CN110684245A - Graphene natural rubber polymer static-control mixed foam material and preparation method thereof - Google Patents
Graphene natural rubber polymer static-control mixed foam material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a graphene natural rubber polymer static control mixed foaming material and a preparation method thereof, wherein the graphene natural rubber polymer static control mixed foaming material is prepared from the following raw materials in parts by weight: 55-65 parts of natural rubber, 8-12 parts of 1R isoprene rubber, 12-18 parts of butadiene rubber, 14-17 parts of carbon black for batteries, 2.5-3.5 parts of graphene, 1.1-1.3 parts of silicone oil, 1.8-2.2 parts of static control oil, 1.6-1.8 parts of zinc oxide, 1.5-1.7 parts of zinc stearate, 1.8-2.1 parts of stearic acid, 0.95-1.15 parts of cross-linking agent, 2.3-2.8 parts of flow promoter and 2.4-2.9 parts of foaming agent. The graphene natural rubber polymer static control mixed foaming material has strong antistatic capability and good static control effect; the tensile strength is high, the elongation at break is large, and the mechanical property is good; the wear resistance is good.
Description
Technical Field
The invention relates to the technical field of rubber products, in particular to a graphene natural rubber polymer static control mixed foaming 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 used as a general material and is commonly used in various tire products, medical supplies, aerospace materials, rubber tubes, gloves, waterproof materials and the like. NR, while having good balance of properties, is an unsaturated, nonpolar rubber. Active chemical property, ageing resistance and poor heat resistance, and is easy to react with hydrocarbon oil solvent. Therefore, in order to improve the performance defects, the NR is usually modified by blending and the like, so that various performances, service life and application range of the NR are improved.
However, the natural rubber foam materials used at present have the following problems:
1. the common natural rubber foaming material has high surface resistivity, poor antistatic performance and no static control effect;
2. the common natural rubber foaming material has low tensile strength, small elongation at break and poor mechanical property;
3. the wear resistance and other comprehensive use performances are poor.
Disclosure of Invention
Based on the above situation, the invention aims to provide a graphene natural rubber polymer static control mixed foam 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 polymer static control mixed foaming material is prepared from the following raw materials in parts by weight: 55-65 parts of natural rubber, 8-12 parts of 1R isoprene rubber, 12-18 parts of butadiene rubber, 14-17 parts of carbon black for a battery, 2.5-3.5 parts of graphene, 1.1-1.3 parts of silicone oil, 1.8-2.2 parts of static control oil, 1.6-1.8 parts of zinc oxide, 1.5-1.7 parts of zinc stearate, 1.8-2.1 parts of stearic acid, 0.95-1.15 parts of a cross-linking agent, 2.3-2.8 parts of a flow assistant and 2.4-2.9 parts of a foaming agent; the static control oil is a fatty acid ester static suppression auxiliary agent; the graphene is single-layer graphene prepared by a CVD (chemical vapor deposition) method, and the thickness of the graphene is 2-12 nm; the foaming agent is a mixture of azodicarbonamide and sodium bicarbonate.
Preferably, the graphene natural rubber polymer static control mixed foaming material is prepared from the following raw materials in parts by weight: 60 parts of natural rubber, 10 parts of 1R isoprene rubber, 15 parts of butadiene rubber, 15 parts of battery carbon black, 3 parts of graphene, 1.2 parts of silicone oil, 2 parts of static control oil, 1.7 parts of zinc oxide, 1.6 parts of zinc stearate, 1.95 parts of stearic acid, 1.05 parts of a cross-linking agent, 2.55 parts of a flow aid and 2.65 parts of a foaming agent.
Preferably, the graphene natural rubber polymer static control mixed foaming material is prepared from the following raw materials in parts by weight: 62 parts of natural rubber, 10.5 parts of 1R isoprene rubber, 15.5 parts of butadiene rubber, 16.2 parts of carbon black for batteries, 2.8 parts of graphene, 1.22 parts of silicone oil, 2.1 parts of static control oil, 1.72 parts of zinc oxide, 1.62 parts of zinc stearate, 1.97 parts of stearic acid, 1.08 parts of cross-linking agent, 2.6 parts of flow promoter and 2.7 parts of foaming agent.
