CN110628095A - Graphene high-elasticity rubber elastomer high polymer material and preparation method thereof - Google Patents
Graphene high-elasticity rubber elastomer high polymer material and preparation method thereof Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 139
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 100
- 239000005060 rubber Substances 0.000 title claims abstract description 88
- 239000000806 elastomer Substances 0.000 title claims abstract description 51
- 239000002861 polymer material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 51
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 51
- 229920001194 natural rubber Polymers 0.000 claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 33
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 32
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 32
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 29
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 29
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 29
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 28
- 239000004088 foaming agent Substances 0.000 claims abstract description 27
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920001577 copolymer Polymers 0.000 claims abstract description 26
- 229920006245 ethylene-butyl acrylate Polymers 0.000 claims abstract description 26
- 239000004698 Polyethylene Substances 0.000 claims abstract description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 24
- 239000003365 glass fiber Substances 0.000 claims abstract description 24
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims abstract description 24
- -1 polyethylene Polymers 0.000 claims abstract description 24
- 229920000573 polyethylene Polymers 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims description 54
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- 239000011593 sulfur Substances 0.000 claims description 19
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims description 19
- 238000007599 discharging Methods 0.000 claims description 18
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 claims description 18
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims description 18
- 238000005187 foaming Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 11
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000007731 hot pressing Methods 0.000 claims description 6
- 230000018984 mastication Effects 0.000 claims description 6
- 238000010077 mastication Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 239000002064 nanoplatelet Substances 0.000 claims description 2
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical group C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 claims 1
- 230000006835 compression Effects 0.000 abstract description 8
- 238000007906 compression Methods 0.000 abstract description 8
- 230000006386 memory function Effects 0.000 abstract description 4
- 239000004604 Blowing Agent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000003712 anti-aging effect Effects 0.000 description 5
- 125000003172 aldehyde group Chemical group 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
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- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical group [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0085—Use of fibrous compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2307/00—Characterised by the use of natural rubber
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- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/06—Copolymers with styrene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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Abstract
The invention discloses a high-elasticity rubber elastomer high polymer material of graphene and a preparation method thereof, wherein the high polymer material is prepared from the following raw materials in parts by weight: 45-50 parts of natural rubber, 15-19 parts of styrene-butadiene rubber, 10-14 parts of ethylene-octene copolymer, 13-16 parts of ethylene-butyl acrylate copolymer, 16-20 parts of ethylene-vinyl acetate copolymer, 2.4-3.0 parts of graphene, 6.5-8.5 parts of silane coupling agent modified glass fiber, 1.6-2.1 parts of foaming agent, 0.82-0.95 part of micropore regulator, 1.8-2.2 parts of bridging agent, 2-4 parts of polyethylene wax, 3-5 parts of maleic anhydride grafted polypropylene, 1.8-2.4 parts of crosslinking agent, 3.5-5.5 parts of antioxidant and 3-4 parts of heat stabilizer. The product of the invention has good rebound resilience and memory function; has high elasticity, low compression set at-40 deg.c and high flexibility.
Description
Technical Field
The invention relates to the technical field of rubber products, in particular to a high-elasticity graphene rubber elastomer high polymer material and a preparation method thereof.
Background
Natural Rubber (NR) is a natural polymer compound containing cis-1, 4-polyisoprene as a main component, 91 to 94% of which is rubber hydrocarbon (cis-1, 4-polyisoprene), and the balance of which is non-rubber substances such as protein, fatty acid, ash, saccharides and the like. The material is generally a flaky solid, has the relative density of 0.94, the refractive index of 1.522 and the elastic modulus of 2-4 MPa, is softened at 130-140 ℃, is sticky and soft at 150-160 ℃, and begins to degrade at 200 ℃. Has high elasticity and slight plasticity at normal temperature and is crystallized and hardened at low temperature. Has better alkali resistance but does not resist strong acid. Is insoluble in water, lower ketones and alcohols, and can swell in nonpolar solvents such as chloroform, carbon tetrachloride, etc.
