CN109206578A - A kind of energy-absorbing method based on hybrid cross-linked dynamic aggregation object - Google Patents

A kind of energy-absorbing method based on hybrid cross-linked dynamic aggregation object Download PDF

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CN109206578A
CN109206578A CN201710523261.5A CN201710523261A CN109206578A CN 109206578 A CN109206578 A CN 109206578A CN 201710523261 A CN201710523261 A CN 201710523261A CN 109206578 A CN109206578 A CN 109206578A
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cross
linking
linked
metal
polymer
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不公告发明人
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Weng Qiumei
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Weng Qiumei
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6212—Polymers of alkenylalcohols; Acetals thereof; Oxyalkylation products thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers

Abstract

The invention discloses a kind of energy-absorbing method based on hybrid cross-linked dynamic aggregation object, the energy-absorbing method uses the hybrid cross-linked dynamic aggregation object acted on containing covalent cross-linking and metal-ligand to carry out energy-absorbing.Since metal-ligand effect has structure abundant, dynamic reversible and can orient identification the advantages that, to embody good energy dissipation and energy absorption characteristics, play the role of damping and shock resistance to material in specific structure, it is combined with covalent bond, it is wide controlled range can be prepared, structure-rich, the polymer material of performance multiplicity, it is carried out using it as energy-absorbing material using good damping can be provided, damping, sound insulation, it eliminates the noise, the functions such as shock resistance, it is especially applied to the body protection of movement and daily life, army and police's body protection, it is explosion-proof, airborne and air-drop protection, automobile collision preventing, electric equipment products defense of resistance to impact etc..

Description

A kind of energy-absorbing method based on hybrid cross-linked dynamic aggregation object
Technical field:
The present invention relates to a kind of energy-absorbing methods, and in particular to one kind is based on being made of metal-ligand effect and covalent cross-linking Hybrid cross-linked dynamic aggregation object energy-absorbing method.
Background technique:
In daily life and actual production process, it is often necessary to which application method or means avoid or slow down shock, vibration Physical impact bring caused by the forms such as dynamic, vibration, explosion, sound influences, wherein widely used is to use A kind of energy-absorbing material progress energy absorption, to play effective protective action to physical impact.Material for energy-absorbing is main There are metal, polymer, composite material etc..Wherein, polymer material energy loss source mainly include the following types: 1, using poly- Close object has the phenomenon that high fissipation factor energy-absorbing near its glass transition temperature.This method is in vitrifying due to material Near transition temperature, the mechanical property of material is sensitive to temperature change, and the mechanical property of material is easily with environment in use The variation of temperature and acute variation, bring difficulty to using；2, it is produced using the fracture of the chemical bonds such as covalent bond and material internal The processes energy-absorbings such as the life crackle even fracture of material entirety, during above-mentioned each, the fracture of covalent bond and macroscopical crackle break Splitting can not only restore, and the mechanical property that also will lead to material reduces, and after primary or a small number of endergonic process several times, material is necessary Replacement could maintain original performance in time；3, the larger deformation institute of deformation, especially polymer rubber state or viscoelastic state is utilized Interior friction energy-absorbing between bring molecule segment, this method, which usually requires the biggish deformation of material generation, could generate significantly Effect, and after the deformation of energy height loss occurs for material, it can not be often restored to original shape, can not be continued to use, it must It must be replaced.Novel shock-resistant and energy-absorbing material are a kind of new material proposed in recent years, choosing of its appearance for material It selects and its performance study has important practical value.The shock resistance energy-absorbing material of various configuration in addition to excellent mechanics, Carrying, shock resistance outside energy absorption characteristics, also have the other functions such as damping, vibration damping, sqouynd absorption lowering noise, stimuli responsive, to meet boat The demand that the high-technology fields such as empty space flight, precision instrument, auto industry propose material.
Energy-absorbing protective materials on the market relies primarily on elastomer foam or relatively relatively soft compressibility material at present As energy absorbing material.It and is to subtract when this material is applied to the shortcomings that being primarily present in physical protection or precision instrument protection Shock stability is limited, and when by severe impact, common protective materials effectively can not effectively be dissipated impact energy, Very strong impact force action is still had on human body or equipment, will lead to personal injury or equipment damage.There is an urgent need to develop A kind of new energy-absorbing method carries out energy-absorbing in particular with the polymer for introducing a kind of new energy absorption and loss mechanism, To solve problems of the prior art.
Summary of the invention
The present invention is directed to above-mentioned background, provides a kind of energy-absorbing method based on hybrid cross-linked dynamic aggregation object, described Hybrid cross-linked dynamic aggregation object is acted on containing covalent cross-linking and metal-ligand；Wherein, covalent cross-linking is at least one crosslinking It is more than the gel point for reaching covalent cross-linking in network.The hybrid cross-linked dynamic aggregation object with good mechanical strength and While certain toughness, good dynamic reversibility is also shown, and metal-ligand effect can be passed through and supermolecule hydrogen bond is made Reversible fracture absorbs energy, assigns dynamic aggregation object with good defense of resistance to impact, also reflects stimuli responsive Property and bionical mechanical property, to provide a kind of novel energy-absorbing method.
The present invention can be achieved by following technical solution:
The present invention relates to a kind of energy-absorbing methods based on hybrid cross-linked dynamic aggregation object, which is characterized in that provides a kind of miscellaneous Change crosslinking dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic is poly- Object is closed, is acted on containing covalent cross-linking and metal-ligand；Wherein, covalent cross-linking reaches covalent at least one cross-linked network It is more than the gel point of crosslinking；Wherein, the metal-ligand act through the ligand groups that contain in dynamic aggregation object structure with Introduced metal center interacts and realizes；Wherein, the polymer chain skeleton of the dynamic aggregation object, side group, on end group Contain ligand groups at least one.
In heretofore described hybrid cross-linked dynamic aggregation object, also optionally contain supermolecule hydrogen bond action, wherein super Molecule hydrogen bond action can be non-crosslinked effect and/or interchain linkage effect and/or non-crosslinked effect in chain.
In embodiments of the present invention, the ligand groups (being indicated with L) be selected from cyclopentadiene and contain at least one The structural unit of a coordination atom (being indicated with A).One coordination atom can be with one or more metal center (including but not Be only limitted to metal ion, the metal center of metallo-chelate, metal-organic metal center, in metal inorganic compound Metal center, indicated with M) form one or more coordinate bonds, a metal center can also be with one or more coordination Atom forms one or more coordinate bond.The quantity for the coordinate bond that one ligand groups and metal center are formed is known as ligand base The number of teeth of group, in embodiments of the present invention, in the same system, a metal center can be with a tooth ligand, bidentate ligand, three One of tooth ligand or multiple ligands form metal-ligand effect, are also possible to connect by metal center between different ligands Cyclization, therefore the present invention can effectively provide type, quantity and performance dynamic metal-ligand effect abundant enough, following Structure shown in general formula is some to provide example, but the present invention is not limited only to this:
Wherein, A is coordination atom, and M is metal center, and each ligand groups and metal center are formed by an A-M key For a tooth, A, which is connected, with singly-bound in formula indicates that the coordination atom belongs to the same ligand groups, when in a ligand groups When containing two or more coordination atoms, A can be identical atom and be also possible to different atoms, including but not only limit In boron, nitrogen, oxygen, sulphur, phosphorus, silicon, arsenic, selenium, tellurium；It is preferred that boron, nitrogen, oxygen, sulphur, phosphorus；More preferable nitrogen, oxygen；Nitrogen.It needs to illustrate , A exists in the form of anion sometimes；It is cyclopentadiene ligand.In the present invention, it is preferred to which a coordination atom is only A coordinate bond is formed with a metal center, therefore the quantity of the coordination atom contained in ligand groups is ligand groups The number of teeth.The metal-ligand that the ligand groups and metal center are formed acts on (with M-LxIt indicates, in x expression and the same metal The quantity of the ligand groups of heart phase separation) power and the type and quantity of coordination atom in ligand groups, metal center Type and valence state and ion pair etc. are related.
The metal center M can be the metal center of any appropriate metal ion or compound/chelate etc., It can be selected from any appropriate ionic species of any one metal, compound/chelate and combinations thereof in the periodic table of elements.
A preferred embodiment (the first polymer network structure) according to the present invention provides a kind of hybrid cross-linked dynamic State polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object only contains a cross-linked network Network, and simultaneously containing covalent cross-linking and metal-ligand effect crosslinking in this cross-linked network.Wherein, the crosslinking of covalent cross-linking Degree is more than its gel point；The degree of cross linking of metal-ligand effect crosslinking is in its gel point above and below.
Another preferred embodiment (second polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object only contains a crosslinking Network, and be crosslinked simultaneously containing covalent cross-linking and metal-ligand effect in this cross-linked network,；Meanwhile in cross-linked network Also it is crosslinked containing supermolecule hydrogen bond action.Wherein, the degree of cross linking of covalent cross-linking is more than its gel point；Metal-ligand effect is handed over The degree of cross linking of connection is in its gel point above and below；The degree of cross linking of hydrogen bond crosslinks is in its gel point above and below.
Another preferred embodiment (the third polymer network structure) according to the present invention, the dynamic aggregation object contain There are two cross-linked network, one of cross-linked network only contains covalent cross-linking and its degree of cross linking more than its gel point；Other one A cross-linked network only contains metal-ligand effect crosslinking and its degree of cross linking more than its gel point.
Another preferred embodiment (the 4th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains there are two cross-linked network, One of cross-linked network contains covalent cross-linking and metal-ligand effect crosslinking simultaneously；Wherein, the degree of cross linking of covalent cross-linking reaches More than gel point, the degree of cross linking of metal-ligand effect crosslinking is in its gel point above and below；Another cross-linked network contains only There is the supermolecule formed by hydrogen bond action crosslinking and its degree of cross linking is more than its gel point.
Another preferred embodiment (the 5th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object is containing there are two cross-linked networks Network, one of cross-linked network contain covalent cross-linking and metal-ligand effect crosslinking simultaneously；Wherein, the degree of cross linking of covalent cross-linking Reach its gel point or more, the degree of cross linking of metal-ligand effect crosslinking is in its gel point above and below；Another cross-linked network Network only contains-metal-ligand effect crosslinking.
Another preferred embodiment (the 6th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object is containing there are two cross-linked networks Network, one of cross-linked network only contain covalent cross-linking and its degree of cross linking more than its gel point；Another cross-linked network contains There is metal-ligand effect crosslinking and its degree of cross linking is more than its gel point；Simultaneously also containing super at least one cross-linked network Molecule hydrogen bond action.
Another preferred embodiment (the 7th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object is containing there are three cross-linked networks Network, one of cross-linked network only contain covalent cross-linking and its degree of cross linking more than its gel point, another cross-linked network is only Containing metal-ligand effect crosslinking, third cross-linked network only contains hydrogen bond crosslinks and its degree of cross linking more than its gel point.
Another preferred embodiment (the 8th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object is containing there are two cross-linked networks Network, one of cross-linked network only contain covalent cross-linking and its degree of cross linking more than its gel point；Another cross-linked network is same Shi Hanyou covalent cross-linking and metal-ligand effect crosslinking, wherein the degree of cross linking of covalent cross-linking more than its gel point, match by metal- The degree of cross linking of body effect crosslinking is in its gel point above and below.
Another preferred embodiment (the 9th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object is containing there are two cross-linked networks Network, one of cross-linked network only contain covalent cross-linking and its degree of cross linking more than its gel point；Another cross-linked network is same Shi Hanyou covalent cross-linking and metal-ligand effect crosslinking, wherein the degree of cross linking of covalent cross-linking more than its gel point, match by metal The degree of cross linking of body effect crosslinking is in its gel point above and below；Also contain supermolecule hydrogen at least one cross-linked network simultaneously Key effect.
Another preferred embodiment (the tenth kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains at least one crosslinking Network, wherein at least one cross-linked network contains the covalent cross-linking of gel point or more, and disperses in wherein at least one network It is noncrosslinking containing metal-ligand effect hydrogen bond action or metal-ligand effect and hydrogen bond action supermolecule polymer.
Another preferred embodiment (a kind of the tenth polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains at least one friendship Networking network, wherein at least one cross-linked network contain the covalent cross-linking of gel point or more, and divide in wherein at least one network Dissipate the existing friendship containing metal-ligand effect or hydrogen bond action or metal-ligand effect and hydrogen bond action in granular form Linked polymer.
In addition to a kind of above-mentioned ten embodiments of hybridization network structure, the present invention can also have other diversified hydridization Network structure embodiment, can contain in an embodiment there are three or its above identical or different network, it is same It can be containing different covalent cross-linking and/or different metal-ligand effects, while also optionally containing identical or not in network Same supermolecule hydrogen bond action, the ingredient containing metal-ligand and/or supermolecule hydrogen bond action are also possible to noncrosslinking ingredient Dispersion is in a network.Those skilled in the art can rationally and effectively be realized with logic according to the present invention and train of thought.
In embodiments of the present invention, the optional supermolecule hydrogen bond action, by being present in dynamic aggregation object Chain backbone (including side chain/branch/bifurcated chain), side group appoint in end group and to form hydrogen bond structure between one or more hydrogen bond group At containing following constituent:
Wherein, it is present in dynamic aggregation object chain backbone (including side chain/branch/bifurcated chain), the hydrogen bond group system on end group Referred to as skeleton hydrogen bond group preferably comprises at least one of following constituent:
Wherein,Indicate with polymer chain, crosslinking link or any other suitable group/atom (including hydrogen original Son) connection；Wherein, the hydrogen bond group being present on dynamic aggregation object chain side group (also including the multilevel structure of side group), is referred to as For side group hydrogen bond group, at least one of structure shown in the following general formula is preferably comprised,
Wherein, X is selected from oxygen atom, sulphur atom, nitrogen-atoms, and Y is selected from oxygen atom, sulphur atom；A is the R's being connected with X atom Number；When X is oxygen atom or sulphur atom, a 0, R is not present；When X is selected from nitrogen-atoms, a=1, R are selected from hydrogen atom, miscellaneous original Subbase group, molecular weight are no more than the small molecule alkyl of 1000Da；J is divalent linking group, is connected selected from singly-bound, hetero atom Base, molecular weight are no more than the divalent small molecule alkyl of 1000Da；Q is end group, is selected from hydrogen atom, heteroatom group, molecular weight Small molecule alkyl no more than 1000Da；Indicate that (including it is more with main polymer chain skeleton, cross-linked network chain backbone, side chain Level structure) or any other suitable group/atom connection；Wherein, J, R, Q any two or it is multiple between can connect Cyclization, the ring include but are not limited to aliphatic ring, aromatic ring, ether ring, condensed ring and combinations thereof, cyclic structure at Annular atom is each independently carbon atom, nitrogen-atoms or other hetero atoms, and the hydrogen atom on each ring member nitrogen atoms can be substituted, It can not also be substituted.
In embodiments of the present invention, a kind of hybrid cross-linked dynamic aggregation object or its composition are provided, and using it as suction It can material progress energy-absorbing；Wherein, the hybrid cross-linked dynamic aggregation object form can be ordinary solid, gel (including water-setting Glue, organogel, oligomer swell gel, plasticizer swell gel, ionic liquid swell gel), elastomer, foamed material Deng.
In embodiments of the present invention, it is poly- to constitute dynamic for a kind of energy-absorbing method based on hybrid cross-linked dynamic aggregation object Close that the raw material components of object further include following any or any two can additive: other polymers, auxiliary agent, filler；
Wherein, addible other polymers are selected from following any or appoint several: natural polymer, synthesis tree Rouge, synthetic rubber, synthetic fibers；
Wherein, addible auxiliary agent is selected from following any or appoints several: catalyst, initiator, antioxidant, light are stablized Agent, heat stabilizer, chain extender, toughener, coupling agent, lubricant, release agent, plasticizer, foaming agent, antistatic agent, emulsifier, Dispersing agent, colorant, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, rheological agent, thickener, levelling agent, antibacterial agent；
Wherein, addible filler be selected from it is following any or appoint several fillers: inorganic non-metallic filler, metal packing, Organic filler.
The energy-absorbing method based on hybrid cross-linked dynamic aggregation object in embodiments of the present invention, can be applied to hinder Buddhist nun, sound insulation, noise elimination, damping, explosion-proof, defense of resistance to impact, shellproof, buffering.
Compared with prior art, the invention has the following advantages:
(1) in energy-absorbing method provided by the invention, for the hybrid cross-linked dynamic aggregation object of energy-absorbing, contained by gold Category-ligand effect dynamic is strong, energy-absorbing effect is prominent.Metal-ligand effect can by its higher dynamic reversibility with And stress sensitivity, cross-linked polymer is made a response in time, promptly to external force, to preferably promote material Energy absorption characteristics.By the strong dynamic acted on based on metal-ligand, polymer can show sensitive and regulatable dilatant Property, it both can produce pure viscosity enhancing, and also can produce from creep properties to elastomeric transformation, greatly improve to impact energy The absorption and dispersibility of amount, to reach excellent shock resistance effect；And the presence of covalent cross-linking, so that polymer has certainly Supportive has excellent practicability.Further, since metal-ligand effect is reversible, it is recoverable, and impart polymerization Object material is with good durability, and after the releasing of extraneous impact stress, metal-ligand effect can be bonded again again, so that dynamic State polymer is still able to maintain higher energy-absorbing effect after this multiple use, this is also itself and existing energy-absorbing method and technology Compared to possessed huge advantage, this is difficult to realize in existing polymeric system.
(2) in energy-absorbing method provided by the invention, for the hybrid cross-linked dynamic aggregation object of energy-absorbing, wherein also containing can The supermolecule hydrogen bond action of choosing, supermolecule hydrogen bond action and metal-ligand act in simultaneous dynamic polymer systems, The dynamic reversibility with orthogonality can be embodied with the variation of environmental stimuli again, so that polymer is to heat, illumination, pressure The environmental stimulis such as power, pH, redox show different responding abilities, and then can have under different environmental conditions not Same energy-absorbing effect；Meanwhile in polymer when by energy damages, the energy of concertedness can be generated according to the difference of environment Dissipation/absorption is measured, cooperative response and energy-absorbing effect is embodied, improves material to the tolerance of external force.
(3) in energy-absorbing method provided by the invention, the hybrid cross-linked dynamic aggregation object component structure for energy-absorbing is abundant, Performance multiplicity, Modulatory character are strong.Metal-ligand effect, covalent cross-linking and optional are combined in dynamic aggregation object structure Supermolecule hydrogen bond action will carry out sufficient utilize and combination the advantages of various effects.By controlling the chemical combination as raw material The parameters such as molecular structure, functional group number, the molecular weight of object can be prepared with different appearance features, performance is adjustable, widely used Dynamic aggregation object.For example, functional group number and other reactive group numbers by control as the compound of raw material, can make It is standby to provide the dynamic aggregation object of different topology structure, to prepare the polymer material with different energy-absorbing effects.In addition, It, can be a wide range of interior by the type and number of ligand groups and hydrogen bond group in control polymer chain skeleton and/or side group Collocation and regulation are combined to the dynamic of polymer, based on metal-ligand effect and supermolecule hydrogen bond action dynamic Difference can obtain the energy-absorbing material that structure more horn of plenty, performance are more various, dynamic reversible effect has more hierarchy.
(4) since hybrid cross-linked dynamic aggregation object employed in the present invention can also embody self-repairability, repeatable Usability, recuperability, fluorescence, so that with broader application range and more permanent using the energy-absorbing material obtained by it Service life.Different fluorescent characteristics especially can be embodied under different energy-absorbing states, is embodied and is worked as by fluorescence phenomenon Preceding energy-absorbing state can be compared its energy charge and accurately hold, be more advantageous to as shock resistance energy-absorbing material.
With reference to following embodiments explanation, embodiment and the appended claims, these and other features of the invention with And advantage will become obvious.
Specific embodiment
The present invention relates to a kind of energy-absorbing methods based on hybrid cross-linked dynamic aggregation object, which is characterized in that provides a kind of miscellaneous Change crosslinking dynamic aggregation object or its composition, and carries out energy-absorbing using it as energy-absorbing material；The hybrid cross-linked dynamic aggregation object, It contains covalent cross-linking and metal-ligand effect；Wherein, covalent cross-linking reaches covalent cross-linking at least one cross-linked network It is more than gel point；Wherein, metal-ligand acts through the ligand groups contained in dynamic aggregation object structure and introduced metal Center interacts and realizes；Wherein, the polymer chain skeleton of the dynamic aggregation object, side group, at least one on end group at contain Ligand groups.
In heretofore described hybrid cross-linked dynamic aggregation object, also optionally contain supermolecule hydrogen bond action, wherein super Molecule hydrogen bond action can be non-crosslinked effect and/or interchain linkage effect and/or non-crosslinked effect in chain.
Term " energy-absorbing " used refers to for caused by the forms such as shock, vibration, vibration, explosion, sound in the present invention The absorption of energy that generates of physical impact, but do not include the only absorption to thermal energy and/or electric energy.
Term " polymerization " reaction/action used in the present invention refers to that the reactant of lower molecular weight passes through polycondensation, adds The reaction formations such as poly-, ring-opening polymerisation form the propagation process/effect with the product of higher molecular weight.Wherein, reactant can Thinking (can spontaneously be polymerize with polymerizing power, or can be polymerize in initiator or outside plus under capable of acting on) The compounds such as monomer, oligomer, prepolymer.Homopolymer is known as by a kind of product that reactant is polymerize.By two kinds Or the product that two or more reactants are polymerize is known as copolymer." polymerization " in the present invention comprising anti- Answer linear growth process, branching process, annulation process and the cross-linking process etc. of object strand；In embodiments of the present invention In, " polymerization " includes caused by the noncovalent interaction of bonding and metal-ligand effect with hydrogen bond action as covalent bond Propagation process.
Term " crosslinking " reaction/action used in the present invention, refer between reactant molecule and/or in reactant molecule altogether The physical action of chemical bonds and metal-ligand effect and/or supermolecule hydrogen bond action between valence link, which is formed, has two three-dimensionals The process of unlimited reticular pattern product.In cross-linking process, polymer chain is general first to be increased in two-dimensional/three-dimensional direction, gradually Two dimension or three-dimensional cluster are formed, developing deeply is three-dimensional infinite network structure.It should be noted that the cross-linked structure in the present invention, Its three-dimensional infinite network structure for refering in particular to gel point or more (containing gel point, similarly hereinafter), and non-crosslinking structure then refers to line style, ring The structures such as shape, branching and gel point two dimension below, three-dimensional cluster structure.Heretofore described " gel point " is (also referred to as Percolation threshold), reactant is referred in cross-linking process, and viscosity is uprushed, and starts gel phenomenon occur, is started crosslinking for the first time and is reached Reflecting point when to a three-dimensional infinite network.When there are a variety of crosslinked actions, except covalent cross-linking is at least one network It is outer to reach its gel point or more, other crosslinked actions can be in its gel point above and below.
