WO2018036425A1 - 基于三维石墨烯改性的橡胶复合材料及其制备方法 - Google Patents

基于三维石墨烯改性的橡胶复合材料及其制备方法 Download PDF

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WO2018036425A1
WO2018036425A1 PCT/CN2017/098066 CN2017098066W WO2018036425A1 WO 2018036425 A1 WO2018036425 A1 WO 2018036425A1 CN 2017098066 W CN2017098066 W CN 2017098066W WO 2018036425 A1 WO2018036425 A1 WO 2018036425A1
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parts
rubber
dimensional graphene
graphene
accelerator
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French (fr)
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段曦东
赵涛楠
毛志浩
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广东纳路纳米科技有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention relates to the technical field of materials, in particular to a rubber composite material based on three-dimensional graphene modification and preparation thereof.
  • Rubber is the basic raw material of the rubber industry. It has the advantages of light weight, corrosion resistance and easy scale production. It can adjust the electrical and mechanical properties of materials according to the needs of use. It is used in the fields of tire, electronics, daily chemical and aerospace. It is becoming more and more widespread. And these applications require rubber products with excellent antistatic, electrical or thermal, mechanical and gas barrier properties.
  • the composite rubber is made of rubber as a matrix and is filled with conductive and thermally conductive fillers to impart certain electrical and thermal conductivity to the rubber.
  • the electrical conductivity of the composite conductive rubber mainly depends on the electrical conductivity of the filler and the uniform dispersion of the filler in the rubber matrix.
  • Commonly used fillers are carbon black, graphite, graphite fiber, and metal powder. Among them, carbon black is the most widely used conductive filler. When the amount of carbon black reaches a critical value, the electrical conductivity of the rubber is significantly improved.
  • the composite conductive rubber needs to achieve high electrical properties, the amount of carbon black to be added is very large, which affects the viscosity and processing properties of the rubber matrix material, and its application is limited.
  • Nano-sized fillers such as carbon fibers, carbon nanotubes, etc. can achieve higher electrical properties with low loading, but the agglomeration problem makes it difficult to achieve good dispersion in the matrix, and there are cost problems that limit the development of its application.
  • the rubber is a poor conductor of heat, and the generated heat cannot be conducted out in time, causing heat to accumulate inside the rubber product.
  • the temperature is too high, the performance of the product is lowered, and the service life of the product is affected.
  • Rubber modification is an effective way to improve the thermal conductivity of materials, and nanomaterials have great potential for rubber reinforcement and functionalization due to their unique molecular structure and properties.
  • the present invention adopts the following technical solutions:
  • the three-dimensional graphene-modified rubber composite material of the present invention comprises, by weight, 100 parts by weight of rubber, 0.01-5 parts of three-dimensional graphene, 0.5 to 5 parts of vulcanizing agent, and 8 to 12 parts of a rubber compounding agent.
  • the rubber comprises at least one of natural rubber, silicone rubber, styrene butadiene rubber, butadiene rubber, butyl rubber, isoprene rubber, butane rubber, nitrile rubber, ethylene propylene rubber, and neoprene rubber.
  • the three-dimensional graphene has a three-dimensional interconnected porous network of submicron to several micrometers.
  • the vulcanizing agent includes at least one of sulfur, a peroxide, a metal oxide, and a sulfur-containing organic substance.
  • the rubber compounding agent includes: a promoting auxiliary agent, an accelerator, and an antioxidant.
  • promotion aid is at least one of zinc oxide or stearic acid
  • the accelerator includes at least one of the accelerator D, the accelerator DM, the accelerator TMTD, the accelerator CZ, the accelerator BZ, and the accelerator MBT;
  • the antioxidant includes at least one of an antioxidant RD, an antioxidant 4010, an antioxidant 124, and an antioxidant DNP.
  • the rubber compounding agent comprises, in parts by mass, 2 parts of stearic acid, 5 parts of zinc oxide, 1 to 2 parts of a promoter, and 1 to 3 parts of an antioxidant.
  • the invention is based on a method for preparing a three-dimensional graphene-modified rubber composite material, comprising:
  • Step 1) preparing graphene oxide by a modified Hummers method
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in the step 1) is ultrasonically dispersed in ultrapure water at a concentration of 1-2 mg/ml, and then transferred to a reaction vessel at 160-200 ° C for 20-24 hours, washed with water. , got To three-dimensional reduction of graphene oxide hydrogel, freeze-drying;
  • Step 3) The rubber, the three-dimensional graphene obtained in the step 2), the rubber compounding agent and the vulcanizing agent are sequentially added to the open mill, kneaded at 40-90 ° C for 10-30 min, and the rubber mixture is allowed to stand for 16-24 h, The vulcanization machine is vulcanized, and the vulcanization condition is vulcanized at 140-170 ° C for 10-40 min to obtain a three-dimensional graphene-modified rubber composite material.
  • the improved Hummers method produces graphene oxide, which is divided into pre-oxidation, oxidation and stripping;
  • the pre-oxidation is: mixing 1 part of natural graphite, 3-10 parts of concentrated sulfuric acid, 0.5-0.9 parts of K 2 S 2 O 8 and P 2 O 5 to 80 ° C, reacting for 6 h, using super Purified pure water to neutral to obtain pre-oxidized graphite;
  • the oxidation is: at 0 ° C, the pre-oxidized graphite is mixed with 6-20 parts of concentrated sulfuric acid, and 1-3 parts of KMnO 4 are gradually added under stirring, and the temperature of the mixture is controlled to be below 20 ° C in the process.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 20-50 parts of ultrapure water was added, stirring was continued for 15 min, and finally 40-150 parts of ultrapure water was added to complete the reaction. Next, 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions, and the resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral;
  • the peeling In order to peel off the graphite oxide, the obtained product was ultrasonicated for 30 min with a 400 W cell pulverizer, and the supernatant was centrifuged at 13,000 rpm, and dried at 90 ° C for 24 h to obtain black-brown graphene oxide.
  • the three-dimensional graphene of the invention has a self-supporting structure, avoids agglomeration and has good dispersibility in rubber; the three-dimensional graphene has excellent electrical, thermal and mechanical properties, and is easy to be in close contact with the substrate of the invention, greatly increasing The electrical conductivity, wear resistance, heat resistance and mechanical strength of the rubber product; the invention has simple preparation process, low production cost, no environmental pollution, and is easy to realize large-scale industrial production.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation 1 part by weight of natural graphite, 6 parts of concentrated sulfuric acid, 0.7 parts of K 2 S 2 O 8 and P 2 O 5 are mixed and heated to 80 ° C, reacted for 6 hours, and washed with ultrapure water until neutral. Pre-oxidized graphite.
  • the obtained product was ultrasonicated with a 400 W cell pulverizer for 30 min, centrifuged at 13,000 rpm to obtain a supernatant, and dried at 90 ° C for 24 h to obtain black-brown graphene oxide;
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in step 1) is ultrasonically dispersed in ultrapure water at a concentration of 1.8 mg/ml, and then transferred to a reaction vessel at 200 ° C for 20 h, washed with water to obtain three-dimensional reduction oxidation.
  • Step 3 100 parts of butadiene rubber, 0.1 part of three-dimensional graphene, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of accelerator CZ, 1.5 parts of antioxidant RD, 1.5 parts of sulfur are sequentially added to the open mill, 50 After mixing for 20 min at ° C, the rubber mixture was allowed to stand for 24 h, and then vulcanized on a flat vulcanizer. The vulcanization conditions were 151 ° C for 25 min to obtain a three-dimensional graphene-modified butadiene rubber composite.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation 1 part by mass of natural graphite, 5 parts of concentrated sulfuric acid, 0.6 parts of K 2 S 2 O 8 and P 2 O 5 are mixed and heated to 80 ° C, reacted for 6 h, and washed with ultrapure water until neutral. Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 8 parts of concentrated sulfuric acid at 0 ° C, and 2 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 30 parts of ultrapure water was added, stirring was continued for 15 min, and finally 50 parts of ultrapure water was added to complete the reaction.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • the obtained product was ultrasonicated with a 400 W cell pulverizer for 30 min, centrifuged at 13,000 rpm to obtain a supernatant, and dried at 90 ° C for 24 h to obtain black-brown graphene oxide;
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in step 1) is ultrasonically dispersed in ultrapure water at a concentration of 1.5 mg/ml, and then transferred to a reaction vessel at 180 ° C for 20 h, washed with water to obtain three-dimensional reduction oxidation.
  • Step 3 100 parts of styrene-butadiene rubber, 0.2 parts of three-dimensional graphene, 5 parts of zinc oxide, 2 parts of stearic acid, 1 part of accelerator BZ, 1 part of antioxidant RD, 1 part of antioxidant 4010, 1 part of sulfur are sequentially added.
  • the mixture was kneaded at 50 ° C for 25 min, and the rubber mixture was allowed to stand for 18 h, and then vulcanized on a flat vulcanizer, and the vulcanization conditions were 150 ° C for 30 min to obtain a three-dimensional graphene-modified styrene-butadiene rubber composite material.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation 1 part by mass of natural graphite, 7 parts of concentrated sulfuric acid, 0.6 parts of K 2 S 2 O 8 and P 2 O 5 are mixed and heated to 80 ° C, reacted for 6 h, and washed with ultrapure water until neutral. Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 9 parts of concentrated sulfuric acid at 0 ° C, and 2 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 20-50 parts of ultrapure water was added, stirring was continued for 15 min, and finally 100 parts of ultrapure water was added to complete the reaction.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • the obtained product was ultrasonicated with a 400 W cell pulverizer for 30 min, centrifuged at 13,000 rpm to obtain a supernatant, and dried at 90 ° C for 24 h to obtain black-brown graphene oxide;
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in the step 1) is ultrasonically dispersed in ultrapure water at a concentration of 1.5 mg/ml, and then transferred to a reaction vessel at 180 ° C for 24 hours, washed with water to obtain three-dimensional reduction oxidation.
  • Step 3 100 parts of nitrile rubber, 0.4 parts of three-dimensional graphene, 5 parts of zinc oxide and 2 parts of stearic acid, 1 part of accelerator TMTD and 0.5 parts of accelerator MBT, 1 part of antioxidant RD and 1 part of antioxidant 4010 2 parts of sulfur were added to the open mill in turn, and kneaded at 40 ° C for 20 min. After the mixture was allowed to stand for 16 h, it was vulcanized on a flat vulcanizing machine, and the vulcanization conditions were 170 ° C for 16 min to obtain a three-dimensional graphene-modified nitrile rubber composite. material.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation Mix 1 part of natural graphite, 3 parts of concentrated sulfuric acid, 0.5 part of K 2 S 2 O 8 and P 2 O 5 to 80 ° C, react for 6 h, and wash with ultrapure water until neutral. oxidised graphite.
  • Pre-oxidized graphite was mixed with 8 parts of concentrated sulfuric acid at 0 ° C, and 2 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 20 parts of ultrapure water was added, stirring was continued for 15 min, and finally 40 parts of ultrapure water was added to complete the reaction.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in step 1) is ultrasonically dispersed in ultrapure water at a concentration of 1 mg/ml, and then transferred to a reaction vessel at 160 ° C for 24 hours, and washed with water to obtain three-dimensional reduced graphite oxide.
  • Step 3 100 parts of natural rubber, 0.6 parts of three-dimensional graphene, 5 parts of zinc oxide, 2 parts of stearic acid, 0.5 parts of accelerator TMTD, 1 part of accelerator CZ, 1 part of antioxidant RD, 1 part of antioxidant 4010, 0.5 parts of sulfur was sequentially added to the open mill, and kneaded at 50 ° C for 12 min. After the mixture was allowed to stand for 24 h, it was vulcanized on a flat vulcanizer, and the vulcanization conditions were 150 ° C for 40 min to obtain a three-dimensional graphene-modified natural rubber composite material.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation 1 part by weight of natural graphite, 9 parts of concentrated sulfuric acid, 0.9 parts of K 2 S 2 O 8 and P 2 O 5 are mixed and heated to 80 ° C, reacted for 6 hours, and washed with ultrapure water until neutral. Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 10 parts of concentrated sulfuric acid at 0 ° C, and 3 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 50 parts of ultrapure water was added, stirring was continued for 15 min, and finally 90 parts of ultrapure water was added to complete the reaction.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • the obtained product was ultrasonicated with a 400 W cell pulverizer for 30 min, centrifuged at 13,000 rpm to obtain a supernatant, and dried at 90 ° C for 24 h to obtain black-brown graphene oxide;
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in step 1) is ultrasonically dispersed in ultrapure water at a concentration of 2 mg/ml, and then transferred to a reaction vessel at 200 ° C for 22 h, washed with water to obtain three-dimensional reduced graphite oxide.
  • Step 3 100 parts of butadiene rubber, 0.8 parts of three-dimensional graphene, 5 parts of zinc oxide, 2 parts of stearic acid, 2 parts of accelerator CZ, 1.5 parts of antioxidant RD and 1 part of antioxidant 4010, 3 parts of sulfur are added to the open mill in turn, and kneaded at 60 ° C for 15 min. After the mixture is allowed to stand for 24 h, it is vulcanized and vulcanized on a flat vulcanizer. The condition was 151 ° C for 25 min to obtain a three-dimensional graphene-modified butadiene rubber composite.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation Mix 1 part of natural graphite, 8 parts of concentrated sulfuric acid, 0.8 parts of K 2 S 2 O 8 and P 2 O 5 to 80 ° C, react for 6 h, and wash with ultrapure water until neutral. Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 10 parts of concentrated sulfuric acid at 0 ° C, and 3 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 35 parts of ultrapure water was added, stirring was continued for 15 min, and finally 90 parts of ultrapure water was added to complete the reaction.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in step 1) is ultrasonically dispersed in ultrapure water at a concentration of 1.8 mg/ml, and then transferred to a reaction vessel at 200 ° C for 24 hours, washed with water to obtain three-dimensional reduction oxidation.
  • Step 3 100 parts of styrene-butadiene rubber, 1 part of 3D graphene, 5 parts of zinc oxide and 2 parts of stearic acid, 1.5 parts of accelerator BZ, 1 part of antioxidant RD and 1 part of antioxidant 4010, 2.5 parts of sulfur are sequentially added.
  • the mixture was kneaded at 50 ° C for 30 min, and the rubber mixture was allowed to stand for 24 h, and then vulcanized on a flat vulcanizing machine, and the vulcanization conditions were 150 ° C for 30 min to obtain a three-dimensional graphene-modified styrene-butadiene rubber composite material.
  • Step 1) Preparation of graphene oxide by modified Hummers method, which is divided into pre-oxidation, oxidation and Stripped.
  • Pre-oxidation 1 part by weight of natural graphite, 10 parts of concentrated sulfuric acid, 0.9 parts of K 2 S 2 O 8 and P 2 O 5 are mixed and heated to 80 ° C, reacted for 6 h, and washed with ultrapure water until neutral. Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 20 parts of concentrated sulfuric acid at 0 ° C, and 3 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 50 parts of ultrapure water was added, stirring was continued for 15 min, and finally 150 parts of ultrapure water was added to complete the reaction.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in step 1) is ultrasonically dispersed in ultrapure water at a concentration of 2 mg/ml, and then transferred to a reaction vessel at 200 ° C for 24 hours, and washed with water to obtain three-dimensional reduced graphite oxide.
  • Step 3 100 parts of nitrile rubber, 2 parts of three-dimensional graphene, 5 parts of zinc oxide and 1 part of stearic acid, 1 part of accelerator TMTD and accelerator 1 part of MBT, 1 part of antioxidant RD and 1 part of antioxidant 4010 4 parts of sulfur was added to the open mill in turn, and kneaded at 40 ° C for 20 min. After the mixture was allowed to stand for 24 h, it was vulcanized on a flat vulcanizer, and the vulcanization conditions were 170 ° C for 16 min to obtain a three-dimensional graphene modified nitrile rubber composite. material.
  • Step 1) Preparation of graphene oxide by a modified Hummers method, which is divided into pre-oxidation, oxidation and exfoliation.
  • Pre-oxidation 1 part by mass of natural graphite, 7 parts of concentrated sulfuric acid, 0.7 parts of K 2 S 2 O 8 and P 2 O 5 are mixed and heated to 80 ° C, reacted for 6 h, and washed with ultrapure water until neutral. Pre-oxidized graphite.
  • Pre-oxidized graphite was mixed with 10 parts of concentrated sulfuric acid at 0 ° C, and 3 parts of KMnO 4 was gradually added under stirring, during which the temperature of the mixture was controlled to be 20 ° C or lower.
  • the mixture was warmed to 35 ° C, and after stirring for 2 h, 50 parts of ultrapure water was added, stirring was continued for 15 min, and finally 80 parts of ultrapure water was added to complete the reaction.
  • 2 parts of 30% H 2 O 2 was added , and the mixture was centrifuged with 10% HCl to remove excess metal ions. The resulting precipitate was repeatedly centrifuged with ultrapure water until the solution was neutral.
  • Step 2) Preparation of three-dimensional graphene:
  • the graphene oxide prepared in step 1) is ultrasonically dispersed in ultrapure water at a concentration of 2 mg/ml, and then transferred to a reaction vessel at 180 ° C for 24 hours, and washed with water to obtain three-dimensional reduced graphite oxide.
  • Step 3) 100 parts of natural rubber, 3 parts of three-dimensional graphene, 5 parts of zinc oxide and 2 parts of stearic acid, 1 part of accelerator TMTD and 1 part of accelerator CZ, 1.5 parts of antioxidant RD and 1 part of antioxidant 4010, 1 part of sulfur and 0.5 part of dicumyl peroxide were sequentially added to the open mill, kneaded at 55 ° C for 10 min, and the mixture was allowed to stand for 18 h, then vulcanized on a flat vulcanizer, and the vulcanization conditions were 150 ° C for 40 min to obtain three-dimensional graphite.
  • Ane modified natural rubber composite 100 parts of natural rubber, 3 parts of three-dimensional graphene, 5 parts of zinc oxide and 2 parts of stearic acid, 1 part of accelerator TMTD and 1 part of accelerator CZ, 1.5 parts of antioxidant RD and 1 part of antioxidant 4010, 1 part of sulfur and 0.5 part of dicumyl peroxide were sequentially added to the open mill, kneaded at 55 °
  • Table 1 shows the performance parameters of the comparative test of the three-dimensional graphene-modified rubber composite prepared in Examples 1-8 and the rubber of Comparative Examples 1-4:
  • the preparation method of the present invention can greatly improve the electrical conductivity, strength, thermal conductivity and wear resistance of the rubber.

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Abstract

基于三维石墨烯改性的橡胶复合材料，组分按重量份包括：100份橡胶、0.01-10份石墨烯、0.5-5份硫化剂、8-12份橡胶配合剂。基于三维石墨烯改性的橡胶复合材料比现有的橡胶在导电、耐磨性、耐热性和强度性能上有很大提高，且制备工艺简单，易于实现大规模生产。

Description

[根据细则37.2由ISA制定的发明名称]　基于三维石墨烯改性的橡胶复合材料及其制备方法 技术领域
本发明涉及材料技术领域，具体涉及一种基于三维石墨烯改性的橡胶复合材料及其制备。
背景技术
橡胶是橡胶工业的基本原料，具备质轻、耐腐蚀、易规模化生产等优点，并可根据使用需要调节材料的电学和机械性能，在轮胎、电子工业、日用化工和航空航天等领域应用日趋广泛。和这些应用需要橡胶制品具有优良的抗静电、导电或热学、力学和气体阻隔性等性能。
复合型橡胶是以橡胶作为基体，加入导电、导热填料，从而赋予橡胶一定的导电和导热性能。复合型导电橡胶的导电性能主要取决于填料的导电性能及填料在橡胶基体中的均匀分散性。常用的填料有炭黑、石墨、石墨纤维、金属粉体。其中，炭黑是应用最多的导电填料，当炭黑用量达到临界值时，橡胶的导电性能得到显著提高。然而当复合型导电橡胶需要达到很高的电性能时需要加入的炭黑量会非常大，这样会影响橡胶基体材料的粘度和加工性能，使其应用受到限制。纳米级填料如碳纤维、碳纳米管等能以低填充量达到较高的电性能，但是团聚问题使其难在基体中达到良好的分散，并且存在成本问题导致限制其应用发展。
同时，橡胶是热的不良导体，产生的热量不能及时传导出去，造成热量在橡胶制品的内部积聚，当温度过高时会降低制品的性能，影响制品使用寿命。橡胶改性是提高材料导热性能的有效途径，而纳米材料以其独特的分子结构及特性在橡胶增强及功能化方面极具应用潜力。目前影响纳米材料/橡胶复合的两 个关键因素为纳米材料的分散以及与基体界面的相互作用。
发明内容
有鉴于此，有必要针对上述的问题，提供一种既具有良好的导电性，又具有优异的力学、热学性能和机械加工性能的基于三维石墨烯改性的橡胶复合材料及其制备。
为实现上述目的，本发明采取以下技术方案：
本发明的基于三维石墨烯改性的橡胶复合材料，组分按重量份包括：100份橡胶、0.01-5份三维石墨烯、0.5～5份硫化剂、8～12份橡胶配合剂。
进一步的，所述的橡胶包括天然橡胶、硅橡胶、丁苯橡胶、顺丁橡胶、丁基橡胶、异戊橡胶、丁戊橡胶、丁腈橡胶、乙丙橡胶、氯丁橡胶中的至少一种。
进一步的，所述的三维石墨烯具有亚微米至数微米的三维连通多孔网络。
进一步的，所述的硫化剂包括硫磺、过氧化物、金属氧化物、含硫有机物中的至少一种。
进一步的，所述橡胶配合剂包括：促进助剂、促进剂、防老剂。
进一步的，所述促进助剂为氧化锌或硬脂酸中的至少一种；
所述促进剂包括促进剂D、促进剂DM、促进剂TMTD、促进剂CZ、促进剂BZ、促进剂MBT中的至少一种；
所述防老剂包括防老剂RD、防老剂4010、防老剂124、防老剂DNP中的至少一种。
进一步的，所述橡胶配合剂按质量份数包括：2份硬脂酸，5份氧化锌，1～2份促进剂，1～3份防老剂。
本发明基于三维石墨烯改性的橡胶复合材料的制备方法，包括：
步骤1)通过改进的Hummers方法制备氧化石墨烯；
步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为1-2mg/ml，之后转移到反应釜中160-200℃反应20-24h，水洗，得 到三维还原氧化石墨烯水凝胶，冷冻干燥；
步骤3)将橡胶、步骤2)得到的三维石墨烯、橡胶配合剂、硫化剂依次加入开炼机中，40-90℃下混炼10-30min，混炼胶静置16-24h后，在平板硫化机上硫化，硫化条件为140-170℃下硫化10-40min，得到三维石墨烯改性的橡胶复合材料。
进一步的，所述改进的Hummers方法制备氧化石墨烯，分为预氧化、氧化和剥离；
所述预氧化为：将质量份为1份的天然石墨、3-10份浓硫酸、0.5-0.9份的K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨；
所述氧化为：0℃下，将预氧化石墨与6-20份的浓硫酸混合，在搅拌下逐渐加入1-3份的KMnO4，在此过程中控制混合物温度在20℃以下。将混合物升温至35℃，搅拌2h后，加入20-50份超纯水，继续搅拌15min，最后加入40-150份超纯水结束反应。接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子，得到的沉淀用超纯水反复离心清洗至溶液呈中性；
所述剥离：为了剥离氧化石墨，将得到的产物用400w的细胞粉碎仪超声30min，13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯。
本发明的有益效果：
本发明的三维石墨烯有自支撑结构，避免了团聚现象，在橡胶中有良好的分散性；三维石墨烯具有优异的电学、热学和力学性能，同时易与本发明的基体紧密接触，大大增加了橡胶制品的导电性、耐磨性、耐热性和机械强度；本发明制备工艺简单、生产成本低、无环境污染，易于实现大规模的工业化生产。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明的技术方案作进一步清楚、完整地描述。需要说明的是，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1：
步骤1)通过改进的Hummers方法制备氧化石墨烯，分为预氧化、氧化和剥离。
预氧化：将质量份为1份的天然石墨、6份浓硫酸、0.7份的K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨。
氧化：0℃下，将预氧化石墨与9份的浓硫酸混合，在搅拌下逐渐加入3份的KMnO4，在此过程中控制混合物温度在20℃以下。将混合物升温至35℃，搅拌2h后，加入30份超纯水，继续搅拌15min，最后加入60份超纯水结束反应。接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子。得到的沉淀用超纯水反复离心清洗至溶液呈中性。
剥离：为了剥离氧化石墨,将得到的产物用400w的细胞粉碎仪超声30min,13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯；
步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为1.8mg/ml，之后转移到反应釜中200℃反应20h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
步骤3)将100份顺丁橡胶、0.1份三维石墨烯、5份氧化锌、2份硬脂酸、2份促进剂CZ、1.5份防老剂RD、1.5份硫磺依次加入开炼机中，50℃下混炼20min，混炼胶静置24h后，在平板硫化机上硫化，硫化条件151℃、25min，得到三维石墨烯改性的顺丁橡胶复合材料。
实施例2：
步骤1)通过改进的Hummers方法制备氧化石墨烯，分为预氧化、氧化和剥离。
预氧化：将质量份为1份的天然石墨、5份浓硫酸、0.6份的K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨。
氧化：0℃下，将预氧化石墨与8份的浓硫酸混合，在搅拌下逐渐加入2份的KMnO4，在此过程中控制混合物温度在20℃以下。将混合物升温至35℃，搅拌2h后，加入30份超纯水，继续搅拌15min,最后加入50份超纯水结束反应。接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子。得到的沉淀用超纯水反复离心清洗至溶液呈中性。
剥离：为了剥离氧化石墨,将得到的产物用400w的细胞粉碎仪超声30min,13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯；
步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为1.5mg/ml，之后转移到反应釜中180℃反应20h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
步骤3)将100份丁苯橡胶、0.2份三维石墨烯、5份氧化锌、2份硬脂酸、1份促进剂BZ、1份防老剂RD、1份防老剂4010、1份硫磺依次加入开炼机中，50℃下混炼25min，混炼胶静置18h后，在平板硫化机上硫化，硫化条件150℃、30min，得到三维石墨烯改性的丁苯橡胶复合材料。
实施例3
步骤1)通过改进的Hummers方法制备氧化石墨烯，分为预氧化、氧化和剥离。
预氧化：将质量份为1份的天然石墨、7份浓硫酸、0.6份的K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨。
氧化：0℃下，将预氧化石墨与9份的浓硫酸混合，在搅拌下逐渐加入2份 的KMnO4，在此过程中控制混合物温度在20℃以下。将混合物升温至35℃，搅拌2h后，加入20-50份超纯水，继续搅拌15min,最后加入100份超纯水结束反应。接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子。得到的沉淀用超纯水反复离心清洗至溶液呈中性。
剥离：为了剥离氧化石墨,将得到的产物用400w的细胞粉碎仪超声30min,13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯；
步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为1.5mg/ml，之后转移到反应釜中180℃反应24h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
步骤3)将100份丁腈橡胶、0.4份三维石墨烯、5份氧化锌和2份硬脂酸、1份促进剂TMTD和0.5份促进剂MBT、1份防老剂RD和1份防老剂4010、2份硫磺依次加入开炼机中，40℃下混炼20min，混炼胶静置16h后，在平板硫化机上硫化，硫化条件170℃、16min，得到三维石墨烯改性的丁腈橡胶复合材料。
实施例4
步骤1)通过改进的Hummers方法制备氧化石墨烯，分为预氧化、氧化和剥离。
预氧化：将质量份为1份的天然石墨、3份浓硫酸、0.5份K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨。
氧化：0℃下，将预氧化石墨与8份的浓硫酸混合，在搅拌下逐渐加入2份KMnO4，在此过程中控制混合物温度在20℃以下。将混合物升温至35℃，搅拌2h后，加入20份超纯水，继续搅拌15min,最后加入40份超纯水结束反应。接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子。得到的沉淀用超纯水反复离心清洗至溶液呈中性。
剥离：为了剥离氧化石墨,将得到的产物用400w的细胞粉碎仪超声30min, 13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯；
步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为1mg/ml，之后转移到反应釜中160℃反应24h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
步骤3)将100份天然橡胶、0.6份三维石墨烯、5份氧化锌、2份硬脂酸、0.5份促进剂TMTD、1份促进剂CZ、1份防老剂RD、1份防老剂4010、0.5份硫磺依次加入开炼机中，50℃混炼12min，混炼胶静置24h后，在平板硫化机上硫化，硫化条件150℃、40min，得到三维石墨烯改性的天然橡胶复合材料。
实施例5
步骤1)通过改进的Hummers方法制备氧化石墨烯，分为预氧化、氧化和剥离。
预氧化：将质量份为1份的天然石墨、9份浓硫酸、0.9份的K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨。
氧化：0℃下，将预氧化石墨与10份的浓硫酸混合，在搅拌下逐渐加入3份的KMnO4，在此过程中控制混合物温度在20℃以下。将混合物升温至35℃，搅拌2h后，加入50份超纯水，继续搅拌15min，最后加入90份超纯水结束反应。接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子。得到的沉淀用超纯水反复离心清洗至溶液呈中性。
剥离：为了剥离氧化石墨，将得到的产物用400w的细胞粉碎仪超声30min，13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯；
步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为2mg/ml，之后转移到反应釜中200℃反应22h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
步骤3)将100份顺丁橡胶、0.8份三维石墨烯、5份氧化锌、2份硬脂酸、 2份促进剂CZ、1.5份防老剂RD和1份防老剂4010、3份硫磺依次加入开炼机中，60℃下混炼15min，混炼胶静置24h后，在平板硫化机上硫化，硫化条件151℃、25min，得到三维石墨烯改性的顺丁橡胶复合材料。
实施例6
步骤1)通过改进的Hummers方法制备氧化石墨烯，分为预氧化、氧化和剥离。
预氧化：将质量份为1份的天然石墨、8份浓硫酸、0.8份的K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨。
氧化：0℃下，将预氧化石墨与10份的浓硫酸混合，在搅拌下逐渐加入3份的KMnO4，在此过程中控制混合物温度在20℃以下。将混合物升温至35℃，搅拌2h后，加入35份超纯水，继续搅拌15min,最后加入90份超纯水结束反应。接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子。得到的沉淀用超纯水反复离心清洗至溶液呈中性。
剥离：为了剥离氧化石墨,得到的产物用400w的细胞粉碎仪超声30min,13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯；
步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为1.8mg/ml，之后转移到反应釜中200℃反应24h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
步骤3)将100份丁苯橡胶、1份三维石墨烯、5份氧化锌和2份硬脂酸、1.5份促进剂BZ、1份防老剂RD和1份防老剂4010、2.5份硫磺依次加入开炼机中，50℃下混炼30min，混炼胶静置24h后，在平板硫化机上硫化，硫化条件150℃、30min，得到三维石墨烯改性的丁苯橡胶复合材料。
实施例7
步骤1)通过改进的Hummers方法制备氧化石墨烯，分为预氧化、氧化和 剥离。
预氧化：将质量份为1份的天然石墨、10份浓硫酸、0.9份的K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨。
氧化：0℃下，将预氧化石墨与20份的浓硫酸混合，在搅拌下逐渐加入3份的KMnO4，在此过程中控制混合物温度在20℃以下。将混合物升温至35℃，搅拌2h后，加入50份超纯水，继续搅拌15min,最后加入150份超纯水结束反应。接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子。得到的沉淀用超纯水反复离心清洗至溶液呈中性。
剥离：为了剥离氧化石墨，得到的产物用400w的细胞粉碎仪超声30min,13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯；
步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为2mg/ml，之后转移到反应釜中200℃反应24h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
步骤3)将100份丁腈橡胶、2份三维石墨烯、5份氧化锌和1份硬脂酸、1份促进剂TMTD和促进剂1份MBT、1份防老剂RD和1份防老剂4010、4份硫磺依次加入开炼机中，40℃下混炼20min，混炼胶静置24h后，在平板硫化机上硫化，硫化条件170℃、16min，得到三维石墨烯改性的丁腈橡胶复合材料。
实施例8
步骤1)通过改进的Hummers方法制备氧化石墨烯，分为预氧化、氧化和剥离。
预氧化：将质量份为1份的天然石墨、7份浓硫酸、0.7份的K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨。
氧化：0℃下，将预氧化石墨与10份的浓硫酸混合，在搅拌下逐渐加入3份的KMnO4，在此过程中控制混合物温度在20℃以下。将混合物升温至35℃， 搅拌2h后，加入50份超纯水，继续搅拌15min，最后加入80份超纯水结束反应。接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子。得到的沉淀用超纯水反复离心清洗至溶液呈中性。
剥离：为了剥离氧化石墨,得到的产物用400w的细胞粉碎仪超声30min,13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯；
步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为2mg/ml，之后转移到反应釜中180℃反应24h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
步骤3)将100份天然橡胶、3份三维石墨烯、5份氧化锌和2份硬脂酸、1份促进剂TMTD和1份促进剂CZ、1.5份防老剂RD和1份防老剂4010、1份硫磺和0.5份过氧化二异丙苯依次加入开炼机中，55℃下混炼10min，混炼胶静置18h后，在平板硫化机上硫化，硫化条件150℃、40min，得到三维石墨烯改性的天然橡胶复合材料。
对比例1、2、3、4所用配方与制法分别与实施例1、2、3、4相同，唯一区别是其中未加入三维石墨烯。
表1中为实施例1-8所制备得到的三维石墨烯改性的橡胶复合材料与对比例1-4的橡胶进行对比测试的性能参数：
表1各实施例所得橡胶的性能参数
Figure PCTCN2017098066-appb-000001
Figure PCTCN2017098066-appb-000002
从上表可知，本发明的制备方法可以大幅度提高橡胶的导电性、强度、导热性和耐磨性。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (9)

  1. 一种基于三维石墨烯改性的橡胶复合材料，其特征在于，组分按重量份包括：100份橡胶、0.01-10份三维石墨烯、0.5～5份硫化剂、8～12份橡胶配合剂。
  2. 根据权利要求1所述的基于三维石墨烯改性的橡胶复合材料，其特征在于，所述的橡胶包括天然橡胶、硅橡胶、丁苯橡胶、顺丁橡胶、丁基橡胶、异戊橡胶、丁戊橡胶、丁腈橡胶、乙丙橡胶、氯丁橡胶中的至少一种。
  3. 根据权利要求1所述的基于三维石墨烯改性的橡胶复合材料，其特征在于，所述的三维石墨烯具有亚微米至数微米的三维连通多孔网络。
  4. 根据权利要求1所述的基于三维石墨烯改性的橡胶复合材料，其特征在于，所述的硫化剂包括硫磺、过氧化物、金属氧化物、含硫有机物的中至少一种。
  5. 根据权利要求1所述的基于三维石墨烯改性的橡胶复合材料，其特征在于，所述橡胶配合剂包括：促进助剂、促进剂、防老剂。
  6. 根据权利要求1所述的基于三维石墨烯改性的橡胶复合材料，其特征在于，所述促进助剂为氧化锌或硬脂酸中的至少一种；
    所述促进剂包括促进剂D、促进剂DM、促进剂TMTD、促进剂CZ、促进剂BZ、促进剂MBT中的至少一种；
    所述防老剂包括防老剂RD、防老剂4010、防老剂124、防老剂DNP中的至少一种。
  7. 根据权利要求6所述的基于三维石墨烯改性的橡胶复合材料，其特征在于，所述橡胶配合剂按质量份数包括：2份硬脂酸，5份氧化锌，1～2份促进剂，1～3份防老剂。
  8. 一种权利要求1所述的基于三维石墨烯改性的橡胶复合材料的制备方法，其特征在于，包括：
    步骤1)通过改进的Hummers方法制备氧化石墨烯；
    步骤2)三维石墨烯的制备：将步骤1)制备的氧化石墨烯超声分散在超纯水中，浓度为1-2mg/ml，之后转移到反应釜中160-200℃反应20-24h，水洗，得到三维还原氧化石墨烯水凝胶，冷冻干燥；
    步骤3)将橡胶、步骤2)得到的三维石墨烯、橡胶配合剂、硫化剂依次加入开炼机中，40-90℃下混炼10-30min，混炼胶静置16-24h后，在平板硫化机上硫化，硫化条件为140-170℃下硫化10-40min，得到三维石墨烯改性的橡胶复合材料。
  9. 根据权利要求8所述的基于三维石墨烯改性的橡胶复合材料的制备方法，其特征在于，包括：所述改进的Hummers方法制备氧化石墨烯，分为预氧化、氧化和剥离；
    所述预氧化为：将质量份为1份的天然石墨、3-10份浓硫酸、0.5-0.9份的K2S2O8及P2O5混合加热至80℃，反应6h，用超纯水清洗至中性得到预氧化石墨；
    所述氧化为：0℃下，将预氧化石墨与6-20份的浓硫酸混合，在搅拌下逐渐加入1-3份的KMnO4，在此过程中控制混合物温度在20℃以下。将混合物升温至35℃，搅拌2h后，加入20-50份超纯水，继续搅拌15min，最后加入40-150份超纯水结束反应。接着，加入2份30％H2O2，将混合物用10％HCl离心清洗以除去多余的金属离子，得到的沉淀用超纯水反复离心清洗至溶液呈中性；
    所述剥离：为了剥离氧化石墨，将得到的产物用400w的细胞粉碎仪超声30min，13000rpm离心取上清液，90℃温度下进行24h干燥，得到黑棕色的氧化石墨烯。
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