Graphene-reinforced antistatic rubber composition and preparation method thereof

文档序号：1638357 发布日期：2020-01-17 浏览：17次中文

阅读说明：本技术 石墨烯增强抗静电橡胶组合物及其制备方法 (Graphene-reinforced antistatic rubber composition and preparation method thereof ) 是由张新和赵露华王浩然张敏刘婷婷徐玮彤徐欢曲波李金来于 2019-09-26 设计创作，主要内容包括：本发明涉及橡胶的技术领域,尤其涉及一种石墨烯增强抗静电橡胶组合物及其制备方法。石墨烯增强抗静电橡胶组合物由材料橡胶、白矿油、石墨烯、碳纳米管、防老剂、硫磺、硫化促进剂制备而成,石墨烯和碳纳米管在体系中相互结合形成了网络结构,可以促进自身的分散,使得体系的力学性能得到显著增强采用两步法混炼方法,通过白油对石墨烯和碳纳米管进行润湿,减少在搅拌过程中的二者的损失；也提高了石墨烯在橡胶基体中的分散性,增强效果更佳,避免了一次混合产生的石墨烯团聚、分散程度不高的缺点。(The invention relates to the technical field of rubber, in particular to a graphene reinforced antistatic rubber composition and a preparation method thereof. The graphene reinforced antistatic rubber composition is prepared from material rubber, white mineral oil, graphene, carbon nano tubes, an anti-aging agent, sulfur and a vulcanization accelerator, wherein the graphene and the carbon nano tubes are combined with each other in a system to form a network structure, so that the self dispersion can be promoted, the mechanical property of the system is remarkably enhanced by adopting a two-step mixing method, the graphene and the carbon nano tubes are wetted by the white oil, and the loss of the graphene and the carbon nano tubes in the stirring process is reduced; the dispersibility of the graphene in the rubber matrix is improved, the reinforcing effect is better, and the defects of graphene agglomeration and low dispersion degree caused by one-time mixing are overcome.)

1. A graphene reinforced antistatic rubber composition is characterized in that: the graphene reinforced antistatic rubber composition mainly comprises the following components:

100 parts of rubber 75 ‒ 100;

0.1 ‒ 10 parts of graphene;

1 ‒ 20 parts of carbon nanotubes;

1 ‒ 25 parts of a flow modifier;

0.1 part of antioxidant 0.1 ‒ 10;

1 ‒ 4 parts of sulfur;

0.01 ‒ 2 parts of vulcanization accelerator.

2. The graphene-reinforced antistatic rubber composition according to claim 1, wherein: the rubber is at least one of natural rubber, chloroprene rubber, butadiene rubber and chlorosulfonated polyethylene rubber.

3. The graphene-reinforced antistatic rubber composition according to claim 1, wherein: the graphene has a radial dimension of 0.5 ‒ 40 [ mu ] m and a thickness of 1 ‒ 20 nm.

4. The graphene reinforced antistatic rubber composition as claimed in claim 1, wherein the length-diameter ratio of the carbon nanotubes is not less than 1000, and the diameter is 2 ~ 30 nm.

5. The graphene-reinforced antistatic rubber composition according to claim 1, wherein: the flow modifier is at least one of polyethylene wax, stearic acid, stearate, paraffin, white oil, EBS and PETS.

6. The graphene-reinforced antistatic rubber composition according to claim 1, wherein: the antioxidant is at least one of aromatic amine antioxidant, hindered phenol antioxidant and phosphite antioxidant.

7. The method for preparing the graphene reinforced antistatic rubber composition according to claim 1, wherein: the preparation method comprises two steps of mixing,

fully mixing graphene, carbon nano tubes, rubber, an antioxidant and a flow modifier in a mixing device according to a ratio, wherein the mixing temperature is 70 ‒ 200 ℃, and the mixing time is 7-60 min to form a master batch which is uniformly premixed;

and secondly, continuously mixing the sulfur and the vulcanization accelerator with the master batch in a mixing device according to a proportion, discharging the mixture when the temperature of the mixed batch reaches 70 ‒ 200 ℃, plasticizing uniformly on a double-roll mill, and discharging the mixture.

8. The method for preparing a graphene-reinforced antistatic rubber composition according to claim 7, wherein: the mixing equipment in the first step and the second step is at least one of a conical mixer, a high-speed mixer, an open mill, a turnover type internal mixer, a continuous type internal mixer, a Z-type kneader, a screw kneader, a vacuum kneader and a horizontal double-helix mixer.