The natural rubber mainly has a macromolecular chain structure, the molecular weight, the distribution and aggregation structure of the molecular weight, the macromolecular chain structural unit of the natural rubber is isoprene, the macromolecular chain is mainly composed of polyisoolefine, the content of the rubber accounts for more than ninety-seven percent, aldehyde groups are arranged on the molecular chain, one aldehyde group is arranged on each macromolecular chain on average, just condensation or reaction with a protein decomposition product is carried out on the aldehyde groups to form branching and crosslinking, so that the viscosity of the rubber in storage is increased, and epoxy groups are arranged on the macromolecular chains of the natural rubber and are more active. The macromolecule end of the natural rubber is generally inferred to be dimethylallyl, the other end of the natural rubber is pyrophosphate, a terminal group, aldehyde group of a molecular chain and polymeric elements are few, the molecular weight range of the natural rubber is wide in the aspects of the molecular weight and the distribution of the molecular weight, the vast majority of the molecular weight is about thirty thousand according to the report from abroad, the strength of the natural raw rubber, the rubber compound and the vulcanized rubber is higher, and the strength of the general natural rubber can reach three megapascals. The main reason for the high mechanical strength of natural rubber is that it is a self-reinforcing rubber series, which, when stretched, orients the macromolecular chains in the direction of stress to form crystals, which act as reinforcement in the amorphous macromolecular fraction, and the same high strength as that without expansion is due to the close agglomeration of the tiny particles in its internal structure.
Natural rubber is a variety with the best coordination between physical and mechanical properties and processing properties in rubber materials, and is widely applied to the fields of daily life, medical treatment and health, transportation, agriculture, scientific experiments, national defense and the like. With the development of society, people put higher demands on the performance of products, such as: the traditional rubber foaming sole has heavy weight, the wear resistance can not meet the requirement, the heat shrinkage resistance is poor, and the rubber foaming sole is often required to be modified.
The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future. In recent years, many studies have been made on modification of rubber materials with graphene, and excellent effects have been obtained. However, in the application process of graphene, the graphene lamellar structure has strong van der waals force or hydrogen bond lamp interaction, so that the graphene lamellar structure is easy to agglomerate and cannot be uniformly and stably dispersed. In general, organic functional groups such as carboxyl, hydroxyl, amino and the like are modified on the surface of the street graphene through chemical grafting, so that the dispersibility of the graphene in a high molecular polymer is improved. However, the method destroys the crystal structure of the graphene, and greatly influences the performance of the graphene.
In addition, the natural rubber foaming material used at present has the problems of poor elasticity, poor rebound resilience and the like.
Disclosure of Invention
Based on the above situation, the present invention aims to provide a high elasticity rubber elastomer polymer material of graphene and a preparation method thereof, which can effectively solve the above problems.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a high-elasticity rubber elastomer high polymer material of graphene is prepared from the following raw materials in parts by weight:
45-50 parts of natural rubber, 15-19 parts of styrene-butadiene rubber, 10-14 parts of ethylene-octene copolymer, 13-16 parts of ethylene-butyl acrylate copolymer, 16-20 parts of ethylene-vinyl acetate copolymer, 2.4-3.0 parts of graphene, 6.5-8.5 parts of silane coupling agent modified glass fiber, 1.6-2.1 parts of foaming agent, 0.82-0.95 part of micropore regulator, 1.8-2.2 parts of bridging agent, 2-4 parts of polyethylene wax, 3-5 parts of maleic anhydride grafted polypropylene, 1.8-2.4 parts of crosslinking agent, 3.5-5.5 parts of antioxidant and 3-4 parts of heat stabilizer; the graphene is a nano graphene microchip; the micropore regulator is a mixture of zinc formate and zinc isooctanoate; the cross-linking agent is a mixture of sulfur, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and zinc diacrylate.
Preferably, the graphene high-elasticity rubber elastomer high polymer material is prepared from the following raw materials in parts by weight: 48 parts of natural rubber, 17.5 parts of styrene-butadiene rubber, 12.5 parts of ethylene-octene copolymer, 14 parts of ethylene-butyl acrylate copolymer, 18 parts of ethylene-vinyl acetate copolymer, 2.7 parts of graphene, 7.5 parts of silane coupling agent modified glass fiber, 1.85 parts of foaming agent, 0.88 part of micropore regulator, 2 parts of bridging agent, 3 parts of polyethylene wax, 4 parts of maleic anhydride grafted polypropylene, 2.1 parts of crosslinking agent, 4.5 parts of antioxidant and 3.5 parts of heat stabilizer.
Preferably, the VA content of the ethylene-vinyl acetate copolymer is 32-38.
Preferably, the mass ratio of the zinc formate to the zinc isooctanoate in the mixture of the zinc formate and the zinc isooctanoate is 1: (0.72-0.84).
Preferably, the thickness of the nano graphene microchip is 2-10 nm.
Preferably, the mass ratio of the sulfur, the 1, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and the zinc diacrylate in the mixture of the sulfur, the 1, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and the zinc diacrylate is 1: (0.6-0.8): (0.35-0.45).
