and is distributed in
The chemical group of chain side.Wherein, " end group " refers to that any chain of same polymer is connected and is located at the change of chain end
Learn group.If not otherwise indicated, side group refers in particular to group of the molecular weight no more than 1000Da for being connected to polymer chain skeleton side
And subunit group therein.When the molecular weight of side chain, branch, bifurcated chain is no more than 1000Da, itself and group thereon are regarded
For side group.For the sake of simplicity, if not otherwise indicated, side chain, branch and bifurcated chain are collectively referred to as side chain.Above-mentioned " side chain ", " side
Base " can have multilevel structure namely side chain/side group that can continue with side chain/side group, side chain/side group side chain/side group
It can continue have side chain/side group.In the present invention, if not otherwise indicated, for hyperbranched and dendroid chain and its relevant link
Structure, the polymer segment of outermost can be considered as side chain, and rest part can be considered as main chain.
Heretofore described " dynamic covalent cross-linking network " is referred to when supermolecular mechanism is all disconnected in covalent cross-linking network
It opens when only remaining common covalent bond and dynamic covalent bond, still with the polymer network of the above structure of gel point;And when dynamic is total
When valence link also all disconnects, original crosslinked polymer network dissociation resolves into following any or appoints several secondary units: monomer gathers
Close object chain segment, polymer cluster, polymer beads more than gel point etc..
Heretofore described " supermolecule cross-linked network " refers to all disconnecting only when the dynamic covalent bond in cross-linked network
When remaining common covalent bond and supermolecule hydrogen bond, still with the polymer network of the above structure of gel point;And work as supermolecule hydrogen bond
When also all disconnecting, following any or several secondary units: monomer, polymer are resolved into original crosslinked polymer network dissociation
Chain segment, polymer cluster, polymer beads more than gel point etc..
Heretofore described " common covalent bond ", what is referred to is traditional covalent in addition to dynamic covalent bond
Key, under typical temperature (is generally not more than 100 DEG C) and (generally less than 1 day) is more difficult in the usual time is broken comprising
But it is 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 " dynamic covalent bond ", refers to the unsaturated carbon carbon that olefin cross metathesis metathesis reaction can occur
Double bond.Wherein, " the olefin cross metathesis metathesis reaction " refers to the unsaturated carbon carbon by metal olefin complex catalysis
Carbon skeleton rearrangement reaction between double bond.Wherein, described " rearrangement reaction " refers to, new carbon-carbon double bond generates in elsewhere and with old
Carbon-carbon double bond dissociate, to generate the exchange of chain and the variation of polymer local topology.For the purpose of the present invention, exist
In this rearrangement process, due to the particularity of reaction, the crosslink density of polymer network is basically unchanged.Wherein, described " can occur "
Refer to, in the presence of a suitable catalyst, when temperature condition, pressure condition, olefin cross metathesis metathesis reaction can be with
It carries out.
Heretofore described " supermolecular mechanism " only refers to supermolecule hydrogen bond action, referred to as " hydrogen bond action " or " hydrogen
Key ".
In embodiments of the present invention, cross-linked network included in hydridization dynamic aggregation object component A at least one,
Either single one network, there can also be the multiple networks being mutually blended, there can also be multiple networks of interpenetrating, it can also be with
Exist simultaneously blending and interpenetrating, etc.;It can using any appropriate crosslinking topological structure, chemical structure, reactive mode and
A combination thereof etc..Wherein, when the cross-linked network quantity included in the hydridization dynamic aggregation object component A is two or more, these
Network can be identical or different;Can be subnetwork only and include dynamic covalent cross-linking and subnetwork only includes that supermolecule is handed over
The combination of connection, or part only include dynamic covalent cross-linking and part while being crosslinked comprising dynamic covalent cross-linking and supermolecule
Combination, or the group that part is only crosslinked comprising dynamic covalent cross-linking and supermolecule comprising supermolecule crosslinking and part simultaneously
It all simultaneously include dynamic covalent cross-linking and supermolecule crosslinking in conjunction or each network, but the present invention is not limited only to this.By
It is crosslinked simultaneously comprising dynamic covalent cross-linking and supermolecule in the cross-linked network of hydridization dynamic aggregation object component A of the present invention, therefore,
The polymer network is known as " hybrid cross-linked network ".
(the first network structure) in a preferred embodiment of the present invention, the hydridization dynamic aggregation object component
Only one cross-linked network in A is crosslinked in the cross-linked network simultaneously containing dynamic covalent cross-linking and supermolecule, wherein dynamic is altogether
The degree of cross linking of valence crosslinking reaches its gel point or more, and the degree of cross linking of supermolecule crosslinking is in its gel point above and below.The network
Structure structure is simple, can keep balanced structure by dynamic covalent cross-linking, supermolecule crosslinking provides dynamic;In specific item
Under part, dynamic covalent cross-linking also can provide covalent dynamic.
In another preferred embodiment of the invention (second of network structure), the hydridization dynamic aggregation object
Only one cross-linked network in component A is crosslinked in the cross-linked network simultaneously containing dynamic covalent cross-linking and supermolecule, wherein dynamic
The degree of cross linking of state covalent cross-linking is in its gel point hereinafter, the degree of cross linking of supermolecule crosslinking is more than its gel point.The network structure
With good dynamic, it is based particularly on the strain-responsive of supermolecule crosslinking;Dynamic covalent cross-linking does not keep flat directly
Weigh structure, but under given conditions, dynamic covalent cross-linking also can provide the work that additional covalent dynamic plays regulation performance
With.
In another preferred embodiment of the invention (the third network structure), the hydridization dynamic aggregation object
Only one cross-linked network in component A is crosslinked in the cross-linked network simultaneously containing dynamic covalent cross-linking and supermolecule, wherein dynamic
The degree of cross linking of state covalent cross-linking in its gel point hereinafter, supermolecule crosslinking the degree of cross linking in its gel point hereinafter, but the two be crosslinked
The sum of degree is more than gel point.Dynamic covalent cross-linking and the degree of cross linking of supermolecule crosslinking are lower in the network structure, network knot
The whole degree of cross linking of structure is not high, and dynamic covalent cross-linking and supermolecule crosslinking extremely close the effect for providing balanced structure regulation performance
It is important.
In another preferred embodiment of the present invention (the 4th kind of network structure), the hydridization dynamic aggregation object group
Divide in A containing there are two networks;Dynamic covalent cross-linking is contained only in 1st network, the degree of cross linking is more than its gel point;In 2nd network
Supermolecule crosslinking is contained only, the degree of cross linking is more than its gel point.In the network structure, the 2nd network has good dynamic, the
1 network provides balanced structure, by the interpenetrating of two networks or the combinations such as Semi-IPN, can preferably play comprehensive effect
Energy;Under given conditions, dynamic covalent cross-linking also can provide additional covalent dynamic and play the role of regulation performance.
In another preferred embodiment of the present invention (the 5th kind of network structure), the hydridization dynamic aggregation object group
Divide in A containing there are two networks;Covalent cross-linking containing dynamic and supermolecule are crosslinked in 1st network, simultaneously containing dynamic in the cross-linked network
State covalent cross-linking and supermolecule crosslinking, wherein the degree of cross linking of dynamic covalent cross-linking is more than its gel point, the friendship of supermolecule crosslinking
Connection degree is in its gel point above and below;Supermolecule crosslinking is contained only in 2nd network, the degree of cross linking is more than its gel point.The net
In network structure, by combinations such as the interpenetrating of two networks, comprehensive effectiveness can be preferably played;And two can be used
Supermolecule crosslinking in network provides collaboration or orthogonal dynamic.
In another preferred embodiment of the present invention (the 6th kind of network structure), the hydridization dynamic aggregation object group
Contain a network in point A, wherein only containing dynamic covalent cross-linking more than gel point, the supermolecule degree of cross linking its gel point with
Under supermolecule polymer be dispersed in dynamic covalent cross-linking network.In the network structure, dynamic covalent cross-linking can keep flat
Weigh structure, and under given conditions, dynamic covalent cross-linking also can provide covalent dynamic;Supermolecule polymer dispersed therein
Dynamic, especially strain-responsive are provided.
In another preferred embodiment of the present invention (the 7th kind of network structure), the hydridization dynamic aggregation object group
Divide and contain a network in A, is crosslinked simultaneously containing dynamic covalent cross-linking and supermolecule in the cross-linked network, wherein dynamic is covalent
The degree of cross linking of crosslinking reaches its gel point or more, and the degree of cross linking of supermolecule crosslinking is in its gel point above and below;Supermolecule is handed over
Connection degree is dispersed in dynamic covalent cross-linking network in its gel point supermolecule polymer below.In the network structure, dynamic is altogether
Valence crosslinking can keep balanced structure, and under given conditions, dynamic covalent cross-linking also can provide covalent dynamic;Supermolecule is handed over
Connection provides dynamic, and supermolecule polymer dispersed therein provides supplement dynamic, especially strain-responsive.
In another preferred embodiment of the present invention (the 8th kind of network structure), the hydridization dynamic aggregation object group
Contain a network in point A, wherein only containing dynamic covalent cross-linking more than gel point, the supermolecule degree of cross linking its gel point with
On supermolecule polymer be dispersed in dynamic covalent cross-linking network with graininess.In the network structure, dynamic covalent cross-linking
Balanced structure can be kept, under given conditions, dynamic covalent cross-linking also can provide covalent dynamic;Supermolecule polymer
Grain provides filling and dynamic, and local viscosity and intensity can be obtained in strain-responsive and is increased.
In another preferred embodiment of the present invention (the 9th kind of network structure), the hydridization dynamic aggregation object group
Divide and contain a network in A, is crosslinked simultaneously containing dynamic covalent cross-linking and supermolecule in the cross-linked network, wherein dynamic is covalent
The degree of cross linking of crosslinking reaches its gel point or more, and the degree of cross linking of supermolecule crosslinking is in its gel point above and below;Supermolecule is handed over
Supermolecule polymer of the connection degree more than its gel point is dispersed in dynamic covalent cross-linking network with graininess.The network structure
In, dynamic covalent cross-linking can keep balanced structure, and under given conditions, dynamic covalent cross-linking also can provide covalent dynamic
Property;Supermolecule crosslinking provides dynamic, and supermolecule polymer particle provides filling and supplement dynamic, and can in strain-responsive
Increased with obtaining viscosity and the intensity of part.
In the present invention, there can also be other diversified embodiments.Those skilled in the art can be according to this
The logic and train of thought of invention, are rationally and effectively realized.
In embodiments of the present invention, the hydridization dynamic aggregation compositions component A can not have vitrifying
Transition temperature can have one or more glass transition temperature.Wherein, a kind of preferred embodiment is described
Hydridization dynamic aggregation compositions component A at least one glass transition temperature be not higher than 25 DEG C, more preferably not above 0
DEG C, more preferably glass transition temperature all when there are multiple glass transition temperatures is not higher than 25 DEG C, most preferably all glass
Change temperature and be not higher than 0 DEG C, helps to embody dynamic and self-repairability of the supermolecule hydrogen bond when room temperature and low temperature use, just
In materials or products such as acquisition adhesive, elastomer, gels;Another preferred embodiment is the hydridization dynamic aggregation
At least one glass transition temperature of compositions component A is higher than 25 DEG C but lower than 40 DEG C, and it is more steady to help to obtain size
Fixed and moving state property is moderate, the higher elastomer of temperature sensitivity, foam and ordinary solid etc.;Another preferred embodiment is
At least one glass transition temperature of the hydridization dynamic aggregation compositions component A is not less than 40 DEG C, more preferably not
Lower than 100 DEG C, more preferably glass transition temperature all when there are multiple glass transition temperatures is not less than 40 DEG C, most preferably when depositing
In multiple glass transition temperatures, all glass transition temperatures are not less than 100 DEG C, facilitate embody material at high temperature dimensional stability,
The characteristics such as the hardness under shape memory, low temperature and room temperature, the readily available gel with property, foam, ordinary solid
Equal materials or product;Another preferred embodiment is at least one of the hydridization dynamic aggregation compositions component A
Glass transition temperature is not higher than 25 DEG C, and in addition at least one glass transition temperature is not less than 100 DEG C, can take into account low temperature
And high-temperature behavior.
In embodiments of the present invention, alkene can occur containing at least one in hydridization dynamic aggregation compositions component A
The unsaturated carbon-carbon double bond of hydrocarbon cross metathesis metathesis reaction, polymerization linking point or crosslinking link as dynamic aggregation object
Point exists as polymerization linking point and crosslinking linking point simultaneously.In addition, the present invention be not excluded for carbon-carbon double bond as side group,
End group and the group of other positions exist.In the present invention, unless making the unsaturated carbon carbon using specific method
Irreproducibility dissociation occurs for double bond, and otherwise degradability variation will not occur for covalent cross-linking network and covalent polymer chain.It is preferred that can
The unsaturated carbon-carbon double bond that olefin cross metathesis metathesis reaction occurs exists only on the chain backbone of cross-linked network.
In embodiments of the present invention, the unsaturated carbon-carbon double bond that olefin cross metathesis metathesis reaction occurs
Type be not particularly limited, at least one small reaction work of steric hindrance shown in following formula is contained preferably in cross-linked network skeletal chain
The high structure of property:
Wherein,Indicate the connection with polymer chain or any other suitable group/atom (including hydrogen atom).
It is such when what is hereinafter occurred againAbove-mentioned definition and range are all continued to use, such as without special case, no longer progress repeated explanation.
In the present invention, the hydrogen bond group for forming supermolecule hydrogen bond action includes being present in polymer chain skeleton
Go up the hydrogen bond group (calling " skeleton hydrogen bond group " in the following text) of (including on main chain/side chain/branch/bifurcated chain backbone) and in polymerization
The hydrogen bond base of hydrogen bond group (calling " side group hydrogen bond group " in the following text) and polymer chain and other compound ends in object chain side group
Group's (calling " end group hydrogen bond group " in the following text).The skeleton hydrogen bond group refers to that at least one atom in the group directly participates in
The building polymer chain skeleton, including main polymer chain, side chain, branch, bifurcated chain skeleton;The side group hydrogen bond base
Group, refers to all atoms on the group in side group;The end group hydrogen bond group refers to all atoms on the group
On end group.
In embodiments of the present invention, the hydrogen bond group can be with skeleton hydrogen bond group, side group hydrogen bond group, end
The combination of any one or more of the forms such as base hydrogen bond group is present in the hydridization dynamic aggregation compositions.Due to
Part hydrogen bond, which does not have directionality and selectivity, can form hydrogen bond under specific circumstances between the hydrogen bond group of different location
Effect, can form between each other between the hydrogen bond group of identical or different position in identical or different polymer molecule
Hydrogen bond action, can also be with the other compositions in polymer as contained by optional other polymers molecule, filler, small molecule etc.
Hydrogen bond group between form hydrogen bond action.As an example, the hydrogen bond action in the present invention includes but is not limited to such as: the side chain
And/or the hydrogen bond group in side group forms interchain hydrogen bond crosslinking between different molecular;Hydrogen bond base in the side chain and/or side group
Interchain hydrogen bond crosslinking is formed in group and the main chain backbone between hydrogen bond group;Hydrogen bond in the part side chain and/or side group
Chain inner ring is independently formed with hydrogen bond between group;It is independently formed between hydrogen bond group in the main chain backbone of part with hydrogen bond
Chain inner ring;Hydrogen bond group collective effect in the part side chain and/or side group forms chain inner ring etc. with hydrogen bond.It may be noted that
It is to be not excluded for part in the present invention to be formed by intrachain hydrogen bond effect neither formation inter-chain action, does not also form chain inner ring, only shape
The effects of at grafting is included but are not limited to.