Preferably, the mass ratio of the azodicarbonamide to the sodium bicarbonate in the mixture of the azodicarbonamide and the sodium bicarbonate is 1: (3.5-5.5).
Preferably, the flow aid is a mixture of polyethylene wax and beeswax.
Preferably, the mass ratio of the polyethylene wax to the beeswax in the mixture of the polyethylene wax and the beeswax is 10: (1.5-2.2).
The polyethylene wax (low polarity) and the beeswax (with multiple polarities) are added in the graphene natural rubber polymer static control mixed foaming material in a proper proportion and serve as a flow aid, and the graphene natural rubber polymer static control mixed foaming material is well compatible with other components such as natural rubber, 1R isoprene rubber, butadiene rubber, carbon black for batteries, graphene and the like, is matched with each other to play a good synergistic effect, and further ensures that the graphene natural rubber polymer static control mixed foaming material has good mechanical properties such as high tensile strength, large breaking elongation and the like.
Preferably, the cross-linking agent is insoluble sulfur.
Preferably, the zinc oxide is activated zinc oxide.
The invention also provides a preparation method of the graphene natural rubber polymer static control mixed foaming material, which comprises the following steps:
A. respectively weighing natural rubber, 1R isoprene rubber, butadiene rubber, carbon black for a battery, graphene, silicone oil, static control oil, zinc oxide, zinc stearate, stearic acid, a cross-linking agent, a flow assistant and a foaming agent 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, 1R isoprene rubber, butadiene rubber, carbon black for a battery, graphene, silicone oil, static control oil, zinc oxide, zinc stearate and stearic acid into an internal mixer, and internally mixing for 10-14 min at the temperature of 82-87 ℃; then banburying for 9-12 min at the temperature of 106-110 ℃; then adding a cross-linking agent, a flow assistant and a foaming agent, banburying at the temperature of 118-121 ℃ for 9-11 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 polymer static-control mixed foaming material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the graphene natural rubber polymer static control mixed foaming material is prepared by selecting raw materials, optimizing the content of each raw material, and selecting natural rubber, 1R isoprene rubber, butadiene rubber, carbon black for a battery, graphene, silicone oil, static control oil, zinc oxide, zinc stearate, stearic acid, a cross-linking agent, a flow assistant and a foaming agent in a proper proportion, so that the advantages of the natural rubber polymer static control mixed foaming material are fully exerted, the advantages are complemented with each other and promoted with each other, the quality stability of the product is improved, and the prepared graphene natural rubber polymer static control mixed foaming material is strong in antistatic capacity (low in surface resistivity) and has a good static control effect; the tensile strength is high, the elongation at break is large, and the mechanical property is good; the wear resistance is good.
The graphene natural rubber polymer static control mixed foaming material is added with natural rubber, 1R isoprene rubber and butadiene rubber in a proper proportion, and the natural rubber, the 1R isoprene rubber and the butadiene rubber are reasonably blended to serve as main raw materials of the graphene natural rubber polymer static control mixed foaming material, so that the graphene natural rubber polymer static control mixed foaming material disclosed by the invention is ensured to have good mechanical properties such as high tensile strength and large elongation at break.
The addition of the carbon black, the graphene and the static control oil in a proper proportion in the graphene natural rubber polymer static control mixed foaming material is matched with other components, and the compatibility with matrix materials such as natural rubber, 1R isoprene rubber, butadiene rubber and the like is good, so that the graphene natural rubber polymer static control mixed foaming material has a good static control effect, is strong in antistatic capacity (low in surface resistivity), plays a good synergistic effect, and can improve the mechanical properties such as strength and the like of the graphene natural rubber polymer static control mixed foaming material.
