CN110684244A - Graphene natural rubber foamed polymer composite material and preparation method thereof - Google Patents
Graphene natural rubber foamed polymer composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a graphene natural rubber foamed polymer composite material and a preparation method thereof, wherein the graphene natural rubber foamed polymer composite material is prepared from the following raw materials in parts by weight: 76-84 parts of natural rubber, 16-22 parts of rare earth isoprene rubber, 10-14 parts of ethylene-vinyl acetate copolymer, 3-5 parts of silane coupling agent modified glass fiber, 3.6-4.4 parts of silane coupling agent modified basalt fiber, 2.5-3 parts of graphene, 1.8-2.4 parts of foaming agent, 0.9-1.2 parts of micropore regulator, 1.5-2.1 parts of polyethylene wax, 1.1-1.5 parts of maleic anhydride grafted polyethylene, 1.6-2.2 parts of crosslinking agent, 3-5 parts of antioxidant and 3-5 parts of heat stabilizer. The product of the invention has low density and ultra-light weight; the compression set rate is low, the rebound resilience is good, the durability is realized, and the deformation is not easy in the using process; the mechanical properties such as tensile strength, elongation at break and the like are good, and the ultralight property and excellent mechanical properties are well considered.
Description
Technical Field
The invention relates to the technical field of rubber products, in particular to a graphene natural rubber foamed polymer composite 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 foam materials used at present have the following problems: 1. or the weight is not light enough, the device is heavy and cannot meet the use requirement of ultralight; 2. or the mechanical properties such as tensile strength, elongation at break and the like after foaming are poor, the compression set is high, and the deformation which cannot be recovered is easy to occur in the using process, so that the using requirement cannot be met. In short, both ultra-light weight and excellent mechanical properties cannot be achieved.
Disclosure of Invention
Based on the above situation, the present invention aims to provide a graphene natural rubber foamed polymer composite material 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 graphene natural rubber foamed polymer composite material is prepared from the following raw materials in parts by weight:
76-84 parts of natural rubber, 16-22 parts of rare earth isoprene rubber, 10-14 parts of ethylene-vinyl acetate copolymer, 3-5 parts of silane coupling agent modified glass fiber, 3.6-4.4 parts of silane coupling agent modified basalt fiber, 2.5-3 parts of graphene, 1.8-2.4 parts of foaming agent, 0.9-1.2 parts of micropore regulator, 1.5-2.1 parts of polyethylene wax, 1.1-1.5 parts of maleic anhydride grafted polyethylene, 1.6-2.2 parts of crosslinking agent, 3-5 parts of antioxidant and 3-5 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 and zinc diacrylate.
Preferably, the graphene natural rubber foamed polymer composite material is prepared from the following raw materials in parts by weight: 80 parts of natural rubber, 19 parts of rare earth isoprene rubber, 12 parts of ethylene-vinyl acetate copolymer, 4 parts of silane coupling agent modified glass fiber, 4 parts of silane coupling agent modified basalt fiber, 2.8 parts of graphene, 2.1 parts of foaming agent, 1.1 parts of micropore regulator, 1.8 parts of polyethylene wax, 1.3 parts of maleic anhydride grafted polyethylene, 1.9 parts of cross-linking agent, 4 parts of antioxidant and 4 parts of heat stabilizer.
Preferably, the VA content of the ethylene-vinyl acetate copolymer is 30-35.
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: (0.58-0.65).
Preferably, the thickness of the nano graphene microchip is 1-10 nm.
Preferably, the mass ratio of the sulfur to the zinc diacrylate in the mixture of the sulfur and the zinc diacrylate is 1: (0.3-0.4).
Preferably, the blowing agent is an AC blowing 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 natural rubber foamed polymer composite material, which comprises the following steps:
A. respectively weighing natural rubber, rare earth isoprene rubber, an ethylene-vinyl acetate copolymer, silane coupling agent modified glass fiber, silane coupling agent modified basalt fiber, graphene, a foaming agent, a micropore regulator, polyethylene wax, maleic anhydride grafted polyethylene, a crosslinking agent, an antioxidant and a heat stabilizer in 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, rare earth isoprene rubber, an ethylene-vinyl acetate copolymer, silane coupling agent modified glass fiber, silane coupling agent modified basalt fiber, graphene, polyethylene wax and maleic anhydride grafted polyethylene into an internal mixer, and internally mixing for 11-14 min at the temperature of 83-87 ℃; then banburying for 9-12 min at the temperature of 104-108 ℃; then adding a cross-linking agent, a foaming agent, a micropore regulator, an antioxidant and a heat stabilizer, banburying at the temperature of 118-122 ℃ for 8-10 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 graphene natural rubber foamed polymer composite material.
