CN107814891A - A kind of energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE) - Google Patents

A kind of energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE) Download PDF

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CN107814891A
CN107814891A CN201610816602.3A CN201610816602A CN107814891A CN 107814891 A CN107814891 A CN 107814891A CN 201610816602 A CN201610816602 A CN 201610816602A CN 107814891 A CN107814891 A CN 107814891A
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thermoplastic elastomer
hydrogen bond
tpe
group
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不公告发明人
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Weng Qiumei
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Abstract

The invention discloses a kind of energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE), the energy-absorbing method uses the thermoplastic elastomer (TPE) of the polymer molecular structure of the multi-segment structure with multiterminal section list interlude to carry out energy-absorbing protection.The thermoplastic elastomer polymer molecule respectively holds section to form reversible split-phase physical crosslinking；Interlude is unformed shape, also, at least one side hydrogen bond group is included at least part segment therein, and the side hydrogen bond group can form interchain supermolecule hydrogen bond dynamic crosslinking.Non-covalent and dynamic reversibility based on hydrogen bond, the functions such as good damping, damping, sound insulation, shock resistance can be provided by being used using dynamic aggregation thing thermoplastic elastomer (TPE) as energy-absorbing material, be especially applicable to the body protection, army and police's body protection, explosion-proof, airborne and air-drop protection, automobile collision preventing, electric equipment products defense of resistance to impact etc. of motion and daily life and work.

Description

A kind of energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE)
Technical field
The present invention relates to a kind of energy-absorbing method, and in particular to a kind of based on the multisection type knot with multiterminal section-mono- interlude The energy-absorbing method for the thermoplastic elastomer (TPE) that the polymer molecule of structure is formed.
Background technology
In the activity such as daily life, motion, amusement and recreation, military affairs, police service, security, medical care, production, human body, animal body It is often subject to hit with article etc., vibrates, shake, exploding, the physical impact such as sound has a strong impact on.By using energy-absorbing material Energy-absorbing is carried out, effective protection, the alleviation to this kind of physical impact can be played.These energy-absorbing methods are divided into active energy-absorbing and quilt Dynamic formula energy-absorbing.The methods of active energy-absorbing is including the use of shock absorber, passive type energy-absorbing is including the use of the material with energy-absorbing function The methods of.Material for energy-absorbing mainly has the materials such as metal, polymer, composite.Wherein, the energy damage of polymeric material Consumption source mainly has following several：1, using polymer, the phenomenon with high fissipation factor is inhaled near its glass transition temperature Energy.For this method because material is near glass transition temperature, the mechanical property of material is sensitive to temperature change, is using The mechanical property of process in which materials acute variation easily with the change of environment temperature, difficulty is brought to use.2, utilize covalent bond Fracture and material internal Deng chemical bond crack the process energy-absorbings such as the fracture that even material is overall.In above-mentioned each process In, the fracture of covalent bond can not only recover with the crackle of macroscopic view, fracture, also reduce the mechanical property for causing material.One After secondary or a small number of endergonic process several times, material must be replaced in time could maintain original performance.3, it is particularly poly- using deformation Interior friction energy-absorbing between molecule segment caused by the relatively large deformation of compound rubbery state or viscoelastic state.This method usually requires material Larger deformation, which occurs, for material could produce significant effect, and after the deformation of the high loss of energy occurs for material, often can not be extensive Original shape is arrived again, can not be continuing with, it is necessary to be replaced.
In the prior art, the common structure of polymeric material for being used as energy-absorbing has based on above-mentioned various energy loss mechanism And design obtained polymer alloy, polymer interpenetration network, polymer elastomer etc..These are often for structures of energy-absorbing The simple superposition of above-mentioned each mechanism, although expanding energy-absorbing scope to a certain extent compared with single above-mentioned mechanism improves suction Energy efficiency, but still its deficiency can not be avoided.
Therefore, it is necessary to develop a kind of new energy-absorbing method, in particular with a kind of new energy absorption of introducing and loss machine The polymer of reason carries out energy-absorbing, to solve problems of the prior art.
The content of the invention
For above-mentioned background, the invention provides a kind of energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE).For This, we introduce side base and/or side chain containing supermolecule hydrogen bond crosslinks in traditional thermoplastic elastomer (TPE) structure, are retaining On the basis of other superperformances of thermoplastic elastomer (TPE), the master of energy-absorbing is used as by the use of the fracture with reversible supermolecule hydrogen bond Want means.
The present invention can be achieved by following technical solution：
In embodiments of the present invention, a kind of energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE), there is provided one Kind dynamic aggregation thing thermoplastic elastomer (TPE), energy-absorbing protection is carried out using this thermoplastic elastic material as energy-absorbing material；Wherein, institute The polymer molecule for the thermoplastic elastomer (TPE) stated has the multi-segment structure of multiterminal section-mono- interlude shown in below general formula,
Wherein, A is end section, and B is interlude；N is the quantity for the end section A being connected between on section B, and it is more than or equal to 2；Respectively Hold section A identical or different, be mutually mixed each other or each independent or be not only mutually mixed to be formed independently of one another again and crystallize Phase or the phase incompatible with interlude B or existing crystalline phase have the phase incompatible with interlude again, to be formed based on each end section Reversible split-phase physical crosslinking；Between the section of any two end across connect they interlude or interlude subchain section, it is and obstructed That crosses in addition to interlude covalently attached is linked；Interlude B is unformed shape, and at least one is included in all or part of segment Side hydrogen bond group, the side hydrogen bond group form interchain supermolecule hydrogen bond dynamic crosslinking.
In embodiments of the present invention, a kind of energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE), it is described In thermoplastic elastomer polymer molecule, each the end section A and interlude B of polymer molecule are gone back in its skeletal chain independently of one another Contain skeleton hydrogen bond group.
In embodiments of the present invention, a kind of energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE), it is described In thermoplastic elastomer polymer molecule, the side base of average every 100 interlude B backbone repeating units access hydrogen bonds group, Number in side chain or side base and side chain is 0.1 to 200.
In embodiments of the present invention, a kind of dynamic aggregation thing thermoplastic elastomer (TPE), wherein also containing other multiterminal sections- The thermoplastic elastomer polymer composition of the multi-segment structure of single interlude, other two-part thermoplastic elastomer polymers into Divide, other soft segments do not contain the thermoplastic elastomer polymer composition of any side hydrogen bond group, other thermoplastic polymer components At least one of.
In embodiments of the present invention, a kind of energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE), it is described Dynamic aggregation thing thermoplastic elastomer (TPE) is solid polymer, hydrogel, ionic liquid gel, oligomer swell gel, plasticizer Swell gel, organogel, foamed material.
In embodiments of the present invention, a kind of energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE), institute is formed State the component of thermoplastic elastomer (TPE) also include it is following any or appoint it is several can additive：Auxiliary agent, additive, filler.
In embodiments of the present invention, a kind of energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE), it is described The body protection, army and police's body protection, explosion-proof, airborne and air-drop that energy-absorbing method is applied to motion and daily life and work are anti- Shield, automobile collision preventing, electric equipment products defense of resistance to impact, sound insulation, damping.
Compared with prior art, the invention has the advantages that：
(1) in energy-absorbing method provided by the invention, the multi-segment structure based on multiterminal section-mono- interlude and end are built first Section to form crosslinking, interlude with the dynamic aggregation thing thermoplastic elastomer (TPE) of hydrogen bond formation crosslinking to crystallize/be separated.Based on centre Dynamic hydrogen bond crosslinks in section, elastomer can produce thickening effect when by physical impact, absorb impact energy；It is another Aspect, when impulsive force is more than the intensity of cross linking hydrogen bonds, cross linking hydrogen bonds forced breakage, produce the energy based on the dissociation of dynamic supermolecule Power is lost, and further produces energy-absorbing function.This multiple energy-absorbing mechanism is that prior art is lacked.In addition, after impact releases, Hydrogen bond crosslinks can regenerate again, and energy-absorbing efficiency, which is used for multiple times, to be also not easy to reduce, and this is also than existing energy-absorbing method and technology There is big advantage.
(2) in energy-absorbing method provided by the invention, the dynamic aggregation thing thermoplastic elastomer (TPE) utilizes side hydrogen bond group shape Multiple energies absorption and dissipation are carried out into interlude interchain linkage, and based on side hydrogen bond crosslinks.Because side hydrogen bond group is in side base And/or on side chain, the group of skeletal chain side is suspended from, the motion of its group and chain is freer, therefore dynamic is stronger, When by physical impact, response is faster；After impact releases, recover also faster, to be advantageous to high frequency and repeatedly protect.
(3) by rational MOLECULE DESIGN, its susceptibility to environment temperature is can adjust, with suitable for broader temperature model Enclose, same product can under different temperature environments using and be not easy performance difference occur, than in existing energy-absorbing method The material used has more advantage.
(4) the interlude interchain supermolecule hydrogen bond crosslinks utilized in the present invention can also provide the toughness of material and review one's lessons by oneself Renaturation is wider than the energy-absorbing material use occasion that is used in existing energy-absorbing method, the life-span is longer.
(5) the dynamic aggregation thing thermoplastic elastomers that energy-absorbing method provided by the invention is utilized have good controllable Property.By structure design and synthesis, it can prepare and gather with different structure, appearance features, the dynamic that performance is adjustable, widely used Compound；By controlling the species and number of hydrogen bond group on side base and/or side chain, it is strong and weak different that dynamic reversibility can be prepared Dynamic aggregation thing thermoplastic elastomer (TPE)；Pass through the ratio of both control terminal section physical crosslinking and interlude supermolecule hydrogen bond crosslinks compositions Example, can prepare the multifarious dynamic aggregation thing thermoplastic elastomer (TPE) such as different mechanical properties, different self-repairabilities.This is being passed It is difficult to inside the material as energy-absorbing of system.
Embodiment
The present invention relates to a kind of energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE), it is characterised in that provides one Kind dynamic aggregation thing thermoplastic elastomer (TPE), energy-absorbing protection is carried out using this thermoplastic elastic material as energy-absorbing material；Wherein institute The polymer molecule for the thermoplastic elastomer (TPE) stated has the multi-segment structure of multiterminal section-mono- interlude, it is each hold between section mutually and/ Or crystalline phase and/or the amorphous phase incompatible with interlude can be formed independently of one another, to form reversible point based on each end section Mutually it is physical crosslinking；Wherein interlude is unformed shape, also, at least part segment therein comprising at least one side base and/ Or the side hydrogen bond group on side chain, the side hydrogen bond group can form interchain supermolecule hydrogen bond dynamic crosslinking.
In the present invention, described energy-absorbing refers to for including but is not limited to hitting, vibrating, shaking, exploding, sound is made Into physical impact energy absorption, do not include absorption only to heat energy and/or electric energy.
Heretofore described " polymerization " be chain propagation process/effect, namely by intermolecular reaction/effect (including Covalent chemical is reacted and non-covalent/supermolecular mechanism) form straight chain, branched, ring, two-dimensional/three-dimensional cluster, three-dimensional infinite network knot The polymer of structure.Term " crosslinking " used in the present invention, refer to that intermolecular and/or intramolecular passes through covalent bond and/or non-common Valency/supramolecular chemistry connects the process to be formed with two-dimensional/three-dimensional cluster type and/or three-dimensional unlimited reticular pattern product.It is being crosslinked During, polymer chain is general first constantly to be increased in two-dimensional/three-dimensional direction, and it (can be two dimension or three to gradually form cluster Dimension), developing deeply is three-dimensional infinite network.Therefore, crosslinking can be considered as a kind of special shape of polymerization.In cross-linking process, just Reach degree of cross linking during a three-dimensional infinite network, referred to as gel point, also referred to as percolation threshold well.More than gel point (contain, Cross-linking products similarly hereinafter), it has three-dimensional infinite network structure, and cross-linked network forms an entirety and across whole polymer knot Structure；Cross-linking products below gel point, it is only lax interchain link structure, does not form three-dimensional infinite network knot Structure, a small amount of two-dimensional/three-dimensional network structure only is being locally lain in, and be not belonging to that across whole polymer architecture one can be formed Individual overall cross-linked network.Unless stated otherwise, the crosslinking in the present invention includes three-dimensional infinite network structure more than gel point With the two-dimensional/three-dimensional cluster structure below gel point.In embodiments of the present invention, what the split-phase for holding section to be formed was physical crosslinking The degree of cross linking can above and below its gel point, side hydrogen bond group formed supermolecule hydrogen bond crosslinks can also above and below its gel point, But the split-phase physical crosslinking that section is formed and the supermolecule hydrogen bond crosslinks sum that side hydrogen bond group is formed are held in total gel of polymer It is more than point；It is preferred that the degree of cross linking for the split-phase physical crosslinking that end section is formed is based on end section split-phase physics on its gel point, to obtain The three-dimensional infinite network of crosslinking, therefore in the case where hydrogen bond supermolecule crosslinking in side will be completely dissociated, dynamic aggregation thing can also be protected Hold balanced structure, namely dimensional stability.
Compound for the minimum unit of synthetic polymer is referred to as monomer.Wherein, the polymerization participated in by a kind of monomer claims For homopolymerization, product is that polymer chain forms single homopolymer；The polymerization participated in by various of monomer is referred to as multi-component copolymer, and product is The multi-component copolymer of polymer chain.
In the present invention, hold between section and interlude at least through a covalent linkage；Must be across between each end section Connect they interlude or interlude subchain section, and be not linked by covalently attached in addition to interlude.Form institute The multi-segment structure of multiterminal section-mono- interlude of thermoplastic elastomer polymer molecule is stated, can be represented with below general formula：
Wherein A is end section, and B is interlude, and n is the quantity for the end section A being connected between on section B, and it is more than or equal to 2.Respectively End section A and interlude B can be respectively seen as a block, but wherein again can be identical comprising one or more independently of one another Or different subchain section.The subchain section can be with the smaller segment on main chain or side chain, side chain, Segment on bifurcated chain；Each end section A can be described different including chemical composition is different, molecular weight is different, opens up with identical or different Flutter structure difference, steric configuration difference etc..In embodiments of the present invention, any one end section, interlude and its subchain section Homopolymerization segment or cosegment can be each independently.In the present invention, respectively end section A can form split-phase thing independently of one another Crosslinking is managed, form split-phase physical crosslinking with being mutually mixed, while each independently and split-phase can also be formed with being mutually mixed Physical crosslinking.The topological structure of each segment does not limit, but at least part segment in interlude B carries side base and/or side chain, And contain the side hydrogen bond group (interlude side hydrogen bond group) that can form hydrogen bond crosslinks at least partly described side base/side chain.Respectively Segment contains optional skeleton hydrogen bond group in its skeletal chain independently of one another, and also containing independently of one another in each end section A can The side hydrogen bond group (end section side hydrogen bond group) of choosing.The side hydrogen bond group can also with the optional skeleton hydrogen bond group it Between form hydrogen bond crosslinks, optional skeleton hydrogen bond group can also be separately formed hydrogen bond crosslinks；The part side hydrogen bond group Between chain inner ring independently can be formed with hydrogen bond, chain independently can also be formed with hydrogen bond between the skeleton hydrogen bond group of part Inner ring, or cooperatively form chain inner ring with the part side hydrogen bond group.But in embodiments of the present invention, though in the presence of Between interlude side hydrogen bond group and interlude skeleton hydrogen bond group and end section side hydrogen bond group and end section skeleton hydrogen bond group Hydrogen bond crosslinks, its content are also smaller.Therefore, the hydrogen bond crosslinks that interlude side hydrogen bond group is formed refer mainly to it in interlude interchain The interchain formed between interlude side hydrogen bond group in different polymer molecules and/or optional interlude skeleton hydrogen bond group Hydrogen bond crosslinks.If not special instruction, hydrogen bond crosslinks then refer in particular to interlude side hydrogen bond group and participate in the interchain hydrogen bond to be formed crosslinking.
In embodiments of the present invention, covalently attached between A, B segment may have chemical constitution and be different from institute's chain The linker of the segment connect, the molecular weight of the linker are not higher than 1000, and the preferably carbon number of linker is not higher than 20, more Preferably no greater than 10.Side base and/or side chain can be linked between its skeletal chain by hydrogen bond action.It is described in the present invention " physical crosslinking " refers between polymer segment or non-polymer segment and functional group by noncovalent interaction power the crosslinking that is formed, Including but not limited to crystallization, phase separation, supermolecular mechanism power etc., polymer is set to have the crosslinking after similar covalent cross-linking physical Matter, including but not limited to big apparent molecular weight, elasticity, dimensional stability, mechanical strength.Physical crosslinking of the present invention has In a heated condition or in good solvent, solution crosslinking can occur for physical crosslinking for invertibity, i.e. described physical crosslinking；Cooling down Under the conditions of or poor solvent in, physical crosslinking can re-form.
In the present invention, except the crystallization based on each end section and/or form the crosslinking that mutually forms incompatible with interlude and be Physical crosslinking is outer, and it is also a kind of physical crosslinking that the side hydrogen bond group in interlude, which participates in the supermolecule hydrogen bond crosslinks to be formed,.At this In invention, end section typically has the crystalline phase and/or and interlude of higher glass transition temperature and/or formation than interlude It is incompatible that mutually there is more preferable heat endurance and/or higher mechanical strength and/or lower molten compared to what interlude was formed Xie Xing, therefore, end section are properly termed as " hard section ", and interlude is properly termed as " soft segment ".In embodiments of the present invention, it is described The hard phase two phase structure that the soft phase of interlude composition and end section are formed in dynamic thermoplastic elastomer (TPE) generally be present；But by different ends The hard phase of difference that section is formed can also be incompatible, and the different soft phases formed by different interludes can also be incompatible, that is, thermoplastic There may be three or more than three incompatible phases in property elastomer.In embodiments of the present invention, interlude is formed The phase topological structure (phase morphology) that the hard phase that soft phase and end section are formed is formed does not limit, including but not limited to spherical, cylinder Shape, helical form, stratiform and combinations thereof form., can be between any phase, including different soft phases between different hard phases It is dispersed in an other phase, double/more continuous phases of IPN or contacting independently of each other can also be mutually formed with other Phase.In embodiments of the present invention, preferably soft phase is continuous phase, hard to be mutually dispersed in for discontinuous phase in soft phase, more preferably firmly Mutually it is dispersed in spherical in soft phase.The size of the discontinuous hard phase is usually more than 100 microns, and more preferably no more than 10 is micro- Rice, most preferably no greater than more preferably no more than 1 micron, 100 nanometers.The total content of the end section of dynamic aggregation thing thermoplastic elastomer (TPE) It is not particularly limited, preferably more than the 35% of the 50% of elastomer gross weight, more preferably less than elastomer gross weight.
Wherein, end section is any homopolymer segment for the split-phase physical crosslinking that can be formed in thermoplastic elastomer (TPE), copolymerization Thing segment, functional group and its any two or times several combinations, preferably homopolymer segment, copolymer segment and combinations thereof.End There is no particular limitation for the topological structure of section, can be linear chain structure, branched structure (including but not limited to starlike, dendroid, comb It is shape, hyperbranched), cyclic structure (including but not limited to monocyclic, polycyclic, bridged ring, nested rings), two-dimensional/three-dimensional cluster structure, gel The more than point particle of crosslinking and its two kinds or times several combinations, preferably linear chain structure.Each end section can with it is identical can not also Together, can be the same or different with each subchain section when different subchain sections be present in the section of one end, this difference includes but is not limited to Chemical composition is different, chain segment molecular weight is different, segment topological structure is different, steric configuration is different, solution crosslinking temperature is different and Any two in above-mentioned each situation appoint several combinations.
Wherein, interlude can be any appropriate homopolymer segment, copolymer segment and its any two or appoint it is several Combine, at least one side hydrogen bond group in side base and/or side chain is included at least part segment.Interlude polymer chain For skeleton to connect the polymer architecture of each end section, there is no particular limitation for the topological structure of interlude chain backbone, can be straight chain Structure, branched structure (including but not limited to starlike, dendroid, pectination, hyperbranched), cyclic structure (it is including but not limited to monocyclic, Polycyclic, bridged ring, nested rings), two-dimensional/three-dimensional cluster structure, the particle more than gel point being crosslinked and its two kinds or appoint several groups Close, preferably linear chain structure.
In the present invention, the side base and side chain are the structure that only one end is connected with skeleton being suspended on chain backbone. In the present invention, two or more side bases and/or side chain can be connected on same atom；Side base/side chain can be with Continuing to carry side base and/or side chain, the side base and/or side chain of side base/side chain can continue to carry side base and/or side chain, namely Side base and/or side chain can have multistage chain structure；The topological structure of side base and/or side chain does not limit, and can be straight-chain, Can also be that the special constructions such as starlike or ring-type, particularly side chain can be linear chain structure, branched structure (including but not limited to star It is shape, dendroid, pectination, hyperbranched), cyclic structure (including but not limited to monocyclic, polycyclic, bridged ring, nested rings), it is more than gel point The particle of crosslinking and its two kinds or several combination.In the present invention, at least part segment contains described side in interlude Base and/or side chain, and contain side hydrogen bond group at least part side base and/or side chain；End section in be also not excluded for containing side base with/ Or side chain, the side base and/or side chain for holding section can also optionally contain side hydrogen bond group.If not otherwise specified, in the present invention Polymer chain includes skeletal chain and any side chain.
In embodiments of the present invention, the soft phase of described dynamic aggregation thing thermoplastic elastomer (TPE) can have one or more Individual glass transition temperature, wherein at least one glass transition temperature are not higher than the lower limit of operating temperature range；Described It is hard mutually to have one or more glass transition temperatures, while can also have one or more solution split-phase physical crosslinking temperature Degree, the solution split-phase physical crosslinking temperature of any hard phase are higher than the upper limit of operating temperature range.When described dynamic aggregation thing contains When the auxiliary agents such as plasticizer or filler make at least one glass transition temperature of its soft phase be not higher than the lower limit of operating temperature range, The solution split-phase physical crosslinking temperature of hard phase is higher than the upper limit of operating temperature range simultaneously, and said composition falls within meaning of the invention " thermoplastic elastomer (TPE) ".Wherein, the glass transition temperature for being preferably entirely each component of soft phase is entirely below operating temperature The lower limit of scope, be advantageous to obtain the high elastomer of pliability.