In the graphene natural rubber polymer static control mixed foaming material, the static control oil is a fatty acid ester static suppression auxiliary agent, and is well compatible with base materials such as natural rubber, 1R isoprene rubber, butadiene rubber and the like, so that the static control effect is improved and the antistatic capability is enhanced while the mechanical property is ensured; the graphene is single-layer graphene prepared by a CVD (chemical vapor deposition) method, and the thickness of the graphene is 2-12 nm, so that the static control effect can be remarkably improved, and the antistatic capability is enhanced; the foaming agent is a mixture of azodicarbonamide and sodium bicarbonate, the foaming process is moderate in speed, less in heat generation, capable of effectively preventing defects (greatly reduced in mechanical property) caused by local excessive foaming, free from yellowing of a foamed product, and good in quality of the product (the graphene natural rubber high-polymer static-control mixed foaming material).
The polyethylene wax (low polarity) and the beeswax (with multiple polarities) are added in the graphene natural rubber polymer static control mixed foaming material in a proper proportion and serve as a flow aid, and the graphene natural rubber polymer static control mixed foaming material is well compatible with other components such as natural rubber, 1R isoprene rubber, butadiene rubber, carbon black for batteries, graphene and the like, is matched with each other, plays a good synergistic effect, and ensures that the graphene natural rubber polymer static control mixed foaming material has good mechanical properties such as high tensile strength, large breaking elongation and the like.
The preparation method disclosed by the invention is simple in process and simple and convenient to operate, saves manpower and equipment cost, and ensures the good performance of the graphene natural rubber polymer static control mixed foaming material.
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 polymer static control mixed foaming material is prepared from the following raw materials in parts by weight: 55-65 parts of natural rubber, 8-12 parts of 1R isoprene rubber, 12-18 parts of butadiene rubber, 14-17 parts of carbon black for a battery, 2.5-3.5 parts of graphene, 1.1-1.3 parts of silicone oil, 1.8-2.2 parts of static control oil, 1.6-1.8 parts of zinc oxide, 1.5-1.7 parts of zinc stearate, 1.8-2.1 parts of stearic acid, 0.95-1.15 parts of a cross-linking agent, 2.3-2.8 parts of a flow assistant and 2.4-2.9 parts of a foaming agent; the static control oil is a fatty acid ester static suppression auxiliary agent; the graphene is single-layer graphene prepared by a CVD (chemical vapor deposition) method, and the thickness of the graphene is 2-12 nm; the foaming agent is a mixture of azodicarbonamide and sodium bicarbonate.
Preferably, the graphene natural rubber polymer static control mixed foaming material is prepared from the following raw materials in parts by weight: 60 parts of natural rubber, 10 parts of 1R isoprene rubber, 15 parts of butadiene rubber, 15 parts of battery carbon black, 3 parts of graphene, 1.2 parts of silicone oil, 2 parts of static control oil, 1.7 parts of zinc oxide, 1.6 parts of zinc stearate, 1.95 parts of stearic acid, 1.05 parts of a cross-linking agent, 2.55 parts of a flow aid and 2.65 parts of a foaming agent.
Preferably, the graphene natural rubber polymer static control mixed foaming material is prepared from the following raw materials in parts by weight: 62 parts of natural rubber, 10.5 parts of 1R isoprene rubber, 15.5 parts of butadiene rubber, 16.2 parts of carbon black for batteries, 2.8 parts of graphene, 1.22 parts of silicone oil, 2.1 parts of static control oil, 1.72 parts of zinc oxide, 1.62 parts of zinc stearate, 1.97 parts of stearic acid, 1.08 parts of cross-linking agent, 2.6 parts of flow promoter and 2.7 parts of foaming agent.
Preferably, the mass ratio of the azodicarbonamide to the sodium bicarbonate in the mixture of the azodicarbonamide and the sodium bicarbonate is 1: (3.5-5.5).
Preferably, the flow aid is a mixture of polyethylene wax and beeswax.
