阅读说明：本技术 一种导电橡胶材料及其制备方法 (Conductive rubber material and preparation method thereof ) 是由 赵金山 于 2020-12-22 设计创作，主要内容包括：本发明公开了一种导电橡胶材料,其特征在于,包括如下按重量份计的各组分制成：超支化聚噻吩15-25份、环氧化SBS 50-70份、环氧橡胶20-30份、石墨烯量子点2-4份、导电填料15-25份、联苯胺双磺酸4-6份、偶联剂2-4份、五氧化二磷2-4份。本发明还提供了一种所述导电橡胶材料的制备方法。本发明提供的导电橡胶材料导电性能更佳,综合性能和性能稳定性更优异,机械力学性能和耐候性更好,使用寿命更长。(The invention discloses a conductive rubber material which is characterized by comprising the following components in parts by weight: 15-25 parts of hyperbranched polythiophene, 50-70 parts of epoxidized SBS, 20-30 parts of epoxy rubber, 2-4 parts of graphene quantum dots, 15-25 parts of conductive filler, 4-6 parts of benzidine disulfonic acid, 2-4 parts of coupling agent and 2-4 parts of phosphorus pentoxide. The invention also provides a preparation method of the conductive rubber material. The conductive rubber material provided by the invention has better conductivity, more excellent comprehensive performance and performance stability, better mechanical property and weather resistance and longer service life.)

1. The conductive rubber material is characterized by comprising the following components in parts by weight: 15-25 parts of hyperbranched polythiophene, 50-70 parts of epoxidized SBS, 20-30 parts of epoxy rubber, 2-4 parts of graphene quantum dots, 15-25 parts of conductive filler, 4-6 parts of benzidine disulfonic acid, 2-4 parts of coupling agent and 2-4 parts of phosphorus pentoxide.

2. The conductive rubber material according to claim 1, wherein the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560, and a silane coupling agent KH 570.

3. The conductive rubber material according to claim 1, wherein the conductive filler is at least one of acetylene black, carbon fiber, superconducting carbon black, graphene, and carbon nanotube.

4. The conductive rubber material as claimed in claim 3, wherein the conductive filler has a particle size of 800-1200 mesh.

5. The conductive rubber material according to claim 1, wherein the epoxy rubber is at least one of epoxy nitrile rubber and epoxy natural rubber.

6. The conductive rubber material of claim 5, wherein the epoxy nitrile rubber is at least one of ETBN 1300X40 epoxy nitrile rubber and ETBN 1300X68 epoxy nitrile rubber.

7. The conductive rubber material of claim 5, wherein the epoxidized natural rubber is at least one of ENR75 epoxidized natural rubber, ENR50 epoxidized natural rubber, ENR25 epoxidized natural rubber.

8. A method for preparing an electrically conductive rubber material according to any one of claims 1 to 7, characterized by comprising the steps of: the conductive rubber material is prepared by mixing the components in parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extrusion.

Technical Field

The invention relates to the technical field of rubber materials, in particular to a conductive rubber material and a preparation method thereof.

Background

In recent years, rubber materials have been widely used in industries such as aviation, aerospace, electrical, chemical, automotive, and mechanical industries, and in various aspects of medical care, health, and daily life. In the using process, charges are generated on the surface of the rubber material due to friction and impact in the forms of air flow, liquid flow and the like, static electricity is easily generated due to accumulation of the surface charges, and when the static electricity is accumulated to a certain degree, discharge is caused, even breakdown or fire disaster is possibly caused, so that the development of the conductive rubber material is particularly important.

Rubber materials are generally insulating, and in order to realize conductivity, conductive fillers are generally added to form filled conductive rubber materials, and the filled conductive rubber materials are widely applied to the fields of electronics, integrated circuit packaging, electromagnetic wave shielding, static resistance and the like. However, in the prior art, the materials are difficult to dissolve and difficult to process and form, and the used conductive fillers are too much and have poor dispersibility, poor conductivity, defects on the surface of the materials, and performance stability and comprehensive performance need to be further improved, so that the defects hinder the wide application of the materials. In addition, the conductive rubber materials on the market also have the defects of more or less limited mechanical properties, poor weather resistance and further improvement of the conductivity.

For example, chinese patent application No. 201610058205.4 provides a conductive rubber material for a flexible sensor, and a preparation method and applications thereof. The conductive rubber material comprises the following components in parts by weight: 100 parts of a silicon rubber matrix; 5-100 parts of conductive filler; 5-30 parts of modified white carbon black; 0.1-10 parts of a coupling agent; and the conductive rubber material is prepared by dispersing a conductive filler in a rubber material and crosslinking the conductive filler by electron beam or gamma ray radiation. The conductive filler is at least one of conductive carbon black, nano graphite, carbon nano tubes, silver plating powder, nickel powder and nickel plating powder. However, these conductive fillers have problems of poor coloring property, high price, high density, small filling amount, poor comprehensive properties of the material, etc. more or less, and the metal powder is easily oxidized in the air, thereby causing unstable conductivity of the particles.