In embodiments of the present invention, the solution crosslinking temperature and mechanical stability of hard mutually reversible split-phase physical crosslinking The solution crosslinking temperature of dynamic hydrogen bond crosslinks and mechanics are stable between hydrogen bond group respectively higher than in interlude side base and/or side chain Property.
In embodiments of the present invention, hold the chemical composition of section to have no particular limits, can be oxygen-containing, sulphur, nitrogen, The heteroatomic hydrocarbon segment such as silicon, fluorine, bromine, chlorine, iodine, boron or without heteroatomic hydrocarbon segment.As an example, dynamic aggregation thing The end section of thermoplastic elastomer polymer molecule can be based on following polymers, group or the segment for wherein appointing several combinations, But it is not limited only to this：Amorphous polymer with high glass-transition temperature, as polystyrene, polyvinyl pyridine, hydrogenation are poly- Bornylene, polyether-ether-ketone, poly- aromatic carbonate, polysulfones etc.；Polymer, polymer segment, group rich in hydrogen bond group, it is such as poly- Acid amides, poly- peptide, the segment rich in urea bond, the segment rich in amino-formate bond, urea groups pyrimidone etc.；Polymerization rich in crystalline phase Thing, such as crystallinity polyethylene, crystalline polypropylene, crystalline polyester, crystallinity polyethers, liquid crystal polymer, mesogenic groups；From Subtype polymer, such as polyacrylate, poly-methyl acrylate, polyacrylamide amine salt, poly styrene sulfonate.
In embodiments of the present invention, interlude polymer backbone can be based on carbochain polymer can also be based on The heteroatomic heterochain polymer such as oxygen-containing, sulphur, nitrogen, silicon, it can optionally contain skeleton hydrogen bond group.Contained skeleton hydrogen bond Group is not crystallized and not formed with interlude and is separated, and the number of teeth is preferably no greater than four teeth.Interlude can by synthesize macromolecule and/ Or natural polymer precursor continue reaction (including import end group and/or pendant active point, import side base and/or side chain, grafting, Chain extension etc.) obtain, it can also polymerize to obtain by monomer and/or prepolymer/oligomer, or be combined by both the above method Arrive.As an example, interlude polymer backbone can be the segment based on following polymers：Acrylic polymer, saturation Olefin polymer, ethylenic unsaturation hydrocarbon-based polymeric thing, halogen-containing olefin polymer, polypropylene nitrile polymer, polyethylene Alcohols polymer, silicone-based polymers, polyether-based polymers, polyester polymer, Biopolvester are birdsed of the same feather flock together the homopolymerization of compound etc. Thing or copolymer.
In embodiments of the present invention, the Drug delivery rate of the side base of interlude hydrogen bond group containing side and/or side chain is without spy Other limitation, the side base of average every 100 backbone repeating units access hydrogen bond group containing side and/or the number of side chain are preferably 0.1 to 200, more preferably 1 to 100, more preferably 10 to 60.In the present invention, hydrogen bond crosslinks can in any crosslinking degree, Preferably reach more than the gel infiltration threshold value of hydrogen bond crosslinks, i.e., can form three-dimensional infinite network only with hydrogen bond crosslinks.
In embodiments of the present invention, the interlude polymer chain can only contain hydrogen bond with side hydrogen bond group The hydrogen bond group of donor or the only hydrogen bond group containing hydrogen bond receptor or contain hydrogen bond donor and hydrogen simultaneously The hydrogen bond group of key acceptor.When all side hydrogen bond groups only contain hydrogen bond donor or hydrogen bond receptor, on interlude skeleton Must contain in corresponding hydrogen bond receptor or hydrogen-bond donor or system must have other additives to contain corresponding hydrogen bond receptor Or hydrogen-bond donor, to meet to form hydrogen bond crosslinks in interlude interchain.The hydrogen bond donor is exactly hydrogen atom (H), the hydrogen bond Acceptor is exactly the electronegative atom for receiving hydrogen atom, and including but not limited to oxygen atom (O), nitrogen-atoms (N), sulphur atom (S), fluorine are former Sub (F) etc..Such atom can exist in group with suitable valence state.In order to be effectively formed in interlude interchain based on side The hydrogen bond crosslinks of hydrogen bond, preferably side hydrogen bond group contain hydrogen bond donor and hydrogen bond receptor simultaneously, further preferably such as following formula (1) or (2) the side hydrogen bond group of the structure shown in：
Wherein, X is any of oxygen atom, sulphur atom, nitrogen-atoms, silicon atom, carbon atom, and Y is oxygen atom, sulphur atom Any of.
Wherein, a is the R being connected with X atoms1、R2Number.
When X is oxygen atom or sulphur atom, a 0, R1、R2It is not present.
When X is nitrogen-atoms, a 1, R1、R2In the presence of.
When X is silicon atom or carbon atom, a 2, R1、R2In the presence of.
Wherein, L is divalent linker.
L structure is not particularly limited, including but not limited to singly-bound, linear chain structure, the branched structure containing side base or ring-type Structure.Wherein, cyclic structure is not particularly limited, and may be selected from aliphatic ring, aromatic ring, sugared ring, condensed ring, preferred aliphat Ring.
L structure is preferably linear chain structure.
L can contain hetero atom, can also be free of hetero atom.
L carbon number is not particularly limited, preferably 1 to 20, more preferably 1 to 10.
L is selected from C1-20Alkylene, divalence C1-20Miscellaneous alkyl, the C of substitution1-20Alkylene, the divalence C of substitution1-20Miscellaneous alkyl and Its any two, the group that is formed of wantonly three kinds of combination.Wherein, atom or substituent is substituted to be not particularly limited, it is former selected from halogen Son, hydrocarbyl substituent, containing heteroatomic substituent.
L is preferably C1-20Open chain alkylidene, C1-20Open chain alkenylene, C1-20Cycloalkylidene, C1-20Sub- cycloalkenyl group, sub- virtue Base, sub- aryl, divalence C1-20Fat miscellaneous alkyl, divalence C1-20Fat miscellaneous thiazolinyl, divalent heteroaryl radical, divalence heteroaryl alkyl, the Asia of substitution Alkyl, the C of substitution1-20Open chain alkenylene, the C of substitution1-20Cycloalkylidene, the C of substitution1-20Sub- cycloalkenyl group, the Asia virtue of substitution Base, the sub- aryl of substitution, the divalence C of substitution1-20Fat miscellaneous alkyl, the divalence C of substitution1-20Fat miscellaneous thiazolinyl, the divalence heteroaryl of substitution The group that base, the divalence heteroaryl alkyl of substitution and its any a variety of combination are formed.
L is more preferably C1-10Open chain alkylidene, C1-10Open chain alkenylene, C3-10Cycloalkylidene, C1-10Sub- cycloalkenyl group, Asia Aryl, sub- aryl, divalence C1-10Fat miscellaneous alkyl, divalence C1-10Fat miscellaneous thiazolinyl, divalent heteroaryl radical, divalence heteroaryl alkyl, substitution Alkylidene, the C of substitution1-10Open chain alkenylene, the C of substitution1-10Cycloalkylidene, the C of substitution1-10Sub- cycloalkenyl group, the Asia virtue of substitution Base, the sub- aralkyl of substitution, the divalence C of substitution1-10Fat miscellaneous alkyl, the divalence C of substitution1-10Fat miscellaneous thiazolinyl, the divalence heteroaryl of substitution The group that base, the divalence heteroaryl alkyl of substitution and its any a variety of combination are formed.
Specifically, L is selected from singly-bound, methylene, ethylidene, propylidene, butylidene, pentylidene, hexylidene, heptamethylene, Asia Octyl group, nonylene, decylene, 1,2- phenylenes, benzal, C1-20Oxaalkylene, C1-20Thia alkylene, C1-20Azepine is sub- Alkyl, azepine aryl and its any two, wantonly three kinds combination formed group.Wherein, atom or substituent is substituted to be selected from halogen Plain atom, hydrocarbyl substituent, containing any in heteroatomic substituent.
L more preferably singly-bound, methylene, 1,2- ethylidene, 1,3- propylidene.
Heretofore described hetero atom is not particularly limited, including but not limited to oxygen atom, sulphur atom, nitrogen-atoms, phosphorus Atom, silicon atom, fluorine atom, chlorine atom, bromine atoms, iodine atom, boron atom etc..Wherein, heteroatomic quantity can be one, Can also be two or more.Hetero atom can be used as substitution atom to exist, can also be independently as divalent linker In the presence of citing such as-O- (epoxide or ehter bond) ,-S- (sulfenyl or thioether bond).
G1、G2For end group.
R1、R2、G1、G2Structure be not particularly limited, including but not limited to linear chain structure, the branched structure containing side base or Cyclic structure.Wherein, cyclic structure is not particularly limited, and may be selected from aliphatic ring, aromatic ring, sugared ring, preferably condensed ring, fat Fat race ring.
R1、R2、G1、G2Structure be preferably linear chain structure.
R1、R2、G1、G2Hetero atom can be contained, hetero atom can also be free of.
R1、R2、G1、G2Carbon number be not particularly limited, preferably 1~20, more preferably 1~10.
R1、R2、G1、G2It is each independently selected from hydrogen atom, halogen atom, C1-20Alkyl, C1-20Miscellaneous alkyl, the C of substitution1-20Hydrocarbon Base or substituted miscellaneous alkyl.Wherein, the substitution atom in R1 and R2 or substituent are not particularly limited, selected from halogen atom, hydrocarbon Base substituent, containing heteroatomic substituent.
R1、R2、G1、G2It is each independent to be more preferably hydrogen atom, halogen atom, C1-20Alkyl, C1-20Unsaturated aliphatic hydrocarbyl moiety, Aryl, aryl, C1-20Miscellaneous alkyl, C1-20Alkyl epoxide acyl group, C1-20Alkylthio acyl group and its any substituted shape Formula.
R1、R2、G1、G2It is each independent to be more preferably hydrogen atom, halogen atom, C1-20Alkyl, C1-20Alkenyl, aryl, aromatic hydrocarbons Base, C1-20Fat miscellaneous alkyl, heteroaryl, heteroaryl alkyl, C1-20Alkoxyacyl, aryloxy acyl group, C1-20Alkyl sulfenyl acyl group, Artyl sulfo acyl group and its any substituted form.
R1、R2、G1、G2It is each independent to be more preferably hydrogen atom, halogen atom, C1-20Alkyl, C1-20Alkenyl, aryl, aromatic hydrocarbons Base, C1-20Fat miscellaneous alkyl, heteroaryl, heteroaryl alkyl, C1-20Alkoxy carbonyl, aryloxycarbonyl, C1-20Alkyl sulfenyl carbonyl, Artyl sulfo carbonyl, C1-20Alkoxy carbonyl, aryloxy thiocarbonyl, C1-20Alkyl sulfenyl thiocarbonyl, artyl sulfo Thiocarbonyl and its any substituted form.
Specifically, R1、R2、G1、G2Be each independently selected from including but not limited to hydrogen atom, fluorine atom, chlorine atom, bromine atoms, Iodine atom, methyl, ethyl, n-propyl, isopropyl, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, ten Dialkyl group, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosane Base, pi-allyl, acrylic, vinyl, phenyl, aminomethyl phenyl, butyl phenyl, benzyl, methoxycarbonyl, ethoxy carbonyl, benzene Epoxide carbonyl, benzyloxycarbonyl, methyl mercapto carbonyl, ethylmercapto group carbonyl, thiophenyl carbonyl, benzylthio carbonyl, B aminocarbonyl, benzyl Amino carbonyl, methoxyl group thiocarbonyl, ethyoxyl thiocarbonyl, phenoxythiocarbonyl, benzyloxy thiocarbonyl, methyl mercapto sulphur For carbonyl, ethylmercapto group thiocarbonyl, phenylthiothiocarbonyl carbonyl, benzylthio thiocarbonyl, the C substituted1-20Alkyl, the C of substitution1-20 Alkenyl, the aryl of substitution, the aryl of substitution, the C of substitution1-20Fat miscellaneous alkyl, substitution heteroaryl, substitution heteroaryl alkyl, Substituted C1-20Alkoxy carbonyl, the aryloxycarbonyl of substitution, the C of substitution1-20Alkyl sulfenyl carbonyl, the artyl sulfo of substitution Carbonyl, the C of substitution1-20Alkoxy carbonyl, the aryloxy thiocarbonyl of substitution, the C of substitution1-20Alkyl alkylthio carbonyl Base, the artyl sulfo thiocarbonyl of substitution.Wherein, butyl includes but is not limited to normal-butyl, the tert-butyl group.Octyl group includes but is not limited to N-octyl, 2- ethylhexyls.Wherein, atom or substituent is substituted to be selected from halogen atom, hydrocarbyl substituent, containing heteroatomic substitution Base.
R1、R2、G1、G2Each it is independent be more preferably hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, The tert-butyl group, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, 15 Alkyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, pi-allyl, benzyl, trityl, phenyl, Benzyl, methyl-benzyl, nitrobenzyl, tert. butyl-sulphenyl, benzyl sulfenyl, 2- pyridinylthios, acetyl group, benzoyl, 2- pyrroles Piperidinyl carbonyl, methoxycarbonyl, ethoxy carbonyl, t-butyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, methyl mercapto carbonyl Base, ethylmercapto group carbonyl, tert. butyl-sulphenyl carbonyl, thiophenyl carbonyl, benzylthio carbonyl, ethylenebis dithiocarbamate carbonyl, the thio carbonyl of phenyl first Base, methoxyl group thiocarbonyl, ethyoxyl thiocarbonyl, tert-butyl group epoxide thiocarbonyl, phenoxythiocarbonyl, benzyloxy are thio Carbonyl, methyl mercapto thiocarbonyl, ethylmercapto group thiocarbonyl, tert. butyl-sulphenyl thiocarbonyl, phenylthiothiocarbonyl carbonyl, benzylthio sulphur For carbonyl, C1-10Halohydrocarbyl, trifluoroacetyl group, halogenophenyl, halogeno-benzyl, nitrobenzophenone, nitrobenzyl and its any Substituted form.Wherein, atom or substituent is substituted to be preferably fluorine atom, alkoxy, nitro.
R1、R2、G1、G2Each independent more preferably hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, the tert-butyl group, Benzyl, trityl, phenyl, benzyl, methyl-benzyl, tert. butyl-sulphenyl, benzyl sulfenyl, 2- pyridinylthios, 2- pyridine radicals carbonyls Base, t-butyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, tert-butyl group epoxide thiocarbonyl, phenoxythiocarbonyl, benzyl Epoxide thiocarbonyl, tert. butyl-sulphenyl thiocarbonyl, phenylthiothiocarbonyl carbonyl, benzylthio thiocarbonyl, trifluoroacetyl group.
R1、R2、G1、G2It is each independent to be more preferably hydrogen atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, tertiary fourth Base, benzyl, trityl, phenyl, benzyl, methyl-benzyl, tert. butyl-sulphenyl, benzyl sulfenyl, 2- pyridinylthios.
R1、R2、G1、G2Each independent is most preferably hydrogen atom, methyl, ethyl, n-propyl, normal-butyl.
Wherein, L can be with R1、R2、G1、G2In be connected to bridge between any group or be not attached into bridge, R1Can be with G1Phase It is linked to be bridge or is not attached into bridge, R2Can be with G2It is connected to bridge or is not attached into bridge.
As an example, can enumerate such as downside hydrogen bond group, but the present invention is not limited only to this.
Wherein, m, n, x are the quantity of recurring group, can be fixed value or average value.M, n spans are 0 With the integer more than or equal to 1；X spans are the integer more than or equal to 1.
In embodiments of the present invention, it can be any to hold the optional skeleton hydrogen bond group contained in section and interlude Suitable hydrogen bond group.The skeleton hydrogen bond group can be the hydrogen bond group that can form optional tooth number.Hydrogen bond on skeleton Group can be the group for having hydrogen bond receptor and hydrogen bond donor simultaneously or the base only containing hydrogen bond receptor or hydrogen bond donor Group, can also be that a part of hydrogen bond group contains hydrogen bond donor another part hydrogen bond group and contains hydrogen bond receptor.But interlude institute The skeleton hydrogen bond group contained participates in the hydrogen bond unit to be formed and does not crystallize and do not form phase separation with soft phase, and the number of teeth is preferably no greater than four Tooth.
As an example, interlude skeleton hydrogen bond group as described below can be enumerated, but the present invention is not limited only to this.
As an example, end section skeleton hydrogen bond group as described below can be enumerated, but the present invention is not limited only to this.
In embodiments of the present invention, hydrogen bond crosslinks are except by described in polymer interlude side base and/or side chain Between the hydrogen bond group of side and with interlude polymer backbone and/or end section optionally between existing skeleton hydrogen bond group Formed outside hydrogen bond crosslinks, the side hydrogen bond group and optional skeleton hydrogen bond of the side base and/or side chain can also be passed through Group forms hydrogen bond crosslinks with the hydrogen bond group in the other components introduced as additive.It is such to participate in forming hydrogen bond friendship The other components of connection include but is not limited to small molecule, polymer, inorganic material, and hydrogen bond group contained therein can arbitrarily may be used To form the group of hydrogen bond with the side hydrogen bond group and skeleton hydrogen bond.Hydrogen bond can also be formed between such other components, but It is preferably formed as being no more than four tooth hydrogen bonds.Such material can be selected from line style, ring-type, branched, cluster polymer and covalent cross-linking Polymer beads, surface be modified organic and inorganic particle, fiber.
In embodiments of the present invention, the dynamic aggregation thing thermoplastic elastomer (TPE), can contain described at least one Multiterminal section-mono- interlude multi-segment structure component of polymer, can also be at least one described multiterminal section-mono- interlude Multi-segment structure component of polymer and other thermoplastic polymer/thermoplastic elastomer polymers the polymer to be formed be blended close Golden elastomer.Wherein, interpenetrating net polymer structure makes its performance be substantially better than its group due to the synergy between network component The single network polymer divided, the mechanical properties such as the toughness higher than single network are produced, therefore be preferably mixed to form with mutual Through the elastomer of the interpenetrating net polymer structure of entanglement.Wherein, matter is preferably comprised in above-mentioned polymer alloy elastomer The multi-segment structure component of polymer of described multiterminal section-mono- interlude of the amount not less than 30%, further preferably quality be not low In the multi-segment structure component of polymer of 50% described multiterminal section-mono- interlude.
In embodiment of the present invention, described dynamic aggregation thing thermoplastic elastomers have the more of multiterminal section-mono- interlude The preparation of the polymer molecule of segmentation structure, can be any appropriate means in its technological principle.Typically there is two ways, from Monomer sets out, and carries out interlude, end section or the polymerization for holding section, interlude successively from inside to outside or from outside to inside；Or first distinguish End section, interlude or the two-part copolymer of end group functional are synthesized, then carries out the intersegmental end group reaction of chain, or pass through other Small molecule realizes coupling or copolymerization.The preparation of the polymer molecule of multi-segment structure with multiterminal section-mono- interlude can be with The combination based on above two mode, for example, end section or interlude first be prepared into macromole evocating agent, trigger interlude and The polymerization of section is held, is reacted further according to the end group for needing progress chain intersegmental；And for example, interlude-end section two-part copolymer is first generated, The multistage with multiterminal section-mono- interlude by the intermediate stage coupling of two or more two-part molecules into the present invention again The polymer molecule of formula structure.The generation or introducing of side hydrogen bond group, can soft end section be connected before, afterwards or during Carry out.Must contain when generating polymer chain cytoskeletal reorganization into the side hydrogen bond group in the ban, on polymer interlude to introduce The active site of the side hydrogen bond group, include but is not limited to amino, secondary amino group, hydroxyl, carboxyl, aldehyde radical, sulfydryl, different as example Cyanic acid ester group, epoxy radicals, ester group, halogen atom, acid halide group, acid anhydrides, carbon-carbon double bond, maleimide, triple carbon-carbon bonds, nitrine Base, itrile group, hydrazine, tetrazine, succinimide ester.
Described polymerization type of prepolymer selected by includes but is not limited to polycondensation, addition polymerization, coordination polymerization and opened Cyclopolymerization, addition polymerization include but is not limited to radical polymerization, active free radical polymerization, anionic polymerisation, cationic polymerization etc..Its In, polymerization process can carry out in a solvent or solvent-free polymerisation in bulk.
The initiation of above-mentioned partial polymerization process needs to use can cause what monomer molecule activated in polymerization process Initiator.Different types of initiator can be selected in embodiment of the present invention as needed.For example, from monofunctional initiators just In the end section or the interlude of both-end exclusive-OR function that prepare single-ended functionalization；And for example, from bifunctional initiator or multifunctional draw The interlude for preparing each end congenerous or each end exclusive-OR function is easy in hair agent；For another example, using the end section or distant of single-ended functionalization The macromole evocating agent that pawl polymer interlude is prepared can continue to trigger the polymerization of the monomer of end section or interlude, obtain embedding Section copolymer.Wherein, the polymer segment for preparing single, double, more end-functionalizations carries active group by reasonable selection itself Initiator, reasonable selection chain-transferring agent, reasonable employment can with initiator residue react functional reagent realize.
In embodiments of the present invention, partially polymerized reaction also needs to use catalyst, changes in polymerization process Become reaction path, reduce reaction activity to accelerate the reaction rate of reactant during the course of the reaction.In partial polymerization process also Need to use the auxiliary agents such as dispersant, emulsifying agent.For example, dispersant is needed to use in suspension polymerization, in emulsion polymerization mistake Emulsifying agent is needed to use in journey.Described dispersant, solid flocculation group is enabled in mixed with polymers liquid to be separated into tiny Particle and be suspended in liquid, it is homogeneous to disperse those and be poorly soluble solid and liquid particles in liquid, while can also prevent The sedimentation and cohesion of grain, form stable suspension.Described emulsifying agent, it can improve each in the mixed with polymers liquid comprising auxiliary agent Kind forms the surface tension between phase, is allowed to form uniform and stable dispersion or emulsion, is preferred for progress emulsion and gathers Close.