Preferably, the mass ratio of the polyethylene wax to the beeswax in the mixture of the polyethylene wax and the beeswax is 10: (1.5-2.2).
Preferably, the cross-linking agent is insoluble sulfur.
Preferably, the zinc oxide is activated zinc oxide.
The embodiment also provides a preparation method of the graphene natural rubber polymer static control mixed foam material, which comprises the following steps:
A. respectively weighing natural rubber, 1R isoprene rubber, butadiene rubber, carbon black for a battery, graphene, silicone oil, static control oil, zinc oxide, zinc stearate, stearic acid, a cross-linking agent, a flow assistant and a foaming agent 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, 1R isoprene rubber, butadiene rubber, carbon black for a battery, graphene, silicone oil, static control oil, zinc oxide, zinc stearate and stearic acid into an internal mixer, and internally mixing for 10-14 min at the temperature of 82-87 ℃; then banburying for 9-12 min at the temperature of 106-110 ℃; then adding a cross-linking agent, a flow assistant and a foaming agent, banburying at the temperature of 118-121 ℃ for 9-11 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 polymer static-control mixed foaming material.
Example 2:
a graphene natural rubber polymer static control mixed foaming material is prepared from the following raw materials in parts by weight: 55 parts of natural rubber, 8 parts of 1R isoprene rubber, 12 parts of butadiene rubber, 14 parts of battery carbon black, 2.5 parts of graphene, 1.1 parts of silicone oil, 1.8 parts of static control oil, 1.6 parts of zinc oxide, 1.5 parts of zinc stearate, 1.8 parts of stearic acid, 0.95 part of cross-linking agent, 2.3 parts of flow aid and 2.4 parts of foaming agent; the static control oil is a fatty acid ester static suppression auxiliary agent; the graphene is single-layer graphene prepared by a CVD (chemical vapor deposition) method, and the thickness of the graphene is 2-5 nm; the foaming agent is a mixture of azodicarbonamide and sodium bicarbonate.
In this embodiment, the mass ratio of azodicarbonamide to sodium bicarbonate in the mixture of azodicarbonamide and sodium bicarbonate is 1: 3.5.
in this example, the flow aid is a mixture of polyethylene wax and beeswax.
In this embodiment, the mass ratio of the polyethylene wax and the beeswax in the mixture of the polyethylene wax and the beeswax is 10: 1.5.
in this example, the cross-linking agent is insoluble sulfur.
In this embodiment, the zinc oxide is activated zinc oxide.
In this embodiment, the preparation method of the graphene natural rubber polymer static control mixed foam material includes the following steps:
A. respectively weighing natural rubber, 1R isoprene rubber, butadiene rubber, carbon black for a battery, graphene, silicone oil, static control oil, zinc oxide, zinc stearate, stearic acid, a cross-linking agent, a flow assistant and a foaming agent 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, 1R isoprene rubber, butadiene rubber, carbon black for batteries, graphene, silicone oil, static control oil, zinc oxide, zinc stearate and stearic acid into an internal mixer, and internally mixing for 14min at 82 ℃; then banburying for 12min at the temperature of 106 ℃; then adding a cross-linking agent, a flow assistant and a foaming agent, banburying at the temperature of 118 ℃ 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 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 polymer static-control mixed foaming material.
Example 3:
a graphene natural rubber polymer static control mixed foaming material is prepared from the following raw materials in parts by weight: 65 parts of natural rubber, 12 parts of 1R isoprene rubber, 18 parts of butadiene rubber, 17 parts of carbon black for batteries, 3.5 parts of graphene, 1.3 parts of silicone oil, 2.2 parts of static control oil, 1.8 parts of zinc oxide, 1.7 parts of zinc stearate, 2.1 parts of stearic acid, 1.15 parts of a cross-linking agent, 2.8 parts of a flow aid and 2.9 parts of a foaming agent; the static control oil is a fatty acid ester static suppression auxiliary agent; the graphene is single-layer graphene prepared by a CVD (chemical vapor deposition) method, and the thickness of the graphene is 8-12 nm; the foaming agent is a mixture of azodicarbonamide and sodium bicarbonate.