In the preferred embodiment of the present invention, only contain side in the hydridization dynamic aggregation compositions component A
Base hydrogen bond group;In another preferred embodiment of the invention, contained only in the hydridization dynamic aggregation compositions component A
There is main chain backbone hydrogen bond group;In another preferred embodiment of the invention, the hydridization dynamic aggregation compositions group
Divide and only contains side chain skeleton hydrogen bond group in A;In another preferred embodiment of the invention, the hydridization dynamic aggregation object
Only contain side chain end group hydrogen bond group in composition component A;In another preferred embodiment of the invention, the hydridization is dynamic
Only contain main chain end group hydrogen bond group in state polymer composition components A;In another preferred embodiment of the invention, institute
It states and only contains pendant hydrogen key group and side chain skeleton hydrogen bond group in hydridization dynamic aggregation compositions component A;Of the invention
In another preferred embodiment, pendant hydrogen key group and main chain are only contained in the hydridization dynamic aggregation compositions component A
Skeleton hydrogen bond group;In another preferred embodiment of the invention, in the hydridization dynamic aggregation compositions component A only
Contain side group hydrogen bond group and main chain end group hydrogen bond group;In another preferred embodiment of the invention, the hydridization is dynamic
Only contain pendant hydrogen key group and side chain end group hydrogen bond group in state polymer composition components A;It is excellent in another kind of the invention
It selects in embodiment, side chain end group hydrogen bond group and main chain backbone is only contained in the hydridization dynamic aggregation compositions component A
Hydrogen bond group;In another preferred embodiment of the invention, only contain in the hydridization dynamic aggregation compositions component A
Side chain end group hydrogen bond group and main chain end group hydrogen bond group;In another preferred embodiment of the invention, the hydridization is dynamic
Only contain main chain end group hydrogen bond group and main chain backbone hydrogen bond group in state polymer composition components A;Of the invention another
In kind preferred embodiment, pendant hydrogen key group, side chain terminal hydrogen are only contained in the hydridization dynamic aggregation compositions component A
Key group and main chain backbone hydrogen bond group;In another preferred embodiment of the invention, the hydridization dynamic aggregation object group
Only contain pendant hydrogen key group, side chain end group hydrogen bond group and main chain end group hydrogen bond group in polymer component A;Of the invention another
In a kind of preferred embodiment, pendant hydrogen key group, side chain end group are only contained in the hydridization dynamic aggregation compositions component A
Hydrogen bond group and side chain skeleton hydrogen bond group;In another preferred embodiment of the invention, the dynamic aggregation object combination
Only contain pendant hydrogen key group, side chain skeleton hydrogen bond group and main chain end group hydrogen bond group in object component A;Of the invention another
In kind preferred embodiment, pendant hydrogen key group, side chain skeleton hydrogen are only contained in the hydridization dynamic aggregation compositions component A
Key group, side chain end group hydrogen bond group and main chain backbone hydrogen bond group;It is described in another preferred embodiment of the invention
Only contain pendant hydrogen key group, side chain skeleton hydrogen bond group, side chain end group hydrogen bond base in hydridization dynamic aggregation compositions component A
Group and main chain end group hydrogen bond group;In another preferred embodiment of the invention, the hydridization dynamic aggregation compositions
In component A containing side group hydrogen bond group, side chain end group hydrogen bond group, side chain skeleton hydrogen bond group, main chain end group hydrogen bond group and
Main chain backbone hydrogen bond group.But the present invention is not limited only to this.
In embodiments of the present invention, since the general quantity of main chain backbone hydrogen bond group is than relatively limited and not easy to control,
And the side chain/side group hydrogen bond group can before polymerized/cross-linked, later or in the process generate, before or after generate
Quantity can be than relatively freely controlling, and side chain/side group hydrogen bond freedom degree is higher is more prone to produce dynamic, therefore,
It is preferred that side chain and/or side group hydrogen bond group.The link structure of side chain/between side group hydrogen bond group and chain backbone, length and its this
The structure of body includes that substituent group and side group etc. can carry out diversified adjusting, so that it is steady to control HYDROGEN BOND INTENSITY, steric hindrance, heat
Qualitative, glass transition temperature etc., and then regulate and control dynamic property, assign the different ultra-tough of polymer, selfreparing, strain-responsive
The performances such as property, shape memory.
In embodiments of the present invention, the hydrogen bond action in the supermolecular mechanism by hydrogen bond group donor (H,
Namely hydrogen atom) and receptor (Q, that is, receive the electronegative atom of hydrogen atom) interaction formed, can be times
The meaning number of teeth.Wherein, the number of teeth refers to being formed by hydrogen bond quantity, each H ... Q group by the donor and receptor of hydrogen bond group
It is combined into a tooth.In following formula, the bonding situation of the schematically illustrate tooth of difference, two teeth and three tooth hydrogen bonds.
The bonding situation of one tooth, two teeth and three tooth hydrogen bonds can concrete example it is as follows:
In embodiments of the present invention, the number of teeth of hydrogen bond is not limited.The number of teeth of hydrogen bond is more, and synergistic effect is got over
Greatly, the intensity of hydrogen bond is bigger.If the number of teeth for being formed by hydrogen bond is more, intensity is big, then the dynamic of hydrogen bond action is just
It is weak, it can be used as structural hydrogen bond and play promotion dynamic aggregation object holding balanced structure and improve mechanical property (modulus and intensity)
Effect.If the number of teeth of formed hydrogen bond is few, intensity is low, and the dynamic of hydrogen bond action is with regard to strong.It is a kind of preferred in the present invention
Embodiment for select be no more than four teeth hydrogen bond dynamic is provided;Another preferred embodiment is to select two kinds or two
Kind or more hydrogen bond group form the different hydrogen bond of dynamic, multi-level dynamic is provided.
In embodiments of the present invention, when the hydrogen bond group is only side group hydrogen bond group, containing following logical
At least one of structure shown in formula (4), (5):
Wherein,Indicate the connection with polymer chain, R is substituent group, and G is end group;Between G,With R it
Between, can be cyclic or not cyclic between G and R.
Wherein, X respectively stands alone as any one of oxygen atom, sulphur atom, nitrogen-atoms, and it is former that Y respectively stands alone as oxygen atom, sulphur
Any one of son.
Wherein, a is the number for the R being connected with X atom.
When X is oxygen atom or sulphur atom, a 0, R is not present.
When X is nitrogen-atoms, a 1, R is respectively individually present.
R, the structure of G is not particularly limited, and respectively independent includes but is not limited to 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, preferably
Aliphatic ring.
R, the structure of G is respectively independently preferably linear chain structure.
R can contain hetero atom, can also be free of hetero atom;G can contain hetero atom, can also be free of hetero atom.
R, the carbon atom number of G is not particularly limited, and respectively independent is preferably 1~20, respective independent more preferably 1~
10。
R, G is each independently selected from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Miscellaneous alkyl, substituted C1-20Alkyl takes
The miscellaneous alkyl in generation.Wherein, the substitution atom in R, G or substituent group are not particularly limited, and are each independently selected from halogen atom, alkyl
Substituent group contains heteroatomic substituent group.
R, G is respectively independently more preferably 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 and its any substituted form.
R, G is respectively independently more preferably hydrogen atom, halogen atom, C1-20Alkyl, C1-20Alkenyl, aryl, aryl, C1-20
Rouge miscellaneous alkyl, heteroaryl, heteroaryl alkyl, C1-20Alkoxyacyl, aryloxy acyl group, C1-20Alkyl sulfenyl acyl group, artyl sulfo
Acyl group and its any substituted form.
R, G is respectively independently more preferably hydrogen atom, halogen atom, C1-20Alkyl, C1-20Alkenyl, aryl, aryl, C1-20
Rouge miscellaneous alkyl, heteroaryl, heteroaryl alkyl, C1-20Alkoxy carbonyl, aryloxycarbonyl, C1-20Alkyl sulfenyl carbonyl, artyl sulfo
Carbonyl, C1-20Alkoxy carbonyl, aryloxy thiocarbonyl, C1-20Alkyl sulfenyl thiocarbonyl, artyl sulfo thiocarbonyl
And its any substituted form.
Specifically, R, G be each independently selected from including but not limited to hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom,
Methyl, ethyl, n-propyl, isopropyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,
Tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, allyl
Base, 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, substituted C1-20Alkyl, substituted C1-20Alkenyl,
Substituted aryl, substituted aryl, substituted C1-20Rouge miscellaneous alkyl, substituted heteroaryl, substituted heteroaryl alkyl, replace
C1-20Alkoxy carbonyl, substituted aryloxycarbonyl, substituted C1-20Alkyl sulfenyl carbonyl, takes substituted artyl sulfo carbonyl
The C in generation1-20Alkoxy carbonyl, substituted aryloxy thiocarbonyl, substituted C1-20Alkyl sulfenyl thiocarbonyl replaces
Artyl sulfo thiocarbonyl.Wherein, butyl includes but is not limited to normal-butyl, tert-butyl.Octyl include but is not limited to n-octyl,
2- ethylhexyl.Wherein, atom or substituent group is replaced to be selected from halogen atom, hydrocarbyl substituent, contain heteroatomic substituent group.
R, G further respectively it is independent be preferably hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl,
Amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, ten
Six alkyl, heptadecyl, octadecyl, nonadecyl, eicosyl, allyl, benzyl, trityl, phenyl, benzyl, first
Base benzyl, nitrobenzyl, tert. butyl-sulphenyl, benzyl sulfenyl, 2- pyridinylthio, acetyl group, benzoyl, 2- pyridyl group carbonyl
Base, methoxycarbonyl, ethoxy carbonyl, t-butyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, methyl mercapto carbonyl, second sulphur
Base carbonyl, tert. butyl-sulphenyl carbonyl, thiophenyl carbonyl, benzylthio carbonyl, ethylenebis dithiocarbamate carbonyl, phenyl first thiocarbonyl, methoxy
Base thiocarbonyl, ethyoxyl thiocarbonyl, tert-butyl oxygroup thiocarbonyl, phenoxythiocarbonyl, benzyloxy thiocarbonyl, first
Alkylthio carbonyl, ethylmercapto group thiocarbonyl, tert. butyl-sulphenyl thiocarbonyl, phenylthiothiocarbonyl carbonyl, benzylthio thiocarbonyl,
C1-10It halohydrocarbyl, trifluoroacetyl group, halogenophenyl, halogeno-benzyl, nitrobenzophenone, nitrobenzyl and its any is substituted
Form.Wherein, replace atom or substituent group is preferably fluorine atom, alkoxy, nitro.
R, G respectively independent more preferably hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, benzyl, three
Benzyl, phenyl, benzyl, methylbenzyl, tert. butyl-sulphenyl, benzyl sulfenyl, 2- pyridinylthio, 2- pyridylcarbonyl, tertiary fourth
Base Epoxide carbonyl, phenyloxycarbonyl, benzyloxycarbonyl, tert-butyl oxygroup thiocarbonyl, phenoxythiocarbonyl, benzyloxy are thio
Carbonyl, tert. butyl-sulphenyl thiocarbonyl, phenylthiothiocarbonyl carbonyl, benzylthio thiocarbonyl, trifluoroacetyl group.
R, G respectively independently be more preferably hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, benzyl,
Trityl, phenyl, benzyl, methylbenzyl, tert. butyl-sulphenyl, benzyl sulfenyl, 2- pyridinylthio.
R, G is respectively independently most preferably hydrogen atom, methyl, ethyl, n-propyl, normal-butyl.
Heretofore described hetero atom is not particularly limited, including but not limited to oxygen atom, sulphur atom, nitrogen-atoms, phosphorus
Atom, silicon atom, fluorine atom, chlorine atom, bromine atom, iodine atom, boron atom etc..Wherein, heteroatomic quantity can be one,
It may be two or more.Hetero atom, which can be used as, replaces atom to exist, can also be independently as divalent linker
In the presence of illustrate such as-O- (oxygroup or ehter bond) ,-S- (sulfenyl or thioether bond).
There is good compatibility with formula (4), the hydrogen bond group of (5) structure and catalytic component B, preferably by isocyanide
The reaction that acid esters compound is participated in obtains, and conveniently performs the derivatization, and obtains structure and performance abundant.Such reaction
Raw material sources are abundant, and synthesis is simple, and operation is easy, and are suitble to large-scale industrial production.
As an example, side group hydrogen bond group as described below can be enumerated, but the present invention is not limited only to this:
Wherein, m, n, x are the quantity of recurring group, can be fixed value, are also possible to average value.M, n value range is 0
Be more than or equal to 1 integer, preferably no greater than 20, more preferably no higher than 10;X value range is the integer more than or equal to 1.
Other optional side group hydrogen bond groups can be selected from including but are not limited to amino, hydroxyl, carboxyl, amide groups, thio
Amide groups, pyrrolidone-base, imidazole radicals, pyrazolyl, nitrogen oxazolyl and its derivative base.
In embodiments of the present invention, main chain and/or side chain skeleton hydrogen bond group can be any appropriate hydrogen bond base
Hydrogen bond donor and hydrogen bond receptor are preferably contained simultaneously in group, contain at least one secondary amino group preferably wherein, further preferably following knot
At least one of composition point:
Wherein,Indicate the connection with polymer chain.
As an example, the hydrogen bond group on main chain and/or side chain skeleton as described below can be enumerated, but the present invention not only limits
In this:
In embodiments of the present invention, end group hydrogen bond group can be any appropriate hydrogen bond group, preferably contain simultaneously
There are hydrogen bond donor and hydrogen bond receptor, contain at least one secondary amino group preferably wherein, in further preferably following constituent extremely
Few one kind:
Wherein,Indicate the connection with polymer chain, L is end group;It can be cyclic or not cyclic with L.
Wherein, Z is each independently selected from oxygen atom or sulphur atom.
The structure of L is not particularly limited, respectively it is independent include but is not limited to 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, preferably rouge
Fat race ring.
The structure of L is respectively independently preferably linear chain structure.
L can contain hetero atom, can also be free of hetero atom.
The carbon atom number of L is not particularly limited, and respectively independent is preferably 1~20, and respective independent more preferably 1~10.
L is each independently selected from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Miscellaneous alkyl, substituted C1-20Alkyl or substitution
Miscellaneous alkyl.Wherein, the substitution atom in L or substituent group are not particularly limited, and are each independently selected from halogen atom, alkyl replaces
Base contains heteroatomic substituent group.
L is respectively independently more preferably hydrogen atom, halogen atom, C1-20Alkyl, C1-20Unsaturated aliphatic hydrocarbyl moiety, aryl, aromatic hydrocarbons
Base, C1-20Miscellaneous alkyl, C1-20Alkyl oxygroup acyl group, C1-20Alkylthio acyl group and its any substituted form.
L is respectively independently more preferably 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
Base and its any substituted form.
L is respectively independently more preferably hydrogen atom, halogen atom, C1-20Alkyl, C1-20Alkenyl, aryl, aryl, C1-20Rouge
Miscellaneous alkyl, heteroaryl, heteroaryl alkyl, C1-20Alkoxy carbonyl, aryloxycarbonyl, C1-20Alkyl sulfenyl carbonyl, artyl sulfo carbonyl
Base, C1-20Alkoxy carbonyl, aryloxy thiocarbonyl, C1-20Alkyl sulfenyl thiocarbonyl, artyl sulfo thiocarbonyl and
Its any substituted form.
Specifically, L is each independently selected from including but 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, substituted C1-20Alkyl, substituted C1-20Alkenyl, replace
Aryl, substituted aryl, substituted C1-20Rouge miscellaneous alkyl, substituted heteroaryl, substituted heteroaryl alkyl, substituted C1-20Alkane
Epoxide carbonyl, substituted aryloxycarbonyl, substituted C1-20Alkyl sulfenyl carbonyl, substituted artyl sulfo carbonyl, replace
C1-20Alkoxy carbonyl, substituted aryloxy thiocarbonyl, substituted C1-20Alkyl sulfenyl thiocarbonyl, substituted virtue
Base alkylthio carbonyl.Wherein, butyl includes but is not limited to normal-butyl, tert-butyl.Octyl includes but is not limited to n-octyl, 2- second
Base hexyl.Wherein, atom or substituent group is replaced to be selected from halogen atom, hydrocarbyl substituent, contain heteroatomic substituent group.