In embodiments of the present invention, covalent cross-linking can have one or more than one kinds of, also can be using any Suitable covalently cross-linked structure and combinations thereof.The covalently cross-linked structure includes chemical structure, topological structure, degree of cross linking etc..? In embodiments of the present invention, cross-linked network can have at least one, namely can be single one network, can also have mutually The multiple networks being blended, can also there is multiple networks of interpenetrating.But in embodiments of the present invention, the covalent cross-linking must It is more than the gel point that must reach covalent cross-linking at least one network.In this way, can just be protected for polymer of the invention Even if card is in the case where only one network, polymer can also keep balanced structure, namely can be in the normal state The insoluble structure not melted.
In embodiments of the present invention, the ligand groups (being indicated with L) include on polymer chain skeleton Ligand groups (calling " framework counterpart " in the following text) and ligand groups (calling " pendant ligands " in the following text) in polymer chain side group and poly- Close object chain and the ligand (calling " end group ligand " in the following text) of other compound ends.The framework counterpart refers in the group At least two atoms directly participate in the building polymer chain skeleton, main polymer chain, covalently friendship including non-covalent Join the skeleton of lattice chain, side chain, branch, bifurcated chain, the skeleton of preferably covalently cross-linked network chain；The pendant ligands, refer to All atoms on the group are in side group；The end group ligand refers to all atoms on the group on end group. In some circumstances, end group ligand is also pendant ligands or framework counterpart.The ligand groups can be in polymer polymerizing/friendship Generated during connection, be also possible to it is pre-generated carry out polymerized/cross-linked again, it is preferably pre-generated.It should be pointed out that except above-mentioned Outside ligand groups, in polymer of the invention can also containing only one atom participate in building polymer chain skeleton other match Body group.
In embodiments of the present invention, metal-ligand acts through polymer backbone ligand, pendant ligands, end group and matches At least one of body ligand groups and introduced metal center interact and realize；It wherein can on same strand With there are one or more identical or different ligand groups.It is any to be not excluded for framework counterpart, pendant ligands, end group ligand Between be combined and through metal center formed metal-ligand effect；And it under certain condition can be between any ligand groups Metal-ligand effect in chain is formed, metal-ligand effect does not generate crosslinked action usually in such chain.In addition, in the present invention In, polymer can be caused to form microphase-separated under metal-ligand effect certain condition, metal-ligand effect is present in hard phase In constitute non-covalent together with hard phase, can on the one hand play increase balanced structure as the useful supplement of covalent cross-linking On the other hand the effect of stability and mechanical strength promotes toughness based on its non-covalent character.In the present invention, any one net Metal-ligand effect in network can preferably reach the gel point that metal-ligand acts on or more in any crosslinking degree.
In the present invention, for non-crosslinking structure, the polymer chain skeleton includes main polymer chain skeleton and polymer The chain backbones such as side chain, branch, bifurcated chain.For cross-linked structure, the polymer chain skeleton includes being present in cross-linked network Any segment skeleton (i.e. cross-linked network chain backbone) and its chain backbones such as side chain, branch, bifurcated chain.
In the present invention, " main polymer chain " refers to having most in polymer architecture if not otherwise indicated The chain of multichain joint number." side chain " refers in polymer architecture with main polymer chain skeleton/cross-linked network chain backbone The molecular weight for being connected and being distributed in its skeleton side is more than the chain structure of 1000Da；Wherein, the branch, bifurcated chain refer to It is the link that the molecular weight come out from main polymer chain skeleton/cross-linked network chain backbone or any other chain bifurcated is more than 1000Da Structure；For the sake of simplicity, the molecular weight of side chain, branch, bifurcated chain if not otherwise indicated, is then collectively referred to as side when being more than 1000Da Chain." side group " refers to being connected in polymer architecture with main polymer chain skeleton/cross-linked network chain backbone and divide Cloth is not higher than the short-side chain of 1000Da in chemical group of the molecular weight of main chain backbone side not higher than 1000Da and molecular weight.It is right In side chain and side group, can have multilevel structure namely side chain that can continue with side group and side chain, the side chain of side chain can be after Continuous to have side group and side chain, side chain therein also includes branch and bifurcated chain isodesmic structure." end group " refers to polymerizeing It is connected and is located at the chemical group of chain backbone end in object structure with polymer chain skeleton；In the present invention, on the downside of specific condition Base can also have end group.
In embodiments of the present invention, the ligand groups (being indicated with L) be selected from cyclopentadiene and contain at least one The structural unit of a coordination atom (being indicated with A).One coordination atom can be with one or more metal center (including but not Be only limitted to metal ion, the metal center of metallo-chelate, metal-organic metal center, in metal inorganic compound Metal center, indicated with M) form one or more coordinate bonds, a metal center can also be with one or more coordination Atom forms one or more coordinate bond.The quantity for the coordinate bond that one ligand groups and metal center are formed is known as ligand base The number of teeth of group, in embodiments of the present invention, in the same system, a metal center can be with a tooth ligand, bidentate ligand, three One of tooth ligand or multiple ligands form metal-ligand effect, are also possible to connect by metal center between different ligands Cyclization, therefore the present invention can effectively provide type, quantity and performance dynamic metal-ligand effect abundant enough, following Structure shown in general formula is some to provide example, but the present invention is not limited only to this:
Wherein, A is coordination atom, and M is metal center, and each ligand groups and metal center are formed by an A-M key For a tooth, A, which is connected, with singly-bound in formula indicates that the coordination atom belongs to the same ligand groups, when in a ligand groups When containing two or more coordination atoms, A can be identical atom and be also possible to different atoms, including but not only limit In boron, nitrogen, oxygen, sulphur, phosphorus, silicon, arsenic, selenium, tellurium；It is preferred that boron, nitrogen, oxygen, sulphur, phosphorus；More preferable nitrogen, oxygen；Nitrogen.It needs to illustrate , A exists in the form of anion sometimes；It is cyclopentadiene ligand.In the present invention, it is preferred to which a coordination atom is only A coordinate bond is formed with a metal center, therefore the quantity of the coordination atom contained in ligand groups is ligand groups The number of teeth.The metal-ligand that the ligand groups and metal center are formed acts on (with M-LxIt indicates, in x expression and the same metal The quantity of the ligand groups of heart phase separation) power and the type and quantity of coordination atom in ligand groups, metal center Type and valence state and ion pair etc. are related.
In embodiments of the present invention, in order to form the crosslinking based on metal-ligand effect, a metal center is extremely It wants that metal-ligand effect (i.e. M-L can be formed with ligand groups described in two parts less2Structure), there can also be multiple match Body and the same metal center form metal-ligand effect, and two of them or multiple ligand groups can be identical or different.One The ligancy of metal center is limited, and the coordination atom of ligand groups is more, and the amount of ligand that a metal center can be coordinated is got over It is few, it is lower based on metal-ligand effect supermolecule degree of cross linking；But each ligand is formed by the number of teeth with metal center and gets over More coordinations are stronger, and dynamic is lower, therefore the ligand groups of three teeth are preferably more than in the present invention.
In embodiments of the present invention, can only have one kind in a polymer chain or a dynamic polymer systems to match Body can also exist simultaneously any appropriate combination of multiple ligands.A kind of ligand refers to a kind of core ligand knot Structure, a framework counterpart, pendant ligands, end group ligand can have same core ligand structure, their difference exists The tie point and/or position difference of polymer chain or small molecule are accessed in core ligand structure.Suitable ligand combination can be with The dynamic aggregation object with particular characteristic is be effectivelyed prepared, such as plays collaboration and/or orthogonal effect, promotes the synthesis of material Performance.Suitable ligand groups (core ligand structure) can be exemplified below, but the present invention is not limited only to this:
One tooth ligand groups are exemplified below:
In addition, it can include other optional tooth ligands, such as Deng；
Bidentate ligand group is exemplified below:
Tridentate ligand group is exemplified below:
Tetradentate ligands group is exemplified below:
Multidentate ligand is exemplified below:
In embodiments of the present invention, when there are the polymer of non-covalent or small molecules in dynamic polymer systems When compound, the ligand groups can also be in the polymer of the non-covalent or the end of small molecule compound as end Base is connected to end group.
In embodiments of the present invention, the metal center M can be any appropriate metal ion or compound/ The metal center of chelate etc. can be selected from any appropriate ionic species, the chemical combination of any one metal in the periodic table of elements Object/chelate and combinations thereof.
Related metal is preferably the metal in the first subgroup to the 7th subgroup and the 8th race.First subgroup Metal into the 7th subgroup and the 8th race further include lanthanide series metal (i.e. La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and actinide metals (i.e. Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr).
Related metal is more preferably the first subgroup (Cu, Ag, Au) metal, the second subgroup (Zn, Cd) metal, the 8th race (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt) metal, group of the lanthanides (La, Eu, Tb, Ho, Tm, Lu) metal, actinium series (Th) metal.Into One step is preferably Cu, Zn, Fe, Co, Ni, Pd, Ag, Pt, Au, La, Ce, Eu, Tb, Th, to obtain stronger dynamic.
In embodiments of the present invention, there is no restriction for related metallo-organic compound, and suitable example can be lifted Under such as:
Other suitable metal organic compounds for being capable of providing metal center include but is not limited to the organic cage of metal-, metal- Organic frame.This metalloid-organic compound can be used alone, or is introduced by suitable covalent chemical on-link mode (OLM) The suitable position of polymer chain.Those skilled in the art can rationally and effectively be realized with logic according to the present invention and train of thought.
In embodiments of the present invention, the oxide of the preferably above-mentioned metal of related metal inorganic compound, vulcanization Composition granule, especially nano particle.
In embodiments of the present invention, the metallo-chelate that can provide suitable metal center preferably has coordination site empty Scarce chelate or some ligands can the chelate replaced the framework counterpart of the invention.
In embodiments of the present invention, there is no particular restriction for the combination of ligand groups and metal center, as long as matching physical efficiency Enough and metal center generates suitable metal-ligand and acts on.Some suitable combinations can be exemplified below, but the present invention is not It is only limitted to this:
In embodiments of the present invention, in addition to containing metal-ligand effect, also optionally make containing supermolecule hydrogen bond With.Wherein supermolecule hydrogen bond action plays the role of including interchain linkage, interchain polymerization, cyclization etc. in chain.
In embodiments of the present invention, the optional supermolecule hydrogen bond action passes through hydrogen for any appropriate The supermolecular mechanism that key is established, big generally by the atom Z big with the electronegativity hydrogen atom being covalently attached to and electronegativity, The small atom Y of radius, using hydrogen as medium, generates the hydrogen bond link of Z-H ... Y shape formula, wherein described Z, the Y is to appoint between Z and Y Suitable electronegativity of anticipating is big and atom that radius is small, can may be not same element for same element, can be selected from F, N, O, the atoms such as C, S, Cl, P, Br, I, more preferably F, N, O atom, more preferably O, N atom.Wherein, the supermolecule hydrogen bond Effect, which can be used as ring formation presence namely hydrogen bond in supermolecule polymerization and/or crosslinking and/or chain, can only play connection two A or more than two chain segment units, which play, to be increased polymer chain dimensions but does not play supermolecule crosslinked action or hydrogen bond only plays chain Between supermolecule be crosslinked, or only play in chain in combination of any two or more in ring formation or three of the above.This hair The bright hydrogen bond that is also not excluded for plays the role of grafting.
In embodiments of the present invention, the hydrogen bond can be optional tooth number.Wherein, the number of teeth refer to by The donor (H, that is, hydrogen atom) and receptor (Y, that is, receive the electronegative atom of hydrogen atom) of hydrogen bond group are formed by Hydrogen bond quantity, each H ... Y group are combined into a tooth.In following formula, the hydrogen of the schematically illustrate tooth of difference, two teeth and three tooth hydrogen bond groups Key bonding situation.
The bonding situation of one tooth, two teeth and three tooth hydrogen bonds can concrete example it is as follows:
The number of teeth of hydrogen bond is more, and synergistic effect is bigger, and the intensity of hydrogen bond is bigger.In embodiments of the present invention, right The number of teeth of hydrogen bond does not limit.If the number of teeth of hydrogen bond is more, intensity is big, then the dynamic of hydrogen bond action is with regard to weak, Ke Yiqi To the effect for promoting dynamic aggregation object to keep balanced structure and raising mechanical property (modulus and intensity).If the number of teeth of hydrogen bond Few, then intensity is low, and the dynamic of hydrogen bond action can provide dynamic property together with metal-ligand supermolecular mechanism with regard to strong.? In embodiments of the present invention, the preferably more than hydrogen bond action of four teeth.It may be constructed under hydrogen bond action certain condition strong non- On the one hand covalent cross-linking can play as the useful supplement of covalent cross-linking and increase balanced structure stability and mechanical strength On the other hand effect promotes toughness based on its non-covalent character.
In the present invention, the hydrogen bond group can be only present on polymer chain skeleton (including side chain/branch/point Fork chain), it also can be only present in polymer chain side group (also including the multilevel structure of side group), also can be only present in polymer On chain/small molecule end group, it can also exist simultaneously in polymer chain skeleton, polymer chain side group, polymer chain/small molecule end group In at least two on.When existing simultaneously in polymer chain skeleton, polymer chain side group, polymer chain/small molecule end group When at least two, under specific circumstances, hydrogen bond, such as skeleton hydrogen bond can be formed between the hydrogen bond group of any different location Group can form hydrogen bond between side group hydrogen bond group.
In embodiments of the present invention, the hydrogen bond group preferably comprises following constituent:
In embodiments of the present invention, described to be present in dynamic aggregation object chain backbone (including side chain/branch/bifurcated Chain), main chain end group, the hydrogen bond group on side chain end group be referred to as skeleton hydrogen bond group, preferably comprise in following constituent At least one:
At least one of further preferably following constituent:
Wherein,Indicate with polymer chain, crosslinking link or any other suitable group/atom (including hydrogen original Son) connection；
In embodiments of the present invention, the dynamic aggregation object chain side group that is present in (also tie by the multistage including side group Structure), the hydrogen bond group on side group end group, be referred to as side group hydrogen bond group, preferably comprise in structure shown in the following general formula extremely Few one kind,
Wherein, X is selected from oxygen atom, sulphur atom, carbon atom, silicon atom, nitrogen-atoms, and Y is selected from oxygen atom, sulphur atom；A be with The number of the connected R of X atom；When X is oxygen atom or sulphur atom, a 0, R is not present；When X is selected from nitrogen-atoms, a=1； When X is carbon atom or silicon atom, a=2；R is selected from the small molecule that hydrogen atom, heteroatom group, molecular weight are no more than 1000Da Alkyl；J is divalent linking group, and the divalent small molecule hydrocarbon of 1000Da is no more than selected from singly-bound, hetero atom linker, molecular weight Base；Q is end group, and the small molecule alkyl of 1000Da is no more than selected from hydrogen atom, heteroatom group, molecular weight；It indicates and poly- Close owner's chain backbone, cross-linked network chain backbone, side chain (including its multilevel structure) or any other suitable group/atom Connection；Wherein, J, R, Q any two or it is multiple between can connect cyclization, the ring include but are not limited to aliphatic ring, Aromatic ring, ether ring, condensed ring and combinations thereof, the ring member nitrogen atoms of cyclic structure be each independently carbon atom, nitrogen-atoms or its His hetero atom, the hydrogen atom on each ring member nitrogen atoms can be substituted, can not also be substituted.In embodiments of the present invention In, hydrogen bond group preferably is selected from carbamate groups, urea groups, thiocarbamate base and derivative of the above group etc..
Wherein, suitable skeleton hydrogen bond group citing such as (but the present invention is not limited only to this):
Wherein, suitable side group hydrogen bond group is in addition to it can have above-mentioned skeleton hydrogen bond group structure, and more citings are such as (but the present invention is not limited only to this):
Wherein, m, n are the quantity of repetitive unit, can be fixed value, are also possible to average value, preferably smaller than 20, more excellent Choosing is less than 5.
It in the present invention, can be same containing one or more kinds of hydrogen bond groups in same polymeric system It can also be a kind of or more containing that can contain in one or more kinds of hydrogen bond group namely dynamic aggregation object in cross-linked network The combination of kind hydrogen bond group.The hydrogen bond group can be formed by the reaction between any appropriate group, such as: it is logical The covalent reaction crossed between carboxyl, acyl halide group, anhydride group, ester group, amide groups, isocyanate groups and amino is formed；It is logical Cross isocyanate groups and hydroxyl, sulfydryl, the covalent reaction between carboxyl are formed；Pass through succinimide group and amino, hydroxyl Covalent reaction between base, sulfydryl is formed.
In the present invention, the supermolecule hydrogen bond action in cross-linked network can have any appropriate degree of cross linking, can be with It, can also be below its gel point more than its gel point.The supermolecule hydrogen bond action can be to carry out in dynamic aggregation object It is generated during covalent cross-linking, also can carry out hydrogen bond friendship when polymer chain carries out covalent cross-linking by the hydrogen bond group Connection；Covalent cross-linking is carried out again after being also possible to pre-generated hydrogen bond crosslinks；It can also be after covalent cross-linking be formed, in dynamic aggregation Hydrogen bond crosslinks are generated during object subsequent forming.
In energy-absorbing method provided by the invention, for the hybrid cross-linked dynamic aggregation object of energy-absorbing, component structure is abundant, Performance multiplicity, raw material sources are extensive, and Modulatory character is strong.Metal-ligand effect is combined in dynamic aggregation object structure, is covalently handed over Connection and optional supermolecule hydrogen bond action, will carry out sufficient utilize and combination the advantages of various effects.Made by control For parameters such as the molecular structure of the compound of raw material, functional group number, molecular weight, can prepare with different appearance features, performance Adjustable, widely used dynamic aggregation object.For example, by control as the functional group number of the compound of raw material and other reactivity Group number can prepare the dynamic aggregation object with different topology structure, to prepare poly- with different energy-absorbing effects Close object material.In addition, by the type and number of ligand groups and hydrogen bond group in control polymer chain skeleton and/or side group, Collocation and regulation can be combined to the dynamic of polymer interior on a large scale, based on metal-ligand effect and supermolecule hydrogen Key acts on the difference of dynamic, can obtain that structure more horn of plenty, performance be more various, dynamic reversible effect has more hierarchy Energy-absorbing material.
In embodiments of the present invention, dynamic aggregation object can be made of one or more cross-linked networks.When dynamic When polymer is only made of a cross-linked network, contain the covalent cross-linking and gold simultaneously in the cross-linked network structure Category-ligand effect.It, can be by two or more mutual blendings when dynamic aggregation object is made of two or more cross-linked networks Cross-linked network constitute, can also be made of two or more mutually interspersed cross-linked networks, can also be by two or more portions The cross-linked network that split-phase is mutually interted is constituted, and can also be combined and be constituted by three cases above；Wherein, two or more networks It can be identical or different；It can be the combination that subnetwork only contains only metal-ligand effect containing covalent cross-linking and subnetwork, The part only combination or part containing covalent cross-linking and part while containing covalent cross-linking and metal-ligand effect It contains only in the combination or each network of metal-ligand effect and part simultaneously containing covalent cross-linking and metal-ligand effect all It is acted on simultaneously containing covalent cross-linking and metal-ligand；But it must satisfy in dynamic polymer systems simultaneously containing described covalent Crosslinking and metal-ligand effect, and the covalent cross-linking at least one network reaches the gel point of covalent cross-linking or more.
For dynamic aggregation object of the invention, covalent cross-linking reaches the solidifying of covalent cross-linking at least one cross-linked network It is more than glue point, it is ensured that even if even if there is only in the case where the covalent cross-linking in the case where only one network, Polymer can also keep balanced structure, namely can have (at least partly) the insoluble structure not melted in the normal state. Can have when there are two or more networks, between heterogeneous networks interaction (including the described metal-ligand effect and/ Or other effects), it can also be mutually indepedent；And except the covalent cross-linking of at least one network must reach the gel of covalent cross-linking Or more it is outer, the crosslinkings of other networks (including the effect of covalent cross-linking, metal-ligand, optional supermolecule hydrogen bond action and its it With) can be more than gel point or in gel point hereinafter, it is preferred that more than gel point.
In embodiments of the present invention, it can be blended in the cross-linked network structure of dynamic aggregation object and/or be interspersed with it Do not have between the one or more polymer chains namely those polymer chains of his non-crosslinked type and its between the cross-linked network Crosslinked action.
A preferred embodiment (the first polymer network structure) according to the present invention provides a kind of hybrid cross-linked dynamic State polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object only contains a cross-linked network Network, and simultaneously containing covalent cross-linking and metal-ligand effect crosslinking in this cross-linked network.Wherein, the crosslinking of covalent cross-linking Degree is more than its gel point；The degree of cross linking of metal-ligand effect crosslinking is in its gel point above and below.For the embodiment party Formula only contains a cross-linked network, and the covalent cross-linking in system is acted on for providing balanced structure by metal-ligand Dynamic and dilatancy realize energy-absorbing effect；And it is upper more convenient in preparation.
Another preferred embodiment (second polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object only contains a crosslinking Network, and simultaneously containing covalent cross-linking and metal-ligand effect crosslinking in this cross-linked network；Meanwhile in cross-linked network Also it is crosslinked containing supermolecule hydrogen bond action.Wherein, the degree of cross linking of covalent cross-linking is more than its gel point；Metal-ligand effect is handed over The degree of cross linking of connection is in its gel point above and below；The degree of cross linking of hydrogen bond crosslinks is in its gel point above and below.In the implementation In mode, by introducing supermolecule hydrogen bond crosslinks in single cross-linked network structure, make it possible to as metal-ligand dynamic One supplement of key, so that polymer reflects dynamic reversible and energy-absorbing effect with hierarchy.
Another preferred embodiment (the third polymer network structure) according to the present invention, the dynamic aggregation object contain There are two cross-linked network, one of cross-linked network only contains covalent cross-linking and its degree of cross linking more than its gel point；Other one A cross-linked network only contains metal-ligand effect crosslinking and its degree of cross linking more than its gel point.In this embodiment, covalently Cross-linked network is responsible for keeping balanced structure, and the network based on metal-ligand effect is responsible for providing dynamic property, covalent cross-linking network Interpenetrating or semi-intercrossing network can be formed with metal-ligand effect network, the advantages of both making full use of, reach collaboration and/or Orthogonal energy-absorbing effect.
Another preferred embodiment (the 4th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains there are two cross-linked network, One of cross-linked network contains covalent cross-linking and metal-ligand effect crosslinking simultaneously；Wherein, the degree of cross linking of covalent cross-linking reaches More than gel point, the degree of cross linking of metal-ligand effect crosslinking is in its gel point above and below；Another cross-linked network contains only There is the supermolecule formed by hydrogen bond action crosslinking and its degree of cross linking is more than its gel point.In this embodiment, by additional Independent supermolecule hydrogen bond crosslinks network is introduced, a supplement as metal-ligand effect dynamic is made it possible to, so that poly- It closes object and reflects dynamic reversible and energy-absorbing effect with hierarchy.
Another preferred embodiment (the 5th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object is containing there are two cross-linked networks Network, one of cross-linked network contain covalent cross-linking and metal-ligand effect crosslinking simultaneously；Wherein, the degree of cross linking of covalent cross-linking Reach its gel point or more, the degree of cross linking of metal-ligand effect crosslinking is in its gel point above and below；Another cross-linked network Network only contains metal-ligand effect crosslinking.In this embodiment, pass through second Dynamic Networks based on metal-ligand effect Network provides additional dynamic property, reaches more preferably resultant effect.