Specifically, as an example, the available polymerization of the present invention includes but is not limited to：Phenylethylene, (methyl) third The thermal initiation general radical polymerization of olefin(e) acid esters monomer, phenylethylene, the light-initiated freedom of (methyl) acrylic ester monomer Base polymerize, the Iniferter radical polymerization of VCM, phenylethylene, (methyl) acrylic ester monomer ATRP (ATRP), phenylethylene, (methyl) esters of acrylic acid, the reversible addition-fracture of acrylonitrile monomer Transferring free-radical polymerization (RAFT), nitroxide-mediated stable free-radical polymerization (NMP), ethene, propylene coordination polymerization, styrene monomer Anionic polymerisation, lactone ring opening polymerization, lactams ring-opening polymerisation, epoxy addition polymerization, cycloolefine ring-opening metathesis polymerization, binary acid Polycondensation between dihydric alcohol, the polycondensation between binary acid and diamine, the click-reaction between binary mercaptan and binary alkene/alkynes Polymerization, click-reaction polymerization, polyurethane/polyurea reaction between binary nitrine and binary alkynes etc..
Initiator, catalyst, other auxiliary agents and reaction condition needed for above-mentioned polymerization and polymerization process etc. are all Be it is open known to routine techniques (such as Pan Zuren is edited,《Polymer chemistry (enhanced edition)》), those skilled in that art can be with Reasonable selection and combination are carried out as needed.
In embodiments of the present invention, the generation or introducing of side hydrogen bond group can use any appropriate reaction, including But it is not limited only to Types Below：The reaction of isocyanates and amino, hydroxyl, sulfydryl, carboxyl, free radical acrylate reaction are double Key radical reaction, double bond cyclization, the reaction of epoxy and amino, hydroxyl, sulfydryl, nitrine-alkynes click-reaction, sulfydryl-bis- Key/alkynes click-reaction, the reaction of urea-amine, amidation process, tetrazine-ENB reaction, active ester and amino, hydroxyl, mercapto The reaction of base, silicone hydroxyl condensation reaction；The reaction of preferred isocyanate and amino, hydroxyl, sulfydryl, the reaction of urea-amine, activity The reaction of ester and amino, hydroxyl, sulfydryl；The more preferably reaction of isocyanates and amino, hydroxyl, sulfydryl.The generation of hydrogen bond group Or reaction type, the reaction means that can have one or more are introduced, the supermolecule crosslinking of side base and/or side chain can have one Or more type, structure.
In embodiments of the present invention, the chemical reaction connection soft segment hard section between segment active end group can be utilized, it is described Chemical reaction include but are not limited to Types Below：The reaction of isocyanates and amino, hydroxyl, sulfydryl, carboxyl, epoxy and ammonia The reaction of base, hydroxyl, sulfydryl, phenolic aldehyde, nitrine-alkynes click-reaction, sulfydryl-double bond/alkynes click-reaction, the reaction of urea-amine, acyl Aminating reaction, esterification, tetrazine-ENB reaction, active ester and reaction of amino, hydroxyl, sulfydryl, silicone hydroxyl condensation are anti- Should.
It polymerize below for the multi-segment structure of dynamic aggregation thing thermoplastic elastomer (TPE) multiterminal section-mono- interlude of the present invention The embodiment of the part preparation method of thing molecule is illustrated.
In embodiments of the present invention, the preparation method of the multi-segment structure polymer of a kind of multiterminal section-mono- interlude Contain the multi-segment structure polymer of multiterminal section-mono- interlude of active site, active site using existing or commercially available interlude With side base of the single functionality reagent reacting generation containing required side hydrogen bond group containing required side hydrogen bond group and/or side Chain.As an example but be not limited to it is following lifted, such as polystyrene-polybutadiene-polystyrene triblock copolymer (SBS) heat Double bond in thermoplastic elastic in polybutadiene interlude containing side hydrogen bond group with (being designated as R in following structural formulaH, RHMeet logical The structure of formula) one end for sulfydryl reagent occur sulfydryl-alkene reaction formed the present invention multiterminal section-mono- interlude multisection type knot Structure polymer.Wherein, the R that side base carriesHGroup previously generates before.
In embodiments of the present invention, the preparation side of the multi-segment structure polymer of another multiterminal section-mono- interlude Method is in polymerizeing end section monomer and interlude monomer successively from outside to inside using bifunctional initiator or polymerizeing successively from inside to outside Between section monomer and end section monomer, wherein interlude monomer includes in side base with required hydrogen bond group RHInterlude monomer, It can include or not include without required side hydrogen bond group RHInterlude monomer.As an example but be not limited to it is following lifted, For example side base is first triggered to carry R using Multifunctional initiator pentaerythriteHThe caprolactone class monomer of group and caprolactone combined polymerization More arm type interludes are generated, then trigger levorotatory lactide polymerization to generate each end section, form the present invention has multiterminal section-mono- middle The polymer molecule of the multi-segment structure of section.Wherein, the R that required initiator and side base carryHThe monomer of group is before polymerization Previously generate.
In embodiments of the present invention, the preparation side of the multi-segment structure polymer of another multiterminal section-mono- interlude Method triggers the polymerization of end section by the use of interlude as macromole evocating agent.As an example but be not limited to it is following lifted, such as, both ends end Base is that NCO side base contains hydrogen bond group RHInterlude based on polybutadiene trigger the ring-opening polymerisation of caprolactam Form the multi-segment structure polymer of multiterminal section-mono- interlude of the present invention.Wherein, side base carries RHThe interlude of group divides greatly The polymerization generation in advance before the polymerization of sub- initiator.
In embodiments of the present invention, the preparation side of the multi-segment structure polymer of another multiterminal section-mono- interlude Method is first to synthesize the end section that both ends or multiterminal interlude and one end with active end group carry active end group, wherein interlude side Base and/or side chain carry required side hydrogen bond group, then each segment is coupled.As an example but be not limited to it is following lifted, such as, Both ends carboxy blocking side base contains required hydrogen bond group RHReacted based on polyester interlude and one end for the end section of nylon 6 of amino Form the multi-segment structure polymer molecule of multiterminal section-mono- interlude of the present invention.Wherein, the end section of end group functional and centre Section polymerization generation in advance before coupling.
In embodiments of the present invention, the preparation side of the multi-segment structure polymer of another multiterminal section-mono- interlude Method is first synthetic mesophase section-end section two-part copolymer, and wherein interlude side base and/or side chain carries required hydrogen bond group And the active group that end group carries, then two segments are coupled.As an example but be not limited to it is following lifted, such as, end group be carboxyl, End section is polysulfones, interlude is based on polyethers, interlude side base contains required RHThe two-part copolymer of group, it is hydroxyl with end group Base, end section are PLA, interlude is based on polyester, interlude side base contains required RHThe two-part copolymer reaction of group, shape Into the multisection type polymer of multiterminal section-mono- interlude of the present invention.Wherein, required two-part copolymer and side base carry RHGroup previously generates before coupling.
In embodiments of the present invention, the preparation side of the multi-segment structure polymer of another multiterminal section-mono- interlude Method is first to prepare the end section that one end is the functional group that may participate in interlude polymerization, then by polymerizeing to form institute with interlude monomer The structure stated.With required hydrogen bond group R in the side base of wherein all or part of interlude monomerH.As an example but it is not limited to It is following to be lifted, such as, first prepare in the polystyrene for containing acrylate group in one end and side base containing required hydrogen bond group RH Acrylic ester monomer, then with without side hydrogen bond group n-butyl acrylate carry out combined polymerization, formed the present invention have The polymer molecule of the multi-segment structure of multiterminal section-mono- interlude.
In addition, the present invention also has other preparation means, and those skilled in the art can also be according to the present invention's Understand, select suitable preparation means, reach preferable purpose.
A kind of dynamic aggregation thing thermoplastic elastomer (TPE) provided by the present invention, multiterminal section-mono- interlude is had according to it The class of main skeleton segment contained on interlude prepolymer or interlude polymer backbone in the polymer of multi-segment structure Type is divided, and can be based on acrylic polymer, ethylenic unsaturation hydrocarbon-based polymeric thing, polyether-based polymers, polyesters Birds of the same feather flock together compound, silicone-based polymers, polyvinyl alcohol based polymer, saturation of olefins of polymer, Biopolvester is birdsed of the same feather flock together compound, halogen The olefin polymer of element, the polymer of polypropylene nitrile polymer etc..Interlude based on above-mentioned polymer polymerize, is middle Duan Duanji introducing and with holding the method for coupling of section to use foregoing usual way.Hereinafter, will be according to interlude The type of contained principal polymeric or prepolymer drawing to the side base of hydrogen bonds group in the present invention and/or side chain in backbone segments Enter to carry out classification explanation.
A kind of preferable interlude of the invention can be copolymerized with acrylic polymer and with acrylic ester monomer Polymer be main backbone segments.As an example, this kind of monomer, which is selected from, includes but is not limited to (methyl) acrylic acid, (methyl) Acrylate, acrylonitrile, vinyl chloride, vinylidene chloride, styrene etc..The preferred preparation side of interlude based on this kind of polymer Method is by the monomer or oligomer of the hydrogen bond group containing side and polymer backbone monomer or oligomer while the preparation method of copolymerization.Its In, it can be used containing side hydrogen bond group monomer by the acrylate containing active site and/or methacrylate-based monomer foregoing Preparation method prepared.As an example, the monomer of the acrylate containing active site or methacrylate-based monomer can be with Include but be not limited to 1,3- propanediol monoacrylates, (methyl) acrylic acid isocyano group ethyl ester, methacrylic acid 2- amino second Base ester hydrochloride, (methyl) allyl acrylate, methacrylic acid methyl allyl ester, GMA, (first Base) acryloyl chloride, 2- methyl -2- acrylic acid -2- sulphur ethyl esters etc..
The another kind of preferable interlude of the present invention is with the unsaturated olefin containing unsaturated carbon-carbon double bond on main chain or side base Birds of the same feather flock together the backbone segments wanted based on compound, as an example, this compound of birdsing of the same feather flock together includes but is not limited to butadiene rubber, 1,2- butadiene Rubber, isoprene rubber, polynorbornene, neoprene, butadiene-styrene rubber, nitrile rubber, polychlorobutadiene, brominated polybutadiene, Poly- limonene carbonic ester (PLimC) rubber, unsaturated polyester (UP), silicon rubber containing alkene ethyl etc..The insatiable hunger being related in the present invention It can according to a conventional method polymerize with olefin polymer precursor, also can directly select commercially available product of the both ends already provided with active site.Base The side base of hydrogen bonds group and/or the importing of side chain in the interlude of this kind of polymer, preferably by be imported into side base and/or The carbon carbon group and polymer backbone that can be chemically reacted with carbon-carbon double bond contained in side chain simultaneously on or in side base Double bond reaction is realized.Wherein, the preferably addition reaction of sulfydryl-double bond fast click-reaction, carbon-carbon double bond.Based on this kind of polymer The side base of the hydrogen bonds group of interlude and/or side chain import can also by the monomer or oligomer of the hydrogen bond group containing side with The preparation method that polymer backbone monomer or oligomer are copolymerized simultaneously is realized.
The another kind of preferable interlude of the present invention is using polyester or polyethers as main backbone segments.As an example, this is a kind of Polymer include but is not limited to polyglycol ether, polypropylene glycol ether, polybutadiene alcohol ether, polylactide, PGA, gather oneself in One or more in the polyester such as ester, fatty poly-ester carbonate, Biopolvester, liquid crystal polyester, polyethers.The side base of hydrogen bonds group And/or the importing of side chain preferably passes through the monomer copolymerization with the hydrogen bond group containing side.
The another kind of preferable interlude of the present invention is using the polyester containing active tertiary hydrogen atoms as main backbone segments.As Citing, this compound of birdsing of the same feather flock together include but is not limited to poly butyric ester, poly- hydroxyl valerate etc..The side base of hydrogen bonds group and/ Or the importing of side chain preferably passes through the reaction between active tertiary hydrogen atoms.
The another kind of preferable interlude of the present invention is with polysiloxane based polymer (organosilicon) for main backbone segments.Institute The polysiloxanes stated using dimethyl siloxane as main repeat unit, meanwhile, the substituent being connected with silicon, except methyl, can contain Can be free of has, and as an example, but is not limited to hydrogen, ethyl, phenyl, trifluoro propyl, cyanoethyl, vinyl and/or side base end With hydroxyl, amino, sulfydryl, epoxy radicals group.Polysiloxanes segment can be prepared by usual way, can also be selected commercially available Functionalization polysiloxanes or oligosiloxane, it is preferably simultaneously living in active side base and active end group and side base and end group The property diverse polysiloxanes of point or oligosiloxane.As an example, described active group includes but is not limited to hydroxyl, ammonia Base, sulfydryl, epoxy radicals, alkenyl, silicon hydrogen atom or other may participate in the atom or group of chemical reaction.
The another kind of preferable interlude of the present invention is to obtain the polymer of pendant hydroxyl group and its altogether containing pendant hydroxyl group or easy alcoholysis Polymers is main backbone segments.As an example, this compound of birdsing of the same feather flock together includes but is not limited to polyvinyl alcohol, fibre with pendant hydroxyl group Element, starch etc. are tieed up, easy alcoholysis generates side hydroxyl for polyvinyl acetate of polyvinyl alcohol etc., in addition to epoxy radicals after polycondensation reaction A kind of polymer of base, and other generate a kind of polymer of pendant hydroxyl group after side base is reacted.What is be related in the present invention contains side The polymer of hydroxyl can polymerize according to a conventional method, and commercially available product also can be selected.The side base of hydrogen bonds group and/or the importing of side chain are excellent Choosing utilizes the reaction of the group such as hydroxyl and NCO, carboxyl, aldehyde radical, alkyl halide, acid anhydrides, sulfuric ester, sulphonic acid ester, more preferably Using the reaction of hydroxyl and NCO, to complete the generation of side hydrogen bond group and the importing of side chain simultaneously.
The another kind of preferable interlude of the present invention is using saturation of olefins polymer and its halides as main backbone segments.Make For citing, this compound of birdsing of the same feather flock together includes but is not limited to polyethylene, polypropylene, polyisobutene, polyvinyl chloride, Vingon, chlorine Change polyethylene, polytrifluorochloroethylene, polyvinyl fluoride, Kynoar, polytetrafluoroethylene (PTFE) and its copolymer etc..It is related in the present invention The interlude based on saturation of olefins polymer and its halogenated polymer, the side base of its hydrogen bonds group and/or the introducing of side chain Copolymerization is participated in preferably by the vinyl monomer of the hydrogen bond group containing side to realize.When the saturation of olefins and its halogenated polymer that are related to Monomer can with acrylic ester monomer, vinyl alcohol or it is vinyl acetate copolymerized when, preferably by above-mentioned embodiment poly- The introducing of side base and/or side chain is realized during conjunction.Be related in the present invention using saturation of olefins and its halogenated polymer as precursor The preferable preparation method of another kind of interlude be to trigger the graft polymerization of side chain, wherein involved side using radical initiator The monomer of chain polymerization grafting is the monomer of the hydrogen bond group containing side, or the graft polymerization for having several monomers to participate in side chain, wherein having one Kind monomer is the monomer of the hydrogen bond group containing side.Be related in the present invention using halogenated polymer as the another excellent of the interlude of precursor The preparation method of choosing is to be broken chain by single electron transfer active free radical polymerization, Nitroxide radical polymerization, reversible addition Transfer method prepares the polymer segment that required end group carries active site, the side base of hydrogen bonds group and/or the importing profit of side chain It is achieved with the reaction between halo atom and other groups, as an example, this kind of reaction includes but is not limited in polyvinyl chloride Chlorine atom and thiophenol derivatives between reaction, and the reaction between chlorine atom in polyvinyl chloride and azide.
The backbone segments that the another kind of preferable interlude of the present invention is wanted based on polyacrylonitrile based polyalcohol.It is based in preparation During the interlude of this compound of birdsing of the same feather flock together, one kind of the side base of hydrogen bonds group and/or the importing of side chain it is preferable that by with Esters of acrylic acid, vinyl alcohol, the vinyl acetate esters monomer copolymerization of the foregoing hydrogen bond group containing side.The side base of hydrogen bonds group And/or another preferred embodiment that side chain imports is to utilize itrile group-nitrine click-reaction.The side base of hydrogen bonds group And/or another preferred embodiment that side chain imports is that first itrile group is converted into or is partially converted into by catalytic hydrogenation Amino, then leading for side base and/or side chain is completed while side hydrogen bond group is generated by the reaction of amino and NCO Enter.
In embodiments of the present invention, can also contain and described multiterminal in dynamic aggregation thing thermoplastic elastomer (TPE) The polymer molecule of the multi-segment structure of section-mono- interlude is mutually perhaps incompatible to be different from described multiterminal section-mono- interlude Multi-segment structure polymer molecule other any appropriate multiterminal sections-mono- interlude multi-segment structure thermoplastic elastomehc Elastomer polymer composition, other any appropriate two-part thermoplastic elastomer polymer composition, other any appropriate soft segments Thermoplastic elastomer polymer composition and other thermoplastic polymer components of any side hydrogen bond group are not contained.Described its His thermoplastic polymer components can contain dynamic hydrogen bond action or not contain hydrogen bond action.Other described thermoplastic elastomer (TPE)s gather Polymer component can form compatible cross-linked network with the polymer molecule of the multi-segment structure of described multiterminal section-mono- interlude Network, incompatible mutual blending/IPN/Semi-IPN isostructural cross-linked network can also be formed；Other thermoplasticity polymerization Thing composition mutually perhaps can incompatibly be dispersed in the polymer molecule shape of the multi-segment structure of described multiterminal section-mono- interlude Into cross-linked network in.
In embodiments of the present invention, can be introduced in dynamic aggregation thing thermoplastic elastomer (TPE) with it is soft mutually compatible but with Hard mutually incompatible solvent prepares dynamic aggregation thing gel.The solvent can include but is not limited to water, organic solvent, ionic liquid Body, oligomer, plasticizer.Wherein, oligomer can also be considered as plasticizer.Hydrogel is turned into using water-swellable system；It is organic The system of solvent swell is referred to as organogel, and the gel of ionic liquid, oligomer and plasticising solvent swell is also referred to as organogel.
A kind of dynamic aggregation thing gel provided by the present invention, preferred ion liquid gel, oligomer swell gel and increasing Mould solvent swell gel, more preferably plasticizer swell gel.
A kind of preparation method of dynamic aggregation thing ionic liquid gel of the present invention, comprises the following steps：Dynamic will be prepared Raw material and the ionic liquid blending of polymer, the mass fraction for making to prepare the raw material of dynamic aggregation thing is 0.5~70%, passes through institute Appropriate means are stated to be polymerize, be coupled or other kinds of chemical reaction, after reaction terminates, that is, be made a kind of dynamic aggregation thing from Sub- liquid gel.The preparation method of another dynamic aggregation thing ionic liquid gel of the present invention, comprises the following steps：Will dynamic Polymer is swollen in the solvent containing ionic liquid, and the mass fraction for making dynamic aggregation thing is 0.5~70%, is fully removed after swelling Solvent, that is, a kind of dynamic aggregation thing ionic liquid gel is made.The upper ionic liquid is typically by organic cation and inorganic the moon Ion forms, and as an example, cation is selected from including but not limited to alkyl quaternary ammonium ion, alkyl quaternary and seen ion, 1,3- dialkyl group Substituted imidazol ion, the alkyl-substituted pyridinium ions of N- etc.；Anion, which is selected from, to be included but is not limited to for halide ion, tetrafluoro boron Acid ion, hexafluorophosphoricacid acid ions, also there is CF3SO3 -、(CF3SO2)2N-、C3F7COO-、C4F9SO3 -、CF3COO-、(CF3SO2)3C-、(C2F5SO2)3C-、(C2F5SO2)2N-、SbF6 -、AsF6 -Deng.In ionic liquid used in the present invention, the preferred miaow of cation Azoles cation, the preferred hexafluorophosphoricacid acid ions of anion and tetrafluoroborate ion.Prepare the dynamic aggregation thing heat of ionic liquid Thermoplastic elastic is preferably that polymer interlude skeleton is to substitute poly- saturation alkene based on the polymer containing acrylic ester monomer, fluorine The polymer segment of hydrocarbon, polymer containing acrylonitrile.
A kind of gel process for preparing of dynamic aggregation thing oligomer swelling of the present invention, comprises the following steps：It is dynamic by preparing Raw material and the oligomer blending of state polymer, the mass fraction for making to prepare the raw material of dynamic aggregation thing is 0.5~70%, passes through institute State appropriate means to be polymerize, be coupled or other kinds of chemical reaction, after reaction terminates, that is, it is neat that a kind of dynamic aggregation thing is made The gel of polymers swelling.The gel process for preparing of another dynamic aggregation thing oligomer swelling of the present invention, comprises the following steps： Dynamic aggregation thing is swollen in the solvent containing oligomer, the mass fraction for making dynamic aggregation thing is 0.5~70%, fully molten Solvent is removed after swollen, that is, a kind of gel of dynamic aggregation thing oligomer swelling is made.The upper oligomer includes but are not limited to gather Ethylene glycol oligomer, polyvinyl alcohol oligomer, polyvinyl acetate ester oligomer, polyacrylic acid N-butyl oligomer, atoleine Deng.