It is preferably hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, penta that L is further respectively independent
Base, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, 16
Alkyl, heptadecyl, octadecyl, nonadecyl, eicosyl, allyl, benzyl, trityl, phenyl, benzyl, methyl
Benzyl, nitrobenzyl, tert. butyl-sulphenyl, benzyl sulfenyl, 2- pyridinylthio, acetyl group, benzoyl, 2- pyridylcarbonyl,
Methoxycarbonyl, ethoxy carbonyl, 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, ethyoxyl thiocarbonyl, tert-butyl oxygroup thiocarbonyl, phenoxythiocarbonyl, benzyloxy thiocarbonyl, first sulphur
Base thiocarbonyl, ethylmercapto group thiocarbonyl, tert. butyl-sulphenyl thiocarbonyl, phenylthiothiocarbonyl carbonyl, benzylthio thiocarbonyl,
C1-10It halohydrocarbyl, trifluoroacetyl group, halogenophenyl, halogeno-benzyl, nitrobenzophenone, nitrobenzyl and its any is substituted
Form.Wherein, replace atom or substituent group is preferably fluorine atom, alkoxy, nitro.
L respectively independent more preferably hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, benzyl, triphen
Methyl, phenyl, benzyl, methylbenzyl, tert. butyl-sulphenyl, benzyl sulfenyl, 2- pyridinylthio, 2- pyridylcarbonyl, tert-butyl
Epoxide carbonyl, phenyloxycarbonyl, benzyloxycarbonyl, tert-butyl oxygroup thiocarbonyl, phenoxythiocarbonyl, the thio carbonyl of benzyloxy
Base, tert. butyl-sulphenyl thiocarbonyl, phenylthiothiocarbonyl carbonyl, benzylthio thiocarbonyl, trifluoroacetyl group.
L is respectively independently more preferably hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, tert-butyl, benzyl, three
Benzyl, phenyl, benzyl, methylbenzyl, tert. butyl-sulphenyl, benzyl sulfenyl, 2- pyridinylthio.
L is respectively independently most preferably hydrogen atom, methyl, ethyl, n-propyl, normal-butyl.
As an example, end group hydrogen bond group as described below can be enumerated, but the present invention is not limited only to this:
Wherein, m, n, x are the quantity of recurring group, can be fixed value, are also possible to average value.M, n value range is 0
With the integer for being more than or equal to 1;X value range is the integer more than or equal to 1.
In embodiments of the present invention, contain other while property is also an option that in the hydridization dynamic aggregation object component
May participate in the other components to form hydrogen bond action containing hydrogen bond group, including but not limited to small molecule, polymer, inorganic material,
Metal material, hydrogen bond group contained therein can be any appropriate group, as an example, including but not limited to general formula (4)-
(9) hydrogen bond group and amino, hydroxyl, imidazole radicals, pyrazolyl, nitrogen oxazolyl and its derivative base described in.Such other components
Between can also form hydrogen bond.In the present invention, the content of other such hydrogen bond groups is not particularly limited, preferably shorter than hydrogen bond
The 50mol% of group total content, more preferably less than 20mol%, even more preferably below 5mol%.
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:
In the present invention, the supermolecule hydrogen bond action, which can be, carries out the friendship of dynamic supermolecule in hydridization dynamic aggregation object
It is generated during connection/polymerization;It is also possible to carry out after pre-generated supermolecule hydrogen bond action dynamic supermolecule crosslinking/poly- again
It closes;Supermolecule can also be generated during hydridization dynamic aggregation object subsequent forming after dynamic supermolecule crosslinking/polymerization is formed
Hydrogen bond action, but the present invention is not limited only to this.
The unsaturated carbon that olefin cross metathesis metathesis reaction occurs of reversible dynamic crosslinking is used to form in the present invention
Carbon double bond group can be the polymer precursor for having contained unsaturated carbon-carbon double bond from selection, can also be without unsaturation
It generates or introduces on the basis of the polymer precursor of carbon-carbon double bond.The generation or introducing of unsaturated carbon-carbon double bond, can be covalent
Before crosslinking, later or in the process carry out.But the reaction condition of the reaction due to generating carbon-carbon double bond is typically more harsh, because
This is it is preferable to use the polymer precursor containing carbon-carbon double bond or using the polymer precursor without containing carbon-carbon double bond and contains carbon
The reagent of carbon double bond reacts, and achievees the purpose that introduce carbon-carbon double bond.
Wherein, contained the polymer precursor of unsaturated carbon-carbon double bond, as an example, including but not limited to butadiene rubber,
1,2- butadiene rubber, isoprene rubber, polynorbornene, neoprene, butadiene-styrene rubber, nitrile rubber, polychlorobutadiene, bromination
Polybutadiene, Ethylene-Propylene-Diene rubber (EPDM), acrylonitrile-butadiene-styrene copolymer (ABS), styrene-fourth two
Alkene rubber (SBR), Styrene-Butadiene-Styrene Block Copolymer (SBS), styrene-isoprene-phenylethene block are total
Polymers (SIS), unsaturated polyester (UP), unsaturated polyether and its copolymer etc..
Wherein, the group containing carbon-carbon double bond or introducing for segment can use any appropriate reaction, including but not only
Be limited to Types Below: isocyanates and amino, hydroxyl, sulfydryl, carboxyl, epoxy group are reacted, carboxylic acid, carboxylic acid halides, acid anhydrides, active ester
It is reacted with amino, hydroxyl, sulfydryl, free radical acrylate reaction, acrylamide radical reaction, double bond radical reaction,
Epoxy group and amino, hydroxyl, sulfydryl react, phenol-formaldehyde reaction, nitrine-alkynes click-reaction, tetrazine-norbornene reaction, silicon hydroxyl
Base condensation reaction;Preferred isocyanate and amino, hydroxyl, sulfydryl react, carboxylic acid halides, acid anhydrides and amino, hydroxyl, sulfydryl it is anti-
It answers, free radical acrylate reaction, acrylamide radical reaction, double bond radical reaction, epoxy and amino, hydroxyl, sulfydryl
Reaction.As an example, the available small organic agents containing carbon-carbon double bond include but is not limited to following lifted: Isosorbide-5-Nitrae-butylene
Glycol, 1,5- di-p oxyphenyl -1,4- pentadiene -3- ketone, single ricinoleic acid glyceride, maleic acid, fumaric acid, transmethyl fourth
Enedioic acid (mesaconic acid), cis-methyl-butene diacid (citraconic acid), chloro maleic acid, 2- methylene-succinic acid (clothing health
Acid), 4,4'- stilbenedicarboxylicacid acid, 1,5- di-p oxyphenyl -1,4- pentadiene -3- ketone, fumaryl chloride, 1,4- phenylene two
Acryloyl chloride, citraconic anhydride, maleic anhydride, dimethyl fumarate, monomethyl ester, diethyl fumarate, citraconic acid diformazan
Bromo- 2- butylene of ester, Isosorbide-5-Nitrae-dichloro-2-butene, Isosorbide-5-Nitrae-two etc. can also be selected double containing carbon carbon on the chain backbone of end group functional
The oligomer of key.
Wherein, the generation of carbon-carbon double bond can use any appropriate method, include but are not limited to following chemical reaction
Type: hydrogen halides reaction is lost in alcohol dehydration reaction, halogenated hydrocarbons, dihalo hydrocarbon loses halogen reaction, Hofmann elimination reaction, amine oxide
Hot tearing reaction, ester hot tearing reaction, xanthate hot tearing reaction, Wittig reaction and Wittig-Horner reaction, alkene it is acyclic
Metathesis polymerization reacts (ADMET), cyclenes ring-opening polymerization etc..Wherein, preferable reaction temperature is not higher than 200 DEG C of reaction.
The generation or introducing of the hydrogen bond group of supermolecular mechanism are used to form in the present invention, can dynamic covalent cross-linking it
Before, carry out later or in the process.It is preferred that carrying out before dynamic covalent cross-linking or in the process, more preferably covalently handed in dynamic
It is carried out before connection.Because must will be generally added by way of swelling in relation to reagent if being carried out after dynamic covalent cross-linking,
Complex process and effect is poor.
In embodiments of the present invention, the generation or introducing of hydrogen bond group can use any appropriate reaction, including but
Be not limited only to Types Below: isocyanates and amino, hydroxyl, sulfydryl, carboxyl react, free radical acrylate reaction, double bond
Radical reaction, double bond cyclization, epoxy and amino, hydroxyl, sulfydryl react, nitrine-alkynes click-reaction, and sulfydryl-double bond/
Alkynes click-reaction, the reaction of urea-amine, amidation process, tetrazine-norbornene reaction, active ester and amino, hydroxyl, sulfydryl
Reaction, silicone hydroxyl condensation reaction;Preferred isocyanate and amino, hydroxyl, sulfydryl react, the reaction of urea-amine, amidation
Reaction, active ester and amino, hydroxyl, sulfydryl react.In any one network structure, hydrogen bond group can have one or its
Above reaction type, reaction means and the structure.
In embodiments of the present invention, for connecting dynamic covalent bond and dynamic covalent bond, dynamic covalent bond and hydrogen bond
The ingredient of group, hydrogen bond group and hydrogen bond group can be small molecule and/or polymer segment.The wherein polymer chain
Section, including but are not limited to main chain is carbon-chain structure, carbon heterochain structure, carbon chain structure, element chain structure, element heterochain knot
The polymer segment of the miscellaneous element chain structure of structure, carbon.The carbon-chain structure is the structure that main chain backbone contains only carbon atom;It is described
Carbon heterochain structure be main chain backbone contain simultaneously carbon atom and it is any or appoint several heteroatomic structures, wherein the miscellaneous original
Son includes but are not limited to sulphur, oxygen, nitrogen;The carbon chain structure be main chain backbone contain simultaneously carbon atom and it is any or
Appoint the structure of several Elements Atoms, wherein Elements Atom includes but are not limited to silicon, boron, aluminium;Based on the element chain structure
Chain backbone is only containing the structure of Elements Atom;The element heterochain structure is main chain backbone simultaneously and only containing at least one miscellaneous
The structure of atom and at least one Elements Atom;The miscellaneous element chain structure of the carbon is main chain backbone while including carbon atom, miscellaneous
The structure of atom and Elements Atom.In an embodiment of the invention, it is carbon that the preferably described polymer segment, which is main chain,
The polymer segment of chain structure and carbon heterochain structure, because of its structure-rich, has excellent performance.As an example, preferred carbochain and carbon
Heterochain polymer segment is included but are not limited to such as acrylic polymer, saturation of olefins quasi polymer, ethylenic unsaturation hydro carbons
Polymer, polystyrenic polymer, halogen-containing olefin polymer, polyacrylonitrile quasi polymer, polyvinyl alcohol Type of Collective
Object, poly- (2- oxazoline) quasi polymer, polyether-based polymers, polyester polymer, Biopolvester quasi polymer, polycarbonate are birdsed of the same feather flock together
Close object, polyurethane polymer, polyureas quasi polymer, polyamide polymers, polyamine quasi polymer, liquid crystal quasi polymer, ring
Homopolymer, copolymer, modifier, the derivative etc. of oxygen quasi polymer, polysulfide ether polymer etc..In another reality of the invention
It applies in mode, preferably the polymer segment is element heterochain structure, by way of example, such as all kinds of poly-organosilicon polymer.Make
For citing, preferred polymer segment includes but are not limited to acrylic polymer, saturation of olefins quasi polymer, unsaturation
Olefin polymer, halogen-containing olefin polymer, poly- (2- oxazoline) quasi polymer, polyether-based polymers, polyester Type of Collective
Object, Biopolvester quasi polymer, polyurethane polymer, polyureas quasi polymer, polysulfide ether polymer, silicone-based polymers
Deng homopolymer, copolymer, modifier, derivative etc..Specifically, currently preferred polymer segment includes but are not limited to
Polymethyl acrylate, polyethyl acrylate, butyl polyacrylate, polyethylene, polypropylene, polyisobutene, polybutadiene, polycyclic are pungent
Alkene, polynorbornene, polyisoprene, polyvinyl chloride, poly- (2- oxazoline), polyethylene glycol, polypropylene glycol, polycaprolactone, poly- β-
Homopolymer, copolymer, modifier, the derivative of butyric ester, polyurethane, polyureas, polythiaether, polyorganosiloxane etc.
Deng.
In yet another embodiment of the present invention, it is preferably described for connect dynamic covalent bond and dynamic covalent bond,
The glass transition temperature of the polymer segment of dynamic covalent bond and hydrogen bond group, hydrogen bond group and hydrogen bond group is not higher than 25
DEG C, more preferably no higher than 0 DEG C, it is presented as flexibility at room temperature before the reaction, it is convenient to carry out adding for subsequent products at normal temperature
Work preparation facilitates and obtains flexible and viscosity product, is also convenient for adjusting by increasing crosslink density or using other additives
The hardness of material matrix is conducive to embody the dynamic of supermolecule hydrogen bond as matrix.In another embodiment party of the invention
In formula, preferably the glass transition temperature of the polymer segment is higher than 25 DEG C but lower than 40 DEG C, and it is quick to be conducive to introducing temperature
The characteristics such as perceptual, moderate elasticity and dynamic.In yet another embodiment of the present invention, the preferably described polymer segment
Glass transition temperature be not less than 40 DEG C, more desirably not less than 100 DEG C, be conducive to introduce shape memory, Temperature Size steady
The characteristics such as qualitative, low temperature and room temperature hardness.In yet another embodiment of the present invention, in the preferably described polymer segment extremely
A kind of few polymer segment that 25 DEG C are not higher than for glass transition temperature, and at least one is not less than for glass transition temperature
100 DEG C of polymer segment, convenient for obtaining the various characteristics under low temperature and high temperature simultaneously.
In embodiments of the present invention, for connecting dynamic covalent bond and dynamic covalent bond, dynamic covalent bond and hydrogen bond
Group, the small molecule of hydrogen bond group and hydrogen bond group and/or polymer segment and/or dynamic aggregation object can have any conjunction
Suitable topological structure includes but are not limited to linear chain structure, branched structure (including but not limited to starlike, H-type, dendroid, comb
It is shape, hyperbranched), cyclic structure (including but not limited to monocycle, polycyclic, bridged ring, grommet, torus), two-dimensional/three-dimensional cluster structure and
Its two kinds or several combination;Wherein, the linear chain structure of synthesis and control structure, the branched structure of structure-rich are preferably facilitated
With can be with the two-dimensional/three-dimensional cluster structure of local enhancement, more preferable linear chain structure and branched structure.In the present invention, or even not
It excludes to carry out the reaction such as further polymerized/cross-linked and connection using the polymer beads of crosslinking.
Selected above-mentioned each quasi polymer and its segment in the present invention, i.e., have hydrogen bond base containing dynamic covalent bond simultaneously again
The polymer and its segment of group, the polymer for not only not contained dynamic covalent bond but also not contained hydrogen bond group and its segment only contain
Polymer and its segment and only polymerization containing hydrogen bond group without dynamic covalent bond of the dynamic covalent bond without hydrogen bond group
Object and its segment can directly select the raw material of commercialization, can also voluntarily polymerize.Polymerization is according to selected polymer
Type includes but is not limited to polycondensation, addition polymerization and ring-opening polymerisation;Wherein, addition polymerization includes but is not limited to free radical polymerization, activity freedom
Base polymerization, anionic polymerisation, cationic polymerization, coordination polymerization etc..Wherein, polymerization process can carry out in a solvent, can also be with
It is solvent-free bulk polymerization.Specifically, as an example, the available polymerization of the present invention includes but is not limited to: styrene
Class, the heat of (methyl) acrylic ester monomer cause general radical polymerization, phenylethylene, (methyl) acrylic ester monomer
Light lnduced Free Radicals polymerization, the Iniferter free radical polymerization of vinyl chloride monomer, phenylethylene, (methyl) acrylic acid
The atom transfer radical polymerization (ATRP) of esters monomer, phenylethylene, (methyl) esters of acrylic acid, acrylonitrile monomer are reversible
Addition-fracture transferring free-radical polymerization (RAFT), nitroxide-mediated stable free-radical polymerization (NMP), ethylene, propylene coordination polymerization, benzene second
The anionic polymerisation of vinyl monomer, lactone ring opening polymerization, lactams ring-opening polymerisation, epoxy addition polymerization, binary acid and dihydric alcohol
Between polycondensation, the polycondensation between binary acid and diamine, between binary mercaptan and binary alkene/alkynes click-reaction polymerization, two
Click-reaction polymerization between first nitrine and binary alkynes, the ring-opening polymerisation of 2- oxazoline derivative, polyurethane/polyurea reaction etc..?