The graphene natural rubber foamed polymer composite material is mainly used as a sole material, and the application field of the graphene natural rubber foamed polymer composite 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 graphene natural rubber foamed polymer composite material disclosed by the invention is prepared by selecting raw materials, optimizing the content of each raw material, and selecting natural rubber, rare earth isoprene rubber, an ethylene-vinyl acetate copolymer, silane coupling agent modified glass fiber, silane coupling agent modified basalt fiber, graphene, a foaming agent, a micropore regulator, polyethylene wax, maleic anhydride grafted polyethylene, a crosslinking agent, an antioxidant and a heat stabilizer in a proper ratio, so that the advantages of the graphene natural rubber foamed polymer composite material are fully exerted, the polyethylene wax, the maleic anhydride grafted polyethylene, the crosslinking agent, the antioxidant and the heat stabilizer are mutually supplemented and promoted, the quality stability of a product is improved, and the prepared graphene natural rubber foamed polymer composite material is low in density which is far lower than that of a common natural rubber foamed material and has ultralight property; the compression set is low, the compression set is obviously lower than that of the common natural rubber foaming material, the rebound resilience is good, the durability is realized, and the deformation is not easy to occur in the using process; the tensile strength and the elongation at break are both greatly superior to those of common natural rubber foaming materials, the mechanical property is good, the ultralight property and the excellent mechanical property are well considered, and the composite material has wide market application prospect.
In the graphene natural rubber foamed polymer composite material, natural rubber is used as a main matrix material.
The structure and the performance of the added rare earth isoprene rubber are most close to those of natural rubber, the added rare earth isoprene rubber can well keep the high tensile and high tear resistance of the natural rubber, can effectively improve the crosslinking density and the elongation at break, and ensure that the foamed graphene natural rubber foamed polymer composite material has low compression set and good rebound resilience; the mechanical properties such as tensile strength, elongation at break and the like are good, and the ultralight property and excellent mechanical properties are well considered.
The addition of a proper amount of ethylene-vinyl acetate copolymer can increase the molecular binding force between the natural rubber and the rare earth isoprene rubber, can also increase the compatibility of other components such as silane coupling agent modified glass fiber, silane coupling agent modified basalt fiber, graphene and the like with the natural rubber and the rare earth isoprene rubber, and can be matched with other components to play a good synergistic effect, thereby effectively ensuring the mechanical properties (after enhancement and modification) of the graphene natural rubber foamed polymer composite material.
The glass fiber modified by adding a proper amount of silane coupling agent has good compatibility in the raw material system, is matched with other components to play a good synergistic effect, and can play a remarkable reinforcing role for the graphene natural rubber foamed polymer composite material.
The graphene natural rubber foamed polymer composite material has the advantages that the proper amount of silane coupling agent modified basalt fiber is added, the compatibility is good in the raw material system, the basalt fiber is matched with other components, a good synergistic effect is achieved, the wear resistance of the graphene natural rubber foamed polymer composite material can be obviously improved, and the mechanical properties such as tensile strength and the like of the graphene natural rubber foamed polymer composite material are improved to a certain extent.
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;
proper amount of polyethylene wax and maleic anhydride grafted polyethylene 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; the use of small molecular auxiliary agents can be reduced, the compatibility of each component in the raw material system is increased, and the mechanical properties of the material and the like are ensured;
adding a proper amount of cross-linking agent, wherein the cross-linking agent is a mixture of sulfur and zinc diacrylate. The zinc diacrylate plays a role in assisting crosslinking, so that the graphene natural rubber foamed polymer composite material is rapidly crosslinked, is moderate in crosslinking and uniform in distribution of crosslinking areas, and ensures that the foamed graphene natural rubber foamed polymer composite material 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 ultralight property and excellent mechanical properties are well considered.
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 graphene natural rubber foamed polymer composite material is prepared from the following raw materials in parts by weight:
76-84 parts of natural rubber, 16-22 parts of rare earth isoprene rubber, 10-14 parts of ethylene-vinyl acetate copolymer, 3-5 parts of silane coupling agent modified glass fiber, 3.6-4.4 parts of silane coupling agent modified basalt fiber, 2.5-3 parts of graphene, 1.8-2.4 parts of foaming agent, 0.9-1.2 parts of micropore regulator, 1.5-2.1 parts of polyethylene wax, 1.1-1.5 parts of maleic anhydride grafted polyethylene, 1.6-2.2 parts of crosslinking agent, 3-5 parts of antioxidant and 3-5 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 and zinc diacrylate.