A kind of gel process for preparing of dynamic aggregation thing plasticising solvent swell of the present invention, comprises the following steps：It is dynamic by preparing Raw material and the plasticizer blending of state polymer, the mass fraction for making to prepare the raw material of dynamic aggregation thing is 0.5~70%, passes through institute State appropriate means to be polymerize, be coupled or other kinds of chemical reaction, after reaction terminates, that is, a kind of dynamic aggregation thing is made and increases Mould the gel of solvent swell.The gel process for preparing of another dynamic aggregation thing plasticising solvent swell of the present invention, comprises the following steps： Dynamic aggregation thing is swollen in the solvent containing plasticizer, the mass fraction for making dynamic aggregation thing is 0.5~70%, fully molten Solvent is removed after swollen, that is, a kind of gel of dynamic aggregation thing plasticising solvent swell is made.The upper plasticizer, which is selected from, to be included but is not limited to It is any below or appoint it is several：Phthalates：Dibutyl phthalate, dioctyl phthalate, phthalic acid Di-isooctyl, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, phthalic acid fourth Double (13) ester of benzyl ester, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid, to benzene two Formic acid two (2- ethyls) own ester；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyls) own ester；Fatty acid ester, Such as the own ester of adipic acid two (2- ethyls), decanedioic acid two (2- ethyls) own ester；Epoxy compound species, such as epoxy glycerite esters, epoxy Fatty-acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, the own ester of epoxystearic acid (2- ethyls), epoxy are big Behenic acid 2- ethylhexyls, the own ester of 4,5- epoxies tetrahydrophthalic acid two (2- ethyls), Chinese littleleaf box methyl acetylricinolate, two First alcohol lipid, such as C5~9Sour glycol ester, C5~9Sour Triethylene Glycol；Chloride class, such as afforest paraffin class, chlorinated fatty acid Ester；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester；Phenyl alkylsulfonate, trimellitic acid Ester, citrate, pentaerythrite and pentaerythritol fatty acid ester etc..Wherein, epoxidised soybean oil is a kind of environment-friendly type of function admirable Plastic plasticizer, refined soybean oil occurs epoxidation reaction with peroxide and prepared, resistance in polymer product to volatilize, be not easy Migrate, be not easy to lose.This is highly beneficial to keeping product light, heat endurance and increasing the service life.Epoxidised soybean oil Toxicity is minimum, is allowed for the packaging material of food and medicine by many countries, is that FDA (Food and Drug Adminstration) ratifies Unique epoxy plasticiser that can be used for packaging material for food.In a kind of gel of dynamic aggregation thing plasticising solvent swell of the present invention In preparation, the preferred epoxidized soybean oil of plasticizer.The dynamic aggregation thing for preparing plasticizer swell gel is preferably polymer interlude Be the polymer based on vinyl-chloride-containing monomer, the polymer containing norbornene monomer, the monomer containing saturation of olefins polymer it is poly- Polymer segments.
In embodiments of the present invention, it can be made based on the split-phase physical crosslinking structure in dynamic aggregation thing thermoplastic elastomer (TPE) Standby dynamic aggregation thing foamed material.Foamed material is particularly conducive to reduce the density of material.
In embodiments of the present invention, the structure of dynamic aggregation thing foamed material is related to open-celled structure, hole-closing structure, half Open three kinds of semi-closure structure etc..In open-celled structure, interconnected between abscess and abscess, or connection completely, one-dimensional or three-dimensional can By gas or liquid, abscess footpath is 0.01 to 3mm.Hole-closing structure, there is individual blisters structure, inner cell and abscess Between there is wall film to separate, the overwhelming majority be not interconnected, abscess footpath be 0.01 to 3mm.The existing phase of contained abscess It is intercommunicated and to have mutual disconnected structure be then half open-celled structure.
In embodiments of the present invention, the difference of foaming method foaming agent used in can be divided into physical blowing method and The major class of chemical blowing process two.
Physical blowing method, it is to make dynamic aggregation thing thermoplastic elastomer foaming using the method for physics, typically there are three kinds Method：(1) first inert gas is dissolved in dynamic aggregation thing under stress, then gas is discharged by decompression, so as in material It is middle to form stomata and foam；(2) it is allowed to vapour by carrying out heating to dissolving in the low-boiling point liquid in polymer or its material composition Change and foam；(3) hollow ball and/or foamable polymer microballoon are added in material composition, is forming dynamic aggregation thing During or afterwards, formed foaming body and foam.Physical blowing agent advantage of lower cost used in physical blowing method, especially Be carbon dioxide and nitrogen cost it is low, and can is fire-retardant, pollution-free, therefore application value is higher；And physical blowing agent foams Afterwards without residue, the influence to material property is little.Using foamable polymer microballoon in technique it is then most simple.
Chemical blowing process is to produce gas using chemical method to make dynamic aggregation thing thermoplastic elastomer foaming, is typically had Two methods：(1) to add the CBA in dynamic aggregation thing (raw material) carry out heating be allowed to decomposition discharge gas and Foaming；(2) can also utilize and the gas that discharges of chemical reaction mutually occur and foam between raw material components, for example, carbonate with The reaction of acid discharges carbon dioxide.
Physical blowing agent may be selected from but be not limited to inert gas and low boiling point solvent, as an example, including but not limited to two Carbonoxide, nitrogen, argon gas, methane, ethane, butane, iso-butane, HCFC -22, HCFC -142b, HFC chemical combination Thing -134a, HFC -152a, CFC -11, CFC -12, CFC -114, wherein, it is preferably environmentally friendly Carbon dioxide, nitrogen, argon gas, more preferably more efficient carbon dioxide, most preferably over-saturation carbon dioxide.Chemistry hair Infusion is divided into inorganic foaming agent and organic foaming agent, and the former includes but is not limited to sodium acid carbonate, ammonium carbonate, carbonic acid ammonia as an example Sodium, azido compound, hydroboron etc., the latter as an example include but is not limited to azodicarbonamide, azodiisobutyronitrile, N, N- dinitrosopentamethlyene tetramine, N, N '-dimethyl-N, N '-dinitroso are to benzene, benzene sulfonyl hydrazide, the double benzene of 4,4 '-oxo Sulfohydrazide, 3,3 '-disulfonyl hydrazide diphenyl sulphone (DPS), 1,3- benzene Erhuang hydrazides, p-toluene sulfonylsemicarbazide, benzenesulfonamido- urea, three hydrazines Base triazine, diazo aminobenzene etc..Partial dynamic polymer can produce in polymerizeing or other chemical reaction processes occur in the present invention Angry body, it now need not additionally use foaming agent.Due to the physical blowing agent advantage of lower cost used in physical blowing method, again Can be fire-retardant, pollution-free, and without residue after physical blowing agent foaming, the influence to foamed polymer physical performance is little, therefore In embodiments of the present invention, preferred physical blowing.Gel like material is particularly suitable for using hollow ball and/or foamable polymerization Thing microballoon is foamed.
In foamed material based on dynamic aggregation thing in preparing embodiment of the present invention, except foaming agent, also often need Want foam stabiliser.As an example, foam stabiliser is selected from, but not limited to, silicone oil, sulfonated aliphatic alcohol, alpha-sulfonated fatty acid, lauryl Sodium sulphate, DDAO, alkylolamides, polyethylene glycol oxide, alkylaryl polyoxyethylene alcohol, tridecane Base ether, Polyoxyethylene sorbitan glycerol monolaurate, the block copolymer etc. of siloxanes-ethylene oxide.
Except using the above-mentioned usual way for preparing foam, foamed material can also be prepared using freeze-drying. The method that foamed material is prepared using freeze-drying, is comprised the following steps：To swell in it is soft it is mutually compatible, with hard mutually or not Hold and the polymer of volatile solvent freezes, solvent is then being escaped in a manner of distillation close under vacuum condition.In solvent During effusion and after effusion, polymer can maintain the profile before freezing, thus obtain the foam material of porous spongy Material.
A kind of embodiment for preparing dynamic aggregation thing foamed material is by dynamic aggregation thing thermoplastic elastomer (TPE), foaming agent It is sufficiently mixed with other auxiliary agents, injects and foaming is completed in mould.Wherein, the dynamic aggregation thing for preparing foamed material is preferably to polymerize Thing interlude is based on saturation of olefins, unsaturated olefin, alkenyl halide, polyethers, polyester, silicon rubber, the polymerization of polyacrylic acid ester group Thing, polyvinyl alcohol based polymer, polyvinyl acetate based polymer, the polymer segment of polyacrylonitrile based polyalcohol.
Dynamic aggregation thing foamed material provided by the present invention further relates to：By welding, gluing, cutting, matching plane, perforation, Impressing, lamination and hot forming, the dynamic aggregation thing foamed material are transformed into any shape that needs, for example, pipe, rod, Sheath, container, ball, piece, volume and band；Purposes of the dynamic aggregation thing foamed material in floating installation；The dynamic aggregation thing Purposes of the foamed material in adiabatic or thermal acoustic insulation any required shape；By be laminated, bond, fuse and it is other even Connection technology, by technology people in the dynamic aggregation thing foamed material and sheet material, film, foam, fabric, stiffener and this area Other materials known to member are combined into the interlayer structure of complexity together；The dynamic aggregation thing foamed material is in packing ring or sealing In purposes；The purposes of the dynamic aggregation thing foamed material in packaging material or in a reservoir.Dynamic on the present invention is gathered Compound, foamable dynamic aggregation thing are such a types so that can be by extruding, being molded, in compression moulding or this area Other forming techniques known to technical staff deform them.
In embodiments of the present invention, except foregoing initiator, catalyst, dispersant, emulsifying agent, foaming agent, bubble Foam stabilizers, in the range of without prejudice to the object of the invention, it can also according to circumstances select to be added or used to other kinds auxiliary agent Filler obtains the composition based on dynamic aggregation thing thermoplastic elastomer (TPE).
Wherein, auxiliary agent may include but be not limited to following one or more of combination, such as stabilizing additive, including anti-oxidant Agent, light stabilizer, heat stabilizer, fire retardant；Improve processing characteristics auxiliary agent, including solvent, lubricant, releasing agent, plasticizer, Thickener, thixotropic agent, levelling agent；Change the auxiliary agent of coloured light, including colouring agent, fluorescent whitening agent, delustering agent；Other auxiliary agents, bag Include antistatic additive, coupling agent, biocide mildewcide etc..
Antioxidant in described auxiliary agent, it can delay the oxidizing process of polymer samples, ensure that material can be suitable It is processed sharply and extends its service life, includes but are not limited to following any or appoint several antioxidant：Hinered phenols, Such as 2,6 di tert butyl 4 methyl phenol, 1,1,3- tri- (hydroxyl -5- tert-butyl-phenyls of 2- methyl -4) butane, four [β-(3,5- Di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2,2 '-di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenols)；Sulfur-bearing by Hinder phenols, such as 4,4 '-thiobis-[3 methy 6 tert butyl phenol], 2,2 '-thiobis-[4- methyl-6-tert-butylphenols]； Triazine system hindered phenol, such as 1,3,5- bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl]-perhydro-s-triazines；Trimerization isocyanide Acid esters Hinered phenols, such as three (3,5- di-tert-butyl-4-hydroxyl benzyl)-triisocyanates；Amine, such as N, N '-two (betanaphthyl) P-phenylenediamine, N, N '-diphenyl-para-phenylene diamine, N- phenyl-N '-cyclohexyl p-phenylenediamine；Sulfur-bearing class, such as thiodipropionic acid dilauryl Osmanthus ester, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole；Phosphorous acid esters, such as triphenyl phosphite, the nonyl benzene of phosphorous acid three Ester, three [2.4- di-tert-butyl-phenyls] phosphite esters etc.；Wherein, the preferred Tea Polyphenols of antioxidant (TP), butylated hydroxy anisole (BHA), dibutyl hydroxy toluene (BHT), TBHQ (TBHQ), three [2.4- di-tert-butyl-phenyls] phosphite esters (irgasfos 168), four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters (antioxidant 1010).Used Antioxidant dosage is not particularly limited, generally 0.01-1wt%.
Light stabilizer in described auxiliary agent, it can prevent polymer samples from light aging occurs, extend its service life, its Include but are not limited to following any or appoint several light stabilizers：Photomask agent, such as carbon black, titanium dioxide, zinc oxide, sulfurous Sour calcium；Ultra-violet absorber, such as ESCALOL 567,2-hydroxy-4-n-octoxybenzophenone, 2- (2- hydroxyls Base -3,5- di-tert-butyl-phenyls) -5- chlorobenzotriazoles, 2- (2- hydroxy-5-methyl bases phenyl) BTA, (the 2- hydroxyls of 2,4,6- tri- Base -4- n-butoxyphenyls) -1,3,5- s-triazine, 2- cyano group -3,3- diphenylacrylate 2- ethylhexyls；Pioneer's type is ultraviolet Light absorbers, such as the p- tert-butyl group phenyl ester of salicylic acid, double acid double phenol A ester；UV quenchers, such as double (3,5- bis- tertiary fourths Base -4- benzylphosphonic acids mono ethyl ester), 2,2 '-thiobis (4- spy's octyl phenol epoxide) nickel；Hindered amine as light stabilizer, such as the last of the ten Heavenly stems two Sour double (2,2,6,6- tetramethyl piperidines) ester, benzoic acid (2,2,6,6- tetramethyl piperidines) ester, three (1,2,2,6,6- pentamethyl piperazines Piperidinyl) phosphite ester；Other light stabilizers, such as 3,5- di-tert-butyl-4-hydroxybenzoic acids (2,4- di-tert-butyl) ester, alkyl Phosphoamide, N, N '-zinc dibutyl dithiocaarbamate, N, the positive fourth positive group aminodithioformic acid nickel of N '-two etc.；Its In, double (2,2,6, the 6- tetramethyl piperidine) esters (light stabilizer 770) of the preferred carbon black of light stabilizer, decanedioic acid.Light used is stable Agent dosage is not particularly limited, generally 0.01-0.5wt%.
Heat stabilizer in described auxiliary agent, enable to polymer samples during processing or use not because heated and Generation chemical change, or delay these changes to reach the purpose to increase the service life, it includes but are not limited to following A kind of or several heat stabilizers：Lead salts, such as lead sulfate tribasic, dibasic lead phosphite, dibasic lead stearate, disalt Base phthalic acid lead, tribasic Malaysia lead plumbate, slag lead silicate, lead stearate, lead salicylate, dibasic phthalic acid Lead, basic lead carbonate, silica gel co-precipitation lead silicate；Metal soap：Such as cadmium stearate, barium stearate, calcium stearate, stearic acid Lead, zinc stearate；Organo-tin compound class, such as di-n-butyltin dilaurate, Bis(lauroyloxy)dioctyltin, maleic acid two (just) butyl tin, double single-ethylhexyl maleate dioctyltins, dimercapto 2-ethyl hexyl ethanoate dioctyltin, capital tin C-102, two mercaptos Guanidine-acetic acid isooctyl stannous methide, two mercaptan stannous methides and its compound；Antimony stabilizer, such as mercaptan antimonic salt, mercaptoacetate Mercaptans type, mercapto-carboxylic ester antimony, carboxylate antimony；Epoxy compound species, such as epoxidized oil, epoxy aliphatic ester, epoxy resin；It is sub- Phosphoric acid ester, such as the aromatic ester of phosphorous acid three, the alkyl ester of phosphorous acid three, the aralkyl ester of phosphorous acid three, alkane virtue mixed ester, aggretion type phosphorous acid Ester；Polyalcohols, such as pentaerythrite, xylitol, mannitol, D-sorbite, trimethylolpropane；Composite thermal stabilizer, such as altogether Precipitate metallic soap, liquid metal soap compound stabilizer, organotin compound stabilizer etc.；Wherein, the preferred barium stearate of heat stabilizer, Calcium stearate, di-n-butyltin dilaurate, maleic acid two (just) butyl tin.Heat stabilizer dosage used does not limit especially It is fixed, generally 0.1-0.5wt%.
Fire retardant in described auxiliary agent, by increasing capacitance it is possible to increase the flame resistance of material, it includes but are not limited to following any Or appoint several fire retardants：Phosphorus system, such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate hexichol Ester；Halogen phosphoric acid ester, such as three (2,3- dibromopropyl) phosphates, tricresyl phosphate (2,3- dichloro the third) ester；Organohalogen compounds are such as high Chlorinty chlorinated paraffin, 1,1,2,2- tetrabromoethanes, deca-BDE, the decane of perchloro- ring penta；Inorganic combustion inhibitor, such as three oxidations two Antimony, aluminium hydroxide, magnesium hydroxide, Firebrake ZB；Reactive flame retardant, such as chlorendic anhydride, double (2,3- dibromopropyl) anti-butylene two Acid esters, tetrabromobisphenol A, tetrabromophthalic anhydride etc.；Wherein, the preferred deca-BDE of fire retardant, triphenyl phosphate, tricresyl phosphate Toluene ester, phosphate toluene diphenyl ester, antimony oxide.Amount of flame-retardant agent used is not particularly limited, generally 1-20wt%.
Solvent in described auxiliary agent, viscosity can be adjusted, is easy to technological operation, made in product preparation process or in preparing With.It includes but are not limited to following any or appointed several：Hydro carbons (such as hexane), halogenated hydrocarbon (such as tetrachloromethane), aromatic hydrocarbons (such as toluene, dimethylbenzene), ketone (such as acetone, methyl ethyl ketone), ethers (such as ether, tetrahydrofuran, dioxane), esters (such as ethyl acetate, butyl acetate), glycol ether-ether (such as ethylene glycol ether acetate, propylene glycol monomethyl ether acetate), dimethyl The intensive polar solvents such as formamide (DMF), 1-METHYLPYRROLIDONE (NMP).Solvent load used is not particularly limited, generally 1-200wt%.
Lubricant in described auxiliary agent, it is possible to increase the lubricity of polymer samples, reduce friction, reduce Interface Adhesion Performance, it includes but are not limited to following any or appoints several lubricants：Saturated hydrocarbons and halogenated hydrocarbon, such as solid paraffin, micro- Spar wax, atoleine, low molecular weight polyethylene, OPE；Fatty acid, such as stearic acid, hydroxy stearic acid；Fat Esters of gallic acid, such as aliphatic acid low-carbon-ester, polyol esters of fatty acids, native paraffin, ester type waxes and saponified wax；Aliphatic amide type is such as hard Acyl amine or stearic amide, oleamide or oleamide, erucyl amide, N, N '-ethylene bis stearamide；Fatty alcohol and polynary Alcohols, such as stearyl alcohol, cetanol, pentaerythrite；Metal soap, as lead stearate, calcium stearate, barium stearate, magnesium stearate, Zinc stearate etc.；Wherein, the preferred solid paraffin of lubricant, atoleine, stearic acid, low molecular weight polyethylene.Lubrication used Agent dosage is not particularly limited, generally 0.5-1wt%.
Releasing agent in described auxiliary agent, it can make polymer samples be easy to be stripped, and surface is smooth, clean, it include but It is not limited only to following any or appoints several releasing agents：Paraffin hydrocarbon, soaps, dimethicone, ethyl silicon oil, aminomethyl phenyl silicon Oil, castor oil, used oil, mineral oil, molybdenum disulfide, polyethylene glycol, vinyl chloride resin, polystyrene, silicon rubber, polyvinyl alcohol Deng；Wherein, the preferred dimethicone of releasing agent, polyethylene glycol.Releasing agent dosage used is not particularly limited, generally 0.5- 2wt%.
Plasticizer in described auxiliary agent, it can increase the plasticity of polymer samples so that the hardness of polymer, mould Amount, softening temperature and brittle temperature decline, and elongation, flexibility and pliability improve, and it includes but are not limited to following any Kind appoints several plasticizer：Phthalates：Dibutyl phthalate, dioctyl phthalate, phthalic acid two Different monooctyl ester, dibutyl phthalate (DHP), diisooctyl phthalate, diisononyl phthalate, phthalic acid fourth benzyl Ester, butyl phthalate butyl glycolate, dicyclohexyl phthalate, phthalic acid double (13) ester, terephthaldehydes Sour two (2- ethyls) own esters；Phosphoric acid ester, such as tricresyl phosphate, phosphoric acid (hexichol -2- ethyls) own ester；Fatty acid ester, such as The own ester of adipic acid two (2- ethyls), decanedioic acid two (2- ethyls) own ester；Epoxy compound species, such as epoxy glycerite esters, epoxy fat Fatty acid monoester class, epoxy tetrahydrophthalic acid esters, epoxidized soybean oil, the own ester of epoxystearic acid (2- ethyls), epoxy soybean Oleic acid 2- ethylhexyls, the own ester of 4,5- epoxies tetrahydrophthalic acid two (2- ethyls), Chinese littleleaf box methyl acetylricinolate, binary Alcohol lipid, such as the sour glycol ester in C5~9, the sour Triethylene Glycol in C5~9；Chloride class, such as afforest paraffin class, chlorinated fatty acid Ester；Polyesters, such as ethanedioic acid 1,2-PD system polyester, decanedioic acid 1,2-PD polyester；Phenyl alkylsulfonate, trimellitic acid Ester, citrate, pentaerythrite and pentaerythritol fatty acid ester etc.；Wherein, plasticizer pref-erable dioctyl phthalate (DOP), neighbour Dibatyl phithalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), adjacent benzene two The isodecyl ester (DIDP) of formic acid two, tricresyl phosphate (TCP).Plasticizer consumption used is not particularly limited, generally 5- 20wt%.
Thickener in described auxiliary agent, can assign the good thixotropy of mixed with polymers liquid and appropriate denseness, and one As the present invention production and semi-finished product storage during use, its include but are not limited to it is following any or appoint several thickenings Agent：Lower-molecular substance, such as soap, fatty alcohol polyoxyethylene ether sulfate, alkyldimethylamine oxide, aliphatic acid monoethanol Acid amides, fatty diglycollic amide, aliphatic acid Isopropamide, anhydro sorbitol tricarboxylic ester, glycerol trioleate, coconut monoethanolamide CAB, 2- alkyl-N- carboxymethyl-N- hydroxyethyl imidazoles quinoline, titanate coupling agent；Polymer substance, such as bentonite, manually Hectorite, fine particle silica, colloidal aluminum, plant polyose class, microbial polysaccharide class, animal protein, cellulose family, starch, Marine alga acids, poly-methyl acrylate, methacrylic acid copolymer, cis-butenedioic anhydride copolymer, crotonic acid-copolymers, polyacrylamide, Polyvinyl pyrrolidone, polyvinyl alcohol, polyethers, polyvinyl methyl ether urethane polymer etc.；Wherein, the preferred hydroxy ethyl fiber of thickener Element, coconut oil diethanol amide, acrylic acid-methacrylic acid copolymer.Thickener dosage used is not particularly limited, typically For 0.1-1.5wt%.
Thixotropic agent in described auxiliary agent, add in dynamic polymer systems, increase the thixotropy of polymeric system.Including But it is not limited only to following any or appoints several：Gas-phase silica, rilanit special, bentonite, silicic acid anhydride, silica derivative, Urea derivative etc..Thixotropic agent dosage used is not particularly limited, generally 0.5-2wt%.