Another preferred embodiment (the 6th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object is containing there are two cross-linked networks Network, one of cross-linked network only contain covalent cross-linking and its degree of cross linking more than its gel point；Another cross-linked network contains There is metal-ligand effect crosslinking and its degree of cross linking is more than its gel point；Simultaneously also containing super at least one cross-linked network Molecule hydrogen bond action.In this embodiment, metal-ligand effect network and covalent cross-linking network are not only individually present, and The supermolecule hydrogen bond action of introducing can also make the dynamic ability of regulation and control of polymer stronger, and synergy is more preferable.
Another preferred embodiment (the 7th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object is containing there are three cross-linked networks Network, one of cross-linked network only contain covalent cross-linking and its degree of cross linking more than its gel point, another cross-linked network is only Containing metal-ligand effect crosslinking, third cross-linked network only contains hydrogen bond crosslinks and its degree of cross linking more than its gel point. In this embodiment, metal-ligand acts on cross-linked network, supermolecule hydrogen bond action cross-linked network, covalent cross-linking network respectively It is individually present, to make dynamic aggregation object reveal difference using the difference of dynamic and stability between different cross-linked networks Orthogonality and concertedness, reach better energy-absorbing effect.
Another preferred embodiment (the 8th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object is containing there are two cross-linked networks Network, one of cross-linked network only contain covalent cross-linking and its degree of cross linking more than its gel point；Another cross-linked network is same Shi Hanyou covalent cross-linking and metal-ligand effect crosslinking, wherein the degree of cross linking of covalent cross-linking more than its gel point, match by metal- The degree of cross linking of body effect crosslinking is in its gel point above and below.In this embodiment, by controlling two covalent cross-linking nets The structure of network can achieve the purpose of Reasonable Regulation And Control dynamic aggregation object balanced structure and mechanical property.
Another preferred embodiment (the 9th kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object is containing there are two cross-linked networks Network, one of cross-linked network only contain covalent cross-linking and its degree of cross linking more than its gel point；Another cross-linked network is same Shi Hanyou covalent cross-linking and metal-ligand effect crosslinking, wherein the degree of cross linking of covalent cross-linking more than its gel point, match by metal The degree of cross linking of body effect crosslinking is in its gel point above and below；Also contain supermolecule hydrogen at least one cross-linked network simultaneously Key effect.In this embodiment, by controlling the structure of two covalent cross-linking networks, it can achieve Reasonable Regulation And Control dynamic aggregation The purpose of object balanced structure and mechanical property, and the supermolecule hydrogen bond action introduced can also make the dynamic of polymer regulate and control Ability is stronger, and collaboration and energy-absorbing effect are more preferable.
Another preferred embodiment (the tenth kind of polymer network structure) according to the present invention provides a kind of hybrid cross-linked Dynamic aggregation object or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains at least one crosslinking Network, wherein at least one cross-linked network contains the covalent cross-linking of gel point or more, and disperses in wherein at least one network It is noncrosslinking containing metal-ligand effect hydrogen bond action or metal-ligand effect and hydrogen bond action supermolecule polymer. The noncrosslinking supermolecule polymer does not generate the transformation of visco-elastic when by physical impact, can more carry out The consume of energy improves energy absorption performance.
Another preferred embodiment (a kind of the tenth polymer network structure) according to the present invention provides a kind of hydridization friendship Link state polymer or its composition, and energy-absorbing is carried out using it as energy-absorbing material；The dynamic aggregation object contains at least one friendship Networking network, wherein at least one cross-linked network contain the covalent cross-linking of gel point or more, and divide in wherein at least one network Dissipate the existing friendship containing metal-ligand effect or hydrogen bond action or metal-ligand effect and hydrogen bond action in granular form Linked polymer.It is described that with particle, there are cross-linked polymers when by physical impact, do not generate can with visco-elastic change or Elasticity enhancing is able to carry out the consume and dispersion of energy, and energy absorption performance is strong and has the function of promoting toughness.
The present invention can also have other diversified hybridization network structural implementations, can contain in an embodiment There are three or above identical or different network, can be containing different covalent cross-linking and/or different in the same network Metal-ligand effect, while also optionally containing identical or different hydrogen bond crosslinks.Those skilled in the art can be according to this The logic and train of thought of invention, are rationally and effectively realized.
Above-mentioned " covalent cross-linking ", process means can be any appropriate covalent cross-linking and means in principle.Refer generally to Then two ways, the prepolymer of first synthetic linear or branching type carry out interchain linkage reaction；Or from monomer, once Property or reaction reach crosslinking.In the present invention, in order to allow, there are ligand groups in chain side group, can be initially formed pendant ligands and then hand over again Connection；In order to allow, there are ligand groups on chain backbone, can be initially formed framework counterpart and then be crosslinked again；Or it is generated while crosslinking Framework counterpart.
In embodiments of the present invention, the covalent cross-linking is established by any appropriate by covalent bond Covalent cross-linking link, includes but are not limited to the covalent cross-linking by carbon-carbon bond formation, the covalent friendship formed by carbon-sulfide linkage Connection, the covalent cross-linking formed by carbon-oxygen bond, the covalent cross-linking formed by carbon-nitrogen bond are formed covalent by silicon-oxygen key Crosslinking.Covalent cross-linking in any one cross-linked network structure of dynamic aggregation object can have at least one chemical structure, at least A kind of degree of branching and at least one reaction type and reaction means.In embodiments of the present invention, the generation of framework counterpart or Introduce the reaction that can use to include but are not limited to Types Below: isocyanates and amino, hydroxyl, sulfydryl, carboxyl react, The electrophilic substitution reaction of heterocycle, the nucleophilic substitution of heterocycle, double bond (including acrylate, acrylamide etc.) free radical are anti- It answers, nitrine-alkynes click-reaction, sulfydryl-double bond/alkynes click-reaction, the reaction of urea-amine, amidation process, tetrazine-norborneol Alkene reaction, active ester are reacted with amino；Preferred isocyanate and amino, hydroxyl, sulfydryl react, double bond radical reaction, Nitrine-alkynes click-reaction, sulfydryl-double bond/alkynes click-reaction, the reaction of urea-amine, amidation process, active ester and amino Reaction；More preferable isocyanates and amino, hydroxyl, sulfydryl react, double bond radical reaction, nitrine-alkynes click-reaction, mercapto Base-double bond/alkynes click-reaction.
In embodiments of the present invention, covalent cross-linking can use any appropriate reaction, include but are not limited to following Type: by between carboxyl, acyl halide group, anhydride group, ester group, amide groups, isocyanate groups, epoxy group and hydroxyl Covalent reaction is crosslinked；Pass through carboxyl, acyl halide group, anhydride group, ester group, amide groups, isocyanate groups, epoxy group Covalent reaction between amino is crosslinked；It is crosslinked by alkene radical reaction, free radical acrylate reaction；It is logical Cross the CuAAC reaction of azido group and alkynyl, the click-reaction progress covalent cross-linking of sulfydryl and alkene；By between silicone hydroxyl Condensation reaction carries out covalent cross-linking.
Be used to form in the present invention supermolecule crosslinking ligand groups generation or introducing, can before covalent cross-linking, It carries out later or in the process.Ligand groups are preferably introduced in the present invention before covalent cross-linking.
In embodiments of the present invention, the generation or introducing of ligand groups can use any appropriate reaction, including but Be not limited only to Types Below: isocyanates and amino, hydroxyl, sulfydryl, carboxyl react, the electrophilic substitution reaction of heterocycle, heterocycle Nucleophilic substitution, double bond radical reaction, the side chain reaction of heterocycle, nitrine-alkynes click-reaction, sulfydryl-double bond/alkynes clicks Reaction, the reaction of urea-amine, amidation process, tetrazine-norbornene reaction, active ester are reacted with amino；It is preferred that isocyanic acid Ester and amino, hydroxyl, sulfydryl react, nitrine-alkynes click-reaction, the reaction of urea-amine, amidation process, active ester and ammonia The reaction of base, sulfydryl-double bond/alkynes click-reaction；More preferable isocyanates and amino, hydroxyl, sulfydryl react, and sulfydryl-double bond/ Alkynes click-reaction, nitrine-alkynes click-reaction.
In embodiments of the present invention, the introducing of metal center can carry out on any suitable opportunity.At least one Lower three kinds of methods can introduce before generating ligand, can formerly with ligand formed metal-ligand effect composition again into Row polymerized/cross-linked can also be re-introduced into after completing polymerized/cross-linked.It is preferred that after generating ligand but before covalent cross-linking It introduces.
In embodiments of the present invention, dynamic aggregation object can use the monomer containing pendant ligands and/or can close At the monomer of pendant ligands, the monomer containing framework counterpart and/or the monomer of framework counterpart, crosslinking agent and/or solid can be synthesized Agent and the substance that can provide metal center are synthesized by chemical reaction.Below for the portion of network structure of the invention The embodiment of point preparation method is illustrated.
For example, the hybrid cross-linked dynamic aggregation object only contains one in the first polymer network structure of the invention A cross-linked network, and contain metal-ligand effect and covalent cross-linking in this cross-linked network, wherein the friendship of covalent cross-linking Connection degree is more than its gel point.Wherein, when framework counterpart there are when, framework counterpart and then can be crosslinked again using being initially formed Process means realize.As an example but be not limited to it is following lifted, for example, dithiol monomer and side group band containing framework counterpart There are the double olefin monomer of pendant ligands and the crosslinking agent of end polyene, first in the present invention can be formed with polymerized/cross-linked Kind polymer network structure.By controlling the formula rate of monomer and crosslinking agent, the covalent cross-linking in network is made to reach covalently solidifying More than glue point, while ligand groups are had in chain backbone and side group.Metal center is added, can be obtained described hybrid cross-linked Dynamic aggregation object.
For another example, framework counterpart covalent cross-linking means are generated using while crosslinking.As an example but it is not limited to following institute It lifts, the reaction of the crosslinking agent of the more cyano of the binary azido compound containing pendant ligands and end, reacts covalent cross-linking using this Form the first network structure in the present invention.By controlling the formula rate of monomer and crosslinking agent, make the covalent friendship in network Connection reaches covalent gel point or more, while ligand groups are had in chain backbone and side group.Metal center is added, can be obtained institute The hybrid cross-linked dynamic aggregation object stated.
When framework counterpart is not present, for example, dithiol monomer and end polyene using side group with RL The first network structure of crosslinking agent direct polymerization/be cross-linked to form in the present invention.By the recipe ratio for controlling monomer and crosslinking agent Example, makes the covalent cross-linking in network reach covalent gel point or more, while pendant ligands are had in chain side group.It is added in metal The heart can be obtained the hybrid cross-linked dynamic aggregation object.
For another example, the unsaturated hydrocarbon monomer containing pendant ligands and have active group (including but not limited to hydroxyl, amine Base, carboxyl, isocyano, sulfydryl, epoxy group, double bond, three keys etc.) unsaturated hydrocarbon monomer under the effect of the catalyst altogether It is poly-, then again with double-active group monomer or polymer carry out subsequent crosslinking.As an example but it is not limited to following institute It lifts, for example, the vinyl compound with pendant ligands and the copolymerization of the vinyl compound with epoxy group, and in diamino base class It is crosslinked under the action of conjunction object, forms the first network structure in the present invention using this reaction covalent cross-linking.Pass through control The formula rate of monomer and crosslinking agent makes the covalent cross-linking in network reach covalent gel point or more, while having and matching in side group Body group.Metal center is added, can be obtained the hybrid cross-linked dynamic aggregation object.
In above-mentioned example, the RL group that side group has can pre-generate before polymerized/cross-linked.
The embodiment of other network structures in the present invention is similar, and those skilled in the art can be according to this hair Bright understanding selects suitable preparation means, reaches ideal purpose.
Hybrid cross-linked dynamic aggregation object of the invention, when containing there are two or its above network Multi net voting structure when, except general Logical blending dispersion is outer, is more preferably intertwined the interpenetrating net for tangling and being formed by two or more polymer networks Network.Interpenetrating net polymer structure is poly- due to single network that the synergistic effect between network component makes its performance be substantially better than its component Object is closed, the mechanical properties such as toughness more higher than single network are generated, mentality of designing introducing metal-of the invention is based particularly on and matches In the case that body acts on.
Interpenetrating net polymer preparation method generally includes one-step method interpenetrating and two-step method interpenetrating.One-step method disposably will All the components are added, and then carry out polymerized/cross-linked, prepare target network.Two-step method first prepares first network polymer, immediately Be immersed in the monomer/pre-polymer solution to form the second network, then cause polymerized/cross-linked obtain on-target hybrid net Network.The preparation with hybrid cross-linked dynamic aggregation object in the present invention can also use one-step method interpenetrating and two-step method interpenetrating, Under specific condition must also using three steps and its more than method.
It is illustrated below for the embodiment of the part preparation method of interpenetrating net polymer of the invention.
For example, in the third polymer network structure of the invention, there are two the hybrid cross-linked dynamic aggregation object contains Cross-linked network, one of cross-linked network only contain covalent cross-linking and its degree of cross linking more than its gel point；Another crosslinking Network only contains metal-ligand effect crosslinking and its degree of cross linking more than its gel point.It is covalently handed over firstly, preparing a kind of be not present Connection, but contain the linear polymer of ligand groups in polymer as the 2nd network.Then, when preparing 1 network, first by the 2nd The monomer (or prepolymer) of network and the 1st network, crosslinking agent etc. are uniformly mixed, then are carried out covalently by above-mentioned covalent cross-linking means Crosslinking, to obtain the semi-interpenetrating network polymer of the 1st network and the 2nd network namely the 2nd network is scattered in the 1st network.? It can be initially formed the 1st network, the 2nd network is then carried out interpenetrating by swelling (can be by solvent) and the 1st network.Metal is added Behind center, the hybrid cross-linked dynamic aggregation object can be obtained.
For another example, in the 8th kind of polymer network structure of the invention, the hybrid cross-linked dynamic aggregation object contains two A cross-linked network, one of cross-linked network only contain covalent cross-linking and its degree of cross linking more than its gel point；Another is handed over Networking network contain simultaneously covalent cross-linking and metal-ligand effect crosslinking, wherein the degree of cross linking of covalent cross-linking its gel point with On, the degree of cross linking of metal-ligand effect crosslinking is in its gel point above and below.Firstly, preparing one kind is not present covalent cross-linking, But contain the linear polymer of ligand groups in polymer as the 2nd network.Then, when preparing 1 network, first by the 2nd net The monomer (or prepolymer) of network and the 1st network, crosslinking agent etc. are uniformly mixed, then are carried out covalently by above-mentioned covalent cross-linking means Crosslinking, to obtain the semi-interpenetrating network polymer of the 1st network and the 2nd network namely the 2nd network is scattered in the 1st network.? It can be initially formed the 1st network, the 2nd network is then carried out interpenetrating by swelling (can be by solvent) and the 1st network.Metal is added Behind center, the hybrid cross-linked dynamic aggregation object can be obtained.
The relative molecular mass of term " molecular weight " used representative species in the present invention, for small molecule compound, small Molecular radical and certain macromolecular compounds with fixed structure, for macro-radical, molecular weight generally has single point Property is dissipated, namely there is fixed member amount；And there is polydispersion for oligomer, high polymer, oligomer residue, high polymer residue etc. The substance of property molecular weight, molecular weight generally refer to average molecular weight.Wherein, the small molecule compound in the present invention, small molecule Group refers in particular to the compound or group that molecular weight is no more than 1000Da；Macromolecular compound, that macro-radical refers in particular to molecular weight is big In the compound or group of 1000 Da.
Term " hetero atom " used refers to nitrogen-atoms, oxygen atom, sulphur atom, phosphorus atoms, silicon atom, boron atom in the present invention Etc. common non-carbon.
Term " alkyl " used refers to the saturated hydrocarbyl with straight or branched structure in the present invention.In appropriate situation Under, alkyl can have specified carbon atom number, for example, C1-4Alkyl, the alkyl be included in linear chain or branched chain arrangement in have 1, 2, the alkyl of 3 or 4 carbon atoms.The example of suitable alkyl includes but is not limited to methyl, ethyl, propyl, normal-butyl, isobutyl Base, tert-butyl, n-pentyl, 2- methyl butyl, 3- methyl butyl, 4- methyl butyl, n-hexyl, 2- methyl amyl, 3- methylpent Base, 4- methyl amyl, 5- methyl amyl, 2- ethyl-butyl, 3- ethyl-butyl, heptyl, octyl, nonyl, decyl.
It, all can be in the case where not specifying when the structure being related in the present invention has isomer Any one of them isomers comprising position isomery, conformational isomerism, chiral photo-isomerisation, cis-trans isomerism etc..
In the present invention " substituted ", by taking " substituted alkyl " as an example, refer to any of any position in substituted " alkyl " A or more than one hydrogen atom can be replaced any substituent group.In the case where being not particularly limited, substituent group therein It is not particularly limited.
For a compound, a group or an atom, can be substituted simultaneously and by hydridization, such as nitrobenzophenone Replace hydrogen atom, for another example-CH2-CH2-CH2It is replaced by-CH2-S-CH(CH3)-。
In order to illustrate simplicity the term is indicated using conjunction "and/or" in the description of the invention 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 embodiments of the present invention, the form of the dynamic aggregation object or its composition can be ordinary solid, coagulate Glue (including hydrogel, organogel, oligomer swell gel, plasticizer swell gel, ionic liquid swell gel), elasticity Body, foamed material etc., wherein the dissolvable small-molecular-weight component content contained in ordinary solid and foamed material is generally not more than 10 wt%, and the small-molecular-weight component content contained in gel is generally not less than 50wt%.The shape and volume ratio of ordinary solid It is relatively fixed, there is better mechanical strength, it can not be by the constraint of sweller.Elastomer has the general properties of ordinary solid, But there is preferable elasticity, and softer simultaneously, be conducive to provide damping/energy-absorbing ability.Gel then has good Flexibility can embody preferable energy absorption characteristics and resilience, suitable for preparing the energy-absorbing material with damping, preferably The gel of oligomer, ionic liquid, plasticizer and boiling point the organic solvent swelling higher than water.Foamed material then have density it is low, The mechanical strength of light advantage, the brittleness and organogel that can also overcome the problems, such as part ordinary solid is relatively low, soft bubble material Characteristic of the material also with good elasticity and energy absorption capacity and soft comfortable.The material of different shape can have in different fields There is suitable purposes.
In embodiments of the present invention, dynamic aggregation object gel can by sweller (including water, organic solvent, One of oligomer, plasticizer, ionic liquid or combinations thereof) in carry out crosslinking acquisition, can also have been prepared in dynamic aggregation object Swelling acquisition is carried out at rear recycling sweller.Certainly, the present invention not only limit and this, those skilled in the art can be according to this hair Bright logic and train of thought, is rationally and effectively realized.
In the preparation process of dynamic aggregation object, mechanical foaming method, physical blowing method, three kinds of chemical blowing process are mainly used Method foams to dynamic aggregation object.
Wherein, the mechanical foaming method is by strong stirring in the preparation process of dynamic aggregation object a large amount of empty Gas or other gases are introduced into lotion, suspension or the solution of polymer and make uniform foams, then pass through physics Or chemical change is allowed to be molded with as foamed material.To shorten, molding cycle can be passed through air and addition emulsifier or surface is living Property agent.
Wherein, the physical blowing method, be realized in the preparation process of dynamic aggregation object using physical principle it is poly- Close the foaming of object comprising but it is not limited only to following methods: (1) inert gas blown method, i.e., indifferent gas under pressurized condition Body is pressed into molten polymer or pasty material, then decompression heating, is made the gas expansion of dissolution and is foamed；(2) low boiling is utilized Point liquid evaporation gasification foaming makes liquid that is, in low-boiling point liquid indentation polymer or under certain pressure, temperature regime It dissolves in polymer (particle), then heats and softens polymer, liquid also gasifies therewith evaporation and foamed；(3) leaching, i.e., It is immersed in polymer with liquid medium and dissolves added solid matter in advance, make to occur a large amount of holes in polymer and be in hair Blister, such as by solable matter salt elder generation and mixed with polymers, put in water repeatedly after being shaped to product, then by product Processing dissolves out solable matter to get open-celled foam product is arrived；(4) hollow microsphere method is added hollow micro- in the material It is combined after ball as obturator-type foamed polymer；(5) expandable particles method is filled, first mixing filling expandable particles, Expandable particles are made to foam in molding or mixed process with the polymer material of activity foaming；Wherein, preferably by polymer In dissolve in inert gas and the method for low-boiling point liquid foams.Using physical blowing method, have operation Poisoning smaller, hair The advantages that bubble cost of material is lower, foaming agent noresidue body.Further, it is also possible to be prepared using freeze-drying.
Wherein, the chemical blowing process is to generate gas along with chemical reaction in dynamic aggregation object foaming process And the method to foam comprising but it is not limited only to following two method: (1) thermal decomposable foaming agent foaming utilizes chemistry The gas decomposed to give off after foaming agent heating foams.(2) it interacts between polymers compositions and generates the foaming of gas, i.e., Using the chemical reaction occurred between two or more components in foaming system, inert gas (such as carbon dioxide or nitrogen are generated Gas) cause polymer to expand and foam.It is carried out in foaming process for control polymerization reaction and foamable reaction balance, to guarantee product There is preferable quality, a small amount of catalyst and foam stabiliser (or surfactant) is generally added.Wherein, preferably by polymerizeing The method for adding chemical foaming agent in object foams.
In the preparation process of dynamic aggregation object, mainly using moulded from foam molding, injection-expansion molded and extrusion hair Three kinds of methods of type are soaked to form dynamic aggregation object foamed material.
Wherein, moulded from foam molding, technical process is simpler, is easy to control, and can be divided into one-step method and two Two kinds of footwork.One step processing refers to that mixed material, which is direct plungeed into die cavity, carries out foaming；Two-step method, which refers to, first will The material prefoam processing mixed, is then placed in die cavity and carries out foaming.Wherein, since one-step method moulded from foam forms ratio Two-step method is easy to operate and high production efficiency, therefore it is preferred that one-step method carries out moulded from foam molding.
Wherein, described injection-expansion molded, technique and equipment are similar with common injection moulding, bubble nucleating rank Section is after screw rod is added in material, by heating and friction is made material become melt state, the control that foaming agent is passed through metering valve Then foaming agent is uniformly mixed by the hybrid element of screw head, in nucleating agent in certain flow rate injecting material melt Under the action of form nuclei of bubbles.Expansion stage and solidifying and setting stage all occur after full of die cavity, when under cavity pressure When drop, the expansion process of gassing core, while so that foam is formed with the cooling of mold.
Wherein, the foam shaping by extrusion, technique and equipment are similar with common extrusion molding, before extrusion or Foaming agent is added in extruder in extrusion process, melt flows through pressure at head and declines, and foaming agent volatilizees and forms requirement Foaming structure.
In the preparation process of dynamic aggregation object, those skilled in the art can be poly- according to practical preparation situation and target Closing physical performance selects suitable foaming method and foamed material forming method to prepare dynamic aggregation object foamed material.