Preferably, the graphene natural rubber foamed polymer composite material is prepared from the following raw materials in parts by weight: 80 parts of natural rubber, 19 parts of rare earth isoprene rubber, 12 parts of ethylene-vinyl acetate copolymer, 4 parts of silane coupling agent modified glass fiber, 4 parts of silane coupling agent modified basalt fiber, 2.8 parts of graphene, 2.1 parts of foaming agent, 1.1 parts of micropore regulator, 1.8 parts of polyethylene wax, 1.3 parts of maleic anhydride grafted polyethylene, 1.9 parts of cross-linking agent, 4 parts of antioxidant and 4 parts of heat stabilizer.
Preferably, the VA content of the ethylene-vinyl acetate copolymer is 30-35.
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: (0.58-0.65).
Preferably, the thickness of the nano graphene microchip is 1-10 nm.
Preferably, the mass ratio of the sulfur to the zinc diacrylate in the mixture of the sulfur and the zinc diacrylate is 1: (0.3-0.4).
Preferably, the blowing agent is an AC blowing 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 natural rubber foamed polymer composite material, which comprises the following steps:
A. respectively weighing natural rubber, rare earth isoprene rubber, an ethylene-vinyl acetate copolymer, silane coupling agent modified glass fiber, silane coupling agent modified basalt fiber, graphene, a foaming agent, a micropore regulator, polyethylene wax, maleic anhydride grafted polyethylene, a crosslinking agent, an antioxidant and a heat stabilizer in 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, rare earth isoprene rubber, an ethylene-vinyl acetate copolymer, silane coupling agent modified glass fiber, silane coupling agent modified basalt fiber, graphene, polyethylene wax and maleic anhydride grafted polyethylene into an internal mixer, and internally mixing for 11-14 min at the temperature of 83-87 ℃; then banburying for 9-12 min at the temperature of 104-108 ℃; then adding a cross-linking agent, a foaming agent, a micropore regulator, an antioxidant and a heat stabilizer, banburying at the temperature of 118-122 ℃ for 8-10 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 graphene natural rubber foamed polymer composite material.
Example 2:
a graphene natural rubber foamed polymer composite material is prepared from the following raw materials in parts by weight:
76 parts of natural rubber, 16 parts of rare earth isoprene rubber, 10 parts of ethylene-vinyl acetate copolymer, 3 parts of silane coupling agent modified glass fiber, 3.6 parts of silane coupling agent modified basalt fiber, 2.5 parts of graphene, 1.8 parts of foaming agent, 0.9 part of micropore regulator, 1.5 parts of polyethylene wax, 1.1 parts of maleic anhydride grafted polyethylene, 1.6 parts of cross-linking agent, 3 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 and zinc diacrylate.
In this example, the ethylene-vinyl acetate copolymer had a VA content of 30.
In this embodiment, the mass ratio of the zinc formate to the zinc isooctanoate in the mixture of the zinc formate and the zinc isooctanoate is 1: 0.58.
in the embodiment, the thickness of the nano graphene microchip is 1-5 nm.
In this embodiment, the mass ratio of the sulfur to the zinc diacrylate in the mixture of sulfur and zinc diacrylate is 1: 0.3.
in this example, the blowing agent was an AC blowing 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 graphene natural rubber foamed polymer composite material includes the following steps:
A. respectively weighing natural rubber, rare earth isoprene rubber, an ethylene-vinyl acetate copolymer, silane coupling agent modified glass fiber, silane coupling agent modified basalt fiber, graphene, a foaming agent, a micropore regulator, polyethylene wax, maleic anhydride grafted polyethylene, a crosslinking agent, an antioxidant and a heat stabilizer in 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, rare earth isoprene rubber, ethylene-vinyl acetate copolymer, silane coupling agent modified glass fiber, silane coupling agent modified basalt fiber, graphene, polyethylene wax and maleic anhydride grafted polyethylene into an internal mixer, and internally mixing for 14min at 83 ℃; then banburying for 12min at the temperature of 104 ℃; then adding a cross-linking agent, a foaming agent, a micropore regulator, an antioxidant and a heat stabilizer, banburying at the temperature of 118 ℃ for 10min, 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 graphene natural rubber foamed polymer composite material.