It levelling agent in described auxiliary agent, can ensure that the flat smooth of polymer coating film is uniform, improve film coated surface matter Amount, dicoration is improved, it includes but are not limited to following any or appoints several levelling agents：Dimethyl silicone polymer, poly- methyl Phenyl siloxane, cellulose acetate butyrate, polyacrylate, organic siliconresin etc.；Wherein, the preferred poly dimethyl of levelling agent Siloxanes, polyacrylate.Levelling agent dosage used is not particularly limited, generally 0.5-1.5wt%.
Colouring agent in described auxiliary agent, polymeric articles can be made to show required color, increase surface color and polish, It includes but are not limited to following any or appoints several colouring agents：Inorganic pigment, such as titanium white, chrome yellow, cadmium red, iron oxide red, molybdenum chromium Red, ultramarine, chrome green, carbon black；Organic pigment, such as lithol red BK directions, lake red C, red, good base R is red, phthalocyanine is red, Yong Guyang The bright red R of red HF3C, the plastics and not red BR of clo, forever solid orange HL, Fast Yellow G, vapour bar plastics Huang R, permanent yellow 3G, permanent yellow H2G, Phthalocyanine blue B, dark green, plastics purple RL, nigrosine；Organic dyestuff, such as thioindigo red, vat yellow 4GF, indanthrene blue RSN, slag rose Rare essence, Oil Yellow etc.；Wherein, the selection of colouring agent is depending on color sample demand, it is not necessary to is particularly limited to.Coloring used Agent dosage is not particularly limited, generally 0.3-0.8wt%.
Fluorescent whitening agent in described auxiliary agent, contaminated material can be made to obtain the sparkling effect of similar fluorite, its Include but are not limited to following any or appoint several fluorescent whitening agents：Stilbene-based, coumarin type, pyrazoline type, benzo Oxygen nitrogen type, BIDA type etc.；Wherein, the preferred stilbene biphenyl sodium disulfonate (fluorescent whitening agent of fluorescent whitening agent CBS), 4,4- double (5 methyl -2- benzoxazolyls) talan (fluorescent whitening agent KSN), 2,2- (4,4 '-diphenylethyllene) Dibenzoxazine (fluorescent whitening agent OB -1).Fluorescent whitening agent dosage used is not particularly limited, generally 0.002- 0.03wt%.
Delustering agent in described auxiliary agent, when enabling to incident light arrival polymer surfaces, diffusing reflection occurs, produces low The matt and delustring outward appearance of gloss, it includes but are not limited to following any or appoints several delustering agents：Settle barium sulfate, dioxy SiClx, aqueous gypsum powder, talcum powder, titanium dioxide, poly- methyl carbamide resin etc.；Wherein, the preferred silica of delustering agent.Used disappears Photo etching dosage is not particularly limited, generally 2-5wt%.
Antistatic additive in described auxiliary agent, the deleterious charge assembled in polymer samples can be guided or eliminated, make it Not to producing and life brings inconvenience or endangered, it includes but are not limited to following any or appoints several antistatic additive：It is cloudy from Subtype antistatic additive, such as alkylsulfonate, to ABPS, alkyl phosphate diethanolamine salt, alkyl phenol Polyoxyethylene groups ether sulfonic acid triethanolamine, to nonyl diphenyl ether potassium sulfonate, alkyl polyoxyethylene base ether sulfonic acid triethanolamine, phosphoric acid Ester derivant, phosphate, phosphoric acid polyethylene oxide alkyl ethers alcohol ester, alkyl double [two (2- ethylol amines)] phosphate, phosphates Derivative, fatty amine sulfonate, butyrate sodium sulfonate；Cationic antistatic agent, such as aliphatic ammonium salt hydrochlorate, lauryl trimethyl Ammonium chloride, dodecyl trimethylamine bromide, N, N- cetyl-ethyl morpholine ethyl-sulfate salt, stearamide propyl (2- hydroxyl second Base) dimethylammonium nitrate, alkyl hydroxyethyl dimethylammonium perchlorate, 2- alkyl -3,3- dihydroxy ethyl imidazolines perchlorate, 2- Heptadecyl -3- ethoxy -4- carboxymethyls imidazoline, double (α-ethoxy)-N-3 (dodecyloxy -2- hydroxypropyls) first of N, N- Ammonium Methylsulfate salt；Amphoteric ion type antistatic additive, such as alkyl dicarboxyl ammonium methyl second inner salt, lauryl betaine, N, N, N- tri- Alkylammonium acetyl (N '-alkyl) amine second inner salt, the polyethylene oxide base-N- ethylphosphonic acids sodium of N- lauryls-N, N- bis-, alkyl two Salt hydroxide, the ethoxy -3- acetic acid alkali imidazolines quaternary amine alkali of 2- alkyl -3, N- alkyl amino acids in (polyoxyethylene) ammonium second Salt；Non-ionic antistatic agent, such as fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide addition product, alkyl phenol epoxy second Alkane addition product, tricresyl phosphate polyoxyethylene groups ether-ether, fatty acid monoglyceride, the PEO of sorbitan mono-laurate Addition product；Polymer Antistatic Agent, ethylene oxide propylene oxide addition product, polyethylene glycol-terephthalic acid (TPA) such as ethylenediamine Ester -3,5- dibenzoates sodium sulfonate copolymers, polyene propionamide N- quaternary ammonium salts substituent, poly- 4- vinyl -1- acetonyl pyrroles Pyridine phosphoric acid-to butyl phenyl ester salt etc.；Wherein, the preferred lauryl trimethyl ammonium chloride of antistatic additive, octadecyldimethyl hydroxyl second Base quaternary ammonium nitrate (antistatic additive SN), alkyl phosphate diethanolamine salt (antistatic additive P).Antistatic additive dosage used does not have It is particularly limited to, generally 0.3-3wt%.
Coupling agent in described auxiliary agent, the interface characteristics of polymer samples and inorganic filler or reinforcing material can be improved Can, the viscosity of material melt is reduced in plastic processes, improves the decentralization of filler to improve processing characteristics, and then make system Product obtain good surface quality and machinery, heat and electrical property, and it includes but are not limited to following any or appoints several couplings Agent：Chromium of organic acid complex compound, silane coupler, titanate coupling agent, sulfonyl azide coupling agent, aluminate coupling agent etc.；Wherein, The preferred gamma-aminopropyl-triethoxy-silane of coupling agent (Silane coupling agent KH550), γ-(oxygen of 2,3- epoxies third) propyl group trimethoxy Base silane (silane coupler KH560).Coupling agent dosage used is not particularly limited, generally 0.5-2wt%.
Dehydrating agent in described auxiliary agent, moisture that can be in removing system, its include but are not limited to it is following any or Appoint several：It is oxazolidine compound (such as 3- Ethyl-2-Methyls -2- (3- methyl butyls) -1,3- oxazolidines), different to Methyl benzenesulfonyl Cyanate, triethyl orthoformate, vinyl silanes, calcium oxide etc..Dehydrating agent dosage used is not particularly limited, generally 0.1-2wt%.
Biocide mildewcide in described auxiliary agent, the growth of bacterium can be suppressed, keep the clean and tidy outward appearance of product, extend and use Life-span；Or protection user, the health for lifting user, such as reduce tinea pedis.It includes organic matter and inorganic matter, including but It is not limited only to following any or appoints several：Isothiazolinone derivatives, such as CMIT, 2- Methyl -4- isothiazoline -3- ketone, N- normal-butyl -1,2- benzisothiazole-3-ketones, octylisothiazolinone, 2,4,4- tri- Chlorine-2-hydroxyl-diphenyl ether, 2- (4- thiazolyls) benzimidazole, copper 8-quinolinolate or double (8-hydroxyquinoline base) copper；It is organic Tin compound, such as tributyl-tin fumarate, tributyltin acetate, double (tributyl tin) sulfide, double (tributyl tin) tin oxide； N, N- dimethyl-N '-phenyl (fluorine dichloromethyl is thio) sulfonamide；Inorganic compound or compound, such as Nano Silver, nano-silica Change titanium, nano silicon, nano zine oxide, superfine cupper powder, inorganic antiseptic YY-Z50, XT inorganic antiseptic, composite antibacterial Agent KHFS-ZN.Biocide mildewcide dosage used is not particularly limited, generally 0.5-2wt%.
Described filler, it primarily serves following effect in polymer samples：1. reducing the shrinkage factor of molded article, carry Dimensional stability, surface smoothness, flatness and the zero diopter of high product or without photosensitiveness etc.；2. adjust the viscosity of material；③ Meet different performance requirement, such as improve material impact intensity and compressive strength, hardness, rigidity and modulus, improve wearability, improve Heat distortion temperature, improve electric conductivity and thermal conductivity etc.；4. improve the coloring effect of pigment；5. assign photostability and chemically-resistant is rotten Corrosion；6. playing compatibilization, cost can be reduced, improves the competitiveness of product commercially.
Described filler, selected from following any or several fillers：Inorganic non-metallic filler, metal packing, organic fill out Material.
Described inorganic non-metallic filler, include but are not limited to following any or appoint several：Calcium carbonate, clay, sulphur It is sour barium, calcium sulfate and calcium sulfite, talcum powder, white carbon, quartz, mica powder, clay, asbestos, asbestos fibre, orthoclase, white Chalk, lime stone, blanc fixe, gypsum, graphite, carbon black, graphene, CNT, molybdenum disulfide, slag, flue dust, wood powder and Shell powder, diatomite, red mud, wollastonite, silica-alumina carbon black, aluminium hydroxide, magnesium hydroxide, flyash, oil shale powder, expanded perlite Powder, conductive black, vermiculite, iron cement, white clay, alkali mud, boron mud, glass microballoon, resin microbeads, foam microspheres, glass dust, cement, Glass fibre, carbon fiber, quartz fibre, charcoal core boron fibre, titanium diboride fiber, calcium titanium fiber, carbon silica fibre, ceramics are fine Dimension, whisker etc..
Described metal packing, include but are not limited to following any or appoint several：Conductive metal filler, metal Grain, metal and alloyed powder, carbon steel, stainless steel, stainless steel fibre etc..
Described organic filler, include but are not limited to following any or appoint several：1. natural organic filler, such as skin Hair, natural rubber, cotton, velveteen, fiber crops, jute, flax, asbestos, cellulose, cellulose acetate, shellac, chitin, chitosan, Lignin, starch, protein, enzyme, hormone, raw lacquer, timber, wood powder, shell powder, glycogen, xylose, silk etc.；2. synthetic resin is filled out Material, such as AAS acrylonitrile acryloid styrene, acrylonitrile-butadiene-styrene copolymer, cellulose acetate, poly- three Fluorine vinyl chloride, haloflex, chliorinated polyvinyl chloride, epoxy resin, ethylene-propylene copolymer, ethylene-vinyl acetate c It is thing, high density polyethylene (HDPE), high impact polystyrene, low density polyethylene (LDPE), medium density polyethylene, melamine formaldehyde resin, poly- Acid amides, polyacrylic acid, polyacrylamide, polyacrylonitrile, polyarylsulfone (PAS), polybenzimidazoles, polybutylene terephthalate (PBT), poly- carbon Acid esters, dimethyl silicone polymer, polyethylene glycol, polyester, polysulfones, polyether sulfone, polyethylene terephthalate, phenolic resin, Tetrafluoroethylene-perfluoro propane copolymer, polyimides, PMA, polymethacrylonitrile, polymethyl methacrylate, Polyformaldehyde, polyphenylene oxide, polypropylene, polyphenylene sulfide, PPSU, polystyrene, polytetrafluoroethylene (PTFE), polyurethane, polyvinyl alcohol, poly- second Vinyl acetate, polyvinyl butyral resin, polyvinyl chloride, vinyl chloride vinyl acetate copolymer, Vingon, polyvinyl alcohol Formal, polyvinylpyrrolidone, Lauxite, ultra-high molecular weight polyethylene, unsaturated polyester (UP), polyether-ether-ketone etc.；3. synthesize Gum filler, such as isoprene rubber, butadiene rubber, butadiene-styrene rubber, nitrile rubber, neoprene, butyl rubber, EP rubbers, silicon Rubber, fluorubber, lactoprene, polysulfide rubber, polyurethane rubber, epichlorohydrin rubber, thermoplastic elastomer (TPE) etc.；4. synthesize Fiberfill, such as viscose fiber, CUP, diethyl ester fiber, triethyl fiber, Fypro, polycarbonate, poly- It is alcohol fibers, polyester fiber, polyurethane fiber, polyacrylonitrile fibre, vinylon, polyvinyl chloride fibre, poly- Olefin(e) fibre, fluorofibre, polytetrafluoroethylene fibre, aromatic polyamide fibre, aramid fiber or aramid fiber etc..
Wherein, wire feeding does not limit, mainly depending on required material property, preferably calcium carbonate, barium sulfate, cunning Stone flour, carbon black, graphene, glass microballoon, glass fibre, carbon fiber, natural rubber, chitosan, starch, protein, polyethylene, Polypropylene, polyvinyl chloride, vinyl-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl acetate, Fypro, poly- carbonic acid Ester fiber, vinal, polyester fiber, polyacrylonitrile fibre；Amount of filler used is not particularly limited, generally 1- 30wt%.
It is former to dynamic aggregation thing thermoplastic elastomer (TPE) each component in the preparation process of dynamic aggregation thing thermoplastic elastomer (TPE) The dosage of material is not particularly limited, and those skilled in the art can prepare situation and target polymerization physical performance according to actual It is adjusted.
The manufacture method of the composition of the present invention is not particularly limited, for example, roller, kneader, extruder, ten thousand can be passed through Additive and dynamic aggregation thing are blended as needed for energy mixer etc., then carry out the subsequent operation such as foam.
In the present invention, the non-covalent and dynamic reversible of side hydrogen bond group in dynamic aggregation thing thermoplastic elastomer (TPE) are utilized Property, when by physical impact, on the one hand elastomer can show thickening response, on the other hand when stress exceedes cross linking hydrogen bonds Intensity when hydrogen bond be broken, reach the multi-absorption to impact energy and loss.Therefore, it can design and prepare with superpower energy-absorbing The polymer fiber of effect, film, sheet material, foam, gel etc..Energy-absorbing material is used as using this dynamic aggregation thing thermoplastic elastomer (TPE) Energy-absorbing is carried out, the effect such as good damping, damping, sound insulation, shock resistance can be provided, in life, production, motion, leisure, joy The area of activities such as pleasure, military affairs, police service, security, medical care tool has been widely used.Due to side hydrogen bond group formed hydrogen bond have it is good Good dynamic property, the dynamic aggregation thing elastomer obtained is in addition to having the function that energy-absorbing, also with certain self-repairability Can be with good toughness, material lifetime is longer in energy-absorbing application process.Multiple heat based on each block component in elastomer turns Temperature, the energy-absorbing material with shape memory function is can be devised by, it is fixed applied to specific occasion, such as personalization Energy-absorbing protector processed.The energy-absorbing method that the present invention is provided based on dynamic aggregation thing thermoplastic elastomer (TPE), especially suitable for human body, dynamic Object, article etc. carry out defense of resistance to impact, such as using the material as protector, in motion and daily life with being carried out in production Body protection, body protection is carried out to army and police, security personnel；It is prepared into explosion-proof tent, blanket, wall, laminated glass, sandwich plate Deng progress explosive-proof protector；Other protective article for cell/apparatus are prepared into, carries out airborne and drops protection, automobile collision preventing, electronic apparatus Defense of resistance to impact of article etc..
Below, dynamic aggregation thing thermoplastic elastomer (TPE) of the present invention is further retouched with reference to some specific embodiments State, and the method that energy-absorbing is provided with the dynamic aggregation thing thermoplastic elastomer (TPE) is provided.Specific embodiment is further specifically The bright present invention, non-limiting protection scope of the present invention.
Embodiment 1
By SBS (SBS), 2- (t-butoxycarbonyl-amino) ethyl mercaptan, light Initiator benzil dimethyl ketal (BDK) reacts in tetrahydrofuran, keeps alkenyl and 2- (tertiary butyloxycarbonyls in polybutadiene Base-amino) ethyl mercaptan and BDK mol ratio is about 50:50:1, obtain in polybutadiene segments containing carbamate groups Modified SBS.
By the mass parts of gained modified SBS 100, the mass parts of naphthenic oil 25, the mass parts of precipitated calcium carbonate 17, the matter of polystyrene 25 Amount part, the mass parts of polyvinyl acetate 8, the mass parts of antioxidant 264 0.8, the mass parts of zinc oxide 2, the mass parts of zinc stearate 1.5, The mass parts of AC foaming agents 2 are well mixed, and are extruded with screw extruder, are then kneaded slice on a mill, in 170 DEG C of 20MPa Lower foaming is molded for 8 minutes.
Performance：Tensile strength 10.2MPa, it is broken rate elongation 710%；Density：87kg/m3.Footwear are used as using this foamed material Bottom, for carrying out buffer protection to people's pin.This sole has excellent wearability again simultaneously.
Embodiment 2
2- chlorine cyclohexanone is dissolved in dichloromethane, adds metachloroperbenzoic acid (mCPBA) 0.12mol, keeps 2- chlorine rings Hexanone and mCPBA mol ratio are 10:12, reaction obtains α-chloro- 6-caprolactone.
Under anhydrous condition, α-molar equivalent of chloro- 6-caprolactone 50 and the molar equivalent of 6-caprolactone 100 are dissolved in toluene, 1 Molar equivalent initiator 2,2- dibutyl -2- tin -1,3- cyclic heptane dioxide react under triggering in 20 DEG C, and it is hydroxy-end capped to obtain both ends Side base contains the random copolymer 2a based on polyester of chlorine atom.
The copolymer 2a that side base contains chlorine atom is dissolved in dimethylformamide, adds the nitrine of the molar equivalent of chlorine atom 2 Change sodium, reaction obtains the copolymer that side base contains azido.
Side base is contained to the random copolymer of azido, the 2- propargyl-N- butylamino first of azido equimolar equivalent Acid esters is dissolved in tetrahydrofuran, under the catalysis of cuprous iodide and pyridine, at 35 DEG C reaction obtain side base and contain carbamate The copolymer 2b of base.
With benzoyl peroxide (BPO) for initiator, TGA is that chain-transferring agent triggers 4- ethene pyrroles at 90-100 DEG C Pyridine polymerize, and it is 1 to keep initiator, monomer, the mol ratio of chain-transferring agent:30:1, obtain poly- (the 4- ethene pyrroles of single-ended carboxy blocking Pyridine).
The copolymer 2b of a certain amount of gained and poly- (4-vinylpyridine) are mixed, the ratio for controlling both molal quantitys is 1: 2, with bicyclic ethyl carbodiimide (DCC) and DMAP (DMAP) for catalyst, using dichloromethane as solvent, obtain The multi-segment structure copolymer thermoplastic elastomer of multiterminal section-mono- interlude.
Performance：Tensile strength 21.6MPa, it is broken rate elongation 1020%.With product, such as car insurance made of this material Thick stick, car damping piece, noise reduction gear, sound panel etc., for damping, impact resistance, sound insulation during use, while foot can be provided Enough intensity.
Embodiment 3
1 molar equivalent inositol six (mercaptopropionic acid ester) and 12 molar equivalent carbon disulfide are dissolved in chloroform, instillation contains 12 The chloroformic solution of molar equivalent triethylamine.After reacting 1 hour at room temperature, the chlorine containing 7 molar equivalent 2 bromopropionic acid methyl esters is instilled Imitative solution.After continuing reaction 2 hours, handled with the aqueous solution of 10% hydrochloric acid and cleaned with silicagel column, obtain six function chain tra nsfers Agent.
Isocyanates ethyl acrylate is reacted with n-propylamine, nafoxidine in methylene chloride respectively, kept different The mol ratio of cyanate and amino is 1:1, obtain acrylate monomer 3a, the 3b containing urea bond and the derivative containing urea bond.
Using six function chain-transferring agents of gained as chain-transferring agent, using AIBN as initiator, using sodium p styrene sulfonate as One monomer, using n-butyl acrylate as second comonomer, using 3a as Third monomer, using 3b as the 4th monomer, using tetrahydrofuran to be molten Agent, the mol ratio for keeping initiator, chain-transferring agent and first, second, third and fourth each monomer are 6:1:60:180:300:60.It will first draw Hair agent and the first monomer are dissolved in solvent, and anhydrous and oxygen-free low pressure is kept after sealing, and carrying out light in room temperature under the irradiation of uviol lamp draws Hair polymerization.After treating the first monomer reaction, add second and third, four monomer mixture solutions.After polymerization terminates, obtain to change Property polyacrylate centered on soft segment, using kayexalate as end hard section, and contain urea in modified polyacrylate side base The star-like six arms dynamic aggregation thing thermoplastic elastomer (TPE) of base and ureido derivatives base.
Performance：Tensile strength 4.3MPa, it is broken rate elongation 1230%.To be used as compound glass and more made of this material The squeegee of secondary sheet material, for shellproof and explosion-proof etc..
Embodiment 4
At -78 DEG C, 1 molar equivalent δ-valerolactone is instilled into the tetrahydrofuran containing 1 molar equivalent lithium diisopropylamine Solution, after stirring, the toluene solution of the 3- propargyl bromides containing 1.1 molar equivalents is added, is reacted at -40 DEG C. After reaction, by crude product at 140 DEG C short-path distillation, obtain internal ester monomer 4a.
Under the conditions of anhydrous and oxygen-free, bipyridine, cuprous bromide, ethyl-alpha-bromopropionate and benzene are sequentially added to reaction vessel Ethene, holding mol ratio are 1:1:1:20, reacted at 110 DEG C.The polystyrene of gained is added four after reaction Hydrogen furans dissolves, and using Lithium Aluminium Hydride as reducing agent, reacting 6 at room temperature, as a child precipitation obtained hydroxy-end capped polyphenyl in methyl alcohol Ethene 4b.Under anhydrous condition, by the internal ester monomer 4a and 50 molar equivalents of the polystyrene 4b of gained and 50 molar equivalents ε- Caprolactone reacts under the catalysis of stannous octoate at 110 DEG C, obtains two-part copolymer 4c.