In specific implementation process, raw materials of compound can utilize above-mentioned any polymerisation process, appoint by the way that this field is general
A kind of suitable polymerization technique is implemented, to obtain hydridization dynamic aggregation object of the invention.
It can be addition-crosslinked or condensation cross-linking for the mechanism of crosslinking of polymer.Wherein, it is addition-crosslinked refer to pass through addition
Form and the cross-linking polymerization carried out, usually by the addition reaction containing multi-functional strand by intermolecular functional group
And cross-linking products are formed, it is generated without by-product.Condensation cross-linking refers to the cross-linking reaction carried out by condensed forms, usually
By forming cross-linking products by intermolecular functional group's condensation reaction containing multi-functional strand, there is by-product generation.
In embodiments of the present invention, crosslinking can be using any appropriate physics and chemical crosslinking technique.Physics is handed over
Connection technique includes but is not limited to heat initiation crosslinking, photo-initiated crosslinking, radiation-induced crosslinking, plasma causes crosslinking, microwave draws
Hair crosslinking etc.;Chemical crosslinking technique includes but is not limited to peroxide crosslinking, nucleopilic reagent substitution crosslinking, isocyanates reaction friendship
Connection, epoxy reaction crosslinking, acrylate reactions crosslinking etc..Cross-linking process can be carried out in the form of ontology, solution, lotion etc..When
Using bulk form, solid end product is conveniently directly obtained;When using solution form, gel is conveniently directly obtained;When using cream
Liquid mode facilitates and obtains particle dispersing but with tack.It should be pointed out that any crosslinking must assure that the carbon carbon
Double bond complete is incompletely dissociated the disintegration that can lead to covalent cross-linking network.
Initiator needed for above-mentioned polymerization, cross-linking method and polymerization, cross-linking process, catalyst, crosslinking agent, other
Auxiliary agent and reaction condition etc. are all open known routine techniques (such as Pan Zuren chief editor, " polymer chemistry (enhanced editions) "),
Those skilled in that art, which can according to need, to be reasonably selected and combines.
It is illustrated below for the embodiment of the part preparation method of network structure of the invention.
For example, the first network structure of the invention can be prepared by following methods: will be easy containing that olefin cross can occur
The unsaturated carbon-carbon double bond group of position metathesis reaction (is denoted as V in following structural formulam) double carboxylic monomers and have skeleton hydrogen
Key group (is denoted as R in following structural formulaH, RHMeet structure described in general formula (4) comprising at least one) double carboxylic monomers and
With side group hydrogen bond group RHPolyhydroxy based cross-linker, the first network structure in the present invention can be formed with polymerized/cross-linked.It is logical
The formula rate of control monomer and crosslinking agent is crossed, the content and ratio of dynamic covalent bond and hydrogen bond group in adjustable network,
The covalent cross-linking in network is set to reach covalent gel point or more.
For another example, the first network structure of the invention can also be realized by Raolical polymerizable: end is had side group
Hydrogen bond group RHAcrylate and with the unsaturated carbon-carbon double bond group V that olefin cross metathesis metathesis reaction can occurm's
The first network structure of double methacrylate by the Raolical polymerizable of alkene, in the available present invention.Pass through control
The dosage of monoolefine, the formula rate of diolefin and the monoolefine without hydrogen bond group selectively used, adjustable net
The content and ratio of dynamic covalent bond and hydrogen bond group, make the covalent cross-linking in network reach covalent gel point or more in network.
For another example, the first network structure of the invention can also be by first carrying out acyclic diene hydrocarbon of the part containing hydrogen bond group
Metathesis polymerization reaction, then it is crosslinked to obtain the first network structure in the present invention.Hydrogen bond is contained or not contain by control
The formula rate of the acyclic diene hydrocarbon of group and the dosage of crosslinking agent, dynamic covalent bond and hydrogen bond group in adjustable network
Content and ratio, so that the covalent cross-linking in network is reached covalent gel point or more.
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.
Hydridization dynamic aggregation compositions component A of the invention, except network structure can have and only one polymeric web
Outside network, other network structures can the Multi net voting structure based on two or its above network.In addition to common blending dispersion, more
Preferably the interpenetrating networks for tangling and being formed are intertwined by two or more polymer networks.Interpenetrating net polymer knot
Structure due between network component collaboration and/or orthogonal effect so that its performance is substantially better than single network polymer of its component, generate ratio
The mechanical properties such as the higher toughness of single network, in the case where being based particularly on mentality of designing introducing hydrogen bond crosslinks of the invention.
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.Between ignore network if supermolecule crosslinking that may be present, of the invention the 6th kind
Network structure and the 7th kind of network structure can be considered semi-intercrossing network, the 4th kind of network structure of the invention and the 5th kind of network
Structure can be considered full interpenetrating networks.
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 the 1st network polymerization
And then object is immersed in the monomer/pre-polymer solution to form the 2nd network, then it is miscellaneous to obtain target for initiation polymerized/cross-linked
Change network.The preparation of hydridization dynamic aggregation object in the present invention can also use one-step method interpenetrating and two-step method interpenetrating, specific
In the case of must also using three steps and its more than method.
It is illustrated below for the embodiment of the part preparation method of interpenetrating net polymer of the invention.With
It is lower to lift only as an example, it not limits the scope of the invention, is lifted the present invention is not limited to following.
For example, the dynamic aggregation object of the hybrid cross-linked network is by two nets in the 4th kind of network structure of the invention
Network is constituted.Firstly, preparing one kind, there is no hydrogen bond groups, but olefin cross metathesis subdivision can occur for presence on polymer chain skeleton
Solve the polymer dynamic co-crosslinking network of the unsaturated carbon-carbon double bond group of reaction.Then, gained dynamic covalent networks are swollen,
It is uniformly mixed with the monomer of supermolecule cross-linked network or prepolymer, crosslinking agent etc., supermolecule crosslinking is carried out, to obtain full interpenetrating
Network polymer namely Supramolecular Network disperse through in dynamic covalent cross-linking.Alternatively, by the list of dynamic covalent cross-linking network
Body or prepolymer, crosslinking agent are uniformly mixed with the monomer of supermolecule cross-linked network or prepolymer, crosslinking agent etc., while carrying out dynamic
Covalent cross-linking and supermolecule are crosslinked to arrive the 4th kind of network structure of the invention.
For another example, in the 7th kind of network structure of the invention, firstly, reasonably selecting preceding method preparation simultaneously containing dynamic
The hybrid cross-linked network with the first network structure of covalent cross-linking and supermolecule crosslinking.It then, will be resulting hybrid cross-linked
Network is sufficiently blended to arrive semi-interpenetrating network polymer with supermolecule polymer.Alternatively, will have the first network structure
Monomer or prepolymer, the crosslinking agent of hybrid cross-linked network are uniformly mixed with supermolecule polymer, Mobile state covalent cross-linking of going forward side by side, i.e.,
Obtain the 7th kind of network structure of the invention.
In the following, in the present invention hydridization dynamic aggregation compositions component B catalyst or its compound carry out specifically
It is bright.
In embodiments of the present invention, the olefin cross metathesis metathesis reaction based on ruthenium, molybdenum, tungsten, titanium,
It is carried out under the catalysis of the metallic catalysts such as palladium, nickel, includes but are not limited to such as document " Recent Advances in High
Oxidation State Mo and W Imido Alkylidene Chemistry ", RichardR.Schrock,
Chem.Rev.2009,109,3211-3226, document " Ruthenium-Based Heterocyclic Carbene-
Coordinated Olefin Metathesis Catalysts ", Georgios C.Vougioukalakis and Robert
H.Grubbs, Chem.Rev.2010,110,1746-1787, document " Olefin Metathesis in Aqueous
Media ", Jasmine Tomasek and J ü rgen Schatz, Green Chemistry, 2013,15,2317-2338, text
Offer " Remote Control Grubbs Catalysts That Modulate Ring-Opening Metathesis
Polymerizations ", Aaron J.Teator and Christopher W.Bielawski, 2017,55,2949-
2960, book " Olefin Metathesis:Theory and Practice " 2014 John Wiley &Sons, Inc., patent
Catalyst is suitable for the invention disclosed in CN201210067234.9.Selected catalyst both can be used alone,
It can also be used cooperatively with two or more;It can be directly dispersing in hydridization dynamic aggregation compositions component A and use,
It can be used in the form of the compound containing catalyst, such as, but not limited to by either physically or chemically coating or loading on
It is used on organic and inorganic, polymer support, and (such as suitable temperature, pressure) has under the conditions of selfreparing with other
The component of low-viscosity high-fluidity is coated in microcapsules or microtubular together and uses;It can also be the nonactive shape of catalyst
Formula can be converted to active catalyst under the appropriate environmental stimuli such as such as heat, soda acid, illumination, free radical.When selected
Catalyst be used alone when need to in each analog assistant filler existing for hydridization dynamic aggregation compositions component A and selectivity
Existing all kinds of groups are compatible.Reasonably selecting catalyst carrier can be enhanced catalyst or its compound in hydridization dynamic aggregation object
Dispersibility in composition component A, reduces the partial size of catalytic clusters, thus improve catalytic efficiency, reduce catalyst amount and
Reduce cost.Reasonably selecting covering material can also avoid catalyst from inactivating in composition preparation process or in the course of work.
The example of available catalyst of the invention or its inactive form includes but is not limited to following lifted:
Wherein, PCy3ForMes isPh is phenyl, and Et is ethyl, and i-Pr is isopropyl
Base, t-Bu are tert-butyl, and PEG is polyethylene glycol.
Wherein, component B is preferably based on the catalyst of ruthenium, molybdenum, tungsten, and more preferable catalytic efficiency is higher and unwise to empty gas and water
The ruthenium catalyst of sense, the catalyst being especially commercialized such as a Grubbs generation, two generations, three generations's catalyst, Hoveyda-
A Grubbs generation, two generation catalyst, (Zhan Shi catalyst is to urge disclosed in patent CN201210067234.9 to Zhan Shi catalyst
Agent) etc..The another kind of component B preferably has catalysis without catalytic activity but under ultraviolet irradiation under normal conditions in the present invention
Active catalyst, it includes but are not limited to catalyst 64-66 etc. as an example.
It is important to note that should be noted its compatibility between component A Zhong Ge functional group when selecting catalyst
Problem need to select suitable catalyst to avoid its failure.For example, causing since amino can form chelate with partial catalyst
Catalyst failure, therefore when containing amino in polymer, the catalyst based on Mo need to be used, or boryl lewis acid is added and keeps away
Exempt from this effect, improves catalytic efficiency;For another example, when in component A there are when itrile group, should be avoided using Grubbs generation catalyst,
And select other catalyst.
In embodiments of the present invention, the preparation method of the compound containing catalyst is not particularly limited, and is used
Method commonly known in the art.
As an example, a kind of preferred embodiment that the compound containing catalyst is prepared in the present invention is by catalyst packet
It overlays in organic carrier.Available organic carrier is not particularly limited, and may be selected from but not limited to paraffin, poly- second as an example
Glycol etc., it is known disclosed technological means that catalyst, which is coated on the method in organic carrier, and the present invention selects common system
Preparation Method.For example, preferred the preparation method comprises the following steps: by selected catalysis by one kind of organic carrier coated catalysts of paraffin
Agent, paraffin and surfactant are sufficiently blended under paraffin molten condition, and blend is poured into the stirring of certain revolving speed and temperature
Higher than in the water of paraffin melting point;After stirring reaches stable state to blending liquid, ice water, which is added, makes water temperature be rapidly cooled to paraffin
Below fusing point;Stop stirring, filtering obtains the catalyst composites of paraffin cladding.
Another preferred embodiment that the compound containing catalyst is prepared in the present invention is by selected catalyst
Through physical absorption or chemical reaction load in organic or inorganic carrier.Available carrier is not particularly limited, as
Example may be selected from but not limited to polystyrene resin beads, magnetic nano-particle, silica gel particle, molecular sieve, other mesoporous materials
Deng being known disclosed technological means by method of the catalyst load on inorganic carrier, for example, Zhu Yinghuai etc. exists
《Magnetic Nanoparticle Supported Second Generation Hoveyda-Grubbs Catalyst
For Metathesis of Unsaturated Fatty Acid Esters ", Adv.Synth.Catal.2009,351,
It is disclosed in 2650-2656 and loads bis- generation of Hoveyda-Grubbs catalyst on magnetic nano-particle simultaneously by chemical means
Method applied to olefin metathesis reaction;For another example, Yang H. etc. is in " Hoveyda-Grubbs Catalyst Confined
in the Nanocages of SBA-1:Enhanced Recyclability for Olefin Metathesis》,
It is disclosed in Chem.Commun.2010,46,8659-8661 by Catalyst Adsorption in molecular sieve and applied to olefin metathesis
Method.The present invention selects common preparation method.
Another preferred embodiment that the compound containing catalyst is prepared in the present invention is by catalyst and other choosings
Auxiliary agent existing for selecting property is coated on using polymer as in the microcapsules of shell.Wherein, as the polymer of microcapsules outer wall without spy
Other limitation as an example but is not limited to following lifted: natural polymer such as Arabic gum, sodium alginate, agar etc., semi-synthetic
Macromolecule such as cellulose derivative, synthesis macromolecule for example polyolefin, polyester, polyethers, polyurethane, polyureas, poly(urea formaldehyde), polyamide,
Polyvinyl alcohol, polysiloxanes etc..It is known disclosed skill that catalyst, which is coated on by the method in the microcapsules of shell of polymer,
Art means, for example, S.H.Cho etc. is at " Polydimethylsiloxane-Based Self-Healing Materials "
The method for preparing polyurethane microcapsule is disclosed in Adv.Mater.2006,18,997-1000;For another example, E.N.Brown etc. exists
《In situ poly(urea-formaldehyde)Microencapsulation of Dicyclopentadiene》
The method of preparation ureaformaldehyde microcapsules is disclosed in J.Microencapsulation 2003,20,719-730.The present invention selects logical
Normal preparation method.
In the following, being deposited to hybrid mode, existence form, other alternatives of hydridization dynamic aggregation compositions in the present invention
Ingredient etc. be described in detail.
In embodiments of the present invention, hydridization can be moved with any appropriate material hybrid mode known in the art
State polymer composition components A (or each material in component A) and component B (or each material in component B) is by being mixed with
Hydridization dynamic aggregation compositions can be interval, semicontinuous or continuous processing form mixing;Similarly, it also may be selected
Intermittently, semicontinuous or continuous processing form forms hydridization dynamic aggregation compositions.The hybrid mode of use include but
Be not limited only to solution be stirred, melt be stirred, mediate, mixing, mill, melting extrusion, ball milling etc., wherein it is preferred that solution
It is stirred, melts and be stirred and melting extrusion.Energy in material mixed process provides form and includes but are not limited to
Heating, illumination, radiation, microwave, ultrasound.The molding mode of use includes but are not limited to extrusion molding, is injection moulded, is molded into
Type, tape casting, calendering formation, cast molding.
In embodiments of the present invention, it is stirred using solution and melting is stirred, mainly in a manner of following two
Carry out: (1) being directly stirred reaction mass in the reactor or heating melting after be stirred reaction, such mode is general
Reaction mass be liquid or lower melting-point solid or reaction mass is more difficult find cosolvent in the case where use;(2) will
Reaction mass is dissolved in respective solvent or is stirred mixing in common solvent in the reactor, and such mode is general
It is used in the case where reaction mass is higher fusing point or solid of not definite melting point.Mixing temperature is not particularly limited, and leads to
Often at 0-200 DEG C, preferably 25-120 DEG C, more preferable 25-80 DEG C, mixing time is not particularly limited, and is preferably controlled in 1 point
Clock is 10-120 minutes more preferable to 12 hours.The product obtained after mixing is poured into suitable mold, suitable
Under the conditions of temperature, preferably at 0-150 DEG C, under the conditions of more preferable 25-80 DEG C of temperature, place the regular hour, preferably 0-48 hours
Polymer samples can be obtained, this can remove solvent as needed in the process.