In embodiments of the present invention, the structure of dynamic aggregation object foamed material is related to open-celled structure, hole-closing structure, half Open three kinds of semi-closure structure.It in open-celled structure, is interconnected between abscess and abscess, or connection completely, one-dimensional or three-dimensional can lead to Gas or liquid are crossed, abscess diameter is that 0.01-3mm is differed.Hole-closing structure, has an individual blisters structure, inner cell and abscess it Between there is wall film to separate, the overwhelming majority be not interconnected, abscess diameter be 0.01-3mm differ.The existing phase interconnection of contained abscess It is then half open-celled structure that leading to again, which has mutual disconnected structure,.It, can also be by mechanical compression for having formed the foaming structure of closed pore Or chemical method becomes open-celled structure, those skilled in the art can select according to actual needs.
In embodiments of the present invention, dynamic aggregation object foamed material can be divided into soft, hard according to its softness With semi-rigid three classes: (1) flexible foam, 23 DEG C and 50% relative humidity under, the elasticity modulus of foamed plastics is less than 70MPa；(2) rigid foam, 23 DEG C and 50% relative humidity under, elasticity modulus be greater than 700MPa；(3) semi-rigid (or half It is soft) foam, the foams between above two class, elasticity modulus is between 70MPa and 700MPa.
In embodiments of the present invention, dynamic aggregation object foamed material can be divided into low ratio foamed, middle hair according to its density again Bubble and high-foaming.The foamed material of low ratio foamed, density are greater than 0.4g/cm3, expansion ratio is less than 1.5；The foam material of middle foaming Material, density are 0.1~0.4g/cm3, expansion ratio is 1.5~9；And the foamed material of high-foaming, density are less than 0.1g/ cm3, expansion ratio is greater than 9.
During the preparation process, certain addible other polymers, auxiliary agent, filler can also be added to be total in dynamic aggregation object With composition dynamic aggregation object material, but these additives it is not necessary to.
It is new can to play improvement material property, imparting material as additive in system for the other polymers Performance improves materials'use and economic benefit, has the function that material comprehensively utilizes.Addible other polymers, it is optional From natural polymer, synthetic macromolecular compound.The present invention is to the character of added polymer and possessed Molecular weight can be that oligomer or high polymer can according to the difference of polymeric species according to the difference of molecular weight without limitation Think homopolymer or copolymer, it in the specific use process should be according to the performance of target material and actual fabrication process It needs and is selected.
When the other polymers are selected from natural polymer, it can be selected from following any or appoint several days Right high-molecular compound: natural rubber, chitosan, chitin, native protein, polysaccharide etc..
When the other polymers are selected from synthetic macromolecular compound, it can be selected from following any or appoint several: Polytrifluorochloroethylene, haloflex, chliorinated polyvinyl chloride, polyvinyl chloride, Vingon, low density polyethylene (LDPE), middle density Polyethylene, high density polyethylene (HDPE), ultra-high molecular weight polyethylene, melamine formaldehyde resin, polyamide, polyacrylic acid, polypropylene Amide, polyacrylonitrile, polybenzimidazoles, polyethylene terephthalate, polybutylene terephthalate (PBT), polycarbonate, Dimethyl silicone polymer, polyethylene glycol, polyester, polyether sulfone, polyarylsulfone (PAS), polyether-ether-ketone, tetrafluoroethylene-perfluoro propane copolymer, Polyimides, polyacrylate, polyacrylonitrile, polyphenylene oxide, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high impact poly Styrene, polysulfones, polytetrafluoroethylene (PTFE), polyurethane, polyureas, polyvinyl acetate, ethylene-propylene copolymer, ethylene-acetic acid second Enoate copolymer, AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, vinyl chloride-second Vinyl acetate copolymer, polyvinylpyrrolidone, epoxy resin, phenolic resin, Lauxite, unsaturated polyester (UP), poly- isoamyl two Alkene, poly- suitable butadiene, styrene-butadiene copolymer, hycar, polychlorobutadiene, isobutene-isoamyl Diene copolymers, polysiloxane, vinylidene-chlorotrifluoroethylene, epichlorohydrin ethylene oxide copoymer Deng.
In the preparation process of dynamic aggregation object material, the certain addible auxiliary agents being added can improve material Preparation process improves product quality and yield, reduces product cost or assign certain distinctive application performance of product.Described Addible auxiliary agent is selected from following any or several auxiliary agents: additive synthesis, including catalyst, initiator；Stabilizing additive, Including antioxidant, light stabilizer, heat stabilizer；Improve the auxiliary agent of mechanical property, including toughener；Improve helping for processing performance Agent, including lubricant, release agent；The auxiliary agent of softness and lighting, including plasticizer, foaming agent；Change helping for surface property Agent, including antistatic agent, emulsifier, dispersing agent；Change the auxiliary agent of coloured light, including colorant, fluorescent whitening agent, delustering agent；It is difficult Burning and suppression cigarette auxiliary agent, including fire retardant；Other auxiliary agents, including nucleating agent, rheological agent, thickener, levelling agent, antibacterial agent.
Catalyst in the addible auxiliary agent can reduce reaction activity by changing reaction path Accelerate the reaction rate of reactant during the reaction.It includes but are not limited to following any or appoints several catalyst: 1. Polyurethane catalyst for synthesizing: amines catalyst, such as triethylamine, triethylenediamine, bis- (dimethylaminoethyl) ethers, 2- (2- Dimethylamino-ethoxy) ethyl alcohol, N, bis- (dimethylamine propyl) isopropanolamines of N-, N- (dimethylamino-propyl) diisopropanolamine (DIPA), four Methyl dipropylenetriamine, N, N- dimethyl cyclohexyl amine, N, N, N ', N '-tetramethyl Alkylenediamine, N, N, N ', N ', N '-five Methyl diethylenetriamines, N, N- dimethylethanolamine, N-ethylmorpholine, 2,4,6- (dimethylamino methyl) phenol, trimethyl- N-2- hydroxypropyl caproic acid, N, N- dimethyl benzylamine, N, N- dimethyl cetylamine etc.；Organometallic catalysts, such as octanoic acid are sub- Tin, dibutyltin dilaurate, dioctyl tin dilaurate, zinc Isoocatanoate, isooctyl acid lead, potassium oleate, zinc naphthenate, ring Alkanoic acid cobalt, ferric acetyl acetonade, phenylmercuric acetate, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octanoate, potassium oleate, calcium carbonate etc.；② Polyolefin catalyst for synthesizing: such as Ziegler-Natta catalyst, π-allyl nickel, alkyl lithium catalyst, metallocene catalysis Agent, aluminium diethyl monochloride, titanium tetrachloride, titanium trichloride, boron trifluoride etherate, magnesia, dimethylamine, stannous chloride, Triethylamine, tetraphenylboron sodium, antimony oxide, sesquialter ethylmercury chloride aluminium, vanadium oxytrichloride, triisobutyl aluminium, nickel naphthenate, aphthenic acids Rare earth etc.；3. CuAAC catalysts: sharing concerted catalysis by monovalence copper compound and amine ligand；Monovalence copper compound is optional From Cu (I) salt, such as CuCl, CuBr, CuI, CuCN, CuOAc；Also selected from Cu (I) complex compound, such as [Cu (CH3CN)4]PF6、 [Cu(CH3CN)4]OTf、CuBr(PPh3)3Deng；Amine ligand can be selected from three [(1- benzyl -1H-1,2,3- triazole-4-yl) methyl] Amine (TBTA), three [(1- tert-butyl -1H-1,2,3- triazole-4-yl) methyl] amine (TTTA), three (2- benzimidazole methyl) amine (TBIA), it is hydrated bathophenanthroline disulfonic acid sodium etc.；4. thiol-ene catalysts: photochemical catalyst, as dimethoxybenzoin, 2- hydroxy-2-methyl phenylacetone, 2,2- dimethoxy -2- phenyl acetophenone etc.；Nucleopilic reagent catalyst, such as ethylenediamine, three Ethanol amine, triethylamine, pyridine, 4-dimethylaminopyridine, imidazoles, diisopropyl ethyl amine etc..Catalyst amount used does not have It is particularly limited to, generally 0.01-0.5wt%.
Initiator in the addible auxiliary agent, can cause in polymerization process monomer molecule activate and Free radical is generated, reaction rate is improved, reaction is promoted to carry out, include but are not limited to following any or appoints several initiators: 1. radical polymerization shares initiator: organic peroxide, such as lauroyl peroxide, benzoyl peroxide (BPO), two carbon of peroxidating Sour diisopropyl ester, di-cyclohexylperoxy di-carbonate, dicetyl peroxydicarbonate bis- (4- tert-butylcyclohexyl) esters, tert-butyl hydroperoxide Benzoic ether, tert-butyl hydroperoxide pivalate, di-tert-butyl peroxide, di-isopropylbenzene hydroperoxide；Azo-compound, such as Azodiisobutyronitrile (AIBN), azobisisoheptonitrile；Inorganic peroxide, such as ammonium persulfate, potassium peroxydisulfate；2. living polymerization With initiator: such as 2,2,6,6- tetramethyl -1- oxygroup piperidines, 1- chloro-1-phenyl ethane/stannous chloride/bis- pyridines ternary system Deng；3. ionic polymerization initiator: such as butyl lithium, sodium/naphthalene system, boron trifluoride/aqueous systems, tin tetrachloride/alkyl halide system Deng；4. coordination polymerization initiator: such as titanium tetrachloride/triethyl aluminum system, two zirconium cyclopentadienyl of dichloro/methylaluminoxane system；⑤ Ring-opening polymerisation initiator: such as sodium methoxide, potassium methoxide, ethylenediamine, hexamethylene diisocyanate, stannous octoate.Wherein, cause The preferred lauroyl peroxide of agent, benzoyl peroxide, azodiisobutyronitrile, potassium peroxydisulfate.Initiator amount used is without spy It does not limit, generally 0.1-1wt%.
Antioxidant in the addible auxiliary agent can delay the oxidation process of polymer material, guarantee material Successfully it can be processed and be prolonged its service life, include but are not limited to following any or appoint several antioxidant: by Hinder phenols, such as 2,6- di-tert-butyl-4-methy phenol, 1,1,3- tri- (- 4 hydroxyl -5- tert-butyl-phenyl of 2- methyl) butane, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert butyl benzene Phenol)；Sulfur-bearing Hinered phenols, such as 4,4 '-thiobis-[3 methy 6 tert butyl phenol], 2,2 '-thiobis-[4- methyl-6-tert Butylphenol]；Triazine system hindered phenol, such as 1,3,5- bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl]-hexahydros equal three Piperazine；Isocyanuric acid ester Hinered phenols, such as three (3,5- di-tert-butyl-4-hydroxyl benzyl)-triisocyanates；Amine, such as N, N '-two (betanaphthyl) p-phenylenediamine, N, N '-diphenyl-para-phenylene diamine, N- phenyl-N '-cyclohexyl p-phenylenediamine；Sulfur-bearing class, such as Dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, Asia Tricresyl phosphate nonyl phenyl ester, three [2.4- di-tert-butyl-phenyl] phosphite esters etc., wherein the preferred tea polyphenols of antioxidant (TP), butyl Hydroxyanisole (BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), three [2.4- di-tert-butyl-phenyls] Phosphite ester (irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010).Antioxidant dosage used is not particularly limited, generally 0.01-1wt%.
Light stabilizer in the addible auxiliary agent can prevent polymer material from light aging occurs, and extending it makes With the service life comprising but be not limited only to following any or appoint several light stabilizers: photomask agent, such as carbon black, titanium dioxide, oxygen Change zinc, calcium sulfite；Ultraviolet absorbing agent, such as ESCALOL 567,2- hydroxyl -4- n-octyloxy hexichol first Ketone, 2- (2- hydroxyl -3,5- di-tert-butyl-phenyl) -5- chlorobenzotriazole, 2- (2- hydroxy-5-methyl base phenyl) benzotriazole, 2, 4,6- tri- (2- hydroxyl -4- n-butoxyphenyl) -1,3,5- s-triazine, 2- cyano -3,3- diphenylacrylate 2- ethylhexyl； Pioneer's type ultraviolet absorbing agent, such as the p- tert-butyl phenyl ester of salicylic acid, double acid double phenol A ester；UV quenchers, such as bis- (3, 5- di-t-butyl -4- benzylphosphonic acid mono ethyl ester), 2,2 '-thiobis (4- spy's octyl phenol oxygroup) nickel；Hindered amine light stabilizer Agent, as bis- (2,2,6, the 6- tetramethyl piperidine) esters of decanedioic acid, benzoic acid (2,2,6,6- tetramethyl piperidine) ester, three (1,2,2,6, 6- pentamethvl base) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acid (2,4- bis- tertiary fourths Base benzene) ester, alkyl phosphoric acid amide, N, N '-zinc dibutyl dithiocaarbamate, N, the positive fourth positive group dithiocarbamates of N '-two Nickel formate etc..Wherein, bis- (2,2,6, the 6- tetramethyl piperidine) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid, institute Light stabilizer dosage is not particularly limited, generally 0.01-0.5wt%.
Heat stabilizer in the addible auxiliary agent, enable to polymer material in processing or use process not Chemical change occurs because heated, or delays these variations to achieve the purpose that prolong the service life comprising but not only limit In following any or several heat stabilizers: lead salts, as lead sulfate tribasic, dibasic lead phosphite, dibasic are stearic Lead plumbate, dibasic phthalic acid lead, tribasic Malaysia lead plumbate, lead stearate, lead salicylate, Dythal, alkali Formula ceruse；Metal soap: such as cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate；Organo-tin compound Class, such as di-n-butyltin dilaurate, Bis(lauroyloxy)dioctyltin, maleic acid two (just) butyl tin, double single-ethylhexyl maleates Dioctyltin, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital tin C-102, dimercapto acetic acid isooctyl stannous methide, two sulphur Alcohol stannous methide and its compound；Antimony stabilizer, such as mercaptan antimonic salt, mercaptoacetate mercaptans type, mercapto-carboxylic ester antimony, carboxylate Antimony；Epoxy compound species, such as epoxidized oil, epoxy aliphatic ester, epoxy resin；Phosphorous acid esters, such as three aromatic ester of phosphorous acid, Asia Tricresyl phosphate alkyl ester, three aralkyl ester of phosphorous acid, alkane virtue mixed ester, aggretion type phosphite ester；Polyalcohols, such as pentaerythrite, xylose Alcohol, mannitol, D-sorbite, trimethylolpropane；It is compound steady to be such as co-precipitated metallic soap, liquid metal soap for composite thermal stabilizer Determine agent, organotin compound stabilizer etc..Wherein, the preferred barium stearate of heat stabilizer, calcium stearate, tin dilaurate di-n-butyl Tin, maleic acid two (just) butyl tin, heat stabilizer dosage used are not particularly limited, generally 0.1-0.5wt%.
Toughener in the addible auxiliary agent can reduce polymer material brittleness, increase toughness, improve material Bearing strength comprising but be not limited only to following any or appoint several toughener: methyl methacrylate-butadiene-benzene second Alkene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modifier, acrylic nitrile-butadiene two Alkene-styrol copolymer, acrylonitrile-butadiene copolymer, the third glue of second, ethylene-propylene diene copolymer, cis-butadiene cement, butadiene-styrene rubber, styrene-fourth Styrene block copolymer etc..Wherein, preferred the third glue of second of toughener, acrylonitrile-butadiene-styrene copolymer (ABS), Styrene-Butadiene-Styrene Block Copolymer (SBS), Methyl Methacrylate-Butadiene-Styrene Copolymer Resin (MBS), chlorinated polyethylene resin (CPE), toughener dosage used are not particularly limited, generally 5-10wt%.
Lubricant in the addible auxiliary agent can be improved material lubricity, reduce friction, reduce Interface Adhesion Performance comprising but be not limited only to following any or appoint several lubricants: saturated hydrocarbons and halogenated hydrocarbon, such as solid paraffin, micro- Spar wax, atoleine, low molecular weight polyethylene, oxidized polyethylene wax；Fatty acid, such as stearic acid；Fatty acid ester, such as rouge Fat acid low-carbon-ester, polyol esters of fatty acids, native paraffin, ester type waxes and saponified wax；Aliphatic amide type, such as stearmide or tristearin Sour amide, oleamide or oleamide, erucyl amide, N, N '-ethylene bis stearamide；Fatty alcohol and polyalcohols, it is such as stearic Alcohol, cetanol, pentaerythrite；Metal soap, such as lead stearate, calcium stearate, barium stearate, magnesium stearate, zinc stearate. Wherein, the preferred solid paraffin of lubricant, atoleine, stearic acid, low molecular weight polyethylene, lubricant quantity used is without spy It does not limit, generally 0.5-1wt%.
Release agent in the addible auxiliary agent, it can make polymer samples be easy to demould, and surface is smooth, clean, It includes but are not limited to following any or appoints several release agents: paraffin hydrocarbon, soaps, dimethicone, ethyl silicon oil, methyl Phenyl silicone oil, castor oil, used oil, mineral oil, molybdenum disulfide, vinyl chloride resin, polystyrene, silicon rubber, polyvinyl alcohol etc.. Wherein, the preferred dimethicone of release agent, remover dosage used are not particularly limited, generally 0.5-2wt%.
Plasticizer in the addible auxiliary agent, can increase the plasticity of polymer material, so that polymer Hardness, modulus, softening temperature and brittle temperature decline, elongation at break, flexibility and flexibility improve comprising but not only limit In following any or several plasticizer: Phthalates: dibutyl phthalate, dioctyl phthalate, neighbour Phthalic acid di-isooctyl, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, adjacent benzene Dioctyl phthalate 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, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyl) own ester；Rouge Fat esters of gallic acid, 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 fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, epoxystearic acid (2- ethyl) oneself Ester, epoxy soybean oleic acid 2- ethylhexyl, the own ester of 4,5- epoxy tetrahydrophthalic acid two (2- ethyl), Chinese littleleaf box acetylated castor oil Sour methyl esters, dihydric alcohol lipid, such as C5~9Sour glycol ester, C5~9Sour Triethylene Glycol；Class containing chlorine such as afforests paraffin class, chlorine Fat subsitutes acid esters；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester；Phenyl alkylsulfonate, Trimellitate, citrate, pentaerythrite and pentaerythritol fatty acid ester etc..Wherein, plasticizer pref-erable dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), diisooctyl phthalate (DIDP), tricresyl phosphate (TCP), plasticizer consumption used do not limit especially It is fixed, generally 5-20wt%.
Foaming agent in the addible auxiliary agent, can make polymer samples foam pore-forming, thus obtain it is light, every Heat, sound insulation, softness or firm polymer material comprising but be not limited only to following any or appoint several foaming agents: physics Foaming agent, such as propane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, fourth Alkane, ether, chloromethanes, methylene chloride, dichloroethylene, dicholorodifluoromethane, trifluorochloromethane；Inorganic foaming agent, such as bicarbonate Sodium, ammonium carbonate, ammonium hydrogen carbonate；Organic foaming agent, such as N, five methine tetramine of N '-dinitro, N, N '-dimethyl-N, N '-two Nitroso terephthalamide, azodicarbonamide, barium azo-biscarbonate, two diisopropyl carbonate of azo, azodicarbonamide first Sour potassium, azodiisobutyronitrile, 4,4 '-oxobenzenesulfonyl hydrazide, benzene sulfonyl hydrazide, trihydrazinotriazine, p-toluene sulfonylsemicarbazide, connection Benzene -4,4 '-disulfonyl nitrine；Physical microballoon/granule foaming agent, such as the production of Akzo Nobel company are expandable micro- Ball；Foamed promoter, such as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, dibasic lead phosphite, tristearin Lead plumbate, cadmium stearate, zinc stearate, zinc oxide；Frothing inhibitor, as maleic acid, fumaric 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 maleic acid tin etc..Wherein, the preferred bicarbonate of foaming agent Sodium, ammonium carbonate, azodicarbonamide (blowing agent AC), N, five methine tetramine (blowing agent H) of N '-dinitro, N, N '-diformazan Base-N, N '-dinitrosoterephthalamine (foaming agent NTA), physical microballoon foaming agent, foaming agent consumption used do not have It is particularly limited to, generally 0.1-30wt%.
The deleterious charge assembled in polymer samples can be guided or be disappeared by the antistatic agent in the addible auxiliary agent It removes, it is made production and life not brought inconvenience or be endangered comprising but be not limited only to following any or appoint several antistatic Agent: anionic antistatic agent, as alkylsulfonate, to Sodium Nonylphenoxypropane Sulfonate, alkyl phosphate diethanolamine salt, To nonyl diphenyl ether potassium sulfonate, phosphate derivative, phosphate, phosphoric acid polyethylene oxide alkyl ethers alcohol ester, phosphate derivative, Fatty amine sulfonate, butyrate sodium sulfonate；Cationic antistatic agent, as aliphatic ammonium salt hydrochlorate, lauryl trimethyl ammonium chloride, Dodecyl trimethylamine bromide；Amphoteric ion type antistatic agent, as alkyl dicarboxyl methyl ammonium second inner salt, lauryl betaine, N, N, N- trialkyl ammonium acetyl (N '-alkyl) amine second inner salt, bis- polyethylene oxide base-N- ethylphosphonic acid of N- lauryl-N, N- Sodium, N- alkylaminoacid salts；Non-ionic antistatic agent, such as fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide addition Object, alkyl phenol ethylene oxide addition product, tricresyl phosphate polyoxyethylene groups ether-ether, fatty acid glyceride；Polymer Antistatic Agent, such as Polyene propionamide N- quaternary ammonium salt substituent, poly- 4- vinyl -1- acetone yl pyridines phosphoric acid-are to butyl phenyl ester salt etc.；Wherein, resist quiet The preferred lauryl trimethyl ammonium chloride of electric agent, alkyl phosphate diethanolamine salt (antistatic agent P), antistatic agent dosage used It is not particularly limited, generally 0.3-3wt%.
Emulsifier in the addible auxiliary agent can improve various compositions in the mixed with polymers liquid containing auxiliary agent Surface tension between phase is allowed to form uniform and stable dispersion or emulsion comprising but be not limited only to following any Kind appoints several emulsifiers: anionic, such as higher fatty acid salt, alkylsulfonate, alkylbenzene sulfonate, alkyl naphthalene sulfonic acid Sodium, sulphosuccinates, petroleum sulfonate, aliphatic alcohol sulfate, castor oil salt, sulphation butyl ricinoleate salt, Phosphate ester salt, fatty acyl-peptide condensation product；Cationic, such as alkylammonium salt, alkyl quaternary ammonium salts, Fixanol；Amphoteric ion Type, such as carboxylic acid ester type, sulfonic acid ester type, sulfuric acid ester type, phosphate type；It is non-ionic, as fatty alcohol polyoxyethylene ether, alkyl phenol are poly- Ethylene oxide ether, polyoxyethylene carboxylate, polypropylene oxide-ethylene oxide adduct, fatty acid glyceride, pentaerythrite fat Acid esters, sorbierite and sorbitan fatty acid ester, sucrose fatty ester, hydramine fatty acid amide etc..Wherein, preferred dodecyl Benzene sulfonic acid sodium salt, sorbitan fatty acid ester, triethanolamine stearate (Emulphor FM), emulsifier used is without spy It does not limit, generally 1-5wt%.