Example 3:
a graphene natural rubber foamed polymer composite material is prepared from the following raw materials in parts by weight:
84 parts of natural rubber, 22 parts of rare earth isoprene rubber, 14 parts of ethylene-vinyl acetate copolymer, 5 parts of silane coupling agent modified glass fiber, 4.4 parts of silane coupling agent modified basalt fiber, 3 parts of graphene, 2.4 parts of foaming agent, 1.2 parts of micropore regulator, 2.1 parts of polyethylene wax, 1.5 parts of maleic anhydride grafted polyethylene, 2.2 parts of cross-linking agent, 5 parts of antioxidant and 5 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 and zinc diacrylate.
In this example, the ethylene-vinyl acetate copolymer had a VA content of 35.
In this embodiment, the mass ratio of the zinc formate to the zinc isooctanoate in the mixture of the zinc formate and the zinc isooctanoate is 1: 0.65.
in the embodiment, the thickness of the nano graphene microchip is 5-10 nm.
In this embodiment, the mass ratio of the sulfur to the zinc diacrylate in the mixture of sulfur and zinc diacrylate is 1: 0.4.
in this example, the blowing agent was an AC blowing 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 graphene natural rubber foamed polymer composite material includes the following steps:
A. respectively weighing natural rubber, rare earth isoprene rubber, an ethylene-vinyl acetate copolymer, silane coupling agent modified glass fiber, silane coupling agent modified basalt fiber, graphene, a foaming agent, a micropore regulator, polyethylene wax, maleic anhydride grafted polyethylene, a crosslinking agent, an antioxidant and a heat stabilizer in 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, rare earth isoprene rubber, ethylene-vinyl acetate copolymer, silane coupling agent modified glass fiber, silane coupling agent modified basalt fiber, graphene, polyethylene wax and maleic anhydride grafted polyethylene into an internal mixer, and internally mixing for 11min at the temperature of 87 ℃; then banburying for 9min at the temperature of 108 ℃; then adding a cross-linking agent, a foaming agent, a micropore regulator, an antioxidant and a heat stabilizer, banburying for 8min at the temperature of 122 ℃, 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 graphene natural rubber foamed polymer composite material.
Example 4:
a graphene natural rubber foamed polymer composite material is prepared from the following raw materials in parts by weight:
80 parts of natural rubber, 19 parts of rare earth isoprene rubber, 12 parts of ethylene-vinyl acetate copolymer, 4 parts of silane coupling agent modified glass fiber, 4 parts of silane coupling agent modified basalt fiber, 2.8 parts of graphene, 2.1 parts of foaming agent, 1.1 parts of micropore regulator, 1.8 parts of polyethylene wax, 1.3 parts of maleic anhydride grafted polyethylene, 1.9 parts of cross-linking agent, 4 parts of antioxidant and 4 parts of heat stabilizer.
In this example, the ethylene-vinyl acetate copolymer had a VA content of 32.5.
In this embodiment, the mass ratio of the zinc formate to the zinc isooctanoate in the mixture of the zinc formate and the zinc isooctanoate is 1: 0.63.
in the embodiment, the thickness of the nano graphene microchip is 4-6 nm.
In this embodiment, the mass ratio of the sulfur to the zinc diacrylate in the mixture of sulfur and zinc diacrylate is 1: 0.35.
in this example, the blowing agent was an AC blowing 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 graphene natural rubber foamed polymer composite material includes the following steps:
A. respectively weighing natural rubber, rare earth isoprene rubber, an ethylene-vinyl acetate copolymer, silane coupling agent modified glass fiber, silane coupling agent modified basalt fiber, graphene, a foaming agent, a micropore regulator, polyethylene wax, maleic anhydride grafted polyethylene, a crosslinking agent, an antioxidant and a heat stabilizer in 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, rare earth isoprene rubber, ethylene-vinyl acetate copolymer, silane coupling agent modified glass fiber, silane coupling agent modified basalt fiber, graphene, polyethylene wax and maleic anhydride grafted polyethylene into an internal mixer, and internally mixing for 13min at the temperature of 85 ℃; then banburying for 10min at the temperature of 106 ℃; then adding a cross-linking agent, a foaming agent, a micropore regulator, an antioxidant and a heat stabilizer, banburying at the temperature of 120 ℃ 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 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 graphene natural rubber foamed polymer composite material.