Used solvent in above-mentioned preparation method, it has to be possible to while dissolve reaction mass respectively, and dissolve
There is the solvent of two class compounds to allow for dissolving each other, reaction mass is not precipitated in the mixed solvent, and solvent used includes but not
Be only limitted to it is following any or appoint several solvents mixed solvents: deionized water, methanol, ethyl alcohol, acetonitrile, acetone, butanone, benzene,
Toluene, dimethylbenzene, chlorobenzene, ethyl acetate, ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran (THF), chloroform, methylene chloride, 1,2-
Dichloroethanes, 1,1,2,2- tetrachloroethanes, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethyl acetamide, N-
Methyl pyrrolidone, isopropyl acetate, n-butyl acetate, trichloro ethylene, mesitylene, dioxanes, trishydroxymethylaminomethane
(Tris) buffer, citrate buffer solution, acetic acid buffer solution, phosphate buffer solution, borate buffer solution etc.;It is preferred that deionization
Water, ethyl alcohol, toluene, chloroform, methylene chloride, 1,2- dichloroethanes, DMF, phosphate buffer solution.
In embodiments of the present invention, the specific of hydridization dynamic aggregation compositions material is mixed with using melting extrusion
A certain amount of reaction mass, is usually added in extruder and carries out extrusion blending reaction by preparation method, and extrusion temperature does not have
Especially limitation, usually 0-280 DEG C, preferably 25-150 DEG C, more preferable 50-100 DEG C.Reaction product can be cut out after direct tape casting
At suitable dimension, sample preparation either is carried out using injection molding machine or moulding press.Injection temperature is not particularly limited, usually 0-280
DEG C, preferably 25-150 DEG C, more preferable 50-100 DEG C;Molding temperature is not particularly limited, usually 0-280 DEG C, preferably 25-150
DEG C, more preferable 50-100 DEG C, clamp time is not particularly limited, usually 0.5-60min, preferably 1-10min.Batten is placed in
In suitable mold, at 25-150 DEG C, under the conditions of preferably 50-80 DEG C of temperature, 0-24h is placed, final composition sample is obtained.
In embodiments of the present invention, in the hydridization dynamic aggregation compositions, the quality of component A account for component A,
The range of the ratio of B quality sum is 90-99.99%, and the range that the quality of component B accounts for the ratio of component A, B quality sum is
0.01-10% can also contain other components in composition.
In the present invention, the form of the hydridization dynamic aggregation compositions can be ordinary solid, elastomer, coagulate
Glue, foam etc..Wherein, the dissolvable small-molecular-weight component content contained in ordinary solid, elastomer and foamed material is generally not
Higher than 10wt%, and the small-molecular-weight component content contained in gel is generally not less than 50wt%.Ordinary solid mechanical property is good,
Mechanics of elastic bodies moderate performance but has the unexistent flexibility of ordinary solid, preparation method is also most easy, therefore more preferably.
Foam is since light and hardness and bendable folding endurance are adjustable, and purposes is wide, therefore also more preferably.In embodiment party of the invention
In formula, sweller can be introduced in hydridization dynamic aggregation compositions, prepare hydridization dynamic aggregation compositions gel.Gel
Product flexibility and bendable folding endurance are all good, and can have certain toughness by structure and formula adjustment, because there are molten
Swollen dose, the unexistent beneficial constituent of material of many other forms can be incorporated, there is special purposes.Wherein, described
Sweller can include but is not limited to organic solvent, ionic liquid, oligomer, plasticizer, water.
A kind of hydridization dynamic aggregation compositions gel provided by the present invention, including organic solvent gel, ionic liquid
Gel, oligomer swell gel, plasticizer swell gel, hydrogel.Wherein, preferred ion liquid gel and plasticising solvent swell are solidifying
Glue.In the presence of hydridization dynamic aggregation compositions are with different existence forms, especially with the shape of hydrogel and ionic gel
It is needed in the presence of formula using adaptable component B.
A kind of preferred preparation method of hydridization dynamic aggregation compositions ionic liquid gel of the invention includes but unlimited
In following steps: each raw material for preparing hydridization dynamic aggregation compositions component A, B and other raw materials are added to ionic liquid
In body, making the sum of prepared mass fraction of hydridization dynamic aggregation compositions component A, B is 0.5~70%, by described
Appropriate means are polymerize, are coupled, are crosslinked or other kinds of chemical reaction, after reaction, that is, a kind of hydridization dynamic are made
Polymer composition ionic liquid gel.Another hydridization dynamic aggregation compositions ionic liquid gel of the invention it is preferred
Preparation method includes but is not limited to following steps: by described hydridization dynamic aggregation compositions component A, B and and other originals
Material is swollen in ionic liquid or solvent containing ionic liquid, makes the quality of hydridization dynamic aggregation compositions component A, B
The sum of score is 0.5~70%, one kind is made in the solvent for sufficiently removing extra ionic liquid after swelling and selectively using
Hydridization dynamic aggregation compositions ionic liquid gel.When selecting ionic liquid and when catalytic component B, should be avoided positive and negative from
Son causes catalyst or its complex components B to decompose inactivation.As an example, the group of preferred ionic liquid and catalytic component B
Conjunction includes but is not limited to: 1- butyl -2,3- methylimidazole/tetrafluoroborate ion/catalyst 33,1- butyl -3- methyl miaow
Azoles bis trifluoromethyl/fluorine-containing sulfimide ion/catalyst 35,1- butyl -3- methylimidazole/hexafluorophosphoricacid acid ions/catalysis
Agent 36 etc..
A kind of preferred preparation method of hydridization dynamic aggregation compositions oligomer swell gel of the invention includes but not
It is limited to following steps: each raw material for preparing hydridization dynamic aggregation compositions component A, B and other raw materials and oligomer is total to
It is mixed, make the mass fraction 0.5~70% of prepared hydridization dynamic aggregation compositions component A, B, passes through the suitable hand
A kind of hydridization dynamic aggregation object is made after reaction in Duan Jinhang polymerization, coupling, crosslinking or other kinds of chemical reaction
Composition oligomer swell gel.The preferred system of another hydridization dynamic aggregation compositions oligomer swell gel of the invention
Preparation Method includes but is not limited to following steps: hydridization dynamic aggregation compositions component A, B and other raw materials is molten
It is swollen in the solvent containing oligomer, make the sum of mass fraction of hydridization dynamic aggregation compositions component A, B be 0.5~
70%, solvent sufficiently is removed after swelling, that is, a kind of hydridization dynamic aggregation compositions oligomer swell gel is made.
A kind of preferred preparation method of hydridization dynamic aggregation compositions plasticizer swell gel of the invention includes but not
It is limited to following steps: each raw material for preparing hydridization dynamic aggregation compositions component A, B and other raw materials is added to plasticising
In agent, making the sum of prepared mass fraction of hydridization dynamic aggregation compositions component A, B is 0.5~70%, by described
Appropriate means are polymerize, are coupled, are crosslinked or other kinds of chemical reaction, after reaction, that is, a kind of hydridization dynamic are made
The gel of polymer composition plasticising solvent swell.Another hydridization dynamic aggregation compositions plasticizer swell gel of the invention
Preferred preparation method include but is not limited to following steps: by hydridization dynamic aggregation compositions component A, B and its
He swells in the solvent containing plasticizer raw material, make hydridization dynamic aggregation compositions component A, B mass fraction it
Be 0.5~70%, sufficiently swelling after remove solvent, that is, a kind of hydridization dynamic aggregation compositions plasticizer swell gel is made.
A kind of preferred preparation method of hydridization dynamic aggregation compositions hydrogel of the invention is including but not limited to as follows
Step: each raw material for preparing hydridization dynamic aggregation compositions component A, B and other raw materials are added to the water, and are made prepared
The sum of the mass fraction of hydridization dynamic aggregation compositions component A, B be 0.5~70%, gathered by the appropriate means
It closes, be coupled, a kind of dynamic aggregation object hydrogel is made after reaction in crosslinking or other kinds of chemical reaction.The present invention
The preferred preparation method of another hydridization dynamic aggregation compositions hydrogel include but is not limited to following steps: will be described
Hydridization dynamic aggregation compositions component A, B and other raw materials are sufficiently swollen in water, make the hydridization dynamic aggregation object group
The sum of mass fraction of polymer component A, B is 0.5~70%, removes extra water, that is, a kind of hydridization dynamic aggregation object group is made
Close object hydrogel.When dynamic aggregation object, which swells in water, forms hydrogel, it should select insensitive to water and have in water molten enough
The component B of Xie Du, as an example, the catalyst that can be used for hydrogel includes but is not limited to such as catalyst 25-32.
In embodiments of the present invention, hydridization dynamic aggregation compositions can be prepared into foamed material.Wherein, foam packet
Include flexible foam or semi-flexible, semi-rigid, micropore or rigid foam.
In embodiments of the present invention, the structure of hydridization dynamic aggregation compositions foamed material be related to open-celled structure,
Three kinds of hole-closing structure, half-open semi-closure structure etc..It in open-celled structure, is interconnected between abscess and abscess, or connection completely, one-dimensional
Or three-dimensional can be transferred through gas or liquid, abscess diameter is 0.01 to 3mm etc..Hole-closing structure has individual blisters structure, internal
There is wall film to separate between abscess and abscess, the overwhelming majority is not interconnected, and abscess diameter is 0.01 to 3mm etc..Contained
Abscess is existing to be interconnected again that have mutual disconnected structure be then half open-celled structure.
In embodiments of the present invention, foaming method is usual way, can be divided according to the difference of foaming agent used
For physical blowing method and chemical blowing process two major classes.Foam can have water or it is anhydrous under the conditions of prepare, mechanical can send out
Bubble or on-mechanical foaming.Wherein, in order to avoid in foaming process component B inactivate at high temperature, preferably entire foaming process temperature
Degree is not higher than 110 DEG C of foaming method.Further, the non-reacted hair of auxiliary known in the art can be used in the preparation of foam
Infusion.
A kind of preparation method of preferred hydridization dynamic aggregation compositions foam of the present invention, includes the following steps: making
When standby single network dynamic aggregation object foam, two component reaction materials are first prepared.Reaction mass one includes to generate hydridization dynamic to gather
All small molecule monomers of polymer composition component A, chain extender, crosslinking agent etc. and component B and the auxiliary agent needed for other;Instead
Answering material two includes foaming agent, foam stabiliser, the catalyst for being catalyzed foaming and/or polymerization crosslinking reaction and other institutes
The auxiliary agent needed.Then two component reaction materials are mixed according to a certain percentage, is stirred, and carry out temperature control as needed, obtained
To the single network polymer of foaming.By the hydridization dynamic aggregation of this preparation method preparation hydridization dynamic aggregation compositions foam
Object is preferably based on the polymer of polyurethane, polyureas.
The preparation method of another preferred hydridization dynamic aggregation compositions foam of the invention is freeze-drying, including
Following steps: the hydridization dynamic aggregation compositions for swelling in volatile solvent are freezed, then close under vacuum condition
Solvent is escaped in a manner of distillation.During solvent evolution and after evolution, composition can maintain the shape before freezing,
Thus the foamed material of porous spongy is obtained.
In hydridization dynamic aggregation compositions foam preparation processes of the invention, when in foam contain multiple polymer networks
When, multiple networks can generate simultaneously, can also be separately generated.
Hydridization dynamic aggregation compositions foamed material provided by the present invention further relates to: by welding, gluing, cutting,
The hydridization dynamic aggregation compositions foamed material is transformed into any by matching plane, perforation, coining, lamination and hot forming
Need shape, such as pipe, stick, sheath, container, ball, piece, volume and band;By lamination, bonding, fusion and other interconnection technique,
By skill in the hydridization dynamic aggregation compositions foamed material and sheet material, film, foam, fabric, stiffener and this field
Other materials known to art personnel are combined into complicated interlayer structure together;The hydridization dynamic aggregation compositions foam material
Expect the purposes in washer or sealing;The hydridization dynamic aggregation compositions foamed material is in packaging material or in a reservoir
Purposes.About hydridization dynamic aggregation compositions of the invention, foamable hydridization dynamic aggregation compositions are such a
Type allows to become them by other forming techniques known to extrusion, injection molding, compression moulding or those of skill in the art
Shape.
Foamed material provided by the present invention is different from common foamed material, three-dimensional prepared by common foamed material
Once being formed, structure cannot change structure again, repair difficulty, not can be recycled after damaged, and foamed material provided by the present invention,
Although the polymer network of crosslinking, can also be repaired after being ruptured under certain condition, or pass through plastotype or recycling again
Regeneration is done him and is used, and there are hydrogen bond actions and dynamic covalent bond while reason is in network structure.It is provided by the present invention
Foamed material solves the problems, such as plastotype again, controllable reparation and the reclaiming of regular-type foam material.
Hydridization dynamic aggregation compositions material of the invention during the preparation process, in the range for not interfering the object of the invention
It is interior, it can also according to circumstances select to be added or used to other polymers, auxiliary agent, filler, sweller and come collectively as hydridization dynamic
The recipe ingredient of polymer composition can improve material processing performance, improve product quality and yield, and reduce product cost
Or assign certain distinctive application performance of product, but these additives it is not necessary to.
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 without limitation, according to the difference of polymeric species,
Can be homopolymer or copolymer, in the specific use process should be according to the performance of target material and the need of actual fabrication process
It wants and is selected.
When the other polymers are selected from natural polymer, it can be selected from following any or appoint several days
Right high-molecular compound: natural rubber, chitosan, chitin, native protein, polysaccharide etc..
When the other polymers are selected from synthetic macromolecular compound, it can be selected from following any or appoint several:
Polytrifluorochloroethylene, haloflex, chliorinated polyvinyl chloride, polyvinyl chloride, Vingon, low density polyethylene (LDPE), middle density
Polyethylene, high density polyethylene (HDPE), ultra-high molecular weight polyethylene, melamine formaldehyde resin, polyamide, polyacrylic acid, polypropylene
Acid esters, polyacrylamide, polyacrylonitrile, polybenzimidazoles, polyethylene terephthalate, polybutylene terephthalate
Ester, polycarbonate, polyethylene glycol, polyester, polyether sulfone, polyarylsulfone (PAS), polyether-ether-ketone, tetrafluoroethylene-perfluoro propane copolymer, polyamides
Imines, polyacrylate, polyacrylonitrile, polyphenylene oxide, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high-impact polyphenyl second
Alkene, polysulfones, polytetrafluoroethylene (PTFE), polyurethane, polyureas, polyvinyl acetate, ethylene-propylene copolymer, ethane-acetic acid ethyenyl ester are total
Polymers, AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, vinyl chloride-acetate
Ester copolymer, polyvinylpyrrolidone, epoxy resin, phenolic resin, Lauxite, unsaturated polyester (UP), polyisoprene, gather it is suitable
Butadiene, styrene-butadiene copolymer, hycar, poly- (the chloro- 1,3- butadiene of 2-), isobutene-are different
Pentadiene copolymer, ethylene-propylene-Isosorbide-5-Nitrae-hexadiene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-
Ethylidene norbornene copolymer, dimethyl silicone polymer, Polymethyl methacrylate, polymethylphenylsiloxane, poly- methyl
Vinyl benzene radical siloxane, poly- methyl ethylene trifluoropropyl siloxane, vinylidene-chlorotrifluoroethylene, inclined fluorine second
Alkene-hexafluoropropylene copolymer, vinylidene-tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene propylene copolymer, polycyclic oxygen
Chloropropane, epichlorohydrin ethylene oxide copoymer, epoxychloropropane-ethylene oxide-propylene oxide copolymer etc..
Wherein, the type of other polymers does not limit, mainly depending on required material property;Other used are poly-
The dosage for closing object is not particularly limited, generally 1-50wt%.