Preferably, the blowing agent is an AC blowing agent.
Preferably, the bridging agent is a DCP bridging agent.
Preferably, the antioxidant is an anti-aging agent 4010 NA-M.
Preferably, the heat stabilizer is a mixture of 1: 1 of zinc stearate and stearic acid.
The invention also provides a preparation method of the graphene high-elasticity rubber elastomer high polymer material, which comprises the following steps:
A. respectively weighing natural rubber, styrene-butadiene rubber, an ethylene-octene copolymer, an ethylene-butyl acrylate copolymer, an ethylene-vinyl acetate copolymer, graphene, silane coupling agent modified glass fiber, a foaming agent, a micropore regulator, a bridging agent, polyethylene wax, maleic anhydride grafted polypropylene, a crosslinking agent, an antioxidant and a heat stabilizer according to parts by weight;
B. feeding natural rubber into an internal mixer, masticating for 12-14 min at the temperature of 144-148 ℃, and discharging; storing the masticated natural rubber at room temperature for more than 48h for later use;
C. b, feeding the natural rubber subjected to the mastication treatment in the step B, styrene butadiene rubber, ethylene-octene copolymer, ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, graphene, silane coupling agent modified glass fiber, polyethylene wax and maleic anhydride grafted polypropylene into an internal mixer, and internally mixing for 11-14 min at the temperature of 90-95 ℃; then banburying for 9-12 min at the temperature of 105-110 ℃; then adding a foaming agent, a micropore regulator, a bridging agent, a cross-linking agent, an antioxidant and a heat stabilizer, banburying at 120-125 ℃ for 9-12 min, and discharging to obtain a banburying rubber mixture;
D. c, conveying the banburying rubber mixture obtained in the step C into an open mill, thinning for 2-4 times on the open mill, and discharging to obtain an open mill rubber mixture;
E. and finally, feeding the open-mill rubber mixture into a mold for hot-pressing foaming, cooling and molding, and cutting a sample to obtain the high-elasticity graphene rubber elastomer high polymer material.
The high-elasticity graphene rubber elastomer high polymer material is mainly used as a sole material, and the application field of the high-elasticity graphene rubber elastomer high polymer material is not limited to the field of shoe materials, and can also be used in other fields.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the high-elasticity rubber elastomer high polymer material of graphene is prepared by selecting raw materials, optimizing the content of each raw material, selecting natural rubber, styrene-butadiene rubber, ethylene-octene copolymer, ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, graphene, silane coupling agent modified glass fiber, foaming agent, micropore regulator, bridging agent, polyethylene wax, maleic anhydride grafted polypropylene, cross-linking agent, antioxidant and heat stabilizer in proper proportion, fully exerting the advantages of the raw materials, supplementing the raw materials and promoting the cross-linking agent, the prepared high polymer material of the high-elasticity rubber elastomer of graphene has good resilience and memory function, the initial bending of the high polymer material of the graphene is obviously greater than that of a common rubber foaming material (, the service life is longer; high elasticity, compression set significantly lower than that of the comparative example; and still has very low compression set rate and good flexibility at-40 ℃ and large impact force.
Among the high-elasticity rubber elastomer polymer materials of graphene, natural rubber is used as a main matrix material.
The elasticity of the graphene high-elasticity rubber elastomer is improved by adding a proper amount of styrene butadiene rubber, the structure and the performance of the styrene butadiene rubber are closer to those of natural rubber, the styrene butadiene rubber is a rubber elastomer, the high-elasticity and high-tear resistance of the natural rubber can be well maintained after the styrene butadiene rubber is added, and the comprehensive performances such as the elasticity and the like of the graphene high-elasticity rubber elastomer high polymer material can be effectively improved.
The high-elasticity rubber elastomer is characterized in that a proper amount of ethylene-octene copolymer, ethylene-butyl acrylate copolymer and ethylene-vinyl acetate copolymer are added, the ethylene-octene copolymer, the ethylene-butyl acrylate copolymer and the ethylene-vinyl acetate copolymer are good thermoplastic elastomers, the polarities of the three are small to large, the compatibility of natural rubber, styrene butadiene rubber, the ethylene-octene copolymer, the ethylene-butyl acrylate copolymer and the ethylene-vinyl acetate copolymer can reach the optimal state through proper proportion, the compatibility of the high-elasticity rubber elastomer is good with other components in the raw material system, and the high-elasticity rubber elastomer is matched with other components to play a good synergistic effect, so that the high-elasticity rubber elastomer high polymer material of graphene has good resilience, a memory function, a large initial bending line, strong fatigue resistance, a low fracture level and a long service life; high elasticity and low compression set rate; and still has very low compression set at-40 deg.C, and very good softness, and large impact force.