In this embodiment, the mass ratio of azodicarbonamide to sodium bicarbonate in the mixture of azodicarbonamide and sodium bicarbonate is 1: 5.5.
in this example, the flow aid is a mixture of polyethylene wax and beeswax.
In this embodiment, the mass ratio of the polyethylene wax and the beeswax in the mixture of the polyethylene wax and the beeswax is 10: 2.2.
in this example, the cross-linking agent is insoluble sulfur.
In this embodiment, the zinc oxide is activated zinc oxide.
In this embodiment, the preparation method of the graphene natural rubber polymer static control mixed foam material includes the following steps:
A. respectively weighing natural rubber, 1R isoprene rubber, butadiene rubber, carbon black for a battery, graphene, silicone oil, static control oil, zinc oxide, zinc stearate, stearic acid, a cross-linking agent, a flow assistant and a foaming agent 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, 1R isoprene rubber, butadiene rubber, carbon black for batteries, graphene, silicone oil, static control oil, zinc oxide, zinc stearate and stearic acid into an internal mixer, and internally mixing for 10min at the temperature of 87 ℃; then banburying for 9min at the temperature of 110 ℃; then adding a cross-linking agent, a flow assistant and a foaming agent, banburying at the temperature of 121 ℃ 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 graphene natural rubber polymer static-control mixed foaming material.
Example 4:
a graphene natural rubber polymer static control mixed foaming material is prepared from the following raw materials in parts by weight: 60 parts of natural rubber, 10 parts of 1R isoprene rubber, 15 parts of butadiene rubber, 15 parts of battery carbon black, 3 parts of graphene, 1.2 parts of silicone oil, 2 parts of static control oil, 1.7 parts of zinc oxide, 1.6 parts of zinc stearate, 1.95 parts of stearic acid, 1.05 parts of a cross-linking agent, 2.55 parts of a flow aid and 2.65 parts of a foaming agent; the static control oil is a fatty acid ester static suppression auxiliary agent; the graphene is single-layer graphene prepared by a CVD (chemical vapor deposition) method, and the thickness of the graphene is 4-6 nm; the foaming agent is a mixture of azodicarbonamide and sodium bicarbonate.
In this embodiment, the mass ratio of azodicarbonamide to sodium bicarbonate in the mixture of azodicarbonamide and sodium bicarbonate is 1: 4.2.
in this example, the flow aid is a mixture of polyethylene wax and beeswax.
In this embodiment, the mass ratio of the polyethylene wax and the beeswax in the mixture of the polyethylene wax and the beeswax is 10: 1.75.
in this example, the cross-linking agent is insoluble sulfur.
In this embodiment, the zinc oxide is activated zinc oxide.
In this embodiment, the preparation method of the graphene natural rubber polymer static control mixed foam material includes the following steps:
A. respectively weighing natural rubber, 1R isoprene rubber, butadiene rubber, carbon black for a battery, graphene, silicone oil, static control oil, zinc oxide, zinc stearate, stearic acid, a cross-linking agent, a flow assistant and a foaming agent 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, 1R isoprene rubber, butadiene rubber, carbon black for batteries, graphene, silicone oil, static control oil, zinc oxide, zinc stearate and stearic acid into an internal mixer, and internally mixing for 12min at the temperature of 84 ℃; then banburying for 10min at the temperature of 108 ℃; then adding a cross-linking agent, a flow assistant and a foaming agent, banburying at the temperature of 119 ℃ 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 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 polymer static-control mixed foaming material.