Wherein, the auxiliary agent may include but be not limited to the combination of following one or more, such as additive synthesis, including catalysis
Agent, initiator;Stabilizing additive, including antioxidant, light stabilizer, heat stabilizer, dispersing agent, emulsifier, fire retardant;Improve
The auxiliary agent of mechanical property, including toughener, coupling agent;Improve the auxiliary agent of processing performance, including solvent, lubricant, release agent, increasing
Mould agent, thickener, thixotropic agent, levelling agent;Change the auxiliary agent of coloured light, including colorant, fluorescent whitening agent, delustering agent;Other are helped
Agent, including antistatic agent, biocide mildewcide, foaming agent, foam stabiliser, nucleating agent, rheological agent etc..
Catalyst in the auxiliary agent can reduce reaction activity by changing reaction path to accelerate to react
The reaction rate of object during the reaction.It includes but are not limited to following any or appoints several catalyst: 1. polyurethane closes
At with catalyst: amines catalyst, such as triethylamine, triethylenediamine, bis- (dimethylaminoethyl) ethers, 2- (2- dimethylamino-
Ethyoxyl) ethyl alcohol, trimethyl hydroxyethylammonium propane diamine, N, bis- (dimethylamine propyl) isopropanolamines of N-, N- (dimethylamino-propyl) two
Isopropanolamine, N, N, N '-trimethyl-N '-ethoxy diamine ethylether, tetramethyl dipropylenetriamine, N, N- dimethyleyelohexane
Amine, N, N, N ', N '-tetramethyl Alkylenediamine, N, N, N ', N ', N '-five methyl diethylentriamine, N, N- dimethyl ethanol
Amine, N-ethylmorpholine, 2,4,6- (dimethylamino methyl) phenol, trimethyl-N-2- hydroxypropyl caproic acid, N, N- dimethyl benzylamine,
N, N- dimethyl cetylamine etc.;Organometallic catalysts, such as stannous octoate, dibutyltin dilaurate, dioctyl tin two
Laurate, zinc Isoocatanoate, isooctyl acid lead, potassium oleate, zinc naphthenate, cobalt naphthenate, ferric acetyl acetonade, phenylmercuric acetate, propionic acid
Benzene mercury, bismuth naphthenate, sodium methoxide, potassium octanoate, potassium oleate, calcium carbonate etc.;2. polyolefin catalyst for synthesizing: such as Ziegler-
Natta catalyst, π-allyl nickel, alkyl lithium catalyst, metallocene catalyst, aluminium diethyl monochloride, titanium tetrachloride, tri-chlorination
Titanium, boron trifluoride etherate, magnesia, dimethylamine, stannous chloride, triethylamine, tetraphenylboron sodium, antimony oxide, sesquialter
Ethylmercury chloride aluminium, vanadium oxytrichloride, triisobutyl aluminium, nickel naphthenate, naphthenic acid rare earth etc.;3. CuAAC catalysts: by monovalence
Copper compound and amine ligand share concerted catalysis;Monovalence copper compound can be selected from Cu (I) salt, as CuCl, CuBr, CuI, CuCN,
CuOAc etc.;Also selected from Cu (I) complex compound, such as [Cu (CH3CN)4]PF6、[Cu(CH3CN)4]OTf、CuBr(PPh3)3Deng;Amine
Ligand can be selected from three [(1- benzyl -1H-1,2,3- triazole-4-yl) methyl] amine (TBTA), three [(1- tert-butyl -1H-1,2,3-
Triazole-4-yl) methyl] amine (TTTA), three (2- benzimidazole methyl) amine (TBIA), hydration bathophenanthroline disulfonic acid sodium etc.;④
Thiol-ene catalysts: photochemical catalyst, such as dimethoxybenzoin, 2- hydroxy-2-methyl phenylacetone, 2,2- dimethoxy
Base -2- phenyl acetophenone etc.;Nucleopilic reagent catalyst, such as ethylenediamine, triethanolamine, triethylamine, pyridine, 4- dimethylamino pyrrole
Pyridine, imidazoles, diisopropyl ethyl amine etc..Catalyst amount used is not particularly limited, generally 0.01-0.5wt%.
Initiator in the auxiliary agent can cause monomer molecule to activate in polymerization process and generate free
Base improves reaction rate, and reaction is promoted to carry out, and includes but are not limited to following any or appoints several initiators: 1. free radical
Polymerization initiator: organic peroxide, such as lauroyl peroxide, benzoyl peroxide (BPO), dicetyl peroxydicarbonate diisopropyl
Bis- (4- tert-butylcyclohexyl) esters of ester, di-cyclohexylperoxy di-carbonate, dicetyl peroxydicarbonate, tert-butyl hydroperoxide benzoic acid
Ester, tert-butyl hydroperoxide pivalate, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide;Azo-compound, such as azo two
Isobutyronitrile (AIBN), azobisisoheptonitrile;Inorganic peroxide, such as ammonium persulfate, potassium peroxydisulfate;2. living polymerization causes
Agent: such as 2,2,6,6- tetramethyl -1- oxygroup piperidines, 1- chloro-1-phenyl ethane/stannous chloride/bis- pyridines ternary system;3. from
Son polymerization initiator: such as butyl lithium, sodium/naphthalene system, boron trifluoride/aqueous systems, tin tetrachloride/alkyl halide system;4. matching
Position polymerization initiator: such as titanium tetrachloride/triethyl aluminum system, two zirconium cyclopentadienyl of dichloro/methylaluminoxane system;5. ring-opening polymerisation
With initiator: such as sodium methoxide, potassium methoxide, ethylenediamine, hexamethylene diisocyanate, stannous octoate.Wherein, the preferred mistake of initiator
Aoxidize lauroyl, benzoyl peroxide, azodiisobutyronitrile, potassium peroxydisulfate.Initiator amount used is not particularly limited, and one
As be 0.1-1wt%.
Antioxidant in the auxiliary agent can delay the oxidation process of polymer samples, guarantee that material can be suitable
It is processed and is prolonged its service life sharply, include but are not limited to following any or appoint several antioxidant: Hinered phenols,
Such as 2,6 di tert butyl 4 methyl phenol, 1,1,3- tri- (- 4 hydroxyl -5- tert-butyl-phenyl of 2- methyl) butane, four [β-(3,5-
Di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol);Sulfur-bearing by
Hinder phenols, such as 4,4 '-thiobis-[3 methy 6 tert butyl phenol], 2,2 '-thiobis-[4- methyl-6-tert-butylphenol];
Triazine system hindered phenol, such as 1,3,5- bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl]-perhydro-s-triazines;Trimerization isocyanide
Acid esters Hinered phenols, such as three (3,5- di-tert-butyl-4-hydroxyl benzyl)-triisocyanates;Amine, such as N, N '-two (betanaphthyl)
P-phenylenediamine, N, N '-diphenyl-para-phenylene diamine, N- phenyl-N '-cyclohexyl p-phenylenediamine;Sulfur-bearing class, such as thiodipropionic acid dilauryl
Osmanthus ester, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole;Phosphorous acid esters, such as triphenyl phosphite, three nonyl benzene of phosphorous acid
Ester, three [2.4- di-tert-butyl-phenyl] phosphite esters etc.;Wherein, the preferred tea polyphenols of antioxidant (TP), butylated hydroxy anisole
(BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), three [2.4- di-tert-butyl-phenyl] phosphite esters
(irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters (antioxidant 1010).Used
Antioxidant dosage is not particularly limited, generally 0.01-1wt%.
Light stabilizer in the auxiliary agent can prevent polymer samples from light aging occurs, prolong its service life,
It includes but are not limited to following any or appoints several light stabilizers: photomask agent, such as carbon black, titanium dioxide, zinc oxide, sulfurous
Sour calcium;Ultraviolet absorbing agent, such as ESCALOL 567,2-hydroxy-4-n-octoxybenzophenone, 2- (2- hydroxyl
Base -3,5- di-tert-butyl-phenyl) -5- chlorobenzotriazole, 2- (2- hydroxy-5-methyl base phenyl) benzotriazole, (the 2- hydroxyl of 2,4,6- tri-
Base -4- n-butoxyphenyl) -1,3,5- s-triazine, 2- cyano -3,3- diphenylacrylate 2- ethylhexyl;Pioneer's type is ultraviolet
Light absorbers, such as the p- tert-butyl phenyl ester of salicylic acid, double acid double phenol A ester;UV quenchers, such as bis- (3,5- bis- tertiary fourths
Base -4- benzylphosphonic acid mono ethyl ester), 2,2 '-thiobis (4- spy's octyl phenol oxygroup) nickel;Hindered amine light stabilizer, such as the last of the ten Heavenly stems two
Bis- (2,2,6,6- tetramethyl piperidine) esters of acid, benzoic acid (2,2,6,6- tetramethyl piperidine) ester, three (1,2,2,6,6- pentamethyl piperazines
Piperidinyl) phosphite ester;Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acid (2,4- di-tert-butyl) ester, alkyl
Phosphoamide, N, N '-zinc dibutyl dithiocaarbamate, N, positive fourth positive group aminodithioformic acid nickel of N '-two etc.;Its
In, bis- (2,2,6, the 6- tetramethyl piperidine) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid.Light used is stablized
Agent dosage is not particularly limited, generally 0.01-0.5wt%.
Heat stabilizer in the auxiliary agent enables to polymer samples in processing or use process not due to heated
Chemical change occurs, or delays these variations to achieve the purpose that prolong the service life comprising but it is not limited only to following
A kind of or several heat stabilizers: lead salts, such as lead sulfate tribasic, dibasic lead phosphite, dibasic lead stearate, disalt
Base phthalic acid lead, tribasic Malaysia lead plumbate, slag lead silicate, lead stearate, lead salicylate, dibasic phthalic acid
Lead, basic lead carbonate, silica gel are co-precipitated lead silicate;Metal soap: such as cadmium stearate, barium stearate, calcium stearate, stearic acid
Lead, zinc stearate;Organo-tin compound class, such as di-n-butyltin dilaurate, Bis(lauroyloxy)dioctyltin, maleic acid two
(just) butyl tin, double single-ethylhexyl maleate dioctyltins, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital tin C-102, two mercaptos
Guanidine-acetic acid isooctyl stannous methide, two mercaptan stannous methides and its compound;Antimony stabilizer, such as mercaptan antimonic salt, mercaptoacetate
Mercaptans type, mercapto-carboxylic ester antimony, carboxylate antimony;Epoxy compound species, such as epoxidized oil, epoxy aliphatic ester, epoxy resin;It is sub-
Phosphoric acid ester, such as three aromatic ester of phosphorous acid, three alkyl ester of phosphorous acid, three aralkyl ester of phosphorous acid, alkane virtue mixed ester, aggretion type phosphorous acid
Ester;Polyalcohols, such as pentaerythrite, xylitol, mannitol, D-sorbite, trimethylolpropane;Composite thermal stabilizer, such as altogether
Precipitate metallic soap, liquid metal soap compound stabilizer, organotin compound stabilizer etc.;Wherein, the preferred barium stearate of heat stabilizer,
Calcium stearate, di-n-butyltin dilaurate, maleic acid two (just) butyl tin.Heat stabilizer dosage used does not limit especially
It is fixed, generally 0.1-0.5wt%.
Dispersing agent in the auxiliary agent enables to solid flocculation group in mixed with polymers liquid to be separated into tiny particle
And be suspended in liquid, those are poorly soluble the solid and liquid particles in liquid for uniform dispersion, while can also prevent particle
Sedimentation and cohesion form stable suspension comprising but be not limited only to following any or appoint several dispersing agents: anionic,
Such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate;Cationic;It is non-ionic, such as aliphatic alcohol polyethenoxy
Ether, sorbitol anhydride fatty acid polyoxyethylene ether;Inorganic type, such as silicate, condensed phosphate;Polymer electrolyte, such as starch, bright
Glue, water-soluble glue, lecithin, carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, lignosulfonates, polyvinyl alcohol
Deng.Wherein, the preferred neopelex of dispersing agent, naphthalene system methylene sulfonate (dispersing agent N), aliphatic alcohol polyethenoxy
Ether, dispersant dosage used are not particularly limited, generally 0.3-0.8wt%.
Emulsifier in the auxiliary agent can improve in the mixed with polymers liquid comprising auxiliary agent between various composition phases
Surface tension is allowed to form uniform and stable dispersion or emulsion comprising but be not limited only to following any or appoint several
Kind emulsifier: anionic, such as higher fatty acid salt, alkylsulfonate, alkylbenzene sulfonate, Negel, succinic acid
Sulfonated ester, petroleum sulfonate, aliphatic alcohol sulfate, castor oil salt, sulphation butyl ricinoleate salt, phosphate ester salt,
Fatty acyl-peptide condensation product;Cationic, such as alkylammonium salt, alkyl quaternary ammonium salts, Fixanol;Amphoteric ion type, such as carboxylate
Type, sulfonic acid ester type, sulfuric acid ester type, phosphate type;It is non-ionic, such as fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, rouge
Fat acid polyoxyethylene ester, polypropylene oxide-ethylene oxide adduct, fatty acid glyceride, pentaerythritol fatty ester, sorbierite
And sorbitan fatty acid ester, sucrose fatty ester, hydramine fatty acid amide etc..Wherein, preferably neopelex, lose
Water Span, triethanolamine stearate (Emulphor FM), emulsifier used are not particularly limited, generally
For 1-5wt%.
Fire retardant in the auxiliary agent can increase the flame resistance of material comprising but be not limited only to following any
Or appoint several fire retardants: phosphorus system, such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate hexichol
Ester;Halogen phosphoric acid ester, such as three (2,3- dibromopropyl) phosphates, tricresyl phosphate (2,3- dichloro the third) ester;Organohalogen compounds are such as high
Chlorinty chlorinated paraffin, 1,1,2,2- tetrabromoethane, deca-BDE, penta decane of perchloro- ring;Inorganic fire retardants, such as three oxidations two
Antimony, aluminium hydroxide, magnesium hydroxide, zinc borate;Reactive flame retardant, such as chlorendic anhydride, bis- (2,3- dibromopropyl) anti-butylene two
Acid esters, tetrabromobisphenol A, tetrabromophthalic anhydride etc.;Wherein, the preferred deca-BDE of fire retardant, triphenyl phosphate, tricresyl phosphate
Toluene ester, phosphate toluene diphenyl ester, antimony oxide.Amount of flame-retardant agent used is not particularly limited, generally 1-20wt%.
Toughener in the auxiliary agent can reduce polymer samples brittleness, increase toughness, and it is strong to improve material carrying
Degree comprising but be not limited only to following any or appoint several toughener: methyl methacrylate-butadiene-styrene copolymerization
Resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modifier, acrylonitrile-butadiene-benzene second
Alkene copolymer, acrylonitrile-butadiene copolymer, the third glue of second, ethylene-propylene diene copolymer, cis-butadiene cement, butadiene-styrene rubber, styrene-butadiene-benzene
Ethylene block copolymer etc.;Wherein, preferred the third glue of second of toughener, acrylonitrile-butadiene-styrene copolymer (ABS), benzene second
Alkene-butadiene-styrene block copolymer (SBS), Methyl Methacrylate-Butadiene-Styrene Copolymer resin (MBS),
Chlorinated polyethylene resin (CPE).Toughener dosage used is not particularly limited, generally 5-10wt%.
Coupling agent in the auxiliary agent can improve the interface characteristics of polymer samples and inorganic filler or reinforcing material
Can, the viscosity of material melt is reduced in plastic processes, improves the dispersion degree of filler to improve processing performance, and then make to make
Product obtain good surface quality and machinery, heat and electrical property comprising but be not limited only to following any or appoint several couplings
Agent: chromium of organic acid complex compound, silane coupling agent, titanate coupling agent, sulfonyl azide coupling agent, aluminate coupling agent etc.;Wherein,
The preferred gamma-aminopropyl-triethoxy-silane of coupling agent (Silane coupling agent KH550), γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy
Base silane (silane coupling agent KH560).Coupling agent dosage used is not particularly limited, generally 0.5-2wt%.