Therefore, the conductive rubber material with better conductivity, more excellent comprehensive performance and performance stability, better mechanical property and weather resistance and longer service life is developed, meets the market demand, has wide market value and application prospect, and plays a very important role in promoting the development of the conductive material industry.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides the conductive rubber material which has better conductivity, more excellent comprehensive performance and performance stability, better mechanical property and weather resistance and longer service life. Meanwhile, the invention also provides a preparation method of the conductive rubber material, and the preparation method is simple, low in equipment investment, low in energy consumption, high in preparation efficiency and suitable for continuous large-scale production.

In order to achieve the purpose, the invention adopts the technical scheme that the conductive rubber material is characterized by comprising the following components in parts by weight: 15-25 parts of hyperbranched polythiophene, 50-70 parts of epoxidized SBS, 20-30 parts of epoxy rubber, 2-4 parts of graphene quantum dots, 15-25 parts of conductive filler, 4-6 parts of benzidine disulfonic acid, 2-4 parts of coupling agent and 2-4 parts of phosphorus pentoxide.

Preferably, the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.

Preferably, the conductive filler is at least one of acetylene black, carbon fiber, superconducting carbon black, graphene and carbon nanotubes.

Preferably, the particle size of the conductive filler is 800-1200 meshes.

Preferably, the graphene quantum dot is prepared by the method in the embodiment 1 of the chinese patent application No. 201910858322.2.

Preferably, the epoxy rubber is at least one of epoxy nitrile rubber and epoxy natural rubber.

Preferably, the epoxy nitrile rubber is at least one of ETBN 1300X40 epoxy nitrile rubber and ETBN 1300X68 epoxy nitrile rubber.

Preferably, the epoxidized natural rubber is at least one of ENR75 epoxidized natural rubber, ENR50 epoxidized natural rubber and ENR25 epoxidized natural rubber.

Preferably, the epoxidized SBS is epoxidized SBS prepared by the method for preparing epoxidized SBS (eSBS46) according to chinese invention patent example 1, application No. 201810344598.4.

Preferably, the hyperbranched polythiophene is prepared by the method of the chinese patent application No. 201710899697.4, example 1.

Another object of the present invention is to provide a method for preparing the conductive rubber material, which comprises the following steps: the conductive rubber material is prepared by mixing the components in parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extrusion.

Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:

1) the preparation method of the conductive rubber material provided by the invention is simple, low in equipment investment, low in energy consumption, high in preparation efficiency and suitable for continuous large-scale production.

2) The conductive rubber material provided by the invention overcomes the defects that the existing conductive rubber material is difficult to process and form, the used conductive filler is too much and has poor dispersibility, poor conductivity, flaws on the surface of the material and performance stability and comprehensive performance to be further improved, and overcomes the defects that the conductive rubber material on the market is more or less limited in mechanical property, poor in weather resistance and further improved in conductivity; through the synergistic effect of the components, the prepared conductive rubber material has better conductivity, more excellent comprehensive performance and performance stability, better mechanical property and weather resistance and longer service life.

3) The conductive rubber material provided by the invention takes the epoxidized SBS and the epoxy rubber as the base materials, and combines the advantages of the two rubber materials, so that the obtained conductive rubber has better comprehensive performance and performance stability, and the epoxy groups on the conductive rubber can perform an epoxy ring-opening reaction with the amino groups on the hyperbranched polythiophene and the benzidine disulfonic acid; the sulfonic acid group on the benzidine disulfonic acid can generate cross-linking reaction with benzene rings on the hyperbranched polythiophene and the epoxidized SBS under the catalytic action of the phosphorus pentoxide, so that the substrates are connected into a three-dimensional network structure by covalent bonds, the comprehensive performance of the material is effectively improved, and the mechanical property and the aging resistance of the material are better.

4) According to the conductive rubber material provided by the invention, the hyperbranched polythiophene is introduced into a rubber molecular chain, so that a conductive bridge is favorably formed, the conductivity is further improved, and the substance is connected to the molecular chain through a covalent bond, so that the performance stability is better.

5) According to the conductive rubber material provided by the invention, the graphene quantum dots and the conductive filler have synergistic effect, so that the conductivity of the rubber material can be improved, and the mechanical property and the oxidation resistance stability of the rubber material can be enhanced. The graphene quantum dots have outstanding surface effect, small size effect and quantum confinement effect, and the comprehensive performance of the material is better under the action of the coupling agent.

Detailed Description

In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.