9. The method for preparing the graphene reinforced antistatic rubber composition according to claim 1, wherein: the preparation method comprises the following steps of,

firstly, shearing and stirring graphene, carbon nano tubes, a flow modifier, an antioxidant and rubber in a banburying device according to a proportion to form a pre-mixed uniform master batch;

secondly, uniformly discharging the obtained master batch on an open mill, standing at room temperature for 24 hours,

and thirdly, adding the masterbatch obtained in the second step into banburying equipment, adding sulfur and a vulcanization accelerator for final refining, and obtaining the graphene reinforced antistatic rubber material when the temperature of the rubber material reaches 70-110 ℃.

Technical Field

The invention relates to a graphene reinforced antistatic rubber, in particular to a graphene reinforced antistatic rubber composition and a preparation method thereof.

Background

The rubber is an electric insulating material, when the surface of the rubber is rubbed, static charges are accumulated to form electric conduction, and when the charges are accumulated to a certain amount and the discharge is slight, the rubber does not harm human bodies; but the discharge may cause an electric shock when it reaches a certain level. In order to ensure personal and property safety in certain locations, antistatic rubber articles must be used.

With the increasing field of antistatic requirements, especially the expansion of the use of electronic computers, the probability of static electricity generation is increased correspondingly, so that people have stronger and stronger antistatic awareness. The antistatic rubber is required to have the function of conducting static electricity and prevent electric shock accidents caused by leakage of low-voltage lines. At present, the antistatic rubber is mainly applied to the following places according to different purposes:

(1) some dangerous places such as roads and vehicles are easy to accumulate static electricity. Compared with metal and concrete floor materials, the antistatic rubber can better ensure the safety and sanitation of workplaces and has better antistatic effect.

(2) Flammable and explosive liquids are easy to be burned and exploded during transportation. In this case, the oil hose made of rubber is liable to be ignited, and if the hose has an antistatic property, the safety of oil transportation can be ensured.

(3) The antistatic conveyor belt used in inflammable and explosive places can eliminate accidents caused by electrostatic sparks. The chemical fiber cleaning device is particularly arranged at the position where the conveyor belt conveys chemical fiber products, and can eliminate accidents caused by the fact that the chemical fibers are adsorbed on the charged surface.

(4) The antistatic rubber shoes are also an antistatic bulk product, the volume resistivity of the antistatic rubber shoes can meet the requirement that the volume resistivity of the antistatic rubber shoes is 103 ~ 109 omega cm, and the antistatic rubber shoes can be used in operating rooms of hospitals to remove the electrostatic influence generated by the ground, moving stretchers and wheels of tool carts.

The conductive materials commonly used in rubber at present are mainly conductive carbon black, ionic surfactants and some metal powders. However, the conductive materials have some problems of the conductive materials, and the conductive carbon black has the defects of large using amount and high cost; the elasticity and flexibility of the rubber can be reduced after the metal powder is added; the large deviation of compatibility between the surfactant and the rubber can cause rapid migration and diffusion, and the antistatic property is difficult to last.

Graphene has poor dispersibility and is easy to form large aggregates due to higher surface energy and surface binding energy of surface atoms of graphene, and the graphene is easy to agglomerate when used as a conductive material of rubber, so that the dispersion degree of graphene in the rubber is low, and the application performance of the graphene in the conductive rubber is influenced.

Disclosure of Invention

The invention aims to solve the defects in the conductive rubber mixing technology, can permanently prevent static electricity, is not influenced by a damp environment, provides the conductive filler which has strong affinity with a rubber matrix and is easy to uniformly disperse, improves the anti-static performance of the material, improves the tear resistance, wear resistance and bending resistance of the material, and has the characteristics of high mechanical strength and the like.

The purpose of the invention is:

the high-performance graphene reinforced antistatic rubber is provided, and products produced by using the conductive rubber have excellent and lasting antistatic performance;

the preparation method of the graphene reinforced antistatic rubber overcomes the adverse effect of rubber on the dispersion unevenness of the conductive filler by adopting a step-by-step mixing technical route, fully peels off and uniformly disperses the carbon nano filler in a rubber matrix to the greatest extent, and ensures excellent conductivity.

In order to achieve the purpose, the invention adopts the technical scheme that: the graphene reinforced antistatic rubber composition mainly comprises the following components:

100 parts of rubber 75 ‒ 100;

0.1 ‒ 10 parts of graphene;

1 ‒ 20 parts of carbon nanotubes;

1 ‒ 25 parts of a flow modifier;

0.1 part of antioxidant 0.1 ‒ 10;

1 ‒ 4 parts of sulfur;

0.01 ‒ 2 parts of vulcanization accelerator.