The glass fiber modified by adding a proper amount of silane coupling agent has good compatibility in the raw material system, and has good synergistic effect by being matched with other components, so that the high-elasticity rubber elastomer high polymer material of graphene can be obviously enhanced, and the comprehensive mechanical properties such as elasticity and the like can be improved.
Adding a proper amount of graphene, wherein the graphene is nano graphene nanoplatelets; according to the invention, through the formula, the graphene has good identity with other components, is easy to disperse uniformly, has a complete structure, keeps good performance and plays a great role in improving mechanical properties.
Adding a proper amount of micropore regulator, wherein the micropore regulator is a mixture of zinc formate and zinc isooctanoate; the foaming agent is matched with the AC foaming agent, so that the foam holes generated by foaming are more uniform, the fineness of the foamed foam holes is good, and the surface of the product is smooth and fine; the foaming multiplying power is improved, and the comprehensive mechanical properties such as elasticity are improved.
Proper amount of polyethylene wax and maleic anhydride grafted polypropylene are added as flow additives, which mainly play a good lubricating role, increase the processing fluidity, and improve the processing performance and the apparent performance of the product; and the use of small molecular aids (the elasticity is obviously reduced due to the excessive use of the small molecular aids) can be reduced, the compatibility of each component in the raw material system is increased, and the comprehensive mechanical properties such as the elasticity of the material are ensured.
Adding a proper amount of cross-linking agent, wherein the cross-linking agent is a mixture of sulfur, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and zinc diacrylate. The zinc diacrylate plays a role in assisting crosslinking, and the sulfur and the 1, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane (peroxide crosslinking agent) are used as a composite crosslinking agent, so that the high-elasticity rubber elastomer high polymer material of the graphene is quickly crosslinked, the crosslinking is moderate, the crosslinked area is uniformly distributed, and the high-elasticity rubber elastomer high polymer material of the foamed graphene is low in compression set rate and good in rebound resilience; the mechanical properties such as tensile strength, elongation at break and the like are good, and the mechanical properties are excellent.
The preparation method has simple process and simple and convenient operation, and saves manpower and equipment cost.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.
Example 1:
a high-elasticity rubber elastomer high polymer material of graphene is prepared from the following raw materials in parts by weight:
45-50 parts of natural rubber, 15-19 parts of styrene-butadiene rubber, 10-14 parts of ethylene-octene copolymer, 13-16 parts of ethylene-butyl acrylate copolymer, 16-20 parts of ethylene-vinyl acetate copolymer, 2.4-3.0 parts of graphene, 6.5-8.5 parts of silane coupling agent modified glass fiber, 1.6-2.1 parts of foaming agent, 0.82-0.95 part of micropore regulator, 1.8-2.2 parts of bridging agent, 2-4 parts of polyethylene wax, 3-5 parts of maleic anhydride grafted polypropylene, 1.8-2.4 parts of crosslinking agent, 3.5-5.5 parts of antioxidant and 3-4 parts of heat stabilizer; the graphene is a nano graphene microchip; the micropore regulator is a mixture of zinc formate and zinc isooctanoate; the cross-linking agent is a mixture of sulfur, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and zinc diacrylate.
Preferably, the graphene high-elasticity rubber elastomer high polymer material is prepared from the following raw materials in parts by weight: 48 parts of natural rubber, 17.5 parts of styrene-butadiene rubber, 12.5 parts of ethylene-octene copolymer, 14 parts of ethylene-butyl acrylate copolymer, 18 parts of ethylene-vinyl acetate copolymer, 2.7 parts of graphene, 7.5 parts of silane coupling agent modified glass fiber, 1.85 parts of foaming agent, 0.88 part of micropore regulator, 2 parts of bridging agent, 3 parts of polyethylene wax, 4 parts of maleic anhydride grafted polypropylene, 2.1 parts of crosslinking agent, 4.5 parts of antioxidant and 3.5 parts of heat stabilizer.
Preferably, the VA content of the ethylene-vinyl acetate copolymer is 32-38.
Preferably, the mass ratio of the zinc formate to the zinc isooctanoate in the mixture of the zinc formate and the zinc isooctanoate is 1: (0.72-0.84).
Preferably, the thickness of the nano graphene microchip is 2-10 nm.