Example 5:
a graphene natural rubber polymer static control mixed foaming material is prepared from the following raw materials in parts by weight: 62 parts of natural rubber, 10.5 parts of 1R isoprene rubber, 15.5 parts of butadiene rubber, 16.2 parts of carbon black for batteries, 2.8 parts of graphene, 1.22 parts of silicone oil, 2.1 parts of static control oil, 1.72 parts of zinc oxide, 1.62 parts of zinc stearate, 1.97 parts of stearic acid, 1.08 parts of cross-linking agent, 2.6 parts of flow promoter and 2.7 parts of foaming agent; the static control oil is a fatty acid ester static suppression auxiliary agent; the graphene is single-layer graphene prepared by a CVD (chemical vapor deposition) method, and the thickness of the graphene is 5-10 nm; the foaming agent is a mixture of azodicarbonamide and sodium bicarbonate.
In this embodiment, the mass ratio of azodicarbonamide to sodium bicarbonate in the mixture of azodicarbonamide and sodium bicarbonate is 1: 4.7.
in this example, the flow aid is a mixture of polyethylene wax and beeswax.
In this embodiment, the mass ratio of the polyethylene wax and the beeswax in the mixture of the polyethylene wax and the beeswax is 10: 1.84.
in this example, the cross-linking agent is insoluble sulfur.
In this embodiment, the zinc oxide is activated zinc oxide.
In this embodiment, the preparation method of the graphene natural rubber polymer static control mixed foam material includes the following steps:
A. respectively weighing natural rubber, 1R isoprene rubber, butadiene rubber, carbon black for a battery, graphene, silicone oil, static control oil, zinc oxide, zinc stearate, stearic acid, a cross-linking agent, a flow assistant and a foaming agent according to parts by weight;
B. feeding natural rubber into an internal mixer, masticating for 13min at the temperature of 147 ℃, 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, 1R isoprene rubber, butadiene rubber, carbon black for batteries, graphene, silicone oil, static control oil, zinc oxide, zinc stearate and stearic acid into an internal mixer, and internally mixing for 12min at 86 ℃; then banburying for 11min at 109 ℃; then adding a cross-linking agent, a flow assistant and a foaming agent, banburying at the temperature of 120 ℃ 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 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 polymer static-control mixed foaming material.
The graphene natural rubber polymer static control mixed foam material obtained in the embodiments 2 to 5 of the present invention and the common natural rubber foam material are subjected to performance tests, and the test results are shown in table 1:
surface resistivity: the DC voltage of 100V was confirmed for each foamed material, and then the current was measured and converted into the resistivity (astm d 257).
TABLE 1
As can be seen from the above table, compared with the common natural rubber foam material, the graphene natural rubber polymer static control mixed foam material of the present invention has the following advantages: the antistatic property is strong (the surface resistivity is low), and the antistatic effect is good; the tensile strength is high, the elongation at break is large, and the mechanical property is good; the wear resistance is good.
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 (9)
1. The graphene natural rubber polymer static control mixed foaming material is characterized by being prepared from the following raw materials in parts by weight: 55-65 parts of natural rubber, 8-12 parts of 1R isoprene rubber, 12-18 parts of butadiene rubber, 14-17 parts of carbon black for a battery, 2.5-3.5 parts of graphene, 1.1-1.3 parts of silicone oil, 1.8-2.2 parts of static control oil, 1.6-1.8 parts of zinc oxide, 1.5-1.7 parts of zinc stearate, 1.8-2.1 parts of stearic acid, 0.95-1.15 parts of a cross-linking agent, 2.3-2.8 parts of a flow assistant and 2.4-2.9 parts of a foaming agent; the static control oil is a fatty acid ester static suppression auxiliary agent; the graphene is single-layer graphene prepared by a CVD (chemical vapor deposition) method, and the thickness of the graphene is 2-12 nm; the foaming agent is a mixture of azodicarbonamide and sodium bicarbonate.