Solvent in the auxiliary agent, adjustable viscosity are convenient for technological operation, make in product preparation process or in preparing
With.Its include but are not limited to it is following any or appoint it is several: hydro carbons (such as hexamethylene, heptane), halogenated hydrocarbon (such as methylene chloride,
Chloroform, tetrachloromethane), aromatic hydrocarbons (such as toluene, dimethylbenzene), ketone (such as acetone, methyl ethyl ketone), ethers (such as ether, tetrahydro furan
Mutter, dioxane), esters (such as ethyl acetate, butyl acetate), glycol ether-ether (such as ethylene glycol ether acetate, propylene glycol list first
Ether acetate), dimethylformamide (DMF), N-Methyl pyrrolidone (NMP) etc..Solvent usage used is not particularly limited,
Generally 1-200wt%.
Lubricant in the auxiliary agent can be improved the lubricity of polymer samples, reduce friction, reduce Interface Adhesion
Performance comprising but be not limited only to following any or appoint several lubricants: saturated hydrocarbons and halogenated hydrocarbon, such as solid paraffin, micro-
Spar wax, atoleine, low molecular weight polyethylene, oxidized polyethylene wax;Fatty acid, such as stearic acid, hydroxy stearic acid;Fat
Esters of gallic acid, such as fatty acid low-carbon-ester, polyol esters of fatty acids, native paraffin, ester type waxes and saponified wax;Aliphatic amide type is such as hard
Acyl amine or stearic amide, oleamide or oleamide, erucyl amide, N, N '-ethylene bis stearamide;Fatty alcohol and polynary
Alcohols, such as stearyl alcohol, cetanol, pentaerythrite;Metal soap, as lead stearate, calcium stearate, barium stearate, magnesium stearate,
Zinc stearate etc.;Wherein, the preferred solid paraffin of lubricant, atoleine, stearic acid, low molecular weight polyethylene.Lubrication used
Agent dosage is not particularly limited, generally 0.5-1wt%.
Release agent in the auxiliary agent, it can make polymer samples be easy to demould, and surface is smooth, clean comprising but
It is not limited only to following any or appoints several release agents: paraffin hydrocarbon, soaps, dimethicone, ethyl silicon oil, aminomethyl phenyl silicon
Oil, castor oil, used oil, mineral oil, molybdenum disulfide, polyethylene glycol, vinyl chloride resin, polystyrene, silicon rubber, polyvinyl alcohol
Deng;Wherein, the preferred dimethicone of release agent, polyethylene glycol.Release agent dosage used is not particularly limited, generally 0.5-
2wt%.
Plasticizer in the auxiliary agent can increase the plasticity of polymer samples, so that the hardness of polymer, mould
Amount, softening temperature and brittle temperature decline, elongation, flexibility and flexibility improve comprising but be not limited only to following any
Kind appoints several plasticizer: Phthalates: dibutyl phthalate, dioctyl phthalate, phthalic acid two
Different monooctyl ester, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, phthalic acid fourth benzyl
Bis- (13) esters of ester, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid, terephthaldehyde
Sour two (2- ethyl) own esters;Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyl) own ester;Fatty acid ester, such as
The own ester of adipic acid two (2- ethyl), decanedioic acid two (2- ethyl) own ester;Epoxy compound species, such as epoxy glycerite esters, epoxy rouge
Fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, the own ester of epoxystearic acid (2- ethyl), epoxy soybean
Oleic acid 2- ethylhexyl, the own ester of 4,5- epoxy tetrahydrophthalic acid two (2- ethyl), Chinese littleleaf box methyl acetylricinolate, binary
Alcohol lipid, such as the sour glycol ester of C5~9, the sour Triethylene Glycol of C5~9;Class containing chlorine such as afforests paraffin class, chlorinated fatty acid
Ester;Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester;Phenyl alkylsulfonate, trimellitic acid
Ester, citrate, pentaerythrite and pentaerythritol fatty acid ester etc.;Wherein, plasticizer pref-erable dioctyl phthalate (DOP), neighbour
Dibatyl phithalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), adjacent benzene two
Formic acid diisodecyl ester (DIDP), tricresyl phosphate (TCP).Plasticizer consumption used is not particularly limited, generally 5-
20wt%.
Thickener in the auxiliary agent, can assign the good thixotropy of mixed with polymers liquid and consistency appropriate, and one
As used during production of the invention and semi-finished product store comprising but be not limited only to following any or appoint several thickenings
Agent: lower-molecular substance, such as fatty acid salt, fatty alcohol polyoxyethylene ether sulfate, alkyldimethylamine oxide, fatty acid monoethanol
Amide, fatty diglycollic amide, fatty acid Isopropamide, anhydro sorbitol tricarboxylic ester, glycerol trioleate, coconut monoethanolamide
Propyl betaine, 2- alkyl-N- carboxymethyl-N- hydroxyethyl imidazole quinoline, titanate coupling agent;Polymer substance, such as bentonite, manually
Hectorite, fine particle silica, colloidal aluminum, plant polyose class, microbial polysaccharide class, animal protein, cellulose family, starch,
Seaweed acids, poly-methyl acrylate, methacrylic acid copolymer, cis-butenedioic anhydride copolymer, crotonic acid-copolymers, polyacrylamide,
Polyvinyl pyrrolidone, polyvinyl alcohol, polyethers, polyvinyl methyl ether urethane polymer etc.;Wherein, the preferred hydroxy ethyl fiber of thickener
Element, coconut oil diethanol amide, acrylic acid-methacrylic acid copolymer.Thickener dosage used is not particularly limited, generally
For 0.1-1.5wt%.
Thixotropic agent in the auxiliary agent is added in polymeric system, increases the thixotropy of polymeric system.Including but not
It is only limitted to following any or appoints several: gas-phase silica, rilanit special, bentonite, silicic acid anhydride, silica derivative, urea
Derivative etc..Thixotropic agent dosage used is not particularly limited, generally 0.5-2wt%.
Levelling agent in the auxiliary agent can guarantee the flat and smooth uniform of polymer coating film, improve film coated surface matter
Amount improves dicoration comprising but be not limited only to following any or appoint several levelling agents: dimethyl silicone polymer, poly- methyl
Phenyl siloxane, cellulose acetate butyrate, polyacrylate, organic siliconresin etc.;Wherein, the preferred poly dimethyl of levelling agent
Siloxanes, polyacrylate.Levelling agent dosage used is not particularly limited, generally 0.5-1.5wt%.
Colorant in the auxiliary agent can make polymeric articles show required color, increase surface color and polish,
It includes but are not limited to following any or appoints several colorants: inorganic pigment, such as titanium white, chrome yellow, cadmium red, iron oxide red, molybdenum chromium
Red, ultramarine, chrome green, carbon black;Organic pigment, such as lithol red BK directions, lake red C, red, good base R is red, phthalocyanine is red, Yong Guyang
The bright red R of red HF3C, the plastics and not red BR of Crow, forever solid orange HL, Fast Yellow G, vapour bar plastics Huang R, permanent yellow 3G, permanent yellow H2G,
Phthalocyanine blue B, dark green, plastics purple RL, nigrosine;Organic dyestuff, such as thioindigo red, vat yellow 4GF, indanthrene blue RSN, slag rose
Rare essence, Oil Yellow etc.;Wherein, the selection of colorant does not need to be particularly limited to depending on color sample demand.Coloring used
Agent dosage is not particularly limited, generally 0.3-0.8wt%.
Fluorescent whitening agent in the auxiliary agent can make contaminated substance obtain the sparkling effect of similar fluorite,
It includes but are not limited to following any or appoints several fluorescent whitening agents: Stilbene-based, coumarin type, pyrazoline type, benzo
Oxygen nitrogen type, phthalimide type etc.;Wherein, the preferred stilbene biphenyl sodium disulfonate (fluorescent whitening agent of fluorescent whitening agent
CBS), bis- (5 methyl -2- benzoxazolyl) talan (fluorescent whitening agent KSN) of 4,4-, 2,2- (4,4 '-diphenylethyllene)
Double benzoxazoles (fluorescent whitening agent OB -1).Fluorescent whitening agent dosage used is not particularly limited, generally 0.002-
0.03wt%.
Delustering agent in the auxiliary agent when incident light being enabled to reach polymer surfaces, occurs diffusing reflection, generates low
The matt and delustring appearance of gloss comprising but be not limited only to following any or appoint several delustering agents: sedimentation barium sulfate, dioxy
SiClx, aqueous gypsum powder, talcum powder, titanium dioxide, poly- methyl carbamide resin etc.;Wherein, the preferred silica of delustering agent.Used disappears
Photo etching dosage is not particularly limited, generally 2-5wt%.
The deleterious charge assembled in polymer samples can be guided or be eliminated, make it by the antistatic agent in the auxiliary agent
Production and life are not brought inconvenience or are endangered comprising but be not limited only to following any or appoint several antistatic agents: yin from
Subtype antistatic agent, such as alkylsulfonate, to Sodium Nonylphenoxypropane Sulfonate, alkyl phosphate diethanolamine salt, alkyl phenol
Polyoxyethylene groups ether sulfonic acid triethanolamine, to nonyl diphenyl ether potassium sulfonate, alkyl polyoxyethylene base ether sulfonic acid triethanolamine, phosphoric acid
Ester derivant, phosphate, phosphoric acid polyethylene oxide alkyl ethers alcohol ester, alkyl bis- [two (2- ethylol amine)] phosphates, phosphate
Derivative, fatty amine sulfonate, butyrate sodium sulfonate;Cationic antistatic agent, such as aliphatic ammonium salt hydrochlorate, lauryl trimethyl
Ammonium chloride, dodecyl trimethylamine bromide, N, N- cetyl-ethyl morpholine ethyl-sulfate salt, stearamide propyl (2- hydroxyl second
Base) dimethylammonium nitrate, alkyl hydroxyethyl dimethylammonium perchlorate, 2- alkyl -3,3- dihydroxy ethyl imidazoline perchlorate, 2-
Heptadecyl -3- ethoxy -4- carboxymethyl imidazoline, N, bis- (α-ethoxy)-N-3 (dodecyloxy -2- hydroxypropyl) first of N-
Ammonium Methylsulfate salt;Amphoteric ion type antistatic agent, such as alkyl dicarboxyl methyl ammonium second inner salt, lauryl betaine, N, N, N- tri-
Alkylammonium acetyl (N '-alkyl) amine second inner salt, bis- polyethylene oxide base-N- ethylphosphonic acid sodium of N- lauryl-N, N-, alkyl two
Salt hydroxide, -3 ethoxy -3- acetic acid alkali imidazoline quaternary amine alkali of 2- alkyl, N- alkyl amino acid in (polyoxyethylene) ammonium second
Salt;Non-ionic antistatic agent, such as fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide addition product, alkyl phenol epoxy second
The polyethylene oxide of alkane addition product, tricresyl phosphate polyoxyethylene groups ether-ether, fatty acid monoglyceride, sorbitan mono-laurate
Addition product;Polymer Antistatic Agent, ethylene oxide propylene oxide addition product, polyethylene glycol-terephthalic acid (TPA) such as ethylenediamine
Ester -3,5- dibenzoate sodium sulfonate copolymers, polyene propionamide N- quaternary ammonium salt substituent, poly- 4- vinyl -1- acetonyl pyrrole
Pyridine phosphoric acid-is to butyl phenyl ester salt etc.;Wherein, the preferred lauryl trimethyl ammonium chloride of antistatic agent, octadecyldimethyl hydroxyl second
Base quaternary ammonium nitrate (antistatic agent SN), alkyl phosphate diethanolamine salt (antistatic agent P).Antistatic agent dosage used does not have
It is particularly limited to, generally 0.3-3wt%.
Dehydrating agent in the auxiliary agent, can moisture in removing system comprising but be not limited only to it is following any or
Appoint several: oxazolidine compound (such as 3- Ethyl-2-Methyl -2- (3- methyl butyl) -1,3- oxazolidine), different to Methyl benzenesulfonyl
Cyanate, triethyl orthoformate, vinyl silanes, calcium oxide etc..Dehydrating agent dosage used is not particularly limited, generally
0.1-2wt%.
Biocide mildewcide in the auxiliary agent can inhibit the growth of bacterium, and the appearance for keeping product clean and tidy extends and uses
Service life;Or protection user, the health for promoting user, such as reduce tinea pedis.It includes organic matter and inorganic matter, including but
It is not limited only to following any or appoints several: isothiazolinone derivatives, such as 5-Chloro-2-methyl-4-isothiazolin-3-one, 2-
Methyl -4- isothiazoline -3- ketone, N- normal-butyl -1,2- benzisothiazole-3-ketone, octylisothiazolinone, 2,4,4- tri-
Chlorine-2-hydroxyl-diphenyl ether, 2- (4- thiazolyl) benzimidazole, copper 8-quinolinolate or bis- (8-hydroxyquinoline base) copper;It is organic
Tin compound, such as tributyl-tin fumarate, tributyltin acetate, bis- (tributyl tin) sulfide, bis- (tributyl tin) tin oxide;
N, N- dimethyl-N '-phenyl (fluorine dichloromethyl is thio) sulfonamide;Inorganic compound or compound, such as nano silver, nano-silica
Change titanium, nano silica, nano zine oxide, superfine cupper powder, inorganic antiseptic YY-Z50, XT inorganic antiseptic, composite antibacterial
Agent KHFS-ZN.Biocide mildewcide dosage used is not particularly limited, generally 0.5-2wt%.
Foaming agent in the auxiliary agent can make polymer samples foaming pore-forming, to obtain light polymeric material
Material comprising but be not limited only to it is following any or appoint several foaming agents: physical blowing agent, as carbon dioxide, nitrogen, argon gas,
Methane, ethane, propane, butane, iso-butane, pentane, neopentane, hexane, isopentane, heptane, isoheptane, acetone, benzene, toluene,
Methyl ether, ether, petroleum ether, chloromethanes, methylene chloride, dichloroethylene, dicholorodifluoromethane, trifluorochloromethane, hydrochlorofluorocarbons-
22, hydrochlorofluorocarbons -142b, hydrofluorocarbons -134a, hydrofluorocarbons -152a, chlorofluorocarbons -11, chlorofluorocarbons -12, chlorine fluorine
Hydrocarbon -114;Inorganic foaming agent, such as sodium bicarbonate, ammonium carbonate, ammonium hydrogen carbonate, carbonate ammonia natrium, azido compound, hydroboron
Deng;Organic foaming agent, such as N, N '-dinitrosopentamethlyene tetramine, N, N '-dimethyl-N, N '-dinitroso paraphenylene terephthalamide
Amine, azodicarbonamide, barium azo-biscarbonate, two diisopropyl carbonate of azo, azodicarbonamide potassium formate, two isobutyl of azo
Nitrile, 4,4 '-oxobenzenesulfonyl hydrazide, 3,3 '-disulfonyl hydrazide diphenyl sulphone (DPS)s, 1,3- benzene Erhuang hydrazides, benzene sulfonyl hydrazide, three diazanyls three
Piperazine, p-toluene sulfonylsemicarbazide, biphenyl -4,4 '-disulfonyl nitrine, diazo aminobenzene;Physical microballoon/granule foaming agent, such as
The expandable microballoon of the companies such as Akzo Nobel production.Wherein, the preferably environmentally friendly carbon dioxide of foaming agent, nitrogen, argon
Gas and sodium bicarbonate, ammonium carbonate, azodicarbonamide (blowing agent AC), N, five methine tetramine (foaming agent of N '-dinitro
H), N, N '-dimethyl-N, N '-dinitrosoterephthalamine (foaming agent NTA), physical microballoon foaming agent.Hair used
Infusion dosage is not particularly limited, generally 0.1-30wt%.