Preferably, the mass ratio of the sulfur, the 1, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and the zinc diacrylate in the mixture of the sulfur, the 1, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and the zinc diacrylate is 1: (0.6-0.8): (0.35-0.45).
Preferably, the blowing agent is an AC blowing agent.
Preferably, the bridging agent is a DCP bridging agent.
Preferably, the antioxidant is an anti-aging agent 4010 NA-M.
Preferably, the heat stabilizer is a mixture of 1: 1 of zinc stearate and stearic acid.
The embodiment also provides a preparation method of the graphene high-elasticity rubber elastomer polymer material, which comprises the following steps:
A. respectively weighing natural rubber, styrene-butadiene rubber, an ethylene-octene copolymer, an ethylene-butyl acrylate copolymer, an ethylene-vinyl acetate copolymer, graphene, silane coupling agent modified glass fiber, a foaming agent, a micropore regulator, a bridging agent, polyethylene wax, maleic anhydride grafted polypropylene, a crosslinking agent, an antioxidant and a heat stabilizer according to parts by weight;
B. feeding natural rubber into an internal mixer, masticating for 12-14 min at the temperature of 144-148 ℃, and discharging; storing the masticated natural rubber at room temperature for more than 48h for later use;
C. b, feeding the natural rubber subjected to the mastication treatment in the step B, styrene butadiene rubber, ethylene-octene copolymer, ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, graphene, silane coupling agent modified glass fiber, polyethylene wax and maleic anhydride grafted polypropylene into an internal mixer, and internally mixing for 11-14 min at the temperature of 90-95 ℃; then banburying for 9-12 min at the temperature of 105-110 ℃; then adding a foaming agent, a micropore regulator, a bridging agent, a cross-linking agent, an antioxidant and a heat stabilizer, banburying at 120-125 ℃ for 9-12 min, and discharging to obtain a banburying rubber mixture;
D. c, conveying the banburying rubber mixture obtained in the step C into an open mill, thinning for 2-4 times on the open mill, and discharging to obtain an open mill rubber mixture;
E. and finally, feeding the open-mill rubber mixture into a mold for hot-pressing foaming, cooling and molding, and cutting a sample to obtain the high-elasticity graphene rubber elastomer high polymer material.
Example 2:
a high-elasticity rubber elastomer high polymer material of graphene is prepared from the following raw materials in parts by weight:
45 parts of natural rubber, 15 parts of styrene-butadiene rubber, 10 parts of ethylene-octene copolymer, 13 parts of ethylene-butyl acrylate copolymer, 16 parts of ethylene-vinyl acetate copolymer, 2.4 parts of graphene, 6.5 parts of silane coupling agent modified glass fiber, 1.6 parts of foaming agent, 0.82 part of micropore regulator, 1.8 parts of bridging agent, 2 parts of polyethylene wax, 3 parts of maleic anhydride grafted polypropylene, 1.8 parts of crosslinking agent, 3.5 parts of antioxidant and 3 parts of heat stabilizer; the graphene is a nano graphene microchip; the micropore regulator is a mixture of zinc formate and zinc isooctanoate; the cross-linking agent is a mixture of sulfur, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and zinc diacrylate.
In this example, the ethylene-vinyl acetate copolymer had a VA content of 32.
In this embodiment, the mass ratio of zinc formate to zinc isooctanoate in the mixture of zinc formate and zinc isooctanoate is 1: 0.72.
in the embodiment, the thickness of the nano graphene microchip is 2-6 nm.
In this embodiment, the mass ratio of the sulfur, the 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and the zinc diacrylate in the mixture of the sulfur, the 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and the zinc diacrylate is 1: 0.6: 0.35.
in this example, the blowing agent was an AC blowing agent.
In this embodiment, the bridging agent is DCP bridging agent.
In the embodiment, the antioxidant is an anti-aging agent 4010 NA-M.
In this embodiment, the heat stabilizer is a mixture of 1: 1 of zinc stearate and stearic acid.