Under the conditions of anhydrous and oxygen-free, 1 molar equivalent aluminium isopropoxide and 4 molar equivalent ethobroms are dissolved in toluene, distillation system Obtain initiator ethobrom aluminium initiator.By the internal ester monomer 4a and 100 molar equivalents of gained initiator and 100 molar equivalents 6-caprolactone reacts at room temperature, is precipitated after HCl treatment in heptane, and it is hydroxyl other end bromine atom side to obtain one end Base contains the random polyester copolymer of acetylene bond.Copolymer, 20 molar equivalent methyl methacrylates obtained by 1 molar equivalent are dissolved in Tetrahydrofuran, under the catalysis of double (triphenyl phosphorus) nickelous bromides, reacted 15 hours in 75 DEG C, it is hydroxyl polyester side to obtain polyester end Base contains polymethyl methacrylate-modified poly ester two-part copolymer 4d of acetylene bond.
By gained copolymer 4c, 4d, ethanedioly chloride in molar ratio 1:1:1 is mixed in dichloromethane, under triethylamine catalysis It is to hold multiterminal section-mono- centre of the section modified poly ester as interlude that reaction, which is obtained using polystyrene and/or polymethyl methacrylate, The multi-segment structure copolymer of section.
By the multi-segment structure copolymer of gained multiterminal section-mono- interlude, 2,5- dehydration -1- nitrine -1- deoxidation-D- grapes Sugar alcohol is dissolved in tetrahydrofuran, and it is 1 to keep the mol ratio of alkynyl and 2,5- dehydration -1- nitrine -1- deoxy-D-glucose alcohol:1, Under the catalysis of cuprous iodide and pyridine, reacted at 35 DEG C and obtain the multisection type for multiterminal section-mono- interlude that side base contains hydroxyl Structure copolymer.The multi-segment structure copolymer for multiterminal section-mono- interlude that the side base of gained contains hydroxyl is dissolved in dichloromethane Alkane, under dibutyl tin dilaurate (DBTDL) catalysis with and pendant hydroxyl group equimolar equivalent ethyl isocyanate reaction, obtain Side base contains the dynamic aggregation thing thermoplastic elastomer (TPE) of carbamate groups.
Performance：Tensile strength 14.3MPa, it is broken rate elongation 1020%.Each based article is made with this elastomeric material, used In buffering energy-absorbing, because it has multiple transition temperature, while also there is shape memory function.
Embodiment 5
Under nitrogen protection, by 10 molar equivalent ethylene glycol monoallyl ethers (mean molecule quantity about 500) and 1 molar equivalent Potassium methoxide is blended, and the epoxy prapanol of 70 molar equivalents is slowly added dropwise at 95 DEG C, and obtaining end group has the alkene of branched structure for hydroxyl Hydrocarbon monomer 5a.
Under nitrogen protection, by end group be hydroxyl have the olefinic monomer 5a of branched structure with and hydroxyl molar equivalent it is different Ethyl cyanate reacts under DBTDL catalysis in dichloromethane, obtains olefinic monomer 5b.
Olefinic monomer 5b and 3- sulfydryls -1,2-PD equimolar are blended, add 1wt% light triggers 2,2- dimethoxies Base -2- phenyl acetophenones, illumination 30 minutes under 300W uviol lamps, obtain containing amino with cladodification side base and cladodification side base end The glycol of formic acid ester group.
By glycol, 5 molar equivalents 1 obtained by 5 molar equivalents, 6- hexylene glycols, the mixing of 8 molar equivalent Adipoyl Chlorides, in three second Under the catalysis of amine, obtaining both ends has the modified poly ester of cladodification side base and cladodification side base end amido-containing acid ester base for hydroxyl.
The hexamethylene diisocyanate of 2- amino-4-hydroxy -6- methylpyrimidines and 7 molar equivalents is reacted at 100 DEG C 16 hours, pentane is added, is precipitated.Precipitation is collected, and compound 5c is dried to obtain after being washed with pentane.
X=direct keys,
It is under anhydrous condition, the both ends obtained by 1 molar equivalent are molten for the modified poly ester of hydroxyl and 2 molar equivalent compound 5c In chloroform, in 60 DEG C of reactions under DBTDL catalysis, the thermoplastic elastic based on polyester that both ends are urea groups pyrimidone is obtained Body.
Gained elastomer is loaded into mould, is placed in autoclave, is passed through supersaturated carbon dioxide.Pressurized, heated is extremely Decompression makes its expanded foamed shaping after 160 DEG C, 12 minutes, and corresponding foamed product is obtained after the demoulding.
Performance：Tensile strength 1.3MPa, it is broken rate elongation 1290%；Density：97kg/m3.It is made with this foamed material Product, available for damping, while also there is insulation.
Embodiment 6
By pi-allyl hydroxyethyl ether and 5- chloromethyl -2- oxazolidones in molar ratio 1:1 is dissolved in toluene, using potassium carbonate to urge Agent, using TBAB as consisting of phase-transferring agent, it is the compound 6a that pi-allyl one end is oxazolidone to obtain one end.
The hexamethylene diisocyanate of 2- amino-4-hydroxy -6- methylpyrimidines and 7 molar equivalents is reacted at 100 DEG C 16 hours, pentane is added, is precipitated.Precipitation is collected, and it is NCO that one end is dried to obtain after being washed with pentane Urea groups pyrimidone.Gained urea groups pyrimidone and allylamine are reacted, obtain the urea groups pyrimidone 6b that one end is alkenyl.
Using chloroplatinic acid as catalyst, by hydrogen containing siloxane and the compound 6a and hard section urea groups pyrimidone of hydrogen bonds group 6b reacts 3 hours in cyclohexanone at 90 DEG C, and silicon hydrogen and the mol ratio of compound 6a, 6b are about in control hydrogen containing siloxane 5:4:1, obtain silicone thermoplastic elastomers.
Performance：Tensile strength 0.9MPa, it is broken rate elongation 790%.The component of electronic product is used as using this elastomer Seal, there is protecting against shock function again while waterproof, be especially suitable for types of applications at low temperature.
Embodiment 7
The HMW poly-β-hybroxybutyric acid (mean molecule quantity about 300000) of 1 molar equivalent is dissolved in dichloromethane, Instill the mixed solution containing 1000 molar equivalent p-methyl benzenesulfonic acid and 10000 molar equivalent 1,4- butanediols.4 are reacted at room temperature After hour, with methanol extraction and product is rinsed, obtains the low molecule amount poly-β-hybroxybutyric acid (mean molecule quantity that both ends are hydroxyl About 10000).
The hydroxy-end capped poly-β-hybroxybutyric acid in both ends and levorotatory lactide are dissolved in toluene, keep modified polycaprolactone and The mol ratio of levorotatory lactide is about 1:30, under the catalysis of stannous 2-ethylhexoate, obtain gathering left-handed breast in 100 DEG C of reactions The multi-segment structure copolymer of acid-beta-hydroxy-butanoic acid ester-PLLA multiterminal section-mono- interlude.
The multi-segment structure copolymer of gained multiterminal section-mono- interlude and maleic anhydride are dissolved in chlorobenzene, make maleic anhydride Initial mass volumetric concentration be 3%.Benzoyl peroxide is added at 130 DEG C, the initial concentration for making benzoyl peroxide is 0.2%, keeping temperature is reacted 6 hours, is obtained middle segment and is grafted for maleic anhydride in the multiterminal section-mono- of poly-β-hybroxybutyric acid Between section multi-segment structure copolymer.
Under inert gas shielding, by the triblock copolymer of gained, 3- amino -1,2,4- triazoles are dissolved in dimethylbenzene, It is 2 to keep maleic anhydride side base and the mol ratio of 3- amino-1,2,4-triazols:3, in 80 DEG C of stirring reactions, obtain intermediate chain The multi-segment structure copolymer thermoplastic elasticity of multiterminal section containing acid amides-triazol radical and carboxyl-mono- interlude in section side base Body.
Performance：Tensile strength 3.7MPa, it is broken rate elongation 1560%.Using the material as athletes ' body protection device, Such as knee-pad, rib material, the protection impacted for external force to body.
Embodiment 8
Under nitrogen protection, 5 molar equivalent bisphenol-As, 6 molar equivalent dichloro diphenyl sulfones are dissolved in 1-METHYLPYRROLIDONE, Using toluene as dehydrating agent, Carbon Dioxide calcium is salt forming agent, is warming up to 140 DEG C and reacts 1 hour, and the water of present invention generation is by toluene Take out of and separate, then heat to 160 DEG C react 4 hours, then to 180 DEG C react 4 hours.After the completion of question response, room is cooled to Temperature, 2 molar equivalent para-aminophenol, toluene and potassium carbonate are added, repeat said process.Crude product obtains both ends through ethanol precipitation For the polysulfones of amino.
2, the 4- toluene di-isocyanate(TDI)s (2,4-TDI) of 2 molar equivalents are dissolved in chloroform, instillation contains 1 molar equivalent both ends For the chloroformic solution of the polysulfones segment of amino, room temperature is down to after being reacted 2 hours at 50 DEG C, then instills the ethamine of 1 molar equivalent, Reaction 2 hours, obtain the polysulfones that one end is isocyanates.
In anhydrous conditions, 1 molar equivalent sodium hydride is dissolved in tetrahydrofuran, solution is cooled to 0 DEG C, instilled 0.8 and rub That equivalent ethyl acetoacetate.After being sufficiently stirred, solution is cooled to -78 DEG C, 1 molar equivalent n-BuLi is instilled into solution, After being sufficiently stirred 30 minutes, the bromo- 1- decene of 1 molar equivalent 10- is added.Solution temperature is slowly increased to room temperature, and it is small to react 16 When, add water quenching and go out reaction, obtain intermediate 8a.By intermediate 8a obtained by 1 molar equivalent and the bromo- 2- second of 1.3 molar equivalent 1- Base hexane is dissolved in DMF, adds 2 molar equivalent potassium carbonate, is reacted 24 hours at 70 DEG C, obtain intermediate 8b.By 1 molar equivalent Gained intermediate 8b is dissolved in ethanol, adds 1 molar equivalent guanidine carbonate.React 24 hours at a reflux temperature, obtain intermediate 8c.
In anhydrous conditions, 1 molar equivalent 8c and 1 molar equivalent 2,6- diisopropyl phenylisocyanates are dissolved in tetrahydrochysene furan Mutter, react 16 hours at room temperature, obtain the UPy derivatives that one end is alkenyl.It is alkenyl by one end obtained by 1 molar equivalent The 3- mercaptopropionic acids of UPy derivatives and 20 molar equivalents are dissolved in DMF, and under 0.5 molar equivalent AIBN catalysis, obtaining one end is The UPy derivatives of carboxyl.In anhydrous conditions, by 1 molar equivalent hydroxyethyl methacrylate and 1 molar equivalent obtained by UPy Derivative is dissolved in chloroform, is reacted under DCC and DMAP catalysis, obtains the methacrylate-based monomer containing UPy.
Under nitrogen protection, 11 molar equivalent 2- bromine isobutyl acylbromides and 5 molar equivalent ethylene glycol are dissolved in dichloromethane, Under the catalysis of 12 molar equivalent triethylamines dual initiator 1,2- pairs (bromine isobutyl acyl-oxygen) is obtained in 0 DEG C of reaction.Anhydrous and oxygen-free condition Under, the methacrylate monomers that 90 molar equivalent n-BMAs and 10 molar equivalent monomers contain UPy are dissolved in Toluene, using cuprous bromide and PMDETA as catalyst, with 1 molar equivalent 1,2- double (bromine isobutyl acyl-oxygens) is initiator, at 90 DEG C Lower reaction 6 hours, obtain the polymethacrylates segment of both ends bromine atoms end-blocking.By the poly- methyl-prop obtained by 1 molar equivalent Olefin(e) acid ester segment and 4 molar equivalent 2 mercapto ethanols are dissolved in dimethyl sulfoxide (DMSO) (DMSO), under the catalysis of triethylenediamine in 40 DEG C of reactions, obtain the polymethacrylates that the hydroxy-end capped side base in both ends contains urea groups pyrimidone.
Under the conditions of anhydrous and oxygen-free, the polymethacrylates obtained by 1 molar equivalent and the polysulfones obtained by 2 molar equivalents are existed In 60 DEG C of reactions under DBTDL catalysis, the multi-segment structure copolymer thermoplastic elastomer of multiterminal section-mono- interlude is obtained.
Performance：25℃：Tensile strength 16.5MPa, it is broken rate elongation 0.7%；75℃：Tensile strength 15.9MPa, fracture are prolonged Long rate 690%.Army and police's protective article, explosion-proof coating etc. are made with the material, for extraneous impulsive force such as explosion wave Snubber.
Embodiment 9
1 molar equivalent ethamine, 2.5 molar equivalent dithiothreitol (DTT)s (DTT), 6 molar equivalent γ-thiobutryolacatone are added (both volume ratios are 1 to the mixed solution of ethanol and 0.5M sodium acid carbonates:1).Reaction in 50 DEG C of progress, obtains under nitrogen protection Compound 9a.
Under nitrogen protection, 1 molar equivalent is dissolved in dichloromethane to fluorobenzoyl chloride and 1.5 molar equivalent alchlors Alkane, reacted 3 hours after being slowly dropped into 1 molar equivalent o-tert-butylphenol at -20 DEG C.After hydrochloric acid and sodium hydroxide solution extraction Recrystallize in methyl alcohol, obtain monomer 4- (4 '-fluorobenzoyl) -2-TBP.
By 1 molar equivalent initiator 4- normal-butyls -2 ', 3 ', 4 ', 5 ', 6 '-five fluorine benzophenone, 1.5 molar equivalent carbonic acid It is 1 that potassium, which is dissolved in 1-METHYLPYRROLIDONE and volume of toluene ratio,:5 mixed solvent, after removing water under azeotropic conditions, add 10 moles Monomer 4- (4 '-fluorobenzoyl) -2-TBP obtained by equivalent, reacted 12 hours at 150 DEG C, add and be dissolved in toluene 0.5 molar equivalent double hydroxy-end capped polybutadiene (mean molecule quantity about 20000), continue reaction 6 hours.It will react molten Liquid is deposited in water and methanol successively, and it is the more of multiterminal section-mono- interlude that polyether-ketone interlude is polybutadiene to obtain both ends section Segmentation structure copolymer.
By the multi-segment structure copolymer of the multiterminal section obtained by 1 molar equivalent-mono- interlude and the chemical combination of 100 molar equivalents Thing 9a is dissolved in toluene, adds the azo-bis-isobutyl cyanide (AIBN) of 0.1 molar equivalent, is reacted at 60 DEG C, obtain both ends Duan Weiju Ether ketone interlude is the multi-segment structure copolymer heat of polybutadiene and multiterminal section-mono- interlude of interlude side base amide-containing Thermoplastic elastic.
By the above-mentioned mass parts of copolymer thermoplastic elastomer 100, the mass parts of antioxidant D 1, the mass parts of accelerant CZ 1, stone The mass parts of wax oil 6, the mass parts of blowing agent H 8 are placed in mould after being sufficiently mixed, and in 125 DEG C of sulfur foams 20 minutes, cooling was de- Continue to vulcanize 15 minutes at 150 DEG C after mould, obtain corresponding foamed product.
Performance：Tensile strength 2.1MPa, it is broken rate elongation 1370%；Density：108kg/m3.Using the foamed product as subtracting Part is shaken, for defense of resistance to impact.
Embodiment 10
2 molar equivalent PABA methyl esters and 5 molar equivalent 4- n-octyloxies benzaldehydes are mixed, at 70 DEG C Lower reaction 30 hours, collect gained and precipitate and cleaned with ethanol, obtain midbody compound 10a.
Compound 10a obtained by 1 molar equivalent is dissolved in mixed solution (tetrahydrofuran, the methanol body of tetrahydrofuran and methanol Product is than being 5:2) 1 molar equivalent sodium borohydride, is added in 0 DEG C of stirring reaction 6 hours.Reaction solution is extracted with water, collection has Machine phase simultaneously recrystallizes in hexane and ethyl acetate, obtains monomer 10b.
Under the conditions of anhydrous and oxygen-free, lithium hexamethyldisilazide is dissolved in tetrahydrofuran and is configured to the solution that concentration is 1M. The solution temperature prepared is down to 0 DEG C, sequentially adds 1 molar equivalent phenol benzoate and 10 molar equivalent monomer 10b.Will be anti- Answer solution to be warmed to room temperature after being kept for 30 minutes at 0 DEG C, continue reaction 6 hours, add ammonium chloride and reaction is quenched.After solvent, Crude product is dissolved in dichloromethane, with water abstraction impurity removal, retains organic phase, water removal, which removes, to be obtained imino group after solvent seasoning and be substituted The polyarylamine segment 10c of protection.It is anti-that gained polyarylamine segment 10c and hydroxy-end capped methyl vinyl silicon oil are subjected to ester exchange Should, methanol is removed in course of reaction.Obtain substituting in polyarylamine-polysiloxanes-substitution polyarylamine multiterminal section-mono- after question response is complete Between section multi-segment structure copolymer.
The methyl isocyanate of 1 molar equivalent 2- aminoothyl mercaptans and 1 molar equivalent is dissolved in dichloromethane, reaction obtains 10d。
By the multi-segment structure copolymer of the multiterminal section of a certain amount of gained-mono- interlude, compound 10d, 2- (tertiary butyloxycarbonyl Base-amino) ethyl mercaptan and photoinitiator b DK react in tetrahydrofuran, keep alkenyl and compound 10d, 2- in polysiloxanes (t-butoxycarbonyl-amino) ethyl mercaptan and BDK mol ratio are about 100:50:50:1, obtain modified polyorganosiloxane segment side The multi-segment structure polymer of multiterminal section-mono- interlude with urea groups and carbamate groups in base.
The multi-segment structure copolymer of the multiterminal section of gained-mono- interlude is dissolved in trifluoroacetic acid, reacted 3 days at room temperature Afterwards, reaction is quenched with saturated sodium bicarbonate solution, is extracted with chloroform, precipitated in methyl alcohol after being dehydrated concentrate solution, obtain poly- virtue The multi-segment structure copolymer thermoplastic elastomer of amine-modified polyorganosiloxane-polyarylamine multiterminal section-mono- interlude.
Performance：Tensile strength 1.6MPa, it is broken rate elongation 1440%.Damper portion in aerospace vehicle is used as using the material Part, for bumper and absorbing shock energy-absorbing.It is especially suitable for requiring larger energy-absorbing application to operating temperature range.
Embodiment 11
By 1 molar equivalent ethylene glycol, 100 molar equivalent expoxy propane, 100 molar equivalent 1- allyloxy -2,3- epoxies It is the polyethers that pendant hydroxyl groups contain alkenyl that propane hybrid reaction, which prepares both ends,.By polyethers obtained by 1 molar equivalent and 2 molar equivalents 2, 4-TDI is dissolved in dichloromethane, under DBTDL catalysis, obtains the modified polyether that both ends end group is NCO.
The sodium hydroxide of the caprolactam of 60 molar equivalents and 1 molar equivalent is mixed to get component A, by 60 molar equivalents Caprolactam and 10 molar equivalents obtained by modified polyether be mixed to get component B.The components of AB two vacuumize dehydration simultaneously, Blending reaction 10 minutes at 170 DEG C, obtain polyamide-modified polyether-polyamide copolymer.
By the copolymer of gained, 3- sulfydryl -1- propyl alcohol, light trigger benzene BDK reacts in tetrahydrofuran, keeps polyether chain Alkenyl and 3- sulfydryl -1- propyl alcohol and BDK mol ratio are 5 in section:5:1, obtain multiterminal section that pendant polyether group contains hydroxyl-mono- The multi-segment structure copolymer of interlude.
Under the conditions of anhydrous and oxygen-free, the multi-segment structure copolymer of a certain amount of multiterminal section-mono- interlude is dissolved in pyridine, 0 Excessive 2- bromine isobutyl acylbromides are slowly added dropwise under DEG C stirring, then are warming up to room temperature reaction 24 hours, obtain brominated more of pendant polyether group Hold the multi-segment structure copolymer of section-mono- interlude.
Under the conditions of anhydrous and oxygen-free, bromine and acrylate monomer 3a mol ratio in the multi-segment structure copolymer of gained are kept For 1:30, under the catalysis of cuprous bromide and pentamethyl-diethylenetriamine (PMDETA), react, obtain under the conditions of 80 DEG C in toluene The multi-segment structure copolymer of multiterminal section to interlude graft polypropylene acid esters and containing side urea groups-mono- interlude.
The above-mentioned mass parts of copolymer 1 00, and the polyethylene glycol oligomer blending that 100 mass parts are alkyl-blocked are taken, will be blended Thing is placed in mould, and 30 minutes are incubated at 180 DEG C.It is poly- based on polyethers dynamic that side base acid esters containing urethane groups are produced after cooling down The polyethylene glycol oligomer swell gel of compound elastomer.
Performance：Tensile strength 2.8MPa, it is broken rate elongation 860%.The gel can be used for damping.
Embodiment 12
6- amino -1- hexanols and methylchloroformate are reacted in dichloromethane, using anhydrous sodium bicarbonate as catalyst, control The molal quantity ratio of amino and methylchloroformate processed is 10:11, obtain compound 12a.
Under nitrogen protection, by high molecular weight nylon 6 (mean molecule quantity about 50000), the n-Decylamine of equimolar equivalent with And be placed in the diphenyl sulphone (DPS) of the quality such as nylon 6 in closed container, reacted at 235 DEG C, obtain single-ended amino-terminated low molecule Measure nylon 6 (mean molecule quantity about 3000).
Low-density cladodification polyethylene (mean molecule quantity is about 20000) is dissolved by heating in dimethylbenzene, 100 moles is added and works as The maleic anhydride of amount, after solution temperature rises to 130 DEG C, add the initiator cumyl peroxide for being dissolved in dimethylbenzene, constant temperature Reaction obtains Research of Grafting Malaic Anhydride Onto Polyethylene after 1 to 3 hour
By the single-ended amino-terminated low molecule amount nylon 6 of the polyethylene obtained by 1 molar equivalent and 10 molar equivalents 200 Melt blending at DEG C, obtain the polycthylene grafted nylon 6 that side base carries maleic anhydride.
Polyethylene obtained by 1 molar equivalent is dissolved by heating to the compound that 100 molar equivalents (excess) are added in dimethylbenzene 12a and paratoluenesulfonic acid sodium salt, in 105 DEG C of stirring reactions, obtain the polycthylene grafted nylon containing carbamate groups in side base 6。
By the odium stearate of the mass parts of polycthylene grafted nylon 6,20 obtained by 100 mass parts, the sodium acid carbonate of 5 mass parts Fully it is blended with 0.1 mass parts vaseline oil, product needed for extrusion molding.