Blowing promotor in the auxiliary agent comprising but be not limited only to foamed promoter, frothing inhibitor, foam and stablize
Agent etc..The foamed promoter comprising but be not limited only to it is following any or appoint it is several: urea, stearic acid, lauric acid,
Salicylic acid, tribasic lead sulfate, dibasic lead phosphite, lead stearate, cadmium stearate, zinc stearate, zinc oxide, ZB-
530,KZ-110,MS-1;The frothing inhibitor comprising but be not limited only to following any or appoint several: maleic acid, richness
Horse acid, stearyl chloride, phthalyl chloride, maleic anhydride, phthalate anhydride, hydroquinone, naphthalenediol, aliphatic amine, amide,
Oxime, isocyanates, mercaptan, thiophenol, thiocarbamide, sulfide, sulfone, cyclohexanone, acetylacetone,2,4-pentanedione, hexacholorocyclopentadiene, dibutyl Malaysia
Sour tin etc.;The foam stabiliser comprising but be not limited only to it is following any or appoint it is several:: silicone oil, sulfonated aliphatic alcohol,
Alpha-sulfonated fatty acid, NaLS, dodecyldimethylamine oxide, alkylolamides, polyethylene glycol oxide, alkylaryl are poly-
Ethylene oxide alcohol, tridecyl ether, Polyoxyethylene sorbitan glycerol monolaurate, siloxanes-ethylene oxide are embedding
Section copolymer etc..Blowing promotor dosage used is not particularly limited, generally 0.05-10wt%.
Nucleating agent in the auxiliary agent can accelerate crystalline rate, increase knot by the crystallization behavior of change polymer
Brilliant density and promote fine grain size, reach and shorten material molding cycle, improves the product transparency, lustrous surface, tension
The purpose of the physical mechanical properties such as intensity, rigidity, heat distortion temperature, creep resistance comprising but be not limited only to following any
Or appoint several nucleating agents: benzoic acid, adipic acid, sodium benzoate, talcum powder, p-phenolsulfonic acid's sodium, silica, two benzal sorbs
Sugar alcohol and its derivative, EP rubbers, ethylene propylene diene rubber etc.;Wherein, the preferred silica of nucleating agent, benzylidene sorbitol
(DBS), ethylene propylene diene rubber.Nucleating agent dosage used is not particularly limited, generally 0.1-1wt%.
Rheological agent in the auxiliary agent can guarantee that polymer has good brushability and appropriate during film
Coating thickness, the sedimentation of solid particle, can be improved its redispersibility comprising but be not limited only to following when preventing storage
A kind of or several rheological agents: inorganic, such as barium sulfate, zinc oxide, alkaline earth oxide, calcium carbonate, lithium chloride, sulfuric acid
Sodium, magnesium silicate, fumed silica, waterglass, colloidal silicon dioxide;Organo-metallic compound, as aluminum stearate, aluminium alkoxide,
Titanium chelate, aluminium chelate compound;Organic, such as organobentonite, rilanit special/amide waxe, isocyanate derivates, acrylic acid
Lotion, acrylic copolymer, polyethylene wax, cellulose esters etc.;Wherein, the preferred organobentonite of rheological agent, polyethylene wax, hydrophobic
Modified alkaline swellable emulsions (HASE), alkali-swellable emulsions (ASE).Rheological agent dosage used is not particularly limited, and one
As be 0.1-1wt%.
The filler primarily serves following effect in polymer samples: 1. reducing the shrinking percentage of molded article, mentions
Dimensional stability, surface smoothness, flatness and the zero diopter of high product or without photosensitiveness etc.;2. adjusting the viscosity of material;③
Meet different performance requirement, such as improves material impact intensity and compressive strength, hardness, rigidity and modulus, improve wearability, improve
Heat distortion temperature improves electric conductivity and thermal conductivity etc.;4. improving the coloring effect of pigment;5. assigning photostability and chemically-resistant being rotten
Corrosion;6. playing compatibilization, cost can be reduced, improves product competitiveness in the market.
The filler, selected from following any or appoint several fillers: inorganic non-metallic filler, organic is filled out at metal packing
Material.
The inorganic non-metallic filler includes but are not limited to following any or appoints several: calcium carbonate, clay, sulphur
It is sour barium, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, asbestos, asbestos fibre, orthoclase, white
Chalk, lime stone, blanc fixe, gypsum, graphite, carbon black, graphene, graphene oxide, fullerene, carbon nanotube, molybdenum disulfide,
Slag, flue dust, wood powder and shell powder, diatomite, red mud, wollastonite, silica-alumina carbon black, aluminium hydroxide, magnesium hydroxide, flyash,
Oil shale powder, swelling perlite powder, aluminum nitride powder, boron nitride powder, vermiculite, iron cement, white clay, alkali mud, boron mud, glass microballoon, tree
Rouge microballon, glass powder, cement, glass fibre, carbon fiber, quartz fibre, charcoal core boron fibre, titanium diboride fiber, calcium titanate are fine
Dimension, silicon carbide fibre, ceramic fibre, whisker etc..In an embodiment of the invention, preferably conductive inorganic non-
Metal packing includes but are not limited to graphite, carbon black, graphene, carbon nanotube, carbon fiber, facilitates and obtains electric conductivity and/or tool
There is the composite material of electric heating function.In yet another embodiment of the present invention, preferably have and make in infrared and/or near infrared light
With the lower non-metallic fillers with heating function, graphene, graphene oxide, carbon nanotube are included but are not limited to, is conveniently obtained
Obtain the composite material heated using infrared and/or near infrared light.Good heating property, the especially fever of remote control property
Performance help to obtain the performances such as controllable shape memory, selfreparing.In yet another embodiment of the present invention, preferably have
There is the inorganic non-metallic filler of thermal conductivity, includes but are not limited to graphite, graphene, carbon nanotube, aluminium nitride, boron nitride, carbon
SiClx facilitates the composite material for obtaining thermally conductive function.
The metal packing, including metallic compound include but are not limited to following any or appoint several: metal powder
End, fiber comprising but it is not limited only to copper, silver, nickel, iron, gold etc. and its powder, the fiber of alloy;Nano-metal particle, packet
Include but be not limited only to nanogold particle, nano-Ag particles, nanoparticle palladium, nano iron particles, nano cobalt granule, nano nickel
Grain, nanometer Fe3O4Particle, nanometer γ-Fe2O3Particle, nanometer MgFe2O4Particle, nanometer MnFe2O4Particle, nano Co Fe2O4?
Grain, nano Co Pt3Particle, nanometer Fe Pt particle, nanometer Fe Pd particle, ferronickel bimetallic magnetic nanoparticle and other red
Outside, near-infrared, ultraviolet, the nano-metal particle that can be generated heat under at least one effect of electromagnetism etc.;Liquid metal comprising but not
It is only limitted to mercury, gallium, gallium indium liquid alloy, gallium indium tin liquid alloy, other gallium base liquid metal alloys;Metallo-organic compound point
Son, crystal and other in infrared, near-infrared, ultraviolet, the substance that can be generated heat under at least one effect of electromagnetism etc..In the present invention
An embodiment in, can preferably carry out electromagnetism and/or near-infrared heating filler, include but are not limited to nanogold,
Nano silver, Technique of Nano Pd, nanometer Fe3O4, to carry out remote sensing heating.In yet another embodiment of the present invention, preferably liquid is golden
Belong to filler, the flexibility and ductility of substrate can be kept while enhancing the thermally conductive of flexible parent metal, electric conductivity.In the present invention
Another embodiment in, preferably in infrared, near-infrared, ultraviolet, the organic gold that can generate heat under at least one effect of electromagnetism
Belong to compound molecule, crystal, on the one hand facilitates compound, another side raising induction is generated heat efficiency and promote heating effect.
The organic filler includes but are not limited to following any or appoints several: 1. natural organic filler, such as natural
Rubber, cotton, velveteen, fiber crops, jute, flax, asbestos, cellulose, cellulose acetate, lignin, starch, wood powder etc.;2. synthesizing
Resin extender, such as AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, acetate fiber
Element, polytrifluorochloroethylene, haloflex, chliorinated polyvinyl chloride, epoxy resin, ethylene-propylene copolymer, ethylene-acetate second
Enoate copolymer, high density polyethylene (HDPE), high impact polystyrene, low density polyethylene (LDPE), medium density polyethylene, melamine-first
Urea formaldehyde, polyamide, polyacrylic acid, polyacrylamide, polyacrylonitrile, polyarylsulfone (PAS), polybenzimidazoles, poly terephthalic acid fourth two
Alcohol ester, polycarbonate, dimethyl silicone polymer, polyethylene glycol, polyester, polysulfones, polyether sulfone, polyethylene terephthalate,
Phenolic resin, tetrafluoroethylene-perfluoro propane copolymer, polyimides, polymethyl acrylate, polymethacrylonitrile, poly- methyl-prop
E pioic acid methyl ester, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, polytetrafluoroethylene (PTFE), polyurethane, polyvinyl alcohol, gathers polyphenylene oxide
Vinyl acetate, polyvinyl butyral, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, Vingon, polyethylene
Alcohol formal, polyvinylpyrrolidone, Lauxite, ultra-high molecular weight polyethylene, unsaturated polyester (UP), polyether-ether-ketone etc.;3. closing
At gum filler, as isoprene rubber, butadiene rubber, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, EP rubbers,
Silicon rubber, fluorubber, lactoprene, polyurethane rubber, epichlorohydrin rubber, thermoplastic elastomer (TPE) etc.;4. synthetic fibers are filled out
Material, such as viscose fiber, copper ammonia fiber, diethyl ester fiber, triethyl fiber, Fypro, polycarbonate, polyvinyl alcohol
Fiber, polyester fiber, polyurethane fiber, polyacrylonitrile fibre, vinylon, polyvinyl chloride fibre, polyolefin are fine
Dimension, fluorofibre, polytetrafluoroethylene fibre, aromatic polyamide fibre, aramid fiber or aramid fiber etc.;5. foamed polymer
Composition granule and expandable polymer beads.
Wherein, wire feeding does not limit, mainly depending on required material property.Amount of filler used is without spy
It does not limit, generally 1-30wt%.
Wherein, the sweller may include but be not limited to water, organic solvent, ionic liquid, oligomer, plasticizer.Its
In, oligomer can also be considered as plasticizer.
Organic solvent in the sweller is selected from as an example and includes but is not limited to any of the following or appoint several
Kind: hydro carbons (such as hexamethylene, heptane), halogenated hydrocarbon (such as methylene chloride, chloroform, tetrachloromethane), aromatic hydrocarbons (such as toluene, dimethylbenzene),
Ketone (such as acetone, methyl ethyl ketone), ethers (such as ether, tetrahydrofuran, dioxane), esters (such as ethyl acetate, acetic acid fourth
Ester), glycol ether-ether (such as ethylene glycol ether acetate, propylene glycol monomethyl ether acetate), dimethylformamide (DMF), N- methyl
Pyrrolidones (NMP) etc..
Ionic liquid in the sweller is generally made of organic cation and inorganic anion, as an example, sun
It includes but is not limited to that alkyl quaternary ammonium ion, alkyl quaternary are seen imidazol ion, the N- alkyl that ion, 1,3- dialkyl group replace that ion, which is selected from,
Substituted pyridinium ion etc.;Anion be selected from include but is not limited to for halide ion, tetrafluoroborate ion, hexafluoro-phosphate radical from
Son also has CF3SO3 -、(CF3SO2)2N-、C3F7COO-、C4F9SO3 -、CF3COO-、(CF3SO2)3C-、(C2F5SO2)3C-、
(C2F5SO2)2N-、SbF6 -、AsF6 -Deng.In ionic liquid used in the present invention, the preferred glyoxaline cation of cation, anion
It is preferred that hexafluorophosphoricacid acid ions and tetrafluoroborate ion.
Oligomer in the sweller is selected from as an example and includes but is not limited to any of the following or appoint several:
Polyethylene glycol oligomer, polyvinyl alcohol oligomer, polyvinyl acetate ester oligomer, polyacrylic acid N-butyl oligomer, liquid stone
Wax etc..
Plasticizer in the sweller is selected from as an example and includes but is not limited to any of the following or appoint several:
Phthalates: dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisooctyl phthalate
(DIOP), dibutyl phthalate (DHP), diisooctyl phthalate (DIDP), diisononyl phthalate (DINP), neighbour
Phthalic acid butyl benzyl, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid are bis- (13)
Ester, terephthalic acid (TPA) two (2- ethyl) own ester;Phosphoric acid ester, as tricresyl phosphate (TCP), phosphoric acid (hexichol -2- ethyl) oneself
Ester;Fatty acid ester, such as the own ester of adipic acid two (2- ethyl), decanedioic acid two (2- ethyl) own ester;Epoxy compound species, such as epoxy
Glyceride type, epoxy fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidised soybean oil, epoxystearic acid (2- second
Base) own ester, epoxy soybean oleic acid 2- ethylhexyl, the own ester of 4,5- epoxy tetrahydrophthalic acid two (2- ethyl), Chinese littleleaf box acetyl
Methyl ricinolcic acid, dihydric alcohol lipid, such as C5~9Sour glycol ester, C5~9Sour Triethylene Glycol;Class containing chlorine such as afforests stone
Wax class, chloro fat acid esters;Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester;Petroleum sulphur
Acid phenenyl ester, trimellitate, citrate, pentaerythrite and pentaerythritol fatty acid ester etc..Wherein, the preferred DBP, DOP of plasticizer,
DIOP, DIDP, DINP, TCP, epoxidised soybean oil.Wherein, epoxidised soybean oil is that a kind of environment-friendly type plastic of function admirable increases
Mould agent, epoxidation reaction preparation occurs for refined soybean oil and peroxide, in polymer product resistance to volatilization, it is not easy to migrate,
Not easy to lose, this is to keeping product light, thermal stability and to prolong the service life be highly beneficial.Epoxidised soybean oil toxicity pole
It is small, it is allowed for the packaging material of food and medicine by many countries, is that the unique of Food and Drug Adminstration of the US's approval can
For the epoxy plasticiser of packaging material for food, therefore it is more highly preferred to.
In the preparation process of hydridization dynamic aggregation compositions, to hydridization dynamic aggregation compositions each component raw material
Dosage is not particularly limited, and those skilled in the art can carry out according to practical preparation situation and objective cross physical performance
Adjustment.
A kind of hydridization dynamic aggregation compositions provided by the present invention have dynamic covalent bond and supermolecule hydrogen simultaneously
Key, performance are adjustable on a large scale.By suitable component selection and formula design, self-repair function can be introduced polymer material,
So that material internal can be repaired independently after generating damage, help to obtain that the service life is longer, more reliable performance and more economical
Material, plug, sealing ring, part, adhesive, film, coating, fiber, tubing, plate, type with self-repairability is made
Material etc. can be applied to electronic device, military aerospace equipment, functional paint and coating, biological medicine, bio-medical material, energy
The fields such as source, building, bionical every field, has broad application prospects.In electronic correlation field, microelectronics polymer device
With adhesive in use, as heat and mechanics fatigue generate microcrack caused by performance forfeiture be long-term existence the problem of, will
Self-repair function introduces these materials, can greatly improve the reliability and service life of microelectronic product;Using material from
Repairing performance, as the plug of the charger interface of mobile phone, tablet computer, notebook, camera etc., data line interface etc.,
The aperture generated in connector swapping process carries out repairing reach the purpose of waterproof.It is additionally aided as self-repair material
To the material with bionical effect, also have wide practical use in biologic medical field, available more durable human body closes
Section or Osteological gel.The material of exploitation specific use is also contributed to as self-repair material, it such as under certain condition can be with
Restore the material of interface performance, conduction and the performances such as thermally conductive, or can as battery/electrode of super capacitor binder, diaphragm
To reduce the damaged service life for increasing electrode material of electrode.The presence of supermolecule hydrogen bond can further enhance polymerization in the present invention
The toughness of object can be prepared into as the splendid film of performance, fiber, tubing, plate, profile.In addition, utilizing its dynamic reversible
Property, the self-repairability polymer material of shape memory can be prepared, can also being applied to preparation, there is visco-elastic magic to turn
Change the toy of effect.
Hydridization dynamic aggregation compositions of the present invention are described further below with reference to some specific embodiments.
Specific embodiment is that present invention be described in more detail, non-limiting protection scope of the present invention.