The following performance tests were performed on the graphene natural rubber foamed polymer composite obtained in examples 2 to 4 of the present invention and the common natural rubber foamed material, and the test results are shown in table 1:
TABLE 1
As can be seen from the above table, compared with the common natural rubber foam material, the graphene natural rubber foam polymer composite material of the present invention has the following advantages: the density of the graphene natural rubber foamed polymer composite material is far lower than that of a common natural rubber foamed material, and the graphene natural rubber foamed polymer composite material has ultralight weight; the compression set rate is obviously lower than that of the common natural rubber foaming material, the rebound resilience is good, the durability is realized, and the deformation is not easy in the using process; the tensile strength and the elongation at break are both greatly superior to those of common natural rubber foaming materials, the mechanical property is good, and the ultralight property and the excellent mechanical property are well considered.
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 graphene natural rubber foamed polymer composite material is characterized by being prepared from the following raw materials in parts by weight:
76-84 parts of natural rubber, 16-22 parts of rare earth isoprene rubber, 10-14 parts of ethylene-vinyl acetate copolymer, 3-5 parts of silane coupling agent modified glass fiber, 3.6-4.4 parts of silane coupling agent modified basalt fiber, 2.5-3 parts of graphene, 1.8-2.4 parts of foaming agent, 0.9-1.2 parts of micropore regulator, 1.5-2.1 parts of polyethylene wax, 1.1-1.5 parts of maleic anhydride grafted polyethylene, 1.6-2.2 parts of crosslinking agent, 3-5 parts of antioxidant and 3-5 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 and zinc diacrylate.
2. The graphene natural rubber foamed polymer composite material according to claim 1, wherein the graphene natural rubber foamed polymer composite material is prepared from the following raw materials in parts by weight: 80 parts of natural rubber, 19 parts of rare earth isoprene rubber, 12 parts of ethylene-vinyl acetate copolymer, 4 parts of silane coupling agent modified glass fiber, 4 parts of silane coupling agent modified basalt fiber, 2.8 parts of graphene, 2.1 parts of foaming agent, 1.1 parts of micropore regulator, 1.8 parts of polyethylene wax, 1.3 parts of maleic anhydride grafted polyethylene, 1.9 parts of cross-linking agent, 4 parts of antioxidant and 4 parts of heat stabilizer.
3. The graphene natural rubber foamed polymer composite material according to claim 1, wherein the ethylene-vinyl acetate copolymer has a VA content of 30-35.
4. The graphene natural rubber foamed polymer composite material according to claim 1, wherein the mass ratio of zinc formate to zinc isooctanoate in the mixture of zinc formate and zinc isooctanoate is 1: (0.58-0.65).
5. The graphene natural rubber foamed polymer composite material according to claim 1, wherein the nano graphene micro-sheets have a thickness of 1-10 nm.
6. The graphene natural rubber foamed polymer composite material according to claim 1, wherein the mass ratio of the sulfur to the zinc diacrylate in the mixture of the sulfur and the zinc diacrylate is 1: (0.3-0.4).
7. The graphene natural rubber foamed polymer composite material according to claim 1, wherein the foaming agent is an AC foaming agent.
8. The graphene natural rubber foamed polymer composite material according to claim 1, wherein the antioxidant is an antioxidant 4010 NA-M.
9. The graphene natural rubber foamed polymer composite material according to claim 1, wherein the heat stabilizer is a mixture of the graphene natural rubber foamed polymer composite material and the heat stabilizer in a mass ratio of 1: 1 of zinc stearate and stearic acid.
10. A method for preparing the graphene natural rubber foamed polymer composite material according to any one of claims 1 to 9, comprising the following steps:
A. respectively weighing natural rubber, rare earth isoprene rubber, an ethylene-vinyl acetate copolymer, silane coupling agent modified glass fiber, silane coupling agent modified basalt fiber, graphene, a foaming agent, a micropore regulator, polyethylene wax, maleic anhydride grafted polyethylene, a crosslinking agent, an antioxidant and a heat stabilizer in 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, rare earth isoprene rubber, an ethylene-vinyl acetate copolymer, silane coupling agent modified glass fiber, silane coupling agent modified basalt fiber, graphene, polyethylene wax and maleic anhydride grafted polyethylene into an internal mixer, and internally mixing for 11-14 min at the temperature of 83-87 ℃; then banburying for 9-12 min at the temperature of 104-108 ℃; then adding a cross-linking agent, a foaming agent, a micropore regulator, an antioxidant and a heat stabilizer, banburying at the temperature of 118-122 ℃ for 8-10 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 graphene natural rubber foamed polymer composite material.
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