Performance：Tensile strength 1.3MPa, it is broken rate elongation 950%；Density：60kg/m3.Lightweight package is used as using the material Material, for damping shock resistance.
Embodiment 13
Nitrogen protection under, by 1 molar equivalent both ends for amino L-PEI and 8 molar equivalent ALANINEs- N- carboxyls-ring inner-acid anhydride is dissolved in dimethylformamide, reacts at room temperature, after question response is complete, with methanol extraction product, obtains Both ends are the multi-segment structure copolymer of multiterminal section-mono- interlude of polypeptide chain.
1 molar equivalent IPDI and 1 molar equivalent n-propylamine are dissolved in dichloromethane, question response is complete The copolymer of a certain amount of gained is added afterwards, and keeps the secondary amine in polyethyleneimine segment to be with the NCO in solution 3:1, obtain the multi-segment structure copolymer for multiterminal section-mono- interlude that side base in polyethyleneimine segment contains urea groups.
Performance：Tensile strength 1.2MPa, it is broken rate elongation 920%.Using the material as coating or squeegee, for buffering Protection, energy-absorbing shock absorbing.
Embodiment 14
Under the conditions of anhydrous and oxygen-free, by ethyl isocyanate Isosorbide-5-Nitrae-pentadiene -3- alcohol, the Isosorbide-5-Nitrae-penta with equimolar equivalent respectively Diene -3- amine and Isosorbide-5-Nitrae-pentadiene -3- thiol reactants, side base is obtained with carbamate groups, urea groups, thiocarbamate Double olefin compound 14a, 14b and 14c of base.
Under the conditions of anhydrous and oxygen-free, by 1 molar equivalent 1,3- diaminoureas and 2 molar equivalents 2,4-TDI is dissolved in ethanol, React 16 hours at room temperature, obtain the triuret intermediate that both ends are NCO.Intermediate obtained by 1 molar equivalent is dissolved in DMSO, the n-butanol of 1.1 molar equivalents and the hydroxy-ethyl acrylate of 1 molar equivalent are added, it is alkene to obtain one end in 60 DEG C of reactions The segment 14d rich in hydrogen bond group of propyl group.
By the polyethylene glycol, 2 molar equivalent compound 14a, 1 molar equivalent compound of 2 molar equivalent diallyls end-blocking 14b, 1 molar equivalent compound 14c, 8 molar equivalents 1,2- dithioglycols are mixed in DMF, drawn by light of benzoin dimethylether Send out agent, the illumination reaction under uviol lamp.After 3 hours, add 2 molar equivalent diallyls end-blocking polyethylene glycol and 2 moles work as 1,2- dithioglycols are measured, continue to carry out illumination reaction under uviol lamp.After 2 hours, 2 molar equivalent segment 14d are added, are continued Illumination reaction, after reaction completely, obtain in side base containing hydrogen bond group and using the segment rich in hydrogen bond for hold section based on polyethers Thermoplastic elastomer (TPE).Before solvent, the 1- ethyl-3-methylimidazole tetrafluoro boron containing aforementioned base materials gross weight phase homogenous quantities is added Hydrochlorate, solvent is removed after well mixed, produces corresponding 1- ethyl-3-methylimidazoles tetrafluoroborate ionic gel.
The modulus of ionic liquid gel prepared by the embodiment can reach 8 times in 48kPa, strain, and fracture strength exists 95kPa.Using this ionic liquid gel as protective pad, the impact for anti-external forces.
Embodiment 15
By 1 molar equivalent ethylene glycol, 100 molar equivalent oxirane, 50 molar equivalents (S)-(oxiranylmethyl) ammonia Base t-butyl formate, 50 molar equivalent 3- [(acetparaminosalol) phenoxy group] -1,2 epoxy prapane hybrid reaction prepare both ends and are Pendant hydroxyl groups contain the polyethers of carbamate groups and amide groups.
By 2 molar equivalents 4,4- hexylmethanes are dissolved in DMSO, and 1 molar equivalent urine is instilled at 70 DEG C Element, room temperature is cooled the temperature to after question response is complete, add 1 molar equivalent ethamine and continue to react.After question response is complete, gained is added Two end groups be pendant hydroxyl groups acid esters containing urethane groups polyethers, and instill catalyst DBTDL, reaction obtains containing in side base Carbamate groups and the thermoplastic elastomer (TPE) using the segment rich in hydrogen bond as both ends end section.
By the mass parts of gained thermoplastic elastomer (TPE) 100, the mass parts of hollow glass micro-ball 50, polyvinylpyrrolidone particle 20 Mould is injected after mass parts blending, produces the foamed product containing tiny balloon.
Performance：Tensile strength 8.3MPa, it is broken rate elongation 1270%；Density：180kg/m3.Bag is used as using the foamed product Package material, for sound insulation, bumper and absorbing shock, while the function such as also heat-insulated, moisture absorption.
Embodiment 16
The 2- ethylbutanoyl chlorine of 4,4 '-di-2-ethylhexylphosphine oxide (phenyl isocyanate) and equimolar equivalent is dissolved in dimethylbenzene, slowly Instill the xylene solution containing 1.5 molar equivalent triethylamines.After reacting 4 hours at a reflux temperature, -15 DEG C are cooled to, filter Insoluble matter is removed, except the crude product that the 16a containing compound is obtained after solvent.
Under the conditions of anhydrous and oxygen-free, 1 molar equivalent aniline and the crude product containing 1 molar equivalent compound 16a are dissolved in toluene, Reacted 2 hours at 4 DEG C, be filtrated to get the intermediate insoluble in toluene.The N- aminoethyl piperazines of 1 molar equivalent are dissolved in DMF, Reacted 1 hour at 20 DEG C, with water sedimentation, obtain product 16b not soluble in water.
Compound 16b is dissolved in acetone, and the intermediate 16a of the equivalent containing equimolar crude product reaction, after 20 minutes, used Hexamethylene precipitates to obtain intermediate.Under nitrogen protection, the N- aminoethyl piperazines of intermediate and equimolar equivalent are dissolved in anhydrous DMF, reacted 1 hour at 20 DEG C, with water sedimentation, obtain product 16c not soluble in water.
Using iodoformum as initiator, Sodium Thiosulfate is catalyst, and the polymerization of VCM is carried out in water, is kept Monomer, catalyst, the mol ratio of initiator are 200:16:1, using Methocel F50 and PVA88 as stabilizer, keep both with The mass ratio of monomer is respectively 420ppm and 980ppm, and using sodium acid carbonate and SPTS as auxiliary agent, at 35 DEG C Reaction 24 hours, obtains the polyvinyl chloride that both ends are blocked with iodine atom.Under the conditions of anhydrous and oxygen-free, by the molar equivalent polychlorostyrene of gained 1 Ethene, 2 molar equivalent sodium sulfites, 2.2 molar equivalent sodium acid carbonates and 10 molar equivalent pi-allyl hydroxyethyl ethers are dissolved in DMSO, reacted 4 hours at 70 DEG C, concentrated reaction solution is precipitated in methyl alcohol, obtains both ends with hydroxy-end capped polyvinyl chloride.
1 molar equivalent 16c and 1 molar equivalent IPDI are dissolved in tetrahydrofuran, after question response is complete 0.5 molar equivalent both ends are added with hydroxy-end capped polyvinyl chloride, under catalyst DBTDL catalysis, obtain both ends with rich in The polyvinyl chloride of the segment end-blocking of hydrogen bond group.
By the multi-segment structure copolymer of gained polyvinyl chloride multiterminal section-mono- interlude and 4- (2- pyrrolidinyls) benzenethiol It is dissolved in hexamethylene to react 12 hours at 60 DEG C, the mol ratio for keeping side base chlorine atom and 4- (2- pyrrolidinyls) benzenethiol is about 3: 2, obtain the multi-segment structure copolymer of the multiterminal section containing parahelium-mono- interlude in polyvinyl chloride segment side base.By in side base Copolymer and methyl isocyanate containing parahelium react in dichloromethane, keep the mol ratio of secondary amino group and methyl isocyanate about For 1:1, obtain the dynamic aggregation thing based on polyvinyl chloride of side base urea groups containing substitution.
By the mass parts of dynamic aggregation thing 100 based on polyvinyl chloride of gained, the mass parts of epoxidized soybean oil 70, tripotassium phosphate The mass parts of phenyl ester 50 are well mixed, and are placed in mould and are incubated 30 minutes in 180 DEG C, and the base of side base urea groups containing substitution is obtained after cooling In the dynamic aggregation thing plasticizer swell gel of polyvinyl chloride.
Performance：Tensile strength 31MPa, it is broken rate elongation 630%.It is excellent for providing using the material as blast wall interlayer Good shock resistance.
Embodiment 17
Two dimethyl carbonates of 6- amino -1- hexanols and equimolar equivalent are dissolved in tetrahydrofuran, reaction obtains compound 17a.The 4- amylene isoxazolecarboxylic acids of compound 17a and equimolar equivalent are dissolved in dichloromethane, reacted under the catalysis of triethylamine To compound 17b.Compound 17b is added into toluene, reaction vessel is cooled to 5 DEG C, cyclopentadiene is added dropwise in low temperature, protects It is 10 that compound 17b, which is held, with cyclopentadiene mol ratio:13.Reflux temperature is warming up to after being added dropwise and continues stirring reaction, is obtained The norbornene derivative 17c of hydrogen bonds group.Under nitrogen protection, by 1 molar equivalent anthracene and 5 molar equivalent norbornadienes Closed reaction vessel is placed in, is reacted 24 hours at 180 DEG C, obtains monomer 17d.
Under the conditions of anhydrous and oxygen-free, 1 molar equivalent Grubbs three generations's catalyst is dissolved in dichloromethane and drops solution temperature To -10 DEG C.15 molar equivalent monomer 17d are dissolved in dichloromethane and add catalyst solution and are reacted 30 minutes, then by 350 moles Equivalent monomer 17c is dissolved in dichloromethane and adds catalyst solution, and temperature is risen into 0 DEG C reacts 6 hours, finally works as 15 moles Amount monomer 17d is dissolved in dichloromethane and adds catalyst solution, cools the temperature to -10 DEG C and reacts 30 minutes, obtains based on poly- drop The multi-segment structure polymer of the multiterminal section of bornylene-mono- interlude.
Performance：Tensile strength 5.4MPa, it is broken rate elongation 1780%.Airborne and air-drop protection material is used as using the material Material, for shock resistance.
Embodiment 18
Cyanuric acid and the chloro- 1- hexenes of 6- keep mol ratio 4:1, anhydrous dimethyl sulphoxide is dissolved in, under potassium carbonate catalysis Stirring reaction 15 hours at 80 DEG C, obtain the olefinic monomer 18a of hydrogen bonds group.
10 molar equivalent compound 18a are added into toluene, reaction vessel are cooled to 5 DEG C, low temperature is added dropwise 13 and rubbed That equivalent cyclopentadiene.Reflux temperature is warming up to after being added dropwise and continues stirring reaction, obtains compound 18b.
Under the conditions of anhydrous and oxygen-free, by 1 molar equivalent initiator 2, the double tert-butoxy molybdenums of 6- diisopropyls imines are dissolved in toluene, 5 molar equivalent conditioning agent trimethyl phosphorus and 30 molar equivalent crystalline polymer monomer ENBs are added, after reacting 1 hour, are added Enter the glassy polymers monomer methyl tetracyclododecen of 20 molar equivalents.After continuing reaction 1 hour, rubbery feel polymer is added Each 450 molar equivalents of polymer soft segment monomer 18b of monomer 5- n-hexyl -2- ENBs and hydrogen bonds group.Finally, add 0.5 molar equivalent coupling agent m-terephthal aldehyde, after reaction completely, product is precipitated in methyl alcohol, obtains five block copolymers.
Five block copolymers of gained are dissolved in hexamethylene, using platinum as catalyst, catalytic hydrogenation is carried out at 100 DEG C, is obtained To hard section be crystalline state-glassy state di-block copolymer soft segment be rubbery state random copolymer based on hydrogenation polynorbornene The multi-segment structure dynamic aggregation thing thermoplastic elastomer (TPE) of multiterminal section-mono- interlude.
Performance：Tensile strength 9.5MPa, it is broken rate elongation 2310%.Using the elastomer as packaging material, available for height Imitate damping.Meanwhile the product has splendid toughness, and resilience is good, and set resistant is small, can carry out large range of stretching.
Embodiment 19
By monomer of N- β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane and octamethylcy-clotetrasiloxane using water as Terminator carries out the ring-opening polymerisation of siloxanes, obtains the polysiloxanes 19a that both ends are hydroxyl.
Under nitrogen protection, urea is added into gained polysiloxanes, it is 1 to keep the mol ratio of urea and amino:1, stirring Under be to slowly warm up to 160 DEG C, after insulation about 1 hour, be down to room temperature, obtain modified polyorganosiloxane 19b.
With 1 molar equivalent benzoyl peroxide (BPO) for initiator, 1 molar equivalent TGA is chain-transferring agent 90 DEG C trigger 30 molar equivalent n-BMAs polymerization, obtain the Vinalac 5920 of single-ended carboxy blocking.
The polysiloxanes 19b of 1 molar equivalent and 2 molar equivalents Vinalac 5920 are dissolved in tetrahydrofuran, Using DCC and DMAP as catalyst, it is more to obtain Vinalac 5920-modified polyorganosiloxane-Vinalac 5920 Hold the multi-segment structure thermoplastic elastomer (TPE) of section-mono- interlude.
Performance：Tensile strength 0.9MPa, it is broken rate elongation 1010%.The material can be used for shock resistance, damping, buffering.
Embodiment 20
Isosorbide-5-Nitrae-pentadiene -3- alcohol and 1H- benzimidazole -5- acyl chlorides are reacted under the catalysis of triethylamine, side base is obtained and contains There is the diene 20a of benzimidazolyl.
Under anhydrous and oxygen-free normal pressure, ethene is passed through reaction vessel, sequentially adds solvent toluene, the first containing MAO Benzole soln, the toluene solution containing zirconium complex catalyst 20b, it is 2000 to keep the mol ratio of aluminium and zirconium, and it is 1 big to keep ethene Air pressure, after reaction being stirred at room temperature 15 minutes, reaction is quenched with the ethanol solution containing 10% hydrogen chloride.By reaction solution in second Precipitated in alcohol, obtain the straight chain crystallinity polyethylene for one end alkenyl end-blocking that mean molecule quantity is about 2000.
By gained diene 20a, diallyl ether and 1,2- dithioglycols in molar ratio 50:50:101 blendings, add 1wt% Light trigger 2,2- dimethoxy -2- phenyl acetophenones, illumination 30 minutes under 300W uviol lamps, obtain sulfydryl end-blocking side base and contain There is the polythiaether of benzimidazolyl.
Polythiaether obtained by 1 molar equivalent is blended with 2 molar equivalents gained polyethylene in chlorobenzene and is heated to 105 DEG C, Add 1 molar equivalent initiator A IBN and trigger sulfydryl-alkene click-reaction, multiterminal section-mono- interlude is obtained after question response is complete Multi-segment structure dynamic aggregation thing thermoplastic elastomer (TPE).
Performance：Tensile strength 4.7MPa, it is broken rate elongation 830%.Protection pad is made with the material to use, for buffering the external world Impulsive force.
Embodiment 21
By 1 molar equivalent 2- vinyl terephthalic acid (TPA) and 2.1 molar equivalent triphenylphosphines be dissolved in anhydrous pyridine obtain it is molten Liquid A.2.1 molar equivalent 4- metoxyphenols and 2.2 molar equivalent carbon trichlorides are dissolved in anhydrous pyridine and obtain solution B.Will be molten Liquid B is slowly dropped into solution A, and liquid crystal monomer vinyl terephthalic acid (TPA) di-p-methoxy phenyl ester (MPCS) is obtained in 60 DEG C of reactions.
1 molar equivalent 1- (2- amino-ethyls) -2- imidazolones and 1 molar equivalent isocyanates ethyl acrylate are dissolved in Dichloromethane, react 6 hours at room temperature, obtain acrylic ester monomer 21a.
Under nitrogen protection, 13 molar equivalent 2- bromine isobutyl acylbromides and 3 molar equivalent pentaerythrites are dissolved in dichloromethane, Under the catalysis of 15 molar equivalent triethylamines tetrafunctional initiator is obtained in 0 DEG C of reaction.Under the conditions of anhydrous and oxygen-free, 1 molar equivalent The tetrafunctional initiator of gained, 2 molar equivalent cuprous bromides, 2 molar equivalent PMDETA, 400 molar equivalent n-butyl acrylates, 400 molar equivalent monomer 21a sequentially add reaction vessel, and the four arms polymerization obtained based on polyacrylate is reacted at 80 DEG C Thing.
Under the conditions of anhydrous and oxygen-free, by 4 molar equivalent stannous chlorides, 4 molar equivalent PMDETA and 200 molar equivalent monomers MPCS is placed in reaction vessel, adds the chlorobenzene solution containing modified polyacrylate obtained by 1 molar equivalent, is reacted at 110 DEG C To the polymer with hub-and-spoke configuration using side chain type liquid crystal macromolecule as end section.
The mass parts of resulting polymers 100 and the mass parts of 1- butyl -3- methylimidazoles hexafluorophosphate 100 are dissolved in DMF simultaneously Fully blending, except obtaining corresponding dynamic aggregation thing ionic gel after solvent.
The modulus of ionic liquid gel prepared by the embodiment can reach 15 times in 17kPa, strain, and fracture strength exists 45kPa, used as gel, for damping shock absorption.
Embodiment 22
Aniline and succinic anhydride are dissolved in dioxane, it is 1 to keep the mol ratio of aniline and succinic anhydride:1.03 add A small amount of zinc powder, reacted at 60 DEG C and obtain 4- carbonyls -4- (phenyl amino) butyric acid.The 4- nitroanilines of 1 molar equivalent are dissolved in Hydrochloric acid, is slowly added dropwise the deionization solution containing 1.03 molar equivalent natrium nitrosums, and reaction adds a small amount of urea after 30 minutes, stirred Mix to remove excessive natrium nitrosum, then rapidly join the hydrogen-oxygen containing 0.95 molar equivalent 4- carbonyls -4- (phenyl amino) butyric acid Change sodium solution (naoh concentration 2mol/L, 4- carbonyl -4- (phenyl amino) butyric acid density is about 0.1g/mL), quickly stir Mix reaction 2 hours.Stir and filter after adding a small amount of hydrochloric acid acidifying, one end end group is obtained after deionized water is washed and is dried is The liquid crystal end section 22a of carboxyl.
Under the conditions of anhydrous no 90 DEG C of air, limonene oxide and catalyst 22b are dissolved in toluene, keep limonene oxide Mol ratio with catalyst is 100:1,10bar carbon dioxide is passed through into reaction vessel, after reaction completely, by crude product first Alcohol precipitates to obtain poly- limonene carbonic ester segment.The poly- limonene carbonic ester segment of gained and 1,3-PD are dissolved in toluene, added Enter catalyst 1,5,7- tri- azabicyclic [4.4.0] decyl- 5- alkene, reacted 3 hours at 80 DEG C, obtaining mean molecule quantity is about 4000 both ends are with hydroxy-end capped poly- limonene carbonic ester segment 22c.
By the poly- limonene carbonic ester 22c containing 100 molar equivalent alkenyls, 50 molar equivalent 3- mercaptopropionic acid -2- ethyls Own ester, 50 molar equivalent compound 9a are dissolved in chloroform, add the AIBN of 0.3 molar equivalent, at 60 DEG C reaction obtain side base and contain There is the poly- limonene carbonic ester of amide groups.
2,4-TDI of 1 molar equivalent hydroxy-end capped poly- limonene carbonic ester and 2 molar equivalents is dissolved in DMF, at 60 DEG C Lower reaction obtains the DMF solution containing isocyanate-terminated poly- limonene carbonic ester.2 molar equivalent liquid crystal chains will be contained again Section 22a DMF solution is slowly dropped into, and is reacted at 75 DEG C, is obtained being based on poly- limonene carbonic ester thermoplastic elastomer (TPE).
Polyamide-the modification that will be obtained in thermoplastic elastomer (TPE) of the gained based on poly- limonene carbonic ester and embodiment 11 Polyphenylene ether-polyamide thermoplastic elastomer (TPE) presses quality 1:1 melt blending, obtain the thermoplastic elastomer (TPE) with inierpeneirating network structure.
Performance：Tensile strength 7.2MPa, it is broken rate elongation 1720%.Using the material as packaging material, subtract for buffering Shake.In addition, the material renewable raw materials, can be widely used for the bumper and absorbing shock of disposable products.
Embodiment 23
Under the conditions of anhydrous and oxygen-free, by the isocyanates ethyl acrylate of ethyl mercaptan and equimolar equivalent under triethylamine catalysis Reacted in dichloromethane, obtain the acrylate monomer 23a containing thio carbamate groups.
Under the conditions of anhydrous and oxygen-free, solvent methyl phenyl ethers anisole is added successively into reaction vessel, 1 molar equivalent rubs to benzene sulfonyl chloride, 2 That equivalent PMDTA and 30 molar equivalent Tert-butyl Methacrylates, after being well mixed, 1 molar equivalent stannous chloride is added, 60 Reacted 12 hours at DEG C, add 50 molar equivalent n-butyl acrylates and 100 molar equivalent monomer 23a mixture, will be anti- After answering system to be maintained at and reacted 12 hours at 60 DEG C, 30 molar equivalent styrene monomers are added, it is small to be warming up to 80 DEG C of reactions 48 When.After reaction terminates, reaction solution and tetrahydrofuran are blended, first filtered with neutral alumina column, then tetrahydrofuran shower.Will After filtrate is collected and concentrated, with methanol extraction, in triplicate, the poly- first that interlude side base contains thiocarbamate base is obtained The multi-segment structure polymer of base tert-butyl acrylate-acrylate copolymer-polystyrene multiterminal section-mono- interlude.