According to another embodiment of the present invention, it is further included that the rubber is at least one of natural rubber, neoprene rubber, cis-butadiene rubber, and chlorosulfonated polyethylene rubber.

According to another embodiment of the present invention, further comprising the graphene has a radial dimension of 0.5 ‒ 40 μm and a thickness of 1 ‒ 20 nm.

According to another embodiment of the invention, the aspect ratio of the carbon nano tube is more than or equal to 1000, and the diameter of the carbon nano tube is 2 ~ 30 nm.

According to another embodiment of the present invention, further comprising the flow modifier is at least one of polyethylene wax, stearic acid, stearate, paraffin wax, white oil, EBS, PETS.

According to another embodiment of the present invention, the antioxidant is at least one of aromatic amine antioxidant, hindered phenol antioxidant, and phosphite antioxidant.

The preparation method of the graphene reinforced antistatic rubber composition comprises two-step mixing,

According to another embodiment of the present invention, it is further included that the mixing device in the first and second steps is at least one of a conical mixer, a high-speed mixer, an open mill, a roll-over mixer, a continuous mixer, a Z-type kneader, a screw kneader, a vacuum kneader, and a horizontal twin-screw mixer.

A preparation method of a graphene reinforced antistatic rubber composition comprises the following steps,

firstly, shearing and stirring graphene, carbon nano tubes, a flow modifier, an antioxidant and rubber in a banburying device for a period of time according to a proportion to form a master batch which is uniformly premixed;

secondly, uniformly discharging the obtained master batch on an open mill, standing at room temperature for 24 hours,

The invention has the beneficial effects that:

1) the graphene and the carbon nano tube are combined with each other in the system to form a network structure, so that the self dispersion can be promoted, and the mechanical property of the system is obviously enhanced;

2) the mixing mode and the processing method for the graphene, the carbon nano tube and the rubber adopt a two-step mixing method, and the graphene and the carbon nano tube are wetted by white oil, so that the loss of the graphene and the carbon nano tube in the stirring process is reduced; the dispersibility of the graphene in the rubber matrix is improved, the reinforcing effect is better, and the defects of graphene agglomeration and low dispersion degree caused by one-time mixing are overcome;

3) the addition amount of carbon black in the traditional conductive rubber is more than 50wt%, while the composite addition amount of graphene and carbon nanotubes in the system is less than 10wt%, the addition amount is reduced by more than 80%, and the surface resistance is improved by 2-3 orders of magnitude;

4) the graphene and carbon nano tube form a network structure, which is beneficial to enhancing the wear resistance of the conductive rubber.

Drawings

The invention is further illustrated with reference to the following figures and examples.

FIG. 1 is a schematic structural diagram of a mixing process of the present invention;

FIG. 2 is a graph showing the results of tests for elongation at break and tensile strength of rubber materials in examples and comparative examples;

FIG. 3 is a graph showing the results of the surface resistance and tear strength tests of the rubber materials in examples and comparative examples.

Detailed Description

The graphene reinforced antistatic rubber composition is prepared from material rubber, white mineral oil, graphene, a carbon nano tube, an anti-aging agent, sulfur and a vulcanization accelerator, and comprises the following specific components:

100 parts of rubber 75 ‒ 100;

0.1 ‒ 10 parts of graphene;

1 ‒ 20 parts of carbon nanotubes;

1 ‒ 25 parts of a flow modifier;

0.1 part of antioxidant 0.1 ‒ 10;

1 ‒ 4 parts of sulfur;

0.01 ‒ 2 parts of vulcanization accelerator.

The main function of graphene in the conductivity of rubber is as follows:

(1) a coupling agent molecular chain is introduced to the surface of the graphene, so that the lipophilicity of the surface of the graphene is greatly improved, the affinity and the interface bonding strength of the graphene and a rubber matrix are improved, and the conductivity of the rubber is improved;

(2) mixing rubber materials by adopting a two-step method, and wetting the graphene and the carbon nano tube by white oil so as to reduce the loss of the graphene and the carbon nano tube in the stirring process; the dispersibility of the graphene in the rubber matrix is improved, the reinforcing effect is better, and the defects of graphene agglomeration and low dispersion degree caused by one-time mixing are overcome;

(3) the graphene and the carbon nano tube have excellent mechanical properties;

(4) and the ultrahigh conductive network structure is constructed by graphene and carbon nano tubes.