Dispersing agent in the addible auxiliary agent enables to solid flocculation group in mixed with polymers liquid to be separated into carefully Small particle and be suspended in liquid, those are poorly soluble the solid and liquid particles in liquid for uniform dispersion, while can also prevent The only sedimentation and cohesion of particle forms stable suspension comprising but be not limited only to following any or appoint several dispersing agents: yin Ionic, such as alkylsurfuric acid ester sodium salt, sodium alkyl benzene sulfonate, petroleum sodium sulfonate；Cationic；It is non-ionic, such as poly alkyl alcohol Ethylene oxide ether, sorbitol anhydride fatty acid polyoxyethylene ether；Inorganic type, such as silicate, condensed phosphate；Polymer electrolyte, it is such as bright Glue, water-soluble glue, lecithin, sodium alginate, lignosulfonates, polyvinyl alcohol etc..Wherein, the preferred detergent alkylate of dispersing agent Sodium sulfonate, naphthalene system methylene sulfonate (dispersing agent N), fatty alcohol polyoxyethylene ether, dispersant dosage used do not limit especially It is fixed, generally 0.3-0.8wt%.
Colorant in the addible auxiliary agent can make polymeric articles show required color, increase Surface color and polish comprising but be not limited only to it is following any or appoint several colorants: inorganic pigment, as titanium white, chrome yellow, cadmium red, Iron oxide red, molybdate red, ultramarine, chrome green, carbon black；Organic pigment, such as lithol red BK directions, lake red C, red, good base R is red, phthalocyanine Red, fast carmine HF3C, the bright red R of plastics and the not red BR of Crow, forever solid orange HL, Fast Yellow G, vapour bar plastics Huang R, permanent yellow 3G, Permanent yellow H2G, phthalocyanine blue B, dark green, plastics purple RL, nigrosine；Organic dyestuff, such as thioindigo red, vat yellow 4GF, indanthrene blue RSN, slag rhodamine toner, Oil Yellow etc..Wherein, the selection of colorant does not need especially to limit depending on color sample demand Fixed, colorant concentrations used are not particularly limited, generally 0.3-0.8wt%.
Fluorescent whitening agent in the addible auxiliary agent can make contaminated substance obtain the sparkling of similar fluorite Effect comprising but be not limited only to following any or appoint several fluorescent whitening agents: Stilbene-based, coumarin type, pyrazoline Type, benzo oxygen nitrogen type, phthalimide type etc..Wherein, (fluorescence increases the preferred stilbene biphenyl sodium disulfonate of fluorescent whitening agent White dose of CBS), bis- (5 methyl -2- benzoxazolyl) talan (fluorescent whitening agent KSN) of 4,4-, 2,2- (4,4 '-hexichol second Alkenyl) double benzoxazoles (fluorescent whitening agent OB -1), fluorescent whitening agent dosage used is not particularly limited, generally 0.002-0.03 wt%.
Delustering agent in the addible auxiliary agent when incident light being enabled to reach polymer surfaces, occurs unrestrained anti- It penetrates, generates the matt and delustring appearance of low gloss comprising but be not limited only to following any or appoint several delustering agents: sedimentation sulphur Sour barium, silica, aqueous gypsum powder, talcum powder, titanium dioxide, poly- methyl carbamide resin etc..Wherein, the preferred titanium dioxide of delustering agent Silicon, delustering agent dosage used are not particularly limited, generally 2-5wt%.
Fire retardant in the addible auxiliary agent, can increase the flame resistance of material comprising but be not limited only to Under it is any or appoint several fire retardants: phosphorus system, such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, phosphoric acid Toluene diphenyl ester；Halogen phosphoric acid ester, such as three (2,3- dibromopropyl) phosphates, tricresyl phosphate (2,3- dichloro the third) ester；Organic halogen Compound, such as high chlorine contents chlorinated paraffin, 1,1,2,2- tetrabromoethane, deca-BDE, penta decane of perchloro- ring；Inorganic fire retardants, Such as antimony oxide, aluminium hydroxide, magnesium hydroxide, zinc borate；Reactive flame retardant, such as chlorendic anhydride, bis- (2,3- dibromos third Base) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride etc..Wherein, the preferred deca-BDE of fire retardant, phosphoric acid Triphenylmethyl methacrylate, tricresyl phosphate, phosphate toluene diphenyl ester, antimony oxide, amount of flame-retardant agent used are not particularly limited, and one As be 1-20wt%.
Nucleating agent in the addible auxiliary agent can accelerate crystallization speed by the crystallization behavior of change polymer Rate increases crystal density and promotes fine grain size, reaches and shortens material molding cycle, improves the product transparency, surface The purpose of the physical mechanical properties such as gloss, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance comprising but Be not limited only to it is following any or appoint several nucleating agents: benzoic acid, adipic acid, sodium benzoate, talcum powder, p-phenolsulfonic acid's sodium, Silica, benzylidene sorbitol and its derivative, EP rubbers, ethylene propylene diene rubber etc..Wherein, the preferred dioxy of nucleating agent SiClx, benzylidene sorbitol (DBS), ethylene propylene diene rubber, nucleating agent dosage used are not particularly limited, generally 0.1-1wt%.
Rheological agent in the addible auxiliary agent can guarantee that polymer has good brushing during film Property and coating thickness appropriate, the sedimentation of solid particle when preventing storage, can be improved its redispersibility comprising but not only limit In following any or several rheological agents: inorganic, such as barium sulfate, zinc oxide, alkaline earth oxide, calcium carbonate, chlorination Lithium, sodium sulphate, magnesium silicate, fumed silica, waterglass, colloidal silicon dioxide；Organo-metallic compound, as aluminum stearate, Aluminium alkoxide, titanium chelate, aluminium chelate compound；Organic, such as organobentonite, castor oil derivative, isocyanate derivates, propylene Yogurt liquid, acrylic copolymer, polyvinyl alcohol, polyethylene wax etc..Wherein, preferably organobentonite, polyethylene wax, hydrophobically modified Alkali-swellable emulsions (HASE), alkali-swellable emulsions (ASE), rheological agent dosage used are not particularly limited, generally 0.1-1wt%.
Thickener in the addible auxiliary agent can assign the good thixotropy of mixed with polymers liquid and appropriate Consistency is wrapped to meet various demands such as its stability and application performance in production, storage and use process It includes but is not limited only to following any or appoints several thickeners: lower-molecular substance, such as fatty acid salt, fatty alcohol polyoxyethylene ether sulphur Hydrochlorate, alkyldimethylamine oxide, fatty monoethanol amide, fatty diglycollic amide, fatty acid Isopropamide, dehydration mountain Pears alcohol tricarboxylic ester, glycerol trioleate, coamidopropyl glycine betaine；Polymer substance, such as bentonite, artificial hectorite, micro- Powder silica, colloidal aluminum, plant polyose class, microbial polysaccharide class, animal protein, seaweed acids, poly-methyl acrylate, first Base acrylic copolymer, cis-butenedioic anhydride copolymer, polyacrylamide, polyvinyl pyrrolidone, polyvinyl alcohol, polyethers, polyvinyl methyl ether urea Alkane polymer etc..Wherein, the preferred coconut oil diethanol amide of thickener, acrylic acid-methacrylic acid copolymer, thickening used Agent dosage is not particularly limited, generally 0.1-1.5wt%.
Levelling agent in the addible auxiliary agent can guarantee the flat and smooth uniform of polymer coating film, improve and apply Film surface quality improves dicoration comprising but be not limited only to following any or appoint several levelling agents: polyacrylate, Organic siliconresin etc..Wherein, the preferred polyacrylate of levelling agent, levelling agent dosage used are not particularly limited, generally 0.5-1.5wt%.
Antibacterial agent in the addible auxiliary agent, can within a certain period of time, make certain micro-organisms (bacterium, fungi, Saccharomycete, algae and virus etc.) growth or breeding be maintained at necessary below horizontal, be generally divided into inorganic antiseptic, You Jikang Microbial inoculum and natural antibacterial agent.Wherein, inorganic antiseptic include but are not limited to silver, copper, zinc, nickel, cadmium, lead, mercury, zinc oxide, Copper oxide, ammonium dihydrogen phosphate, lithium carbonate etc.；Organic antibacterial agent includes but are not limited to vanilla aldehydes, ethyl vanillin aldehydes, acyl group The organic compounds such as phenyl amines, imidazoles, thiazoles, isothiazolone derivative, quaternary ammonium salt, double croak classes, phenols；Natural antibacterial Agent includes but are not limited to chitin, mustard, castor oil, horseradish etc..Wherein, antibacterial agent preferably silver, zinc, vanilla aldehydes chemical combination Object, ethyl vanillin aldehydes compound, antibacterial agent dosage used are not particularly limited, generally 0.05-0.5wt%.
The addible filler, primarily serves following effect in the polymeric material: 1. reducing molded article Shrinking percentage improves dimensional stability, surface smoothness, flatness and the zero diopter of product or without photosensitiveness etc.；2. adjusting material Viscosity；3. meeting different performance requirement, such as raising material impact intensity and compressive strength, hardness, rigidity and modulus, raising are resistance to Mill property improves heat distortion temperature, improves electric conductivity and thermal conductivity etc.；4. improving the coloring effect of pigment；5. assigning photostability And chemical corrosion resistance；6. playing compatibilization, cost can be reduced, improves product competitiveness in the market.
The addible filler, selected from following any or several fillers: inorganic non-metallic filler, metal are filled out Material, organic filler.
The addible inorganic non-metallic filler includes but are not limited to following any or appoints several: calcium carbonate, Clay, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, asbestos, asbestos fibre, just Feldspar, chalk, lime stone, blanc fixe, gypsum, graphite, carbon black, graphene, graphene oxide, carbon nanotube, fullerene, two Molybdenum sulfide, slag, flue dust, wood powder and shell powder, diatomite, red mud, wollastonite, silica-alumina carbon black, aluminium hydroxide, magnesium hydroxide, Flyash, oil shale powder, swelling perlite powder, conductive black, vermiculite, iron cement, white clay, alkali mud, boron mud, (hollow) glass are micro- Pearl, foam microspheres, expandable particles, glass powder, cement, synthesis inorganic rubber, synthetic inorganic fiber, glass fibre, carbon fiber, Quartz fibre, charcoal core boron fibre, titanium diboride fiber, calcium titanium fiber, carbon silica fibre, ceramic fibre, whisker etc..
The addible metal packing, including metal simple-substance, metal alloy, metal oxide, metal inorganic chemical combination Object, metallo-organic compound etc. comprising but be not limited only to following any or appoint several: copper, silver, nickel, iron, gold etc. and its conjunction Powder, nano particle and the fiber of gold；Wherein, nano particle includes but are not limited to nanogold particle, nano-Ag particles, nanometer Palladium particle, nano cobalt granule, nano nickle granules, nano magnetic particle (such as γ-Fe2O3、CoFe2O4、NiFe2O4、MnFe2O4、 Fe3O4、FeN、Fe2N、ε-Fe3N、Fe16N etc.)；It additionally include liquid metal comprising but it is not limited only to mercury, gallium, gallium indium liquid State alloy, gallium indium tin liquid alloy, other gallium base liquid metal alloys；Wherein, metallo-organic compound includes some ultraviolet The metallo-organic compound molecule or crystal that can be generated heat under line, infrared ray or electromagnetic action.
The addible organic filler includes but are not limited to following any or appoints several: fur, natural rubber Glue, synthesis organic rubber, synthetic organic fibre, cotton, velveteen, fiber crops, jute, flax, asbestos, shellac, lignin, protein, Enzyme, hormone, raw lacquer, wood powder, shell powder, xylose, silk, artificial silk, vinylon, phenolic aldehyde microballon, resin microbeads etc..
Wherein, the wire feeding of addition does not limit, mainly depending on required material property, preferably calcium carbonate, sulphur Sour barium, talcum powder, carbon black, graphene, (hollow) glass microballoon, foam microspheres, expandable particles, glass fibre, carbon fiber, gold Belong to powder, natural rubber, protein, resin microbeads, amount of filler used is not particularly limited, generally 1-30wt%.
In the preparation process of dynamic aggregation object material, the preferred antioxidant of addible auxiliary agent, light stabilizer, thermostabilization Agent, toughener, plasticizer, foaming agent, fire retardant.The preferred calcium carbonate of addible filler, barium sulfate, talcum powder, carbon black, glass Microballon, expandable particles, graphene, glass fibre, carbon fiber.
In the preparation process of dynamic aggregation object, special limit is not done to the additive amount of dynamic aggregation object each component raw material Fixed, those skilled in the art can be adjusted according to practical preparation situation and target polymerization physical performance.
The manufacturing method of composition of the invention is not particularly limited, for example, roller, kneader, extruder, ten thousand can be passed through Can blender etc. additive the subsequent operations such as be blended to prepolymer as needed, then be crosslinked, foamed.
The gold of dynamic aggregation object elastomer of the invention due to the good dynamic characteristics formed in skeleton with ligand groups Category-ligand effect, dynamic aggregation object obtained have certain modulus, toughness, self-healing properties simultaneously, can be extensive Applied to the elastic component etc. in adhesive, coating, film and structural composite material with energy absorption ability.
It is provided by the present invention a kind of with hybrid cross-linked dynamic aggregation object gel rubber material, preferably aqueous solution type gel material Material, organic solvent type gel rubber material and plasticizer swell gel material, more preferable plasticizer swell gel.
A kind of preparation method of dynamic aggregation object aqueous solution type gel rubber material of the invention, includes the following steps: for parent Aqueous monomers, by the raw material of hybrid cross-linked dynamic aggregation object (including the molecule containing ligand, metal center, chain extender, crosslinking agent And various auxiliary agents etc.) be added in aqueous solution, make prepared hybrid cross-linked dynamic aggregation object (reality according to the present invention Apply mode or be the dynamic aggregation object of single network or be interpenetrating networks dynamic aggregation object) mass fraction be 0.5 ~50%, covalent cross-linking is carried out by appropriate means, after reaction, a kind of dynamic aggregation object water-setting is made in natural cooling Glue, that is, one-step method prepare gel rubber material；The polymer chain network containing ligand can also be first prepared, makes it in aqueous solution Metal center is added after middle swelling, extra aqueous solution is removed after its gelation reaction.The aqueous solution is deionized water.
A kind of preparation method of dynamic aggregation object organic solvent type gel rubber material of the invention, include the following steps: for The raw material of hybrid cross-linked dynamic aggregation object is added in suitable organic solvent, makes prepared hydridization by the monomer of hydrophily difference The mass fraction for being crosslinked dynamic aggregation object is 0.5~50%, carries out covalent cross-linking by appropriate means, after reaction, natural It is cooling, that is, a kind of dynamic aggregation object organic solvent type gel rubber material is made, that is, one-step method prepares gel rubber material；It can also be first The polymer chain network containing ligand is prepared, metal center is added after being swollen it in suitable organic solution, it is solidifying to it It is taken out after gelatinization reaction and removes extra organic solvent.The organic solvent be acetone, butanone, N,N-dimethylformamide, One of chloroform, methylene chloride, dimethyl sulfoxide, tetrahydrofuran, methanol, dehydrated alcohol, ether, pentane and toluene Or it is a variety of.
A kind of dynamic aggregation object plasticizer swell gel material preparation method of the invention, includes the following steps: will have The raw material of hybrid cross-linked dynamic aggregation object is added in suitable plasticizer, makes the matter of prepared hybrid cross-linked dynamic aggregation object Measuring score is 0.5~50%, carries out covalent cross-linking by suitable method, after reaction, one kind is made in natural cooling Dynamic aggregation object is plasticized the gel of solvent swell, that is, one-step method prepares gel rubber material；It can also first prepare containing ligand Metal center is added after being swollen it in suitable plasticizer in polymer chain network, takes out and removes after its gelation reaction Extra plasticizer.Upper the plasticizer is selected from following any or appoints several: Phthalates: two fourth of phthalic acid Ester, dioctyl phthalate, diisooctyl phthalate, dibutyl phthalate (DHP), diisooctyl phthalate, neighbour Phthalic acid dinonyl, BBP(Butyl Benzyl Phthalate, butyl phthalate butyl glycolate, dicyclohexyl Bis- (13) esters of ester, phthalic acid, terephthalic acid (TPA) two (2- ethyl) own ester；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyl) own ester；Fatty acid ester, such as the own ester of adipic acid two (2- ethyl), decanedioic acid two (2- ethyl) own ester；Ring Oxygen compound class, as epoxy glycerite esters, epoxy 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, two (2- second of 4,5- epoxy tetrahydrophthalic acid Base) own ester, Chinese littleleaf box methyl acetylricinolate, dihydric alcohol lipid, such as C5~9Sour glycol ester, C5~9Sour Triethylene Glycol； Class containing chlorine such as afforests paraffin class, chloro fat acid esters；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2- third Diol polyester；Phenyl alkylsulfonate, trimellitate, citrate, pentaerythrite and pentaerythritol fatty acid ester etc..Wherein, epoxy Change a kind of Environment-friendlyplastic plastic plasticizer of function admirable of soybean oil, epoxidation reaction system occurs for refined soybean oil and peroxide It is standby.It is resistance in polrvinyl chloride product to volatilize, is not easy to migrate, not easy to lose.This is to holding product light, thermal stability and extends use Service life is highly beneficial.Epoxidised soybean oil toxicity is minimum, is allowed for the packing timber of food and medicine by many countries Material is the epoxy plasticiser that uniquely can be used for packaging material for food of Food and Drug Adminstration of the US's approval.Of the invention In a kind of gel preparation of dynamic aggregation object plasticising solvent swell, the preferred epoxidized soybean oil of plasticizer.
In embodiments of the present invention, the oligomer is included but are not limited to: epoxy acrylate, modified epoxy third Olefin(e) acid ester, epoxy linseed oil triacrylate, polyester acrylic ester prepolymer, polyether acrylate, urethane acrylate Prepolymer, tripropylene glycol methoxy-ether mono acrylic ester, methoxy-ether neopentyl glycol propoxyl group mono acrylic ester, methoxy-ether three Hydroxymethyl-propane ethyoxyl diacrylate, the polymerization of amine modification acrylate, atoleine, number-average molecular weight less than 10000 Object；It is preferred that epoxy acrylate, polyester acrylate, polyether acrylate prepolymer, number-average molecular weight are poly- less than 10000 Urea, polycarbonate, polyester, polyethers or polyamide.
In embodiments of the present invention, the ionic liquid is included but are not limited to: glyoxaline ion liquid, pyridines Ionic liquid, quaternary ammonium ionic liquid, quaternary phosphine class ionic liquid, pyrrolidines ionic liquid, piperidines ionic liquid, alkenyl function Ionic liquid, Hydroxyl-functionalized Ionic Liquids, ether functionalized ion liquid, ester group functionalized ion liquid, carboxyl function can be changed Ionic liquid, itrile group functionalized ion liquid, amino functional ionic liquid, sulfonic acid funtionalized ionic liquid, benzyl function can be changed Ionic liquid, guanidine ionic liquid can be changed；It preferably specifically is selected from: 1- ethyl-3-methylimidazole tetrafluoroborate, 1- hexyl -2,3- Methylimidazole hexafluorophosphate, 1- ethyl-3-methylimidazole bromide, N- octylpyridinium bromide, tributyhnethylammonium chloride, four Butyl bromide phosphine, N- butyl-N- crassitude bromide, N- butyl-N- methyl piperidine bromide, 1- vinyl -3- butyl imidazole Hexafluorophosphate, 1,2- dimethyl -3- hydroxyethyl imidazole toluenesulfonate, 1- ethyl diethyldithiocarbamate ether -3- methylimidazole hexafluoro Phosphate, 1- ethyl acetate base -3- methylimidazole hexafluorophosphate, 1- carboxyethyl -3- methylimidazole bromide, 1- nitrile propyl -3- Methylimidazole hexafluorophosphate, 1- amine propyl -3- methylimidazole hexafluorophosphate, N- sulfonic acid butyl-pyridinium fluoroform sulphonate, 1- benzyl -3- methyl imidazolium tetrafluoroborate, tetramethylguanidine trifluoro-methanyl sulfonate.
It is provided by the present invention it is a kind of have hybrid cross-linked dynamic aggregation object foamed material can be soft, semi-rigid or Person's rigid foam.Foam can have water or it is anhydrous under the conditions of prepare, foaming method can be physical blowing, chemistry hair One of bubble, mechanical foaming are a variety of.Further, it is non-reacted that suitable auxiliary type known in the art can be used in foam Foaming agent.
A kind of preparation method of dynamic aggregation object foamed material of the invention includes the following steps: in preparation single network When dynamic aggregation object foamed material, reaction mass component A and reaction mass component B is first independently made；Reaction mass component A It is by 8 parts~20 parts of polyol compound, 0.05 part~1.0 parts of chain extender, 0.05 part~1.0 parts of crosslinking agent, organic metal class 0.01-0.5 parts of catalyst, 0.01-0.5 parts of amines catalyst, in 5-35 DEG C of material temperature, the condition of mixing speed 50-200r/min Under stir evenly it is obtained；Reaction mass component B is by 10 parts~20 parts of polyisocyanate compound, foaming agent 0.5 part~3.5 Part, 0.05 part~0.2 part of foam stabiliser, the system of stirring evenly under conditions of 5-35 DEG C of mixing speed 50-200r/min of material temperature ?；Then reaction mass component A is mixed with reaction mass component B according to 1.0~1.5:1 mass ratio, it is quick through professional equipment Stir to get the single network dynamic aggregation object of foaming.Finally, the single network dynamic aggregation object after foaming is added to mold In, solidify 30min~60min at room temperature, then solidifies at high temperature and steeped to get to the dynamic aggregation object based on single network Foam material.At least one component contains ligand groups in the component A and component B.It is cured as at a high temperature of described in temperature Degree is solidifies 6h at 60 DEG C, or in temperature is 80 DEG C of solidification 4h, or in temperature is 120 DEG C of solidification 2h.Above-mentioned polyol compound In hydroxyl (OH) group and polyisocyanate compound in isocyanates (NCO) group molar ratio may make it is final poly- Urethane foam is free of free-end NCO group.The molar ratio of NCO/OH is preferably 0.9/1 to 1.2/1.NCO/OH is 1/1 Molar ratio correspond to isocyanate index be 100.In the case where water is used as foaming agent, the isocyanate index is preferably big In 100, such isocyanate groups can be reacted with water.