In this embodiment, the preparation method of the high-elasticity graphene rubber elastomer polymer material includes the following steps:
A. respectively weighing natural rubber, styrene-butadiene rubber, an ethylene-octene copolymer, an ethylene-butyl acrylate copolymer, an ethylene-vinyl acetate copolymer, graphene, silane coupling agent modified glass fiber, a foaming agent, a micropore regulator, a bridging agent, polyethylene wax, maleic anhydride grafted polypropylene, a crosslinking agent, an antioxidant and a heat stabilizer according to parts by weight;
B. feeding natural rubber into an internal mixer, masticating for 14min at the temperature of 144 ℃, and discharging; storing the masticated natural rubber at room temperature for more than 48h for later use;
C. b, feeding the natural rubber subjected to the mastication treatment in the step B, styrene-butadiene rubber, ethylene-octene copolymer, ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, graphene, silane coupling agent modified glass fiber, polyethylene wax and maleic anhydride grafted polypropylene into an internal mixer, and internally mixing for 14min at the temperature of 90 ℃; then banburying for 12min at the temperature of 105 ℃; then adding a foaming agent, a micropore regulator, a bridging agent, a cross-linking agent, an antioxidant and a heat stabilizer, banburying at 120 ℃ for 12min, and discharging to obtain a banburying rubber mixture;
D. c, conveying the banburying rubber mixture obtained in the step C into an open mill, thinning for 2 times on the open mill, and discharging to obtain an open mill rubber mixture;
E. and finally, feeding the open-mill rubber mixture into a mold for hot-pressing foaming, cooling and molding, and cutting a sample to obtain the high-elasticity graphene rubber elastomer high polymer material.
Example 3:
a high-elasticity rubber elastomer high polymer material of graphene is prepared from the following raw materials in parts by weight:
50 parts of natural rubber, 19 parts of styrene-butadiene rubber, 14 parts of ethylene-octene copolymer, 16 parts of ethylene-butyl acrylate copolymer, 20 parts of ethylene-vinyl acetate copolymer, 3.0 parts of graphene, 8.5 parts of silane coupling agent modified glass fiber, 2.1 parts of foaming agent, 0.95 part of micropore regulator, 2.2 parts of bridging agent, 4 parts of polyethylene wax, 5 parts of maleic anhydride grafted polypropylene, 2.4 parts of crosslinking agent, 5.5 parts of antioxidant and 4 parts of heat stabilizer; the graphene is a nano graphene microchip; the micropore regulator is a mixture of zinc formate and zinc isooctanoate; the cross-linking agent is a mixture of sulfur, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and zinc diacrylate.
In this example, the ethylene-vinyl acetate copolymer had a VA content of 38.
In this embodiment, the mass ratio of zinc formate to zinc isooctanoate in the mixture of zinc formate and zinc isooctanoate is 1: 0.84.
in the embodiment, the thickness of the nano graphene microchip is 6-10 nm.
In this embodiment, the mass ratio of the sulfur, the 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and the zinc diacrylate in the mixture of the sulfur, the 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and the zinc diacrylate is 1: 0.8: 0.45.
in this example, the blowing agent was an AC blowing agent.
In this embodiment, the bridging agent is DCP bridging agent.
In the embodiment, the antioxidant is an anti-aging agent 4010 NA-M.
In this embodiment, the heat stabilizer is a mixture of 1: 1 of zinc stearate and stearic acid.
In this embodiment, the preparation method of the high-elasticity graphene rubber elastomer polymer material includes the following steps:
A. respectively weighing natural rubber, styrene-butadiene rubber, an ethylene-octene copolymer, an ethylene-butyl acrylate copolymer, an ethylene-vinyl acetate copolymer, graphene, silane coupling agent modified glass fiber, a foaming agent, a micropore regulator, a bridging agent, polyethylene wax, maleic anhydride grafted polypropylene, a crosslinking agent, an antioxidant and a heat stabilizer according to parts by weight;
B. feeding natural rubber into an internal mixer, masticating for 12min at the temperature of 148 ℃, and discharging; storing the masticated natural rubber at room temperature for more than 48h for later use;
C. b, feeding the natural rubber subjected to the mastication treatment in the step B, styrene-butadiene rubber, ethylene-octene copolymer, ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, graphene, silane coupling agent modified glass fiber, polyethylene wax and maleic anhydride grafted polypropylene into an internal mixer, and internally mixing for 11min at the temperature of 95 ℃; then banburying for 9min at the temperature of 110 ℃; then adding a foaming agent, a micropore regulator, a bridging agent, a cross-linking agent, an antioxidant and a heat stabilizer, banburying at the temperature of 125 ℃ for 9min, and discharging to obtain a banburying rubber mixture;
D. c, conveying the banburying rubber mixture obtained in the step C into an open mill, thinning for 4 times on the open mill, and discharging to obtain an open mill rubber mixture;
E. and finally, feeding the open-mill rubber mixture into a mold for hot-pressing foaming, cooling and molding, and cutting a sample to obtain the high-elasticity graphene rubber elastomer high polymer material.
Example 4:
a high-elasticity rubber elastomer high polymer material of graphene is prepared from the following raw materials in parts by weight:
48 parts of natural rubber, 17.5 parts of styrene-butadiene rubber, 12.5 parts of ethylene-octene copolymer, 14 parts of ethylene-butyl acrylate copolymer, 18 parts of ethylene-vinyl acetate copolymer, 2.7 parts of graphene, 7.5 parts of silane coupling agent modified glass fiber, 1.85 parts of foaming agent, 0.88 part of micropore regulator, 2 parts of bridging agent, 3 parts of polyethylene wax, 4 parts of maleic anhydride grafted polypropylene, 2.1 parts of crosslinking agent, 4.5 parts of antioxidant and 3.5 parts of heat stabilizer.
In this example, the ethylene-vinyl acetate copolymer had a VA content of 35.
In this embodiment, the mass ratio of zinc formate to zinc isooctanoate in the mixture of zinc formate and zinc isooctanoate is 1: 0.77.
in the embodiment, the thickness of the nano graphene microchip is 4-8 nm.
In this embodiment, the mass ratio of the sulfur, the 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and the zinc diacrylate in the mixture of the sulfur, the 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and the zinc diacrylate is 1: 0.7: 0.4.
in this example, the blowing agent was an AC blowing agent.
In this embodiment, the bridging agent is DCP bridging agent.
In the embodiment, the antioxidant is an anti-aging agent 4010 NA-M.
In this embodiment, the heat stabilizer is a mixture of 1: 1 of zinc stearate and stearic acid.
In this embodiment, the preparation method of the high-elasticity graphene rubber elastomer polymer material includes the following steps:
A. respectively weighing natural rubber, styrene-butadiene rubber, an ethylene-octene copolymer, an ethylene-butyl acrylate copolymer, an ethylene-vinyl acetate copolymer, graphene, silane coupling agent modified glass fiber, a foaming agent, a micropore regulator, a bridging agent, polyethylene wax, maleic anhydride grafted polypropylene, a crosslinking agent, an antioxidant and a heat stabilizer according to parts by weight;
B. feeding natural rubber into an internal mixer, masticating for 13min at the temperature of 146 ℃, and discharging; storing the masticated natural rubber at room temperature for more than 48h for later use;
C. b, feeding the natural rubber subjected to the mastication treatment in the step B, styrene-butadiene rubber, ethylene-octene copolymer, ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, graphene, silane coupling agent modified glass fiber, polyethylene wax and maleic anhydride grafted polypropylene into an internal mixer, and internally mixing for 13min at the temperature of 93 ℃; then banburying for 10min at the temperature of 108 ℃; then adding a foaming agent, a micropore regulator, a bridging agent, a cross-linking agent, an antioxidant and a heat stabilizer, banburying at the temperature of 123 ℃ for 11min, and discharging to obtain a banburying rubber mixture;
D. c, conveying the banburying rubber mixture obtained in the step C into an open mill, thinning for 3 times on the open mill, and discharging to obtain an open mill rubber mixture;
E. and finally, feeding the open-mill rubber mixture into a mold for hot-pressing foaming, cooling and molding, and cutting a sample to obtain the high-elasticity graphene rubber elastomer high polymer material.
Comparative example:
the comparative example is a chinese patent application publication No. CN 102276887A.
The following performance tests were performed on the high elasticity rubber elastomer polymer materials of graphene obtained in examples 2 to 4 of the present invention and comparative examples, and the test results are shown in table 1:
TABLE 1
As can be seen from the above table, compared to the comparative example, the high elasticity rubber elastomer polymer material of graphene of the present invention has the following advantages:
1. the elastic resilience is good, the memory function is realized, the initial bending and folding performance of the elastic material is obviously greater than that of a comparative example, the fatigue resistance is also obviously superior to that of the comparative example, the crack grade is also obviously lower than that of the comparative example, and the service life is longer;
2. high elasticity, compression set significantly lower than that of the comparative example; and still has very low compression set at-40 deg.C, and very good softness, and large impact force.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (10)
1. The high-elasticity rubber elastomer high polymer material of graphene is characterized by being prepared from the following raw materials in parts by weight:
45-50 parts of natural rubber, 15-19 parts of styrene-butadiene rubber, 10-14 parts of ethylene-octene copolymer, 13-16 parts of ethylene-butyl acrylate copolymer, 16-20 parts of ethylene-vinyl acetate copolymer, 2.4-3.0 parts of graphene, 6.5-8.5 parts of silane coupling agent modified glass fiber, 1.6-2.1 parts of foaming agent, 0.82-0.95 part of micropore regulator, 1.8-2.2 parts of bridging agent, 2-4 parts of polyethylene wax, 3-5 parts of maleic anhydride grafted polypropylene, 1.8-2.4 parts of crosslinking agent, 3.5-5.5 parts of antioxidant and 3-4 parts of heat stabilizer; the graphene is a nano graphene microchip; the micropore regulator is a mixture of zinc formate and zinc isooctanoate; the cross-linking agent is a mixture of sulfur, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and zinc diacrylate.
2. The graphene high-elasticity rubber elastomer high polymer material as claimed in claim 1, wherein the graphene high-elasticity rubber elastomer high polymer material is prepared from the following raw materials in parts by weight: 48 parts of natural rubber, 17.5 parts of styrene-butadiene rubber, 12.5 parts of ethylene-octene copolymer, 14 parts of ethylene-butyl acrylate copolymer, 18 parts of ethylene-vinyl acetate copolymer, 2.7 parts of graphene, 7.5 parts of silane coupling agent modified glass fiber, 1.85 parts of foaming agent, 0.88 part of micropore regulator, 2 parts of bridging agent, 3 parts of polyethylene wax, 4 parts of maleic anhydride grafted polypropylene, 2.1 parts of crosslinking agent, 4.5 parts of antioxidant and 3.5 parts of heat stabilizer.
3. The high-elasticity graphene rubber elastomer high polymer material as claimed in claim 1, wherein the ethylene-vinyl acetate copolymer has a VA content of 32-38.
4. The graphene high-elasticity rubber elastomer high-molecular material as claimed in claim 1, wherein the mass ratio of zinc formate to zinc isooctanoate in the mixture of zinc formate and zinc isooctanoate is 1: (0.72-0.84).
5. The high-elasticity rubber elastomer high polymer material of graphene according to claim 1, wherein the thickness of the nano graphene nanoplatelets is 2-10 nm.
6. The high-elasticity rubber elastomer high polymer material of graphene as claimed in claim 1, wherein the mass ratio of the sulfur, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and zinc diacrylate in the mixture of the sulfur, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and zinc diacrylate is 1: (0.6-0.8): (0.35-0.45).
7. The high-elasticity rubber elastomer polymer material of graphene according to claim 1, wherein the foaming agent is an AC foaming agent; the bridging agent is DCP bridging agent.
8. The high-elasticity rubber elastomer high polymer material of graphene as claimed in claim 1, wherein the antioxidant is antioxidant 4010 NA-M.
9. The high-elasticity graphene rubber elastomer high polymer material as claimed in claim 1, wherein the heat stabilizer is a mixture of 1: 1 of zinc stearate and stearic acid.
10. A method for preparing the high-elasticity rubber elastomer polymer material of graphene according to any one of claims 1 to 9, comprising the following steps:
A. respectively weighing natural rubber, styrene-butadiene rubber, an ethylene-octene copolymer, an ethylene-butyl acrylate copolymer, an ethylene-vinyl acetate copolymer, graphene, silane coupling agent modified glass fiber, a foaming agent, a micropore regulator, a bridging agent, polyethylene wax, maleic anhydride grafted polypropylene, a crosslinking agent, an antioxidant and a heat stabilizer according to parts by weight;
B. feeding natural rubber into an internal mixer, masticating for 12-14 min at the temperature of 144-148 ℃, and discharging; storing the masticated natural rubber at room temperature for more than 48h for later use;
C. b, feeding the natural rubber subjected to the mastication treatment in the step B, styrene butadiene rubber, ethylene-octene copolymer, ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, graphene, silane coupling agent modified glass fiber, polyethylene wax and maleic anhydride grafted polypropylene into an internal mixer, and internally mixing for 11-14 min at the temperature of 90-95 ℃; then banburying for 9-12 min at the temperature of 105-110 ℃; then adding a foaming agent, a micropore regulator, a bridging agent, a cross-linking agent, an antioxidant and a heat stabilizer, banburying at 120-125 ℃ for 9-12 min, and discharging to obtain a banburying rubber mixture;
D. c, conveying the banburying rubber mixture obtained in the step C into an open mill, thinning for 2-4 times on the open mill, and discharging to obtain an open mill rubber mixture;
and finally, feeding the open-mill rubber mixture into a mold for hot-pressing foaming, cooling and molding, and cutting a sample to obtain the high-elasticity graphene rubber elastomer high polymer material.
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Application publication date: 20191231 |