2. The graphene natural rubber polymer static control mixed foaming material according to claim 1, wherein the graphene natural rubber polymer static control mixed foaming material is prepared from the following raw materials in parts by weight: 60 parts of natural rubber, 10 parts of 1R isoprene rubber, 15 parts of butadiene rubber, 15 parts of battery carbon black, 3 parts of graphene, 1.2 parts of silicone oil, 2 parts of static control oil, 1.7 parts of zinc oxide, 1.6 parts of zinc stearate, 1.95 parts of stearic acid, 1.05 parts of a cross-linking agent, 2.55 parts of a flow aid and 2.65 parts of a foaming agent.
3. The graphene natural rubber polymer static control mixed foaming material according to claim 1, wherein the graphene natural rubber polymer static control mixed foaming material is prepared from the following raw materials in parts by weight: 62 parts of natural rubber, 10.5 parts of 1R isoprene rubber, 15.5 parts of butadiene rubber, 16.2 parts of carbon black for batteries, 2.8 parts of graphene, 1.22 parts of silicone oil, 2.1 parts of static control oil, 1.72 parts of zinc oxide, 1.62 parts of zinc stearate, 1.97 parts of stearic acid, 1.08 parts of cross-linking agent, 2.6 parts of flow promoter and 2.7 parts of foaming agent.
4. The graphene natural rubber polymer static electricity control mixed foaming material according to any one of claims 1 to 3, wherein the mass ratio of azodicarbonamide to sodium bicarbonate in the mixture of azodicarbonamide and sodium bicarbonate is 1: (3.5-5.5).
5. The graphene natural rubber polymer static electricity control mixed foaming material according to any one of claims 1 to 3, wherein the flow aid is a mixture of polyethylene wax and beeswax.
6. The graphene natural rubber polymer static electricity control mixed foaming material according to claim 5, wherein the mass ratio of the polyethylene wax to the beeswax in the mixture of the polyethylene wax and the beeswax is 10: (1.5-2.2).
7. The graphene natural rubber polymer static electricity control hybrid foam material according to any one of claims 1 to 3, wherein the cross-linking agent is insoluble sulfur.
8. The graphene natural rubber polymer static electricity control hybrid foam material according to any one of claims 1 to 3, wherein the zinc oxide is active zinc oxide.
9. The preparation method of the graphene natural rubber polymer static control mixed foaming material as claimed in any one of claims 1 to 3, characterized by comprising the following steps:
A. respectively weighing natural rubber, 1R isoprene rubber, butadiene rubber, carbon black for a battery, graphene, silicone oil, static control oil, zinc oxide, zinc stearate, stearic acid, a cross-linking agent, a flow assistant and a foaming agent 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, 1R isoprene rubber, butadiene rubber, carbon black for a battery, graphene, silicone oil, static control oil, zinc oxide, zinc stearate and stearic acid into an internal mixer, and internally mixing for 10-14 min at the temperature of 82-87 ℃; then banburying for 9-12 min at the temperature of 106-110 ℃; then adding a cross-linking agent, a flow assistant and a foaming agent, banburying at the temperature of 118-121 ℃ for 9-11 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 polymer static-control mixed foaming material.
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| CN110066427A (en) * | 2019-05-23 | 2019-07-30 | 福建五持恒科技发展有限公司 | Graphene reclaimed rubber foamed shoe-pad and preparation method thereof |
| CN110144075A (en) * | 2019-06-05 | 2019-08-20 | 福建五持恒科技发展有限公司 | A kind of graphene reclaimed rubber foamed shoe sole micelle and preparation method thereof |
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| CN109627512A (en) * | 2019-01-08 | 2019-04-16 | 福建五持恒科技发展有限公司 | Sole ultralight graphene rubber pange micelle and preparation method thereof |
| CN110066427A (en) * | 2019-05-23 | 2019-07-30 | 福建五持恒科技发展有限公司 | Graphene reclaimed rubber foamed shoe-pad and preparation method thereof |
| CN110144075A (en) * | 2019-06-05 | 2019-08-20 | 福建五持恒科技发展有限公司 | A kind of graphene reclaimed rubber foamed shoe sole micelle and preparation method thereof |
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