In dynamic aggregation object foamed material preparation method of the invention, binary hybrid crosslinking dynamic aggregation object foam is being prepared When material, the step of according to above-mentioned preparation single network dynamic aggregation object, the 1st network is first prepared；Then the 2nd network mistake is being prepared The 1st network is added in the reaction mass A ' by Cheng Zhong, i.e., reaction mass component A ' at this time be 8 parts~20 parts of polyol compound, 0.05 part~1 part of chain extender, 0.05 part~0.4 part of crosslinking agent, 0.01~0.5 part of organometallic catalysts, amines catalyst 0.01~0.5 part, the 1st 0.1 part of network polymer~15 parts, under conditions of 5-35 DEG C of mixing speed 50-200r/min of material temperature It stirs evenly obtained；Reaction mass component B ' is 10 parts~20 parts of polyisocyanate compound, 2 parts of foaming agent~3.5 parts, foam It 0.05 part~0.2 part of stabilizer, is stirred evenly under conditions of 5-50 DEG C of mixing speed 50-200r/min of material temperature obtained.Then Reaction mass component A ' is mixed with reaction mass component B ' according to 1.0~1.5:1 mass ratio, is quickly stirred through professional equipment To the hybrid cross-linked dynamic aggregation object of foaming.Finally, the hybrid cross-linked dynamic aggregation object after foaming is added in mold, in room Temperature is lower to solidify 30min~60min, then solidifies at high temperature to get to based on hybrid cross-linked dynamic aggregation object foamed material. At least one component contains ligand groups in the component A ' and component B '.Be cured as at a high temperature of described be in temperature Solidify 6h at 60 DEG C, or in temperature be 80 DEG C of solidification 4h, or in temperature is 120 DEG C of solidification 2h.And so on, it is miscellaneous in preparation ternary When changing crosslinking dynamic aggregation object foamed material, the 1st network and the 2nd network are first prepared, then when preparing 3 network, the 1st net is added Network and the 2nd network are sufficiently mixed and foam.
In the preparation process of hybrid cross-linked dynamic aggregation object, the additive amount of dynamic aggregation object each component raw material is not done Special to limit, those skilled in the art can be adjusted according to practical preparation situation and target polymerization physical performance.
In the present invention, the dynamic of metal-ligand effect and optional supermolecule hydrogen bond action in dynamic aggregation object is utilized Invertibity, when by external impacts, on the one hand polymer can show thickening responsiveness, on the other hand can also pass through gold Category-ligand effect reaches multi-absorption and the dissipation to impact energy with the reversible fracture of optional supermolecule hydrogen bond action.It is logical It crosses and suitable component selection and formula design is carried out to dynamic aggregation object, the polymer with excellent energy-absorbing effect can be prepared Fiber, film, plate, foam, gel etc..Energy-absorbing is carried out using this dynamic aggregation object as energy-absorbing material, can be embodied good Damping, damping, sound insulation, noise elimination, shock resistance the effects of, thus life, production, movement, leisure, amusement, military affairs, police service, There is extensive purposes in the fields such as security, medical care.For example, polymer material can be applied to production damping shock absorber, for each Kind of motor vehicles, mechanical equipment, bridge, building vibration isolation, when being vibrated, the big energy that can dissipate plays resistance Buddhist nun's effect, to effectively mitigate the vibration of vibration body；Stress response possessed by dynamic aggregation object can also be used, generate friendship There is flexible and strong elasticity transformation, plays the role of effective disperses impact forces, so as to as energy-absorbing buffering in the variation of connection degree Material is applied to amortizing packaging material, athletic protective article, the police protective materials of surge guard product and army etc., reduces Article or human body suffered under external force vibration and impact, the shock wave etc. generated including explosion；It can be devised by Energy-absorbing material with shape memory function is applied to specific occasion, such as the energy-absorbing protector of personalized customization.The present invention is mentioned The energy-absorbing method based on hybrid cross-linked dynamic aggregation object supplied, especially suitable for carrying out shock resistance to human body, animal body, article etc. Protection, such as using the material as protector, body is protected in daily life, production and movement；It is prepared into explosion-proof Tent, blanket, wall, bulletproof glass squeegee, sandwich plate etc. carry out explosive-proof protector to article；It is prepared into other protective article for cell/use Tool, applied to airborne and air-drop protection, automobile collision preventing, the defense of resistance to impact of electronic apparatus article etc..
Dynamic aggregation object material of the present invention is described further below with reference to some specific embodiments.Specifically Embodiment is that present invention be described in more detail, non-limiting protection scope of the present invention.
Embodiment 1
3- hydroxy-3-methyl pentane -1,5- diacid is dissolved in methylene chloride, it is sub- that a certain amount of dichloro is then added Sulfone, the back flow reaction at 70 DEG C, so that two carboxyl chlorides of 3- hydroxy-3-methyl pentane -1,5- diacid are finally removed 3- hydroxy-3-methyl pentane -1,5- diacid chloride is made in generated impurity.3,5- bis- (amino methyl) pyridine is dissolved in tetrahydro Furans is placed in No. 1 reactor, is slowly added to 3- hydroxy-3-methyl pentane -1,5- diacid chloride, is carried out polycondensation reaction, is obtained Skeleton has the polymer 1 of hydroxyl with pyridine groups, side group.Polymer 1 is dissolved in dry methylene chloride and is placed on No. 2 instead It answers in device, is slowly added to a certain amount of 4- isocyanato-pyridin, the polymerization that skeleton has carboxyl with pyridine groups, side group is made Object 1 '.A:10 parts of above-mentioned polymer 1 ' of reaction mass component, 0.5 part of chain extender 1,4- butanediol, 0.1 part are weighed in parts by weight Dibutyl tin dilaurate, 0.05 part of triethylenediamine, 0.1 part of organic silicone oil, 7 parts of methylene chloride, 0.5 part of silver nitrate are molten Liquid is added in No. 3 reactors, is stirred evenly under conditions of 35 DEG C of material temperature, mixing speed 200r/min；Reaction mass component B:10 parts of 1,4- diamino fourth dioxanes；Then reaction mass component A and reaction mass component B is mixed according to 1.2:1 mass ratio It closes, is quickly stirred through professional equipment to bubble is generated, stand 72h, the hybrid cross-linked dynamic aggregation object after being foamed.It will foaming Hybrid cross-linked dynamic aggregation object afterwards is added in No. 5 reactors, is solidified 30min at room temperature, is then solidified at 120 DEG C 2h to get arrive dynamic aggregation object foamed material.Performance test: density (kg/m3): 126.23 ± 12.12；50% compressive strength (MPa): 2.67 ± 0.62；Tensile strength (MPa): 7.23 ± 0.97；Elongation at break (%): 232.15 ± 25.36.The product It can be prepared to damping Package casing material.
Embodiment 2
52g4- vinylpyridine and 23g propenyl are mixed and are added in No. 1 reactor after being dissolved in the dimethylbenzene of 100mL, then It is added 1g azodiisobutyronitrile (AIBN), is stirred to react 6h after being warming up to 90 DEG C, polymer 2 is made.It weighs in parts by weight anti- Answer 2,0.1 parts of dibutyl tin dilaurates of A:10 parts of material component above-mentioned polymer, 0.05 part of triethylenediamine, 0.1 part have Machine silicone oil, 0.5 part of nitric acid gold solution, are added in No. 2 reactors, under conditions of 35 DEG C of material temperature, mixing speed 200r/min It stirs evenly；B:10 parts of 1,4- toluene di-isocyanate(TDI)s of reaction mass component；Then by reaction mass component A and reaction mass group Divide B to mix according to 1.2:1 mass ratio, is quickly stirred through professional equipment to bubble is generated, stand 72h, the hydridization after being foamed It is crosslinked dynamic aggregation object.Hybrid cross-linked dynamic aggregation object after foaming is added in No. 5 reactors, is solidified at room temperature Then 30min solidifies 2h at 120 DEG C to get dynamic aggregation object foamed material is arrived.Performance test: density (kg/m3): 113.13±9.12；70% compressive strength (MPa): 1.42 ± 0.24；Tensile strength (MPa): 4.54 ± 0.79；Elongation at break (%): 212.41 ± 13.27.The product can be prepared to defense of resistance to impact pad applied to fitness equipment.
Embodiment 3
90g4,4'- divinyl pyridine and 60g1,4- butanediol vinyl ethers are mixed after being dissolved in the dimethylbenzene of 200mL It is added in No. 1 reactor, adds 1.5g azodiisobutyronitrile (AIBN), be stirred to react 6h after being warming up to 90 DEG C, polymerization is made Object 3.Weigh 3,0.2 parts of dibutyl tin dilaurates of A:15 parts of reaction mass component above-mentioned polymer in parts by weight, 0.06 part Triethylenediamine, 0.2 part of organic silicone oil, 0.5 part of nitric acid cadmium solution, are added in No. 2 reactors, in 35 DEG C of material temperature, stirring It is stirred evenly under conditions of speed 200r/min；B:13 parts of 1,4- hexamethylene diisocyanates of reaction mass component；It then will reaction Material component A is mixed with reaction mass component B according to 1.2:1 mass ratio, is quickly stirred through professional equipment to bubble is generated, is stood 72h, the hybrid cross-linked dynamic aggregation object after being foamed.Hybrid cross-linked dynamic aggregation object after foaming is added to No. 5 reactions In device, solidify 30min at room temperature, solidifies 2h at 120 DEG C then to get dynamic aggregation object foamed material is arrived.Performance test: Density (kg/m3): 67.49 ± 5.31；70% compressive strength (MPa): 1.81 ± 0.29；Tensile strength (MPa): 5.54 ± 1.13；Elongation at break (%): 252.19 ± 23.42.The product can be prepared to the protective materials such as handguard, knee-pad.
Embodiment 4
70g polyethylene glycol, 2g catalyst KOH are added first into BUSS formula outer circulation reactor, then carries out nitrogen displacement, Bis- (the 1- methyl-1 H- imidazoles -2- of 400g 2- allyl hexadecyl ethylene oxide, 156g 2,6- are separately added into after being heated to 120 DEG C Base) -4- (ethylene oxide -2- ylmethyl) pyridine reacted, and reaction temperature controls 140~150 DEG C.Under constant temperature conditions, into Row slaking reaction 40 minutes, when reactor pressure no longer declines, start as reactor content cooling.When temperature is reduced to 70 DEG C Acetic acid is added and carries out neutralization reaction, until the pH of reaction system is 6.8, polymer 4 is made.Reaction mass A is weighed in parts by weight: 12 parts of polymer, 4,0.3 parts of chain extenders, 0.2 part of dibutyl tin dilaurate, 0.2 part of triethylenediamine, 0.1 part of organosilicon Oil, 17 parts of deionized waters, are added in No. 1 reactor, stir under conditions of 35 DEG C of material temperature, mixing speed 200r/min equal It is even；B:7 parts of 1,3- dimercaptopropanes of reaction mass, 0.5 part of zinc dichloride solution, 0.01 part of antioxidant BHT；By component B and group Divide A mixing to be added in No. 2 reactors, be warming up to 60 DEG C, and stirred, 1h is then irradiated under the ultraviolet lamp of 300W, takes out After be put into 60 DEG C of baking ovens, maintain after temperature 12h to get to dynamic aggregation object hydrogel.Performance test: 90% compression is strong It spends (MPa): 2.43 ± 0.68；Tensile strength (MPa): 7.43 ± 1.34；It is broken elongation at break (%): 590.47 ± 64.29.The product can be prepared to a kind of damping energy-absorbing material, can also be with selfreparing even if cracking is impaired.
Embodiment 5
2- hydroxy succinic acid is dissolved in methylene chloride, a certain amount of thionyl chloride is then added, is flowed back at 70 DEG C Reaction, so that two carboxyl chlorides of 2- hydroxy succinic acid are finally removed generated impurity, 2- hydroxysuccinimidyl acyl is made Chlorine.3- (6,8- dimethyl-[1,2,4] triazol [4,3-b] pyridin-7-yl)-propionic acid is dissolved in methylene chloride, then A certain amount of thionyl chloride is added, the back flow reaction at 70 DEG C, thus 3- (6,8- dimethyl-[1,2,4] triazol [4,3- B] pyridin-7-yl)-propionic acid carboxyl chloride, finally remove caused by impurity, be made 3- (6,8- dimethyl-[1,2,4] Triazol [4,3-b] pyridin-7-yl)-propionyl chloride.In No. 1 reactor be added 45g2,2'- bipyridyl -4,4'- diamines and 36g2- hydroxysuccinimidyl acyl chlorides is warming up to 60 DEG C of progress polycondensation reactions, and polymer 5 is made.In parts by weight in No. 2 reactors 10 parts of polymer 5 are added, and the methylene chloride of 100mL is added, stir to dissolve, side stirring is slowly dropped into 5 parts of 3- (6,8- Dimethyl-[1,2,4] triazol [4,3-b] pyridine -7- base)-propionyl chloride, polymer 5 ' is made.Reaction is weighed in parts by weight A:10 parts of polymer 5 ' of material component, 0.5 part of chain extender 1,4-butanediol, 2 0.1 parts of dibutyl tin laurates, 0.05 part of Sanya Ethyldiamine, 0.1 part of organic silicone oil, 0.5 part of copper chloride solution, are added in No. 3 reactors, in 35 DEG C of material temperature, mixing speed It is stirred evenly under conditions of 200r/min；B:8 parts of reaction mass component bis- (3- isocyanatophenyi) methane, are added to No. 4 In reactor, stirred evenly under conditions of 35 DEG C of mixing speed 200r/min of material temperature；Then by reaction mass component A and instead It answers material component B to mix according to 1.1:1 mass ratio, after mixing, stands 72h to get dynamic aggregation object ordinary solid is arrived.It will Its dumbbell shape batten that 80.0 × 10.0 × 2.0mm size is made carries out extension test using cupping machine, and rate of extension is 10mm/min, measuring sample tensile strength is 17.41 ± 3.23MPa, and elongation at break is 58.12 ± 7.31%, obtained poly- Closing object sample has biggish surface hardness and compression strength.In the present embodiment, polymer material can be used for as electrical Switching device, printed wiring chassis, instrument board electronic package material shell guard block, surge protection is played to interior arrangement Effect.
Embodiment 6
42g1,4- pentadiene -3- alcohol, 74g1,4- benzene (diformazan mercaptan) and 0.5g antioxidant are added in No. 1 reactor BHT is mixed, and is placed under 300W ultraviolet lamp and irradiates 1h, obtains polymer 6.By 5,6- dihydro -4H- benzo [d] [1,8] naphthalene Then a certain amount of thionyl chloride is added in methylene chloride in pyridine -5- carboxylic acid, the back flow reaction at 70 DEG C, thus 5, The carboxyl chloride of 6- dihydro -4H- benzo [d] [1,8] naphthyridines -5- carboxylic acid finally removes generated impurity, is made 5,6- Dihydro -4H- benzo [d] [1,8] naphthyridines -5- acyl chlorides.10 parts of polymer 6,200mL are added in parts by weight in No. 2 reactors Methylene chloride, stirring dissolve it sufficiently, are then slowly added to 2 parts of 5,6- dihydro -4H- benzo [d] [1,8] naphthalenes while stirring Pyridine -5- acyl chlorides, obtains polymer 6 '.A:12 parts of polymer 6 ' of reaction mass component, 0.5 part of chain extender are weighed in parts by weight 1,4-butanediol, 2 0.1 parts of dibutyl tin laurates, 0.05 part of triethylenediamine, 0.15 part of organic silicone oil, 6 parts of dichloromethanes Alkane, 4 parts of water, 0.7 part of Zn4O(BTB)2(MOF-177), it is added in No. 3 reactors, in 35 DEG C of material temperature, mixing speed 200r/ It is stirred evenly under conditions of min；Reaction mass component B:8 part 1,5- naphthalene diisocyanate are added in No. 4 reactors, are expecting It is stirred evenly under conditions of 35 DEG C of mixing speed 200r/min of temperature；Then by reaction mass component A and reaction mass component B according to The mixing of 1.2:1 mass ratio quickly stirs to bubble is generated through professional equipment, stands 72h, the hybrid cross-linked dynamic after being foamed Polymer.Hybrid cross-linked dynamic aggregation object after foaming is added in No. 5 reactors, solidifies 30min at room temperature, then exists Solidify 2h at 120 DEG C to get dynamic aggregation object foamed material is arrived.Performance test: density (kg/m3): 98.23 ± 12.43；50% Compressive strength (MPa): 3.64 ± 0.97；Tensile strength (MPa): 9.19 ± 1.68；Elongation at break (%): 260.94 ± 23.17.The product can be prepared to damping, buffering ground cushion.
Embodiment 7
57g (bis- (dimethylamino) pyridin-4-yls of 2,6-) methacrylate, 42g naphthalene-is added in No. 1 reactor 2,6- bis- mercaptan, 18g3- butene-1-ol, 0.5g antioxidant CA stir under conditions of 35 DEG C of mixing speed 200r/min of material temperature It mixes uniformly, is then placed under the ultraviolet lamp of 300W and irradiates 1h, obtain polymer 7.Reaction mass component is weighed in parts by weight 7,0.4 parts of chain extender 1,4-butanediol of A:10 parts of polymer, 2 0.1 parts of dibutyl tin laurates, 0.05 part of triethylene two Amine, 0.1 part of organic silicone oil, 0.5 part of trifluoromethanesulfonic acid zinc solution, are added in No. 2 reactors, in 35 DEG C of material temperature, mixing speed It is stirred evenly under conditions of 200r/min；B:5 parts of paraphenylene diisocyanate of reaction mass component, are added in No. 3 reactors, It is stirred evenly under conditions of 35 DEG C of mixing speed 200r/min of material temperature；Then by reaction mass component A and reaction mass component B is mixed according to 1.2:1 mass ratio, after mixing, stands 72h to get dynamic aggregation object ordinary solid is arrived.It is made into The dumbbell shape batten of 80.0 × 10.0 × 2.0 mm sizes carries out extension test, rate of extension 10mm/ using cupping machine Min, measuring sample tensile strength is 13.31 ± 2.14MPa, and elongation at break is 48.31 ± 5.12%, polymer-like obtained Product have biggish surface hardness and compression strength.Explosiveproof isolation wall can be prepared in the product.
Embodiment 8
50g2,6- diaminopurine, 1.5g catalyst KOH is added into BUSS formula outer circulation reactor first, then carries out Nitrogen displacement is added 100g2- (ethylene oxide -2- ylmethoxy) second -1- alcohol after being heated to 120 DEG C and is reacted, reaction temperature 140~150 DEG C of degree control.Under constant temperature conditions, it carries out slaking reaction 30 minutes, when reactor pressure no longer declines, starts For reactor content cooling.Acetic acid is added when temperature is reduced to 70 DEG C and carries out neutralization reaction, until the pH of reaction system is 6.8, system Obtain polymer 8.10 parts of polymer 8,150mL methylene chloride are added in parts by weight in No. 1 reactor, stirring keeps it sufficiently molten Solution, is then slowly added to 2 parts of 4- isothiocyanato -1,3- dimethyl -1H- pyrazoles while stirring, obtains polymer 8 '.It presses Parts by weight weigh A:9 parts of polymer 8 ' of reaction mass component, 0.3 part of chain extender 1,4- butanediol, 2 0.06 parts of lauric acid two Butyl tin, 0.05 part of triethylenediamine, 0.1 part of organic silicone oil, 6 parts of methylene chloride, 3 parts of water, 0.5 part of liquor zinci chloridi, 0.5 part of copper nitrate solution is added in No. 2 reactors, is stirred under conditions of 35 DEG C of material temperature, mixing speed 200r/min equal It is even；B:6 parts of isophorone diisocyanate of reaction mass component, are added in No. 3 reactors, in 35 DEG C of mixing speeds of material temperature It is stirred evenly under conditions of 200r/min；Then reaction mass component A is mixed with reaction mass component B according to 1:1 mass ratio, It is quickly stirred through professional equipment to bubble is generated, stands 72h, the hybrid cross-linked dynamic aggregation object after being foamed.After foaming Hybrid cross-linked dynamic aggregation object be added in No. 4 reactors, solidify 30min at room temperature, then solidify 2h at 120 DEG C, Obtain dynamic aggregation object foamed material.Performance test: density (kg/m3): 138.64 ± 14.53；50% compressive strength (MPa): 3.35 ± 0.84；Tensile strength (MPa): 11.28 ± 2.38；Elongation at break (%): 215.14 ± 44.21.The production Product can be prepared to cushioned floor mat, can be layed in welfare home floor, prevent old man or child's tumble injury.
Embodiment 9
12 parts of methyl acrylates are weighed in parts by weight and 10 parts of acrylamides are added after mixing in No. 1 reactor, 0.1 part of initiator A IBN is added, is reacted after being sufficiently stirred, takes out reactor and is placed in 50 DEG C of baking ovens for 24 hours further reaction, Obtain polymer 9.Polymer 9 and methylene diisocyanate are mixed and are dissolved in the dry methylene chloride of 300mL, at 70 DEG C Lower stirring 6h, obtains the 1st network polymer.The 1st network polymer of reaction mass A:10 part, 3 part 2 are weighed in parts by weight, 6- dimethyl -3,5- amide, 0.2 part of dibutyl tin dilaurate, 0.2 part of triethylenediamine, 0.1 part, 12 parts of organic silicone oil Dehydrated alcohol is added in No. 3 reactors, is stirred evenly under conditions of 35 DEG C of material temperature, mixing speed 200r/min；Reactant Expect B:3 parts of 2- (4- pyridyl group) malonic acid, 0.5 part of platinum nitrate solution, 0.2 part of lanthanum nitrate；Component B and component A is mixed and is added In No. 4 reactors, 60 DEG C are warming up to, and stirred, 1h is then irradiated under the ultraviolet lamp of 300W, 60 DEG C of bakings are put into after taking-up In case, maintain after temperature 2h to get to a kind of dynamic aggregation object organogel.Performance test: 90% compressive strength (MPa): 5.57±1.23；Tensile strength (MPa): 16.87 ± 2.41；Elongation at break (%): 690.34 ± 94.23.The product can be with It is prepared into a kind of energy-absorbing buffering gasket, for precision instrument or the damping and silencing of electronic product.
Embodiment 10
A:12 parts of bisphenol-A polyethylene glycol oxide ethers of reaction mass component, 0.1 part of di lauric dibutyl are weighed in parts by weight Tin, 0.1 part of triethylenediamine are added in No. 1 reactor, are stirred under conditions of 35 DEG C of material temperature, mixing speed 200r/min It mixes uniformly；B:15 parts of triphenylmethane triisocyanates (TTI) of reaction mass component, are added in No. 2 reactors, in material temperature It is stirred evenly under conditions of 35 DEG C of mixing speed 200r/min；Then by reaction mass component A and reaction mass component B according to The mixing of 1.1:1 mass ratio, is quickly stirred through professional equipment, stands 72h to get to the 1st network polymer.It weighs in parts by weight The 1st network polymer of reaction mass component A:12 part, 5 parts of methyl acrylates, 0.2 part of dibutyl tin dilaurate, 0.2 part three Ethylene diamine, 10 parts of dioctyl phthalates, 0.1 part of organic silicone oil, are added in No. 3 reactors, 35 DEG C of material temperature, It is stirred evenly under conditions of mixing speed 200r/min；B:8 parts of 4'- vinyl -2,2 ' of reaction mass component: 6 ', 2 "-three connection pyrroles Pyridine, 0.5 part of scandium chloride solution, 0.2 part of nitric acid lawrencium solution, 0.1 part of initiator A IBN；Component B and component A is mixed and is added No. 4 In reactor, 60 DEG C are warming up to, and stirred, are put into after taking-up in 60 DEG C of baking ovens, maintained after temperature 2h to get to one kind Dynamic aggregation object plasticizer swell gel.Performance test: 90% compressive strength (MPa): 5.34 ± 1.02；Tensile strength (MPa): 15.65±2.43；It is broken elongation at break (%): 423.68 ± 78.21.The product can be prepared into the covering of sharp materials Object, such as table angle, chair angle etc., prevent human body from wounding.Collaboration under the action of pulling force, between hydrogen bond and metal-ligand effect Function and effect make the tensile strength of the dynamic aggregation object and elongation at break obtain certain promotion, and energy-absorbing effect is more preferable.When When the gel is in polar solvent, hydrogen bond action weakens, the mechanical properties decrease of gel, in polar solvent environment, Metal-ligand effect and hydrogen bond show orthogonal energy-absorbing effect.
Embodiment 11
The second network polymer is prepared first, 10 parts of polyvinyl alcohol is added in parts by weight in No. 1 reactor, and be added 100mL methylene chloride, stirs to dissolve, and side stirring is slowly dropped into 3 parts of 9- isothiocyanato acridines, obtains the 2nd network Polymer.The 2nd network polymer of reaction mass component A:10 part, 5 parts of polypropylene oxide triols, 0.2 part are weighed in parts by weight Dibutyl tin dilaurate, 0.2 part of triethylenediamine, 0.2 part of organic silicone oil, 8 parts of methylene chloride, 4 parts of water, 0.2 part of nitric acid Gold solution, 0.5 part of silver nitrate are added in No. 2 reactors, are stirred under conditions of 35 DEG C of material temperature, mixing speed 200r/min equal It is even；B:8 parts of reaction mass component；Then reaction mass component A is mixed with reaction mass component B according to 1.2:1 mass ratio, is passed through Professional equipment is quickly stirred to bubble is generated, and stands 72h, the hybrid cross-linked dynamic aggregation object after being foamed.After foaming Hybrid cross-linked dynamic aggregation object is added in No. 3 reactors, solidifies 30min at room temperature, then solidifies 2h at 120 DEG C, i.e., Obtain a kind of flexibel polyurethane base foamed material.Performance test: density (kg/m3): 68.64 ± 9.43；70% compressive strength (MPa): 2.15 ± 0.69；Tensile strength (MPa): 6.22 ± 1.54；Elongation at break (%): 335.24 ± 30.94.The product It can be prepared to soft package foam, cladding fragile article etc. has damaged material.
Embodiment 12
The preparation method of N- (2,9- dimethyl -1,10- phenanthroline -5- base) propine amide: by 2,9- dimethyl -1,10- Phenanthroline first carries out nitration, and nitro is then reduced into amino again.Dimethyl -1 90g2,9- is added in No. 1 reactor, 10- phenanthroline -5- amino and 30g propiolic acid are dissolved in the dry DMF of 200mL, it is sub- to add 3g condensing agent dicyclohexyl carbon two Amine (DCC) and 1g activator 4-N, N- lutidines (DMAP), are stirred at room temperature for 24 hours, and N- (2,9- dimethyl-can be made 1,10- phenanthroline -5- base) propine amide.The preparation method of N- (7- propionamide naphthalene -2- base) propine amide: in No. 2 reactors Middle addition 50g naphthalene -2,7- diamines and 25g propiolic acid are dissolved in the dry DMF of 200mL, add 2g condensing agent dicyclohexyl Carbodiimide (DCC) and 1g activator 4-N, N- lutidines (DMAP), are stirred at room temperature for 24 hours, and N- (7- third can be made Amide naphthalene -2- base) propine amide.The preparation method of 1,3,5- tri- (azido-methyl) benzene: by 35.6g1,3,5- tri- (bromomethyl) benzene It with 23.4g sodium azide in 100mL DMF solution, is put into No. 3 reactors, stirs 2 days, 1,3,5- tri- (nitrine first are made Base) benzene.22gN- (2,9- dimethyl -1,10- phenanthroline -5- base) propine amide, 31g1,3,5- tri- is added in No. 4 reactors (azido-methyl) benzene, 25gN- (7- propionamide naphthalene -2- base) propine amide, 200mL dimethylformamide, stirring carry out nitrine-alkynes Reaction, obtain the 2nd network polymer.The 2nd network polymer of reaction mass component A:10 part, 12 are weighed in parts by weight Part polydimethyl siloxane fluid, 0.2 part of dibutyl tin dilaurate, 0.2 part of triethylenediamine, 0.2 part of organic silicone oil, 8 parts of dichloros Methane, 4 parts of water, 0.2 part of nitric acid rhenium solution, 0.3 part of copper-bath are added in No. 5 reactors, in 35 DEG C of material temperature, stirring speed It is stirred evenly under conditions of degree 200r/min；4,4 ˊ of reaction mass component B:6 part, 4 〞-triphenylmethane triisocyanate；Then will Reaction mass component A is mixed with reaction mass component B according to 1:1 mass ratio, is quickly stirred through professional equipment to generation bubble, quiet 72h is set, the hybrid cross-linked dynamic aggregation object after being foamed.Hybrid cross-linked dynamic aggregation object after foaming is added to No. 6 instead It answers in device, solidifies 30min at room temperature, solidify 2h at 120 DEG C then to get dynamic aggregation object foamed material is arrived.Performance is surveyed Examination: density (kg/m3): 152.14 ± 12.52；50% compressive strength (MPa): 6.67 ± 1.32；Tensile strength (MPa): 17.25±2.73；Elongation at break (%): 248.34 ± 20.14.The product can be prepared to divider wall or army and police's protective garment Liner.
Embodiment 13
The 2nd network is prepared first, and bis- mercaptan of 32g pyridine -2,6-, 36g3- vinyl amyl- 1 are added in No. 1 reactor, 4- diene and 0.3g antioxidant 164 carry out reaction 30min with the ultraviolet light irradiation of 300W, and polymer 10 is made.In parts by weight 10 parts of polymer 10 are added in No. 2 reactors, and 100mL methylene chloride is added, stir to dissolve, side stirring is slowly dripped Enter 3 parts of 1,8- naphthyridines -4- mercaptan, polymer 10 ' is made.The third two sulphur of A:10 parts of 1,3- of reaction mass component is weighed in parts by weight Alcohol, 10 parts of fluorine containing silicone oils, 0.2 part of dibutyl tin dilaurate, 0.2 part of triethylenediamine, 0.2 part of organic silicone oil, 8 parts of dichloros Methane, 4 parts of water, 0.2 part of nitric acid molybdenum solution, 0.3 part of manganous chloride solution are added in No. 3 reactors, in 35 DEG C of material temperature, stirring It is stirred evenly under conditions of speed 200r/min；B:8 parts of polymer 10 ' of reaction mass component, 0.1 part of antioxidant 164；Reactant Expect component C:8 parts of HDI trimer；Then reaction mass component A is mixed with reaction mass component B according to 1:1 mass ratio, is used The ultraviolet light irradiation of 300W takes out after carrying out reaction 30min, and reaction mass component C is added, and is quickly stirred through professional equipment to production Anger bubble, stands 72h, the hybrid cross-linked dynamic aggregation object after being foamed.Hybrid cross-linked dynamic aggregation object after foaming is added Enter into No. 6 reactors, solidify 30min at room temperature, solidifies 2h at 120 DEG C then to get dynamic aggregation object foam material is arrived Material.Performance test: density (kg/m3): 87.34 ± 11.23；70% compressive strength (MPa): 2.65 ± 0.79；Tensile strength (MPa): 7.23 ± 2.47；Elongation at break (%): 334.26 ± 45.32.The product can be prepared to handguard, knee-pad et al. Body safety device.
Embodiment 14
200g polyethylene glycol, 2g catalyst KOH are added first into BUSS formula outer circulation reactor, then carries out nitrogen and sets It changes, is separately added into epoxy prapanol 35g after being heated to 120 DEG C and is reacted, reaction temperature controls 140~150 DEG C.In constant temperature item Under part, slaking reaction 40min is carried out, when reactor pressure no longer declines, is started as reactor content cooling.It is reduced to temperature Acetic acid is added at 70 DEG C and carries out neutralization reaction, until the pH of reaction system is 6.8, polymer 11 is made.By the cinchonine and 9g of 29g Methyl isocyanate reacted in the dry methylene chloride of 100mL, convert carbamate groups for the hydroxyl in cinchonine Group.Cinchonine by 63g2- (butyl- 3- alkene -1- base) ethylene oxide and 14g with carbamate groups, which mixes, is dissolved in 100mL Dimethylbenzene after be added No. 1 reactor in, add 1g azodiisobutyronitrile (AIBN), be stirred to react 6h after being warming up to 90 DEG C, Polymer 11 ' is made.It is mixed that parts by weight are weighed into 3 parts of polymer 11 ', 1 part of hexamethylene diisocyanate, 0.2 part of organic silicone oil It closes with No. 2 reactors, is warming up to 60 DEG C, obtain the 2nd network polymer after stirring 60min.Reaction is weighed in parts by weight The 2nd network polymer of material component A:12 part, 10 parts of polymer, 11,0.2 parts of dibutyl tin dilaurates, 0.1 part of triethylene Diamines, 0.1 part of organic silicone oil, 8 parts of methylene chloride, 3 parts of water, 0.2 part of thorium nitrate solution are added in No. 4 reactors, in material temperature 35 DEG C, stir evenly under conditions of mixing speed 200r/min；B:6 parts of hexamethylene diisocyanates of reaction mass component；Then Reaction mass component A is mixed with reaction mass component B according to 1:1.2 mass ratio, is quickly stirred through professional equipment to generation gas Bubble stands 72h, the hybrid cross-linked dynamic aggregation object after being foamed.Hybrid cross-linked dynamic aggregation object after foaming is added to 5 In number reactor, solidify 30min at room temperature, solidifies 2h at 120 DEG C then to get dynamic aggregation object foamed material is arrived.Property It can test: density (kg/m3): 68.59 ± 8.23；70% compressive strength (MPa): 2.15 ± 0.83；Tensile strength (MPa): 7.23±1.32；Elongation at break (%): 432.17 ± 64.23.The product can be prepared to mattress, pillow, pillow etc. and relax Suitable resting appliance.
Embodiment 15
Hydrogeneous methyl-silicone oil and a certain amount of propenyl are mixed, is put into No. 1 reactor and stirs evenly, in control reaction Double bond molal quantity in the molal quantity and propenyl of active hydrogen atom (hydrogen atom being directly connected with Si) in hydrogeneous methyl-silicone oil Ratio is about 1:1.2, and addition reaction occurs using chloroplatinic acid as catalyst, and obtained side group contains the methyl silicon of polyhydroxy group Oil, i.e., a kind of poly-organosilicon polyalcohol (molecular weight is about 7000).Then itself and 1,2- diisocyanate root ethane are mixed and (presses hydroxyl Base and isocyanates molar ratio are 1:1), it using triethylamine as catalyst, reacts in methylene chloride, the 1st network polymerization is made Object.Hydrogeneous methyl-silicone oil and a certain amount of propenyl are mixed, is put into No. 2 reactors and stirs evenly, it is hydrogeneous in control reaction Double bond in the molal quantity of active hydrogen atom and 6- (allyloxy) -2,4- two (pyridine -2- base) -1,3,5- triazine in methyl-silicone oil The ratio of molal quantity is about 2:1, and addition reaction occurs using chloroplatinic acid as catalyst, and obtained side group contains the first of polyhydroxy group Base silicone oil, i.e., a kind of poly-organosilicon polyalcohol (molecular weight is about 8000).A:10 parts of reaction mass component are weighed in parts by weight 1st network polymer, the product in 6 parts of (2) steps, 0.2 part of dibutyl tin dilaurate, 01 part of triethylenediamine, 0.2 part Organic silicone oil, 0.1 part of chloroplatinic acid are added in No. 3 reactors, are stirred under conditions of 35 DEG C of material temperature, mixing speed 200r/min It mixes uniformly；B:2 parts of 1,3- butadiene of reaction mass component, 0.5 part of nanoscale ferroso-ferric oxide；Then by reaction mass component A It is mixed with reaction mass component B according to 1:1.2 mass ratio, after mixing, stands 72h to get dynamic aggregation object elastomer is arrived. It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm size, carries out extension test, rate of extension using cupping machine For 50 mm/min, measuring sample tensile strength is 9.78 ± 2.25MPa, and stretch modulus is 21.54 ± 3.20MPa, extension at break Rate is 782.56 ± 104.87%.Dynamic aggregation object elastomer in the present embodiment has excellent tensile toughness and energy Absorbability can be made into cushion use.
Embodiment 16
50g acrylic monomers is added in No. 1 reactor, increases the temperature to 80 DEG C, 3g initiator A IBN is added and is subject to It stirs, is taken out after polymerization reaction 60min, remove unreacted monomer, obtain acrylic acid polymer.Polyacrylic acid is dissolved In methylene chloride, a certain amount of thionyl chloride is then added, the back flow reaction at 70 DEG C, thus the carboxyl acyl of polyacrylic acid Chlorination finally removes generated impurity, poly acryloyl chloride is made.40g poly acryloyl chloride, 5g are added in No. 2 reactors 1,3- third diamino, 0.2g triethylamine are warming up to 60 DEG C, and stirring crosslinking polymerization obtains the 1st network polymerization after reacting 30min Object.It is dry that bis- (2- the amino-ethyl) -1- hydroxyethyl benzene of 50g 3,5-, 32g malonyl chloride, 200mL are added in No. 3 reactors Dry methylene chloride is heated to 70 DEG C of beginning polymerization reactions, after reacting 4h, 8g 4- isocyanato-pyridin is added, the reaction was continued 2h obtains polymer 12.Weigh in parts by weight the 1st network polymer of reaction mass component A:10 part, 6 parts of polymer 12, 0.5 part of chain extender 1,4- butanediol, 0.15 part of dibutyl tin dilaurate, 0.1 part of triethylenediamine, 0.1 part of organic silicone oil, 5 parts of methylene chloride, 0.5 part of nickel chloride solution, 0.3 part of manganese chloride solution, are added in No. 4 reactors, in 35 DEG C of material temperature, stir It mixes and stirs evenly under conditions of speed 200r/min；B:8 parts of TDI of reaction mass component；Component B is slowly added to No. 4 reactors In, 60 DEG C are warming up to, and stirred, after reacting 2h, reactant is transferred in No. 5 reactors of wide-mouth, stops stirring, dimension After holding temperature 6h, residual solvent is removed to get a kind of dynamic aggregation object elastomer is arrived.It is made into 80.0 × 10.0 × The dumbbell shape batten of 2.0mm size carries out extension test using cupping machine, and rate of extension is 50 mm/min, measures sample Tensile strength be 12.21 ± 2.45MPa, stretch modulus be 28.15 ± 3.20MPa, elongation at break be 282.56 ± 54.87%.The product can be prepared into a kind of energy-absorbing buffering gasket, for precision instrument or the damping and silencing of electronic product.
Embodiment 17
100g acrylic monomers is added in No. 1 reactor, increases the temperature to 80 DEG C, 2g initiator A IBN is added and is subject to It stirs, is taken out after polymerization reaction 60min, remove unreacted monomer, obtain acrylic acid polymer.In No. 2 reactors 80g polyacrylamide, 10g 4- isocyano pyridine, are warming up to 60 DEG C, stirring crosslinking polymerization, after reacting 30min, obtain the 1 network polymer.The 1st network polymer of reaction mass component A:10 part, 6 parts of urea, 3 parts of 6- amino-are weighed in parts by weight 1H- pyrrolo- [3,4-c] pyridine -1,3 (2H)-diketone, 0.5 part of chain extender 1,4- butanediol, 0.15 part of di lauric dibutyl Tin, 0.1 part of triethylenediamine, 0.1 part of organic silicone oil, 10 parts of polyvinyl acetate ester oligomers, 0.5 part of Metal Organic Molecular cage (MOC-16), it is added in No. 3 reactors, is stirred evenly under conditions of 35 DEG C of material temperature, mixing speed 200r/min；Reactant Expect component B:8 parts of IPDI；Component B is slowly added in No. 3 reactors, is warming up to 60 DEG C, and stirred, it, will after reacting 2h Reactant is transferred in No. 4 reactors of wide-mouth, stops stirring, is maintained after temperature 6h to get neat to a kind of dynamic aggregation object Polymers swell gel.Performance test: 90% compressive strength (MPa): 10.34 ± 2.13；Tensile strength (MPa): 22.24 ± 3.56；It is broken elongation at break (%): 346.29 ± 86.39.The product can be prepared into a kind of hermetically sealed cushion sheet material Material.
Embodiment 18
180g allyl-ethyl 3-oxobutanoate monomer is added in No. 1 reactor, increases the temperature to 80 DEG C, 5g is added Initiator A IBN is simultaneously stirred, and is taken out after polymerization reaction 60min, and unreacted monomer is removed, and obtains polyallyl -3- oxygen For ethyl butyrate polymer.The dichloro of 100g polyacrylamide, 12g pyridine -2- amido, 200mL zinc chloride in No. 2 reactors Dichloromethane is warming up to 160 DEG C of beginning polymerization reactions, after reacting 4h, obtains the 1st network polymer.Add in No. 3 reactors Enter 100g isocyanates acrylic acid ethyl ester monomer, increase the temperature to 80 DEG C, 2g initiator A IBN is added and is stirred, polymerization is anti- It is taken out after answering 60min, removes unreacted monomer, obtain polyisocyanate X 4460.In No. 4 reactors Polyisocyanate ethyl acrylate obtained and a certain amount of 4- hydroxyl -7- methoxyl group-[1,8] benzodiazine are mixed, with three Ethamine reacts in dry methylene chloride as catalyst, different in polyisocyanate ethyl acrylate side group in control reaction The ratio of the molal quantity of hydroxyl is about 3:2 in the molal quantity and propyl alcohol of cyanate radical, so that polyisocyanate ethyl acrylate has Pendant ligands.The 1st network polymer of reaction mass component A:15 part, 9 parts of above-mentioned side groups are weighed in parts by weight with amino first The polyisocyanate ethyl acrylate of acid esters group, 5 parts of 1- ethyl-3-methylimidazole tetrafluoroborates, 0.5 part of chain extender 1,4- Butanediol, 0.3 part of dibutyl tin dilaurate, 0.2 part of triethylenediamine, 0.2 part of organic silicone oil, 5 parts of methylene chloride, 0.3 Part ferric chloride solution, 0.1 part of platinum nitrate solution, be added in No. 3 reactors, in 35 DEG C of material temperature, mixing speed 200r/min Under the conditions of stir evenly；B:8 parts of amine terminated polyethers of reaction mass component；Component B is added in No. 3 reactors, is warming up to 60 DEG C, and stirred, after reacting 2h, reactant is transferred in No. 4 reactors of wide-mouth, stops stirring, maintains temperature 6h Afterwards to get arrive a kind of dynamic aggregation object ionic liquid swell gel.Performance test: 90% compressive strength (MPa): 3.52 ± 0.79；Tensile strength (MPa): 12.34 ± 2.45；Elongation at break (%): 846.29 ± 132.68.The product can be prepared into A kind of elastic cushion of changeable colour possesses the material of different colours at various pressures.
Embodiment 19
133g 3 is added in No. 1 reactor, 3'- dimethyl -4,4'- biphenylene diisocyanate is warming up to 80 DEG C Afterwards, 67g 6- ethyleneamino -1,3,5-triazines -2,4- diamines is added, and is stirred, after reacting 2h, polymer is made 13.Polymer 13,43g 4- mercaptopyridine, 0.6g antioxidant BHT are mixed, reactor is transferred to 300W after mixing evenly 30min is irradiated under ultraviolet lamp, obtains the 1st network polymer.Ethyleneamino -1,3 67g 6- are added in No. 2 reactors, After being warming up to 80 DEG C, 90g 1- adamantyl isocyanate is added, and stirred in 5- triazine -2,4- diamines, after reacting 2h, Compound 1 is made.10 parts of compound 1 and 10 part acrylamide monomers are weighed in parts by weight, are added in No. 3 reactors after mixing It stirs evenly, 0.5 part of initiator A IBN is then added, is taken out after polymerization reaction 60min, removes unreacted monomer, obtain Polymer 13 '.The 1st network polymer of reaction mass component A:10 part, 10 parts of polymer 13 ', 0.2 part are weighed in parts by weight Dibutyl tin dilaurate, 0.2 part of triethylenediamine, 0.2 part of organic silicone oil, 8 parts of methylene chloride, 5 parts of water, 0.2 part of nitric acid Terbium and 0.1 part of silver nitrate solution are added in No. 4 reactors, are stirred under conditions of 35 DEG C of material temperature, mixing speed 200r/min Uniformly；B:8 parts of 3,3'- dimethyl -4,4'- biphenylene diisocyanates of reaction mass component；Then by reaction mass component A It is mixed with reaction mass component B according to 1:1 mass ratio, is quickly stirred through professional equipment to bubble is generated, stand 72h, sent out Hybrid cross-linked dynamic aggregation object after bubble.Hybrid cross-linked dynamic aggregation object after foaming is added in No. 5 reactors, in room temperature Then lower solidification 30min solidifies 2h at 120 DEG C to get dynamic aggregation object foamed material is arrived.Performance test: density (kg/ m3): 168.34 ± 23.67；50% compressive strength (MPa): 5.13 ± 1.83；Tensile strength (MPa): 15.16 ± 3.15；It is disconnected It splits elongation (%): 121.37 ± 22.34.The product can be prepared to the comfortably auxiliary product such as cushion, backing cushion.
Embodiment 20
5- Hydroxy M Phthalic Acid is dissolved in methylene chloride, a certain amount of thionyl chloride is then added, at 70 DEG C Back flow reaction, so that the carboxyl chloride of 5- Hydroxy M Phthalic Acid is finally removed generated impurity, is made between 5- hydroxyl Phthalyl chloride.In parts by weight in No. 1 reactor be added 10 parts of 2,6- (4,4'- diamino-phenyl) benzo dioxazoles, 200mL methylene chloride, stirring dissolve it sufficiently, are then slowly added to 5 parts of 5- hydroxyl m-phthaloyl chlorides while stirring, stir Polymer 14 is obtained after reaction 2h；By polymer 14 and 2, the chloro- 4- isocyano pyridine of 6- bis- is mixed, and obtains the 1st Network polymer.92g tri o cresyl thiophosphate phenyl isocyanate and 32g2,3- pyrazine acid are added in No. 2 reactors, is stirred to react Polymer 14 ' is made afterwards.10 parts of polymer 14 ', 200mL methylene chloride are added in parts by weight in No. 3 reactors, stirring makes It is sufficiently dissolved, and is then slowly added to 2 parts of 6- methylimidazoles simultaneously [2,1-B] [1,3] thiazole-5-carboxylic acid while stirring, and stirring is anti- Polymer 14 " is obtained after answering 2h.The 1st network polymer of reaction mass component A:11 part, 10 parts of polymerizations are weighed in parts by weight Object 14 ", 0.2 part of dibutyl tin dilaurate, 0.2 part of triethylenediamine, 0.2 part of organic silicone oil, 8 parts of methylene chloride, 5 parts Water, the miscellaneous benzene of 0.5 part of osmium, 0.5 part of cobaltous dichloride solution are added in No. 4 reactors, in 35 DEG C of material temperature, mixing speed 200r/ It is stirred evenly under conditions of min；B:8 parts of ethylene glycol of reaction mass component and 2 parts of 1,3- glycerine are uniformly mixed；It then will be anti- It answers material component A to mix with reaction mass component B according to 1:1.2 mass ratio, is quickly stirred through professional equipment to generation bubble, it is quiet 72h is set, the hybrid cross-linked dynamic aggregation object after being foamed.Hybrid cross-linked dynamic aggregation object after foaming is added to No. 5 instead It answers in device, solidifies 30min at room temperature, solidify 2h at 120 DEG C then to get dynamic aggregation object foamed material is arrived.Performance is surveyed Examination: density (kg/m3): 268.34 ± 21.34；10% compressive strength (MPa): 25.23 ± 4.23；Tensile strength (MPa): 52.16±7.78；Elongation at break (%): 27.24 ± 4.39.It is explosion-proof that the product can be prepared to blast wall, explosion-proof shield etc. Safety device.