The graphene quantum dots used in the following embodiments of the present invention are graphene quantum dots prepared by the method in chinese patent application No. 201910858322.2, example 1; the epoxidized SBS is prepared by the preparation method of the epoxidized SBS (eBSS 46) in Chinese patent application No. 201810344598.4 in the embodiment 1; the hyperbranched polythiophene is prepared by the method of the Chinese invention patent embodiment 1 with the application number of 201710899697.4; other raw materials were all purchased commercially.

Example 1

The conductive rubber material is characterized by comprising the following components in parts by weight: 15 parts of hyperbranched polythiophene, 50 parts of epoxidized SBS, 20 parts of epoxy rubber, 2 parts of graphene quantum dots, 15 parts of conductive filler, 4 parts of benzidine disulfonic acid, 2 parts of coupling agent and 2 parts of phosphorus pentoxide.

The coupling agent is a silane coupling agent KH 550; the conductive filler is acetylene black; the particle size of the conductive filler is 800 meshes; the epoxy rubber is epoxy nitrile rubber; the epoxy nitrile rubber is ETBN 1300X40 epoxy nitrile rubber; .

The preparation method of the conductive rubber material is characterized by comprising the following steps of: the conductive rubber material is prepared by mixing the components in parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extrusion.

Example 2

The conductive rubber material is characterized by comprising the following components in parts by weight: 17 parts of hyperbranched polythiophene, 55 parts of epoxidized SBS, 23 parts of epoxy rubber, 2.5 parts of graphene quantum dots, 17 parts of conductive filler, 4.5 parts of benzidine disulfonic acid, 2.5 parts of coupling agent and 2.5 parts of phosphorus pentoxide.

The coupling agent is a silane coupling agent KH 560; the conductive filler is carbon fiber; the particle size of the conductive filler is 800 meshes; the epoxy rubber is epoxy natural rubber; the epoxy natural rubber is ENR75 epoxy natural rubber.

The preparation method of the conductive rubber material is characterized by comprising the following steps of: the conductive rubber material is prepared by mixing the components in parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extrusion.

Example 3

The conductive rubber material is characterized by comprising the following components in parts by weight: 20 parts of hyperbranched polythiophene, 60 parts of epoxidized SBS, 25 parts of epoxy rubber, 3 parts of graphene quantum dots, 20 parts of conductive filler, 5 parts of benzidine disulfonic acid, 3 parts of coupling agent and 3 parts of phosphorus pentoxide.

The coupling agent is a silane coupling agent KH 570; the conductive filler is superconducting carbon black; the particle size of the conductive filler is 1000 meshes; the epoxy rubber is epoxy nitrile rubber; the epoxy nitrile rubber is ETBN 1300X40 epoxy nitrile rubber.

The preparation method of the conductive rubber material is characterized by comprising the following steps of: the conductive rubber material is prepared by mixing the components in parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extrusion.

Example 4

The conductive rubber material is characterized by comprising the following components in parts by weight: 23 parts of hyperbranched polythiophene, 65 parts of epoxidized SBS, 28 parts of epoxy rubber, 3.5 parts of graphene quantum dots, 23 parts of conductive filler, 5.5 parts of benzidine disulfonic acid, 3.5 parts of coupling agent and 3.5 parts of phosphorus pentoxide.

The coupling agent is formed by mixing a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH570 according to the mass ratio of 1:2: 3; the conductive filler is formed by mixing acetylene carbon black, carbon fibers, superconducting carbon black, graphene and carbon nanotubes according to a mass ratio of 1:1:3:2: 1; the particle size of the conductive filler is 1100 meshes; the epoxy rubber is formed by mixing epoxy nitrile rubber and epoxy natural rubber according to the mass ratio of 3: 5; the epoxy nitrile rubber is prepared by mixing ETBN 1300X40 epoxy nitrile rubber and ETBN 1300X68 epoxy nitrile rubber according to the mass ratio of 1: 3; the epoxy natural rubber is prepared by mixing ENR75 epoxy natural rubber, ENR50 epoxy natural rubber and ENR25 epoxy natural rubber according to the mass ratio of 3:5: 2.

The preparation method of the conductive rubber material is characterized by comprising the following steps of: the conductive rubber material is prepared by mixing the components in parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extrusion.

Example 5

The conductive rubber material is characterized by comprising the following components in parts by weight: 25 parts of hyperbranched polythiophene, 70 parts of epoxidized SBS, 30 parts of epoxy rubber, 4 parts of graphene quantum dots, 25 parts of conductive filler, 6 parts of benzidine disulfonic acid, 4 parts of coupling agent and 4 parts of phosphorus pentoxide.

The coupling agent is a silane coupling agent KH 550; the conductive filler is a carbon nano tube; the particle size of the conductive filler is 1200 meshes; the epoxy rubber is epoxy natural rubber; the epoxy natural rubber is ENR75 epoxy natural rubber.

The preparation method of the conductive rubber material is characterized by comprising the following steps of: the conductive rubber material is prepