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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- 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
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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 |