Embodiment 21
2,4- hexadienoic acid is dissolved in methylene chloride, a certain amount of thionyl chloride is then added, is flowed back at 70 DEG C Reaction, so that 2, the carboxyl chloride of 4- hexadienoic acid finally removes generated impurity, 2,4- hexadiene acyl chlorides is made. The bromo- 2,6-diaminopyridine of 10 parts of 4-, 200mL methylene chloride are added in parts by weight in No. 1 reactor, stirring makes it sufficiently Dissolution, is then slowly added to 8 parts of 2,4- hexadiene acyl chlorides while stirring, obtains polymer 15 after being stirred to react 2h.By weight Number is added 10 parts of polymer 15 and 3 part 4-vinylpridines in No. 2 reactors and is mixed, and is warming up to 100 DEG C, control is double The molal quantity ratio of alkene molal quantity and double bond is 10:7, and polymer 15 ' is made.6 parts are added in No. 3 reactors in parts by weight to gather It closes object 15 ' and 2 parts of Isosorbide-5-Nitraes-pentadiene is mixed, be warming up to 100 DEG C, obtain the 1st network polymer.In No. 4 reactors 30g 6- nitrine hexylamine, 28g 2, bis- (acetenyl) pyridines of 6- is added, stirring carries out the reaction of nitrine-alkynes, obtains compound 2.53g compound 2,4,4 ˊ of 100g are added in No. 5 reactors, 4 〞-triphenylmethane triisocyanate stirs and is warming up to 70 DEG C, polymer 15 " is made.10 parts of polymer 15 " and 3 parts of 4- (3- pyridyl group) -2- ammonia are added in No. 6 reactors in parts by weight Yl pyrimidines are mixed, and are warming up to 100 DEG C, and the molal quantity ratio for controlling diene molal quantity and double bond is 10:7, and polymer is made 15"'.The 1st network polymer of reaction mass component A:10 part, 6 parts of 1,6-HDs, 0.2 part of two laurel are weighed in parts by weight Sour dibutyl tin, 0.2 part of triethylenediamine, 0.2 part of organic silicone oil, 5 parts of methylene chloride, 3 parts of water, 0.2 part of nitric acid gold and 0.3 Part trifluoromethanesulfonic acid cerium mixed solution is added in No. 7 reactors, is stirred under conditions of 35 DEG C of material temperature, mixing speed 200r/min It mixes uniformly；B:9 parts of polymer 15 " of reaction mass component '；Then by reaction mass component A and reaction mass component B according to 1: The mixing of 1.2 mass ratioes quickly stirs to bubble is generated through professional equipment, stands 72h, and the hybrid cross-linked dynamic after being foamed is poly- Close object.Hybrid cross-linked dynamic aggregation object after foaming is added in No. 8 reactors, solidifies 30min at room temperature, then exists Solidify 2h at 120 DEG C to get a kind of hard polyurethane ester group foamed material is arrived.Performance test: density (kg/m3): 159.24 ± 21.12；10% compressive strength (MPa): 27.27 ± 4.21；Tensile strength (MPa): 48.23 ± 7.36；Elongation at break (%): 16.65±2.13.The product can be prepared to blast wall.
Embodiment 22
32g 4- Amide-6-hydroxy-2-mercaptopyrimidine, 45g 4- (1- butenyl phenyl) pyrrole are added in No. 1 reactor Pyridine, 0.3g antioxidant DNP after stirring by mixing, are placed under 300W ultraviolet lamp and irradiate 30min, obtain polymer 16.16,5 parts of 1,4- butane diisocyanates of A:6 parts of polymer of reaction mass component, 0.1 part of tin dilaurate are weighed in parts by weight Dibutyl tin, 0.1 part of triethylenediamine, 0.1 part of organic silicone oil are added in No. 2 reactors, in 35 DEG C of material temperature, mixing speed It is stirred evenly under conditions of 200r/min；B:13 parts of 1,4- butane diisocyanates of reaction mass component；Then by reaction mass group Divide A and reaction mass component B to be mixed according to 1:1.2 mass ratio, be warming up to 60 DEG C, it is poly- to obtain the 1st network after reaction 2h Close object.Together by 300g polyacrylonitrile, 13g 2- nitrine pyridine, 17g 2,5- dehydration -1- nitrine -1- deoxy-D-glucose alcohol It is dissolved in the dimethylformamide of 300mL, is placed in No. 3 reactors, ultrasound 50min heats up after enabling each component be sufficiently mixed at room temperature To 125 DEG C of stirring 48h, compound 3 is obtained.The 1st network polymer of reaction mass component A:12 part, 7 are weighed in parts by weight 3,0.2 parts of dibutyl tin dilaurates of part compound, 0.2 part of triethylenediamine, 0.15 part of organic silicone oil, 7 parts of dichloromethanes Alkane, 4 parts of water, 0.2 part of iron chloride and 0.3 part of copper chloride mixed solution are added in No. 4 reactors, in 35 DEG C of material temperature, stirring speed It is stirred evenly under conditions of degree 200r/min；B:10 parts of 1,4- diisocyanate bases butanes of reaction mass component；Then by reactant Material component A is mixed with reaction mass component B according to 1:1.1 mass ratio, is quickly stirred through professional equipment to bubble is generated, is stood 72h, the hybrid cross-linked dynamic aggregation object after being foamed.Hybrid cross-linked dynamic aggregation object after foaming is added to No. 5 reactions In device, solidify 30min at room temperature, solidifies 2h at 120 DEG C then to get dynamic aggregation object foamed material is arrived.Performance test: Density (kg/m3): 78.53 ± 13.23；70% compressive strength (MPa): 3.35 ± 0.89；Tensile strength (MPa): 10.14 ± 2.35；Elongation at break (%): 377.83 ± 54.23.The product can be prepared to a kind of comfortable sole material.
Embodiment 23
18g 1- amino -6- methyl -2- oxo -1,2- dihydropyridine -3- carboxylic acid is added in No. 1 reactor, is warming up to 11g isocyanate group methane is added after 80 DEG C, reacts it sufficiently by stirring, obtains compound 4.Add in No. 2 reactors Enter poly- 1, the 2- butadiene of 50g, and 100mL methylene chloride is added, stirring makes it that 10g compound 4 be added after completely dissolution, heats up To 90 DEG C, polymer 17 is made after stirring sufficiently reaction.30g polymer 17,5g dithioglycol, 0.05g antioxidant BHT are mixed It stirs evenly, is placed in No. 3 reactors, be then placed under the ultraviolet lamp of 300W and irradiate 30min, obtain the 1st network polymer. In No. 4 reactors, under nitrogen protection, 1g urea is added in 300g amination dimethyl siloxane, stirs lower slowly heating To 160 DEG C, after heat preservation about 1 hour, it is down to room temperature, obtains polymer 17 '.Reaction mass component A:11 is weighed in parts by weight Part the 1st network polymer, 5 parts of polymer 17 ', 0.3 part of chain extender 1,4- butanediol, 0.2 part of dibutyl tin dilaurate, 0.15 Part triethylenediamine, 0.2 part of organic silicone oil, 5 parts of methylene chloride, 0.2 part of manganese chloride solution, 0.2 part of nickel nitrate solution, are added Into No. 5 reactors, stirred evenly under conditions of 35 DEG C of material temperature, mixing speed 200r/min；Reaction mass component B:8 part 1, 8- diisocyanate zinc alkane；Then reaction mass component A is mixed with reaction mass component B according to 1:1.1 mass ratio, through special Industry equipment is quickly stirred to bubble is generated, and stands 72h, the hybrid cross-linked dynamic aggregation object after being foamed.It will be miscellaneous after foaming Change crosslinking dynamic aggregation object be added in No. 5 reactors, solidify 30min at room temperature, then at 120 DEG C solidify 2h to get To dynamic aggregation object foamed material.Performance test: density (kg/m3): 86.43 ± 22.13；70% compressive strength (MPa): 3.25 ±0.91；Tensile strength (MPa): 9.23 ± 1.89；Elongation at break (%): 367.12 ± 76.38.The product can be used for essence The damping and silencing of close instrument or electronic product.
Embodiment 24
Weigh in parts by weight 10 parts of 1,6- heptadiene, 14 parts to dimercaptobenzene, 1.5 parts of triallylamines and 0.5 part peace The fragrant double methyl ethers (DMPA) of breath are put into No. 1 reactor, after stirring is sufficiently mixed, is placed under 300W ultraviolet lamp and is irradiated 30min, that is, make Obtain the 1st network polymer.30g guanine and 32g paraphenylene diisocyanate are added in No. 2 reactors, is warming up to 80 DEG C, stirring It is allowed to sufficiently polymerize, obtain.100g polyvinyl alcohol is dissolved in 200mL methylene chloride in No. 3 reactors, after completely dissolution plus Enter 50g compound 5, load onto reflux unit, be warming up to 80 DEG C, after being stirred to react 2h, obtains the 2nd network polymer.32g is different Cyanate ethyl acrylate is dissolved in 100mL methylene chloride in No. 4 reactors, and 5g isoxanthopterin is added after completely dissolution, loads onto Reflux unit is warming up to 80 DEG C, after being stirred to react 2h, obtains compound 6.Reaction mass component A:8 is weighed in parts by weight Part the 1st network polymer, 9 part of the 2nd network polymer, 10 parts of 1,2,3- glycerine, 0.2 part of dibutyl tin dilaurate, 0.2 Part triethylenediamine, 0.2 part of organic silicone oil, 10 parts of methylene chloride, 4 parts of water, 0.2 part of trifluoromethanesulfonic acid europium and 0.3 part of trifluoro Methanesulfonic acid zinc mixed solution is added in No. 5 reactors, is stirred under conditions of 35 DEG C of material temperature, mixing speed 200r/min equal It is even；B:9 parts of compounds 6 of reaction mass component；Then by reaction mass component A and reaction mass component B according to 1:1.2 mass ratio Mixing quickly stirs to bubble is generated through professional equipment, stands 72h, the dynamic aggregation object after being foamed.It will be dynamic after foaming State polymer is added in No. 6 reactors, solidifies 30min at room temperature, solidifies 2h at 120 DEG C then to get poly- to dynamic Polymer foam.Performance test: density (kg/m3): 158.23 ± 23.56；50% compressive strength (MPa): 7.23 ± 1.87；Tensile strength (MPa): 22.54 ± 3.66；Elongation at break (%): 422.15 ± 121.34.The product can be produced At a kind of lining of helmet or mattress material.
Embodiment 25
50g polyethylene glycol, 1.25g catalyst KOH are added into BUSS formula outer circulation reactor, then carries out nitrogen displacement, heats 140g1 is added after to 120 DEG C, 2- epoxy -3- butylene is reacted, and reaction temperature controls 140~150 DEG C.In constant temperature Under, it carries out slaking reaction 40 minutes, when reactor pressure no longer declines, starts as reactor content cooling.It is reduced to temperature Acetic acid is added at 70 DEG C and carries out neutralization reaction, until be cooled to room temperature when the pH of reaction system is 6.8, obtain side group contain it is double The polymer 21 of key.21,3 parts of 12 parts of polymer bis- (2- mercaptoethyl) thioethers and 0.2 part of antioxidant are weighed in parts by weight TNP mixing is put into No. 1 reactor, is placed under 300W ultraviolet lamp after mixing evenly and is irradiated 30min, it is cooling take out after obtain the 1 network polymer.The dry methylene chloride of 100mL is added into No. 2 reactors, 68g3- (azido methyl) -1,2,4- dislikes two Azoles -5- formamide, stirring and dissolving is uniform, and 34g isopropyl isocyanate is added after being warming up to 80 DEG C, cooling after being stirred to react 2h, Unreacted reactant is removed, compound 8 is obtained.300mL methylene chloride, the poly- (butadiene-propylene of 150g are added into No. 3 reactors Nitrile), 24g compound 8, stirring dissolves it sufficiently, loads onto reflux unit, be warming up to 125 DEG C, the 2nd network is made after stirring 48h Polymer.25g1,3- dicyanobenzenes, 51g3'- azido -2', 3'- di-deoxyuridine, 200mL are added in No. 4 reactors Dimethylformamide loads onto reflux unit after being uniformly mixed, and is warming up to 125 DEG C, and compound 9 is made after persistently stirring 48h. The dry methylene chloride of 200mL, 63g compound 9,46g1,8- octane diisothio-cyanate, stirring are added into No. 5 reactors It is uniformly mixed it and is warming up to 80 DEG C, react cooling, removing unreacted reactant after 2h, i.e., polymer 21 ' processed.It weighs in parts by weight The 1st network polymer of reaction mass component A:10 part, 8 part of the 2nd network polymer, 7 parts of polymer 21 ', 0.3 part of chain extender 1,4- Butanediol, 0.2 part of dibutyl tin dilaurate, 0.2 part of triethylenediamine, 0.15 part of organic silicone oil, 10 parts of methylene chloride, 0.2 part of cadmium chloride solution, 0.2 part of trifluoromethanesulfonic acid ferrous solution, are added in No. 6 reactors, in 35 DEG C of material temperature, mixing speed It is stirred evenly under conditions of 200r/min；B:8 parts of triethanolamines of reaction mass component；Component B is added in No. 5 reactors, is risen Temperature is stirred to 80 DEG C, and after reacting 2h, reactant is transferred in No. 7 reactors of wide-mouth, stops stirring, and maintaining should After temperature 6h to get arrive dynamic aggregation object elastomer.It is made into the dumbbell shape batten of 80.0 × 10.0 × 2.0mm size, benefit Extension test is carried out with cupping machine, rate of extension 50mm/min, measuring sample tensile strength is 8.13 ± 2.16MPa, Stretch modulus is 18.18 ± 4.25MPa, and elongation at break is 258 ± 177%.Obtained polymer samples can be used to make Energy-absorbing safety device is applied to athletic protective or army and police protect.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks Domain is included within the scope of the present invention.

Claims (17)

1. a kind of energy-absorbing method based on hybrid cross-linked dynamic aggregation object, which is characterized in that it is poly- to provide a kind of hybrid cross-linked dynamic Object or its composition are closed, and carries out energy-absorbing using it as energy-absorbing material；Wherein, the hybrid cross-linked dynamic aggregation object, contains Covalent cross-linking and metal-ligand effect；Wherein, covalent cross-linking reaches the gel point of covalent cross-linking at least one cross-linked network More than.
2. the energy-absorbing method according to claim 1 based on hybrid cross-linked dynamic aggregation object, which is characterized in that the dynamic The polymer chain skeleton of polymer, side group, at least one on end group at contain ligand groups.
3. the energy-absorbing method according to claim 1 based on hybrid cross-linked dynamic aggregation object, which is characterized in that the dynamic Also contain supermolecule hydrogen bond action in polymer architecture.
4. the energy-absorbing method according to claim 1 based on hybrid cross-linked dynamic aggregation object, which is characterized in that described is dynamic State polymer only contains a cross-linked network, and acts on simultaneously containing covalent cross-linking and metal-ligand in this cross-linked network Crosslinking, wherein the degree of cross linking of covalent cross-linking is more than its gel point；The degree of cross linking of metal-ligand effect crosslinking is in its gel point Above and below.
5. the energy-absorbing method according to claim 1 based on hybrid cross-linked dynamic aggregation object, which is characterized in that described is dynamic State polymer only contains a cross-linked network, and acts on simultaneously containing covalent cross-linking and metal-ligand in this cross-linked network Crosslinking；Meanwhile being also crosslinked containing supermolecule hydrogen bond action in cross-linked network, wherein the degree of cross linking of covalent cross-linking is in its gel Or more；The degree of cross linking of metal-ligand effect crosslinking is in its gel point above and below；The degree of cross linking of hydrogen bond crosslinks is in its gel Point above and below.
6. the energy-absorbing method according to claim 1 based on hybrid cross-linked dynamic aggregation object, which is characterized in that the dynamic Polymer contains there are two cross-linked network, one of cross-linked network only contain covalent cross-linking and its degree of cross linking its gel point with On；Another cross-linked network only contains metal-ligand effect crosslinking and its degree of cross linking more than its gel point.
7. the energy-absorbing method according to claim 1 based on hybrid cross-linked dynamic aggregation object, which is characterized in that the dynamic Polymer contains there are two cross-linked network, and one of cross-linked network contains covalent cross-linking and metal-ligand effect crosslinking simultaneously；Its In, the degree of cross linking of covalent cross-linking reaches gel point or more, the degree of cross linking of metal-ligand effect crosslinking more than its gel point or with Under；Another cross-linked network only contains the supermolecule crosslinking formed by hydrogen bond action and its degree of cross linking more than its gel point.
8. the energy-absorbing method according to claim 1 based on hybrid cross-linked dynamic aggregation object, which is characterized in that described is dynamic State polymer contains there are two cross-linked network, and one of cross-linked network contains covalent cross-linking and metal-ligand effect crosslinking simultaneously； Wherein, the degree of cross linking of covalent cross-linking reaches its gel point or more, and the degree of cross linking of metal-ligand effect crosslinking is more than its gel point Or it is following；Another cross-linked network only contains-metal-ligand effect crosslinking.
9. the energy-absorbing method according to claim 1 based on hybrid cross-linked dynamic aggregation object, which is characterized in that described is dynamic State polymer contains there are two cross-linked network, one of cross-linked network only contain covalent cross-linking and its degree of cross linking its gel point with On；Another cross-linked network contains metal-ligand effect crosslinking and its degree of cross linking more than its gel point；Simultaneously at least one Also contain supermolecule hydrogen bond action in a cross-linked network.
10. the energy-absorbing method according to claim 1 based on hybrid cross-linked dynamic aggregation object, which is characterized in that described Dynamic aggregation object contains there are three cross-linked network, and one of cross-linked network only contains covalent cross-linking and its degree of cross linking in its gel point More than, another cross-linked network only contain metal-ligand effect crosslinking, third cross-linked network only contain hydrogen bond crosslinks and its The degree of cross linking is more than its gel point.
11. the energy-absorbing method according to claim 1 based on hybrid cross-linked dynamic aggregation object, which is characterized in that described Dynamic aggregation object contains there are two cross-linked network, and one of cross-linked network only contains covalent cross-linking and its degree of cross linking in its gel point More than；Another cross-linked network contains covalent cross-linking and metal-ligand effect crosslinking simultaneously, wherein the crosslinking of covalent cross-linking Degree is more than its gel point, and the degree of cross linking of metal-ligand effect crosslinking is in its gel point above and below.
12. the energy-absorbing method according to claim 1 based on hybrid cross-linked dynamic aggregation object, which is characterized in that described Dynamic aggregation object contains there are two cross-linked network, and one of cross-linked network only contains covalent cross-linking and its degree of cross linking in its gel point More than；Another cross-linked network contains covalent cross-linking and metal-ligand effect crosslinking simultaneously, wherein the crosslinking of covalent cross-linking Degree is more than its gel point, and the degree of cross linking of metal ligand effect crosslinking is in its gel point above and below；Simultaneously at least one Also contain supermolecule hydrogen bond action in cross-linked network.
13. the energy-absorbing method according to claim 1 based on hybrid cross-linked dynamic aggregation object, which is characterized in that described dynamic State polymer contains at least one cross-linked network, and wherein at least one cross-linked network contains the covalent cross-linking of gel point or more, and And be scattered in wherein at least one network it is noncrosslinking containing metal-ligand effect hydrogen bond action or metal-ligand effect With the supermolecule polymer of hydrogen bond action.
14. the energy-absorbing method according to claim 1 based on hybrid cross-linked dynamic aggregation object, which is characterized in that described dynamic State polymer contains at least one cross-linked network, and wherein at least one cross-linked network contains the covalent cross-linking of gel point or more, and And it is scattered in wherein at least one network existing containing metal-ligand effect or hydrogen bond action or metal-in granular form The cross-linked polymer of ligand effect and hydrogen bond action.
15. the energy-absorbing method according to claim 1 based on hybrid cross-linked dynamic aggregation object, which is characterized in that constitute dynamic The recipe ingredient of state polymer further include it is following any or appoint it is several can additive: other polymers, auxiliary agent, filler；
Wherein, addible other polymers are selected from following any or appoint several: natural polymer, synthesis macromolecule Compound；
Wherein, addible auxiliary agent is selected from following any or appoints several: catalyst, initiator, antioxidant, light stabilizer, heat Stabilizer, chain extender, toughener, coupling agent, lubricant, release agent, plasticizer, foaming agent, antistatic agent, emulsifier, dispersion Agent, colorant, fluorescent whitening agent, delustering agent, fire retardant, nucleating agent, rheological agent, thickener, levelling agent, antibacterial agent；
Wherein, addible filler is selected from following any or appoints several: inorganic non-metallic filler, metal packing, organic filler.
16. according to claim 1 to the energy-absorbing method based on hybrid cross-linked dynamic aggregation object described in any one of 15, feature It is, form of the dynamic aggregation object or its composition has following any: ordinary solid, elastomer, hydrogel, organic Gel, plasticizer swell gel, ionic liquid swell gel, oligomer swell gel, foamed material.
17. according to claim 1 to the energy-absorbing method based on hybrid cross-linked dynamic aggregation object described in any one of 15, feature It is, is applied to damping, sound insulation, noise elimination, damping, explosion-proof, defense of resistance to impact, shellproof, buffering.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114001114A (en) * 2020-01-21 2022-02-01 厦门天策材料科技有限公司 Flexible energy absorption system with concave corner structure
US20220251308A1 (en) * 2019-07-17 2022-08-11 Solvay Specialty Polymers Italy S.P.A. Method for damping shocks and vibrations
CN115521451A (en) * 2021-06-25 2022-12-27 北京理工大学 Preparation method of propiolate-terminated polyether

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220251308A1 (en) * 2019-07-17 2022-08-11 Solvay Specialty Polymers Italy S.P.A. Method for damping shocks and vibrations
US11725082B2 (en) * 2019-07-17 2023-08-15 Solvay Specialty Polymers Italy S.P.A. Method for damping shocks and vibrations
CN114001114A (en) * 2020-01-21 2022-02-01 厦门天策材料科技有限公司 Flexible energy absorption system with concave corner structure
CN115521451A (en) * 2021-06-25 2022-12-27 北京理工大学 Preparation method of propiolate-terminated polyether

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