The multi-segment structure polymer of multiterminal section obtained by 1 molar equivalent-mono- interlude is dissolved in 1,2- dichloroethanes, added Enter 30 molar equivalent trifluoroacetic acids, the stirring reaction at 60 DEG C.Treat that the hydrolysis of polymethyl tert-butyl acrylate segment is complete, gathered Methacrylic acid-acrylate copolymer-polystyrene dynamic aggregation thing thermoplastic elastomer (TPE).
Performance：Tensile strength 1.8MPa, it is broken rate elongation 1670%.The material can prepare subtracting for all kinds of electronic apparatus Shake, buffer protection film.Meanwhile the material also provides splendid toughness and shape memory function.
Embodiment 24
A certain amount of 5- cyclo-octene -1,2- glycol and 2- imidazolidinone -4- carboxylic acids are mixed, the ratio of both molal quantitys of control Value about 1:2, using DCC and DMAP as catalyst, dichloromethane is solvent, obtains monomer 24a.
Under the conditions of anhydrous and oxygen-free, a certain amount of monomer 24a and cyclo-octene are mixed, the ratio of both molal quantitys of control is about For 1:2, using Grubbs bis- generations catalyst as catalyst, using maleic acid as chain-transferring agent, keep catalyst, chain-transferring agent and monomer Mol ratio be 1:4000:20000.Using tetrahydrofuran as solvent, reacted 2 hours at 40 DEG C.It is quenched with vinyl ethyl ether poly- Reaction, and precipitated product in methyl alcohol are closed, it is polycyclic octene of the carboxyl side group containing imidazolidinonyl to obtain two end groups.
The hydroxy-end capped polystyrene 4b of modification polycyclic octene obtained by 1 molar equivalent and 2 molar equivalent one end is dissolved in Dichloromethane, using DCC and DMAP as catalyst, obtain the multi-segment structure copolymer of multiterminal section-mono- interlude.
1 molar equivalent both ends are dissolved in dichloromethane for the polyisobutene (mean molecule quantity about 2000) of amino, with 2 moles The chloroacetic chloride of equivalent reacts under the catalysis of pyridine, obtains the polyisobutene hydrogen bond connection auxiliary agent of both ends amide-containing.Will be above-mentioned Copolymer connects auxiliary agent in mass ratio 9 with gained hydrogen bond:1 blending, obtains the dynamic aggregation thing thermoplasticity of hydrogeneous key connection auxiliary agent Elastomer.
Performance：Tensile strength 2.3MPa, it is broken rate elongation 970%.Using the material as packaging material, device outer case, tool There is damping, buffering function.
Embodiment 25
Using toluene as solvent, zirconium complex Et [H4-Ind]2ZrCl2For catalyst, MAO is co-catalyst, is entered Row propylene polymerization, obtain the isotactic polypropylene of one end alkenyl end-blocking., will be poly- obtained by 1 molar equivalent under the conditions of anhydrous and oxygen-free Propylene adds chlorobenzene, and in 105 DEG C of fully dissolvings.The 3- mercaptopropionic acids of 20 molar equivalents and the AIBN of 0.5 molar equivalent are added, Reaction 5 hours, precipitated product, obtains the isotactic polypropylene that one end is carboxy blocking in ethanol.
Under the conditions of anhydrous and oxygen-free, 1 molar equivalent azo dimethyl N-2- hydroxyl butyl propionamides are dissolved in toluene, add 105 The vinylacetate of molar equivalent.React 16 hours at a reflux temperature, obtain the polyvinyl acetate that both ends are hydroxyl.
2 molar equivalent isotactic polypropylene, 1 molar equivalent polyvinyl acetate are dissolved in toluene, in urging for butyl titanate Under change, reacted 5 hours in 110 DEG C, obtain isotactic polypropylene-modified polyvinyl acetate-isotactic polypropylene multiterminal section-mono- centre The multi-segment structure copolymer of section.
The multi-segment structure copolymer of gained multiterminal section-mono- interlude is dissolved in tetrahydrofuran, addition contains potassium hydroxide Methanol solution, react at room temperature, obtain polyvinyl acetate partial hydrolysis into the more of multiterminal section-mono- interlude of pendant hydroxyl group Segmentation structure copolymer.The multi-segment structure copolymer of gained multiterminal section-mono- interlude is dissolved in chloroform, pendant hydroxyl group etc. is added and rubs The ethyl isocyanate of your equivalent, under DBTDL catalysis, after pendant hydroxyl group reaction completely, obtain containing ammonia in interlude side base The multi-segment structure copolymer of the multiterminal section of carbamate base-mono- interlude.
The above-mentioned mass parts of polymer 100, the mass parts of azodicarbonamide 5.5, the mass parts of lead sulfate tribasic 1 are fully mixed After conjunction, it is placed in mould, foaming is plastified under 170 DEG C of 3.5MPa pressure, is heat-treated 8 minutes at 100 DEG C afterwards, cooling and demolding, Obtain corresponding foamed product.
Performance：Tensile strength 4.2MPa, it is broken rate elongation 780%；Density：105kg/m3.Fortune is made with the foamed material Dynamic protector, such as knee-pad, elbow support, lining of helmet use, for the shock resistance protection to human body.
Embodiment 26
Metachloroperbenzoic acid is gradually added to the dichloromethane solution of Isosorbide-5-Nitrae-cyclohexanedione monoethylene acetal, flowed back Under the conditions of reaction obtain 5- ethylene ketals -6-caprolactone.
Under anhydrous condition, by the polylactide of monohydroxy end-blocking and 5- ethylene ketals -6-caprolactone of 40 molar equivalents Toluene is dissolved in the 6-caprolactone of 40 molar equivalents, is reacted under the catalysis of stannous octoate at 110 DEG C, after question response is complete, 20 molar equivalent levorotatory lactides are added, continues reaction and obtains PLLA that interlude contains ethylene ketal side base-change The multi-segment structure copolymer of property polycaprolactone-PLLA multiterminal section-mono- interlude.
The multi-segment structure copolymer of gained multiterminal section-mono- interlude and triphenyl tetrafluoro boric acid carbon are dissolved in dichloromethane Alkane, it is 1 to keep ethylene ketal side base and the mol ratio of triphenyl tetrafluoro boric acid carbon in copolymer:1.1, react at room temperature, will Ethylene ketal side base is converted into carbonyl.Gained copolymer and sodium borohydride are dissolved in dichloromethane/ethanol volume ratio for 5:2 Blend solvent, it is 1 to keep the mol ratio of carbonyl and sodium borohydride in copolymer:1.2, react at room temperature, carbonyl is converted into Pendant hydroxyl group.
The multi-segment structure copolymer of multiterminal section of the gained containing pendant hydroxyl group-mono- interlude is dissolved in dichloromethane, joining side The ethyl isocyanate of hydroxyl equimolar equivalent, under DBTDL catalysis, reaction obtains the multiterminal of interlude amido-containing acid ester base The multi-segment structure copolymer thermoplastic elastomer of section-mono- interlude.
By the mass parts of multi-segment structure copolymer 1 00 of multiterminal section-mono- interlude, biodegradable polyesters PHB100 mass With injecting mould after the blending of the mass parts of biodegradable polyesters tiny balloon 50, producing can be dropped part containing tiny balloon based on biology Solve the dynamic aggregation thing foamed product of polyester.
Performance：Tensile strength 23MPa, it is broken rate elongation 1270%；Density：170kg/m3.Manufactured and steeped with the foamed material Foam seat, for damping energy-absorbing.
Embodiment 27
Under the conditions of anhydrous and oxygen-free, using 1 molar equivalent cumyl dithiobenzoic acid ester as chain-transferring agent, trigger at 140 DEG C 30 molar equivalent styrene polymerizations.After reaction 6 hours, precipitated in absolute methanol is freezed, and suction filtration is washed with ethanol, put down The right about 20 polystyrene macromolecular chain-transferring agent of homopolymerization.By the polystyrene macromolecular chain tra nsfer obtained by 1 molar equivalent Agent, 150 molar equivalent acrylonitrile, 1 molar equivalent AIBN are dissolved in DMF, are reacted 48 hours at 65 DEG C, and obtaining polyacrylonitrile end is The polystyrene-polypropylene nitrile two-part copolymer of dithiobenzoic acid ester.
Under the conditions of anhydrous and oxygen-free, by the two-part copolymer of the dithiobenzoic acid ester end-blocking obtained by 1 molar equivalent, 20 rub That equivalent tributylphosphine and 50 molar equivalent acrylic acid are dissolved in tetrahydrofuran, the sodium borohydride of 20 molar equivalents are added, in room temperature Lower reaction 20 hours, methanol is deposited in by product, is obtained the polystyrene-polypropylene nitrile two-part that polyacrylonitrile end is carboxyl and is total to Polymers.
By the polyester end of gained two-part copolymer and equimolar equivalent be pendant hydroxyl groups contain the polystyrene of acetylene bond- Modified poly ester two-part copolymer 4c is dissolved in dichloromethane, using bicyclic ethyl carbodiimide and DMAP as catalysis Agent, obtain polystyrene-polypropylene nitrile-modified poly ester-polystyrene copolymer.
By 2, the 5- dehydrations -1- nitrine -1- deoxy-D-glucoses alcohol and nitrile of gained copolymer, and itrile group equimolar equivalent The zinc chloride of the molar equivalent of base 5 is dissolved in DMF, and ultrasound makes each component be warming up to 125 DEG C of stirrings after being sufficiently mixed for 5 minutes anti-at room temperature Should, itrile group is converted into pendant hydroxyl group.By the 2,5- dehydration -1- nitrine -1- deoxidations of gained copolymer and alkynyl equimolar equivalent - D-Glucose alcohol is dissolved in tetrahydrofuran, under the catalysis of cuprous iodide and pyridine, is reacted at 35 DEG C, and alkynyl is converted into side hydroxyl Base.The copolymer that the side base of gained contains hydroxyl is reacted under DBTDL catalysis with ethyl isocyanate, side base is obtained and contains ammonia The dynamic aggregation thing of carbamate base.
Resulting polymers are swollen in Isosorbide-5-Nitrae-dioxane solvent, be placed in mould freezed at -80 DEG C it is complete, - Aspiration pump is opened at 50 DEG C, maintains dry air pressure to be less than 50 μ atm 24 hours, obtained foamed material is placed in 20 DEG C of vacuum Dried in drying box, extract whole solvents, obtain corresponding foamed material.
Performance：Tensile strength 15.6MPa, it is broken rate elongation 1320%, density：93kg/m3.Painting is used as using the foamed material Layer or carrier, for buffer protection, sound absorption shock absorbing.
Embodiment 28
By a certain amount of bisphenol A diglycidyl ether, polyethylene glycol oligomer (molecular weight is about 500) and catalyst trifluoro Change borate ether to be sufficiently mixed, it is 4 to keep the mol ratio of bisphenol A diglycidyl ether and polyethylene glycol:3, the dosage of catalyst is The 1% of polyethylene glycol quality.Mixture is reacted at 80 DEG C, side base is obtained and is gathered for hydroxyl both ends with the epoxy of epoxy radicals end-blocking Compound.
The epoxy polymer of gained and the segment 16b rich in hydrogen bond are sufficiently mixed, keep mol ratio 1:2, slowly heating To 160 DEG C and 2 hours are incubated, obtains the multi-segment structure copolymer of the multiterminal section based on epoxy polymer-mono- interlude.
Gained copolymer and ethyl isocyanate are fully blended, and it is 1 to keep the mol ratio of pendant hydroxyl group and isocyanates:1. The mass parts of blends described above 100 are taken, is placed in mould, delays with the alkyl-blocked mass parts of polyethylene glycol oligomer 100 blending It is slow to be warming up to 180 DEG C and be incubated 2 hours.The dynamic aggregation thing polyethylene glycol of side base amido-containing acid ester base is produced after cooling down Oligomer swell gel.
Performance：Tensile strength 80kPa, it is broken rate elongation 450%.Airborne and air-drop product bags are used as using the gel rubber material Dress, for buffering protecting against shock.
Embodiment 29
Polystyrene 4b using 1 molar equivalent one end as hydroxyl is initiator, triggers 100 molar equivalent oxirane, 50 Molar equivalent (S)-(oxiranylmethyl) t-butyl carbamate ring-opening polymerisation, prepare polyethers end and contain amino for pendant hydroxyl groups The polystyrene-poly ether two-part copolymer of formic acid ester group.
Under nitrogen protection, gained two-part copolymer, maleic anhydride and catalyst pyridine are reacted 6 hours at 170 DEG C, The hydroxyl at polyethers end is converted into carboxyl.
It is pendant hydroxyl groups by two-part copolymer that one end obtained by 1 molar equivalent is carboxyl and 1 molar equivalent polyester end Polymethyl methacrylate containing acetylene bond-modified poly ester 4d is dissolved in dichloromethane, using DCC and DMAP as catalyst, obtain with Polystyrene, polymethyl methacrylate be both ends section using modified polyether and modified poly ester as the multiterminal section-mono- of interlude among The multi-segment structure copolymer of section.
Gained copolymer, 2- azido second ammonia are dissolved in tetrahydrofuran, holding alkynyl, the mol ratio of 2- azido second ammonia are 1:1, under the catalysis of cuprous iodide and pyridine, reacted at 35 DEG C and obtain the Tetrablock copolymer that side base contains amino.By institute Side base contain amino Tetrablock copolymer and ethyl isocyanate reaction, obtain side base and contain carbamate groups and urea groups Dynamic aggregation thing thermoplastic elastomer (TPE).
Performance：Tensile strength 10.1MPa, it is broken rate elongation 1240%.Using the material as pad, for silencing and damping.
Embodiment 30
Hydrogenated SBS is dissolved by heating to the maleic anhydride that 100 molar equivalents are added in dimethylbenzene, when solution temperature rises to 130 After DEG C, the initiator cumyl peroxide for being dissolved in dimethylbenzene is added, isothermal reaction obtains maleic anhydride grafting after 1 to 3 hour Hydrogenated SBS.Under inert gas shielding, compound 12a and gained maleic anhydride grafting Hydrogenated SBS are dissolved in dimethylbenzene, stirred Lower addition catalyst paratoluenesulfonic acid sodium salt, in 105 DEG C of stirring reactions, obtains the modified hydrogenated SBS containing side carbamateyl.
By the SBS30 of gained in the modified hydrogenated mass parts of SBS 100 of gained and the mass parts of Hydrogenated SBS 30 and embodiment 1 Mass parts are fully blended, and obtain three component dynamic aggregation thing elastomer alloys.
Performance：Tensile strength 13.1MPa, it is broken rate elongation 830%.It is used to buffer with product made from the polymer alloy Protection.
Embodiment 31
The acrylic acid that one end is hydroxy-end capped polystyrene 4b and equimolar equivalent is dissolved in dichloromethane, in DCC and React, obtained with the polystyrene of acrylate-based end-blocking under DMAP catalysis.
By 45 molar equivalent n-butyl acrylates, 50 molar equivalent acrylate monomer 3a, 5 molar equivalents are able to propylene Perester radical end-blocking polystyrene be dissolved in toluene, using azo-bis-isobutyl cyanide as initiator, reacted 10 hours at 80 DEG C, obtain with Polystyrene is the thermoplastic elastomer (TPE) for holding section using modified polyacrylate as interlude.
Performance：Tensile strength 4.7MPa, it is broken rate elongation 1450%.With adhesive, closure glue, folder made from the elastomer Layer glue, has the function that bumper and absorbing shock.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair The equivalent structure or equivalent flow conversion that bright description is made, or directly or indirectly it is used in other related technology necks Domain, it is included within the scope of the present invention.

Claims (12)

1. a kind of energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE), it is characterised in that a kind of dynamic aggregation thing is provided Thermoplastic elastomer (TPE), energy-absorbing protection is carried out using this thermoplastic elastic material as energy-absorbing material；Wherein, described thermoplastic elastomehc The polymer molecule of property body has the multi-segment structure of multiterminal section-mono- interlude shown in below general formula,
Wherein, A is end section, and B is interlude；N is the quantity for the end section A being connected between on section B, and it is more than or equal to 2；Each end section A is identical or different, be mutually mixed each other it is each independent or be not only mutually mixed again independently of one another formation crystalline phase or Incompatible phase or existing crystalline phase have the phase incompatible with interlude again with interlude B, to form reversible point based on end section Mutually it is physical crosslinking；Across the subchain section of their interlude of connection or interlude between the section of any two end, and not by except in Between covalently attached beyond section be linked；Interlude B is unformed shape, and at least one side hydrogen bond is included in all or part of segment Group, the side hydrogen bond group form interchain supermolecule hydrogen bond dynamic crosslinking.
A kind of 2. energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE) according to claim 1, it is characterised in that Side hydrogen bond group on described thermoplastic elastomer polymer molecule interlude B is to contain hydrogen bond donor and hydrogen bond receptor simultaneously Form the hydrogen bond group no more than four tooth hydrogen bonds.
A kind of 3. energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE) according to claim 1, it is characterised in that Side hydrogen bond group on described thermoplastic elastomer polymer molecule interlude B contains in structure shown in following formulas at least One kind,
Wherein, X is selected from oxygen atom, sulphur atom, nitrogen-atoms, silicon atom, carbon atom, and Y is selected from oxygen atom, sulphur atom；
Wherein, a is the R being connected with X atoms1Or R2Number；
When X is oxygen atom or sulphur atom, a 0, R1And R2It is not present；
When X is nitrogen-atoms, a 1, R1And R2It is each independently selected from hydrogen atom, substitution atom or substituent；
When X is silicon atom or carbon atom, a 1, each R1And R2It is each independently selected from hydrogen atom, substitution atom or substitution Base；
Wherein, G1、G2For end group；
Wherein, L is divalent linker；
Wherein, L and R1、R2、G1、G2In be connected to bridge between any group or be not attached into bridge, R1With G1It is connected to bridge or non-phase It is linked to be bridge, R2With G2It is connected to bridge or is not attached into bridge.
A kind of 4. energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE) according to claim 3, it is characterised in that In side hydrogen bond group on described thermoplastic elastomer polymer molecule interlude B, R1、R2、G1、G2It is each independently selected from hydrogen Atom, halogen atom, C1-20Alkyl, C1-20Miscellaneous alkyl, the C of substitution1-20Alkyl, the miscellaneous alkyl of substitution；L is selected from C1-20Alkylene, Divalence C1-20Miscellaneous alkyl, the C of substitution1-20Alkylene, the divalence C of substitution1-20The base that miscellaneous alkyl and its any a variety of combination are formed Group.
A kind of 5. energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE) according to claim 3, it is characterised in that In side hydrogen bond group on described thermoplastic elastomer polymer molecule interlude B, R1、R2、G1、G2It is each independently selected from hydrogen Atom, methyl, ethyl, n-propyl, isopropyl, normal-butyl, the tert-butyl group, benzyl, trityl, phenyl, benzyl, methyl-benzyl, Tert. butyl-sulphenyl, benzyl sulfenyl, 2- pyridinylthios, 2- PYRIDYLCARBONYLs, t-butyloxycarbonyl, phenyloxycarbonyl, benzyloxy Base carbonyl, tert-butyl group epoxide thiocarbonyl, phenoxythiocarbonyl, benzyloxy thiocarbonyl, tert. butyl-sulphenyl thiocarbonyl, benzene Alkylthio carbonyl, benzylthio thiocarbonyl, trifluoroacetyl group；L be selected from singly-bound, methylene, ethylidene, propylidene, butylidene, Pentylidene, hexylidene, heptamethylene, octamethylene, nonylene, decylene, 1,2- phenylenes, benzal, C1-20Oxaalkylene, C1-20Thia alkylene, C1-20Aza-alkylene, azepine aryl.
A kind of 6. energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE) according to claim 1, it is characterised in that In described thermoplastic elastomer polymer molecule, each the end section A and interlude B of polymer molecule are independently of one another in its skeleton Also contain skeleton hydrogen bond group on chain.
A kind of 7. energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE) according to claim 1, it is characterised in that In described thermoplastic elastomer polymer molecule, average every 100 interlude B backbone repeating units access hydrogen bond group containing side Side base, the number in side chain or side base and side chain be 0.1 to 200.
A kind of 8. energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE) according to claim 1, it is characterised in that The thermoplastic elastomer polymer of multi-segment structure in described thermoplastic elastomer (TPE) also containing other multiterminal sections-mono- interlude Composition, other two-part thermoplastic elastomer polymer compositions, other soft segments do not contain the thermoplastic elastomehc of any side hydrogen bond group At least one of elastomer polymer composition, other thermoplastic polymer components.
A kind of 9. energy-absorbing based on dynamic aggregation thing thermoplastic elastomer (TPE) according to any one of claim 1-3,6,7,8 Method, it is characterised in that described dynamic aggregation thing thermoplastic elastomer (TPE) be solid polymer, hydrogel, ionic liquid gel, Oligomer swell gel, plasticizer swell gel, organogel, foamed material.
10. a kind of energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE) according to claim 1, its feature exist In, form the component of thermoplastic elastomer (TPE) also include it is following any or appoint it is several can additive：Auxiliary agent, additive, filler.
11. a kind of energy-absorbing method based on dynamic aggregation thing thermoplastic elastomer (TPE) according to claim 1 or 10, its feature It is, in the component of described dynamic aggregation thing thermoplastic elastomer (TPE), the auxiliary agent or additive that can be added or used to are selected from following It is any or appoint it is several：Antioxidant, light stabilizer, heat stabilizer, fire retardant, solvent, lubricant, releasing agent, plasticizer, increasing Thick dose, thixotropic agent, levelling agent, colouring agent, fluorescent whitening agent, delustering agent, antistatic agent, coupling agent, dehydrating agent, fungus and mildew resistance Agent；Addible filler is selected from following any or appointed several：Inorganic non-metallic filler, metal packing, organic filler.
A kind of 12. energy-absorbing side based on dynamic aggregation thing thermoplastic elastomer (TPE) according to claim 1-3,6,7,8,10 Method, it is characterised in that described energy-absorbing method is applied to motion and daily life to be prevented with body protection, the army and police's body to work Shield, explosion-proof, airborne and air-drop protection, automobile collision preventing, electric equipment products defense of resistance to impact, sound insulation, damping.
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CN112166153A (en) * 2018-03-26 2021-01-01 佐治亚理工研究公司 Transient polymer formulations, articles thereof, and methods of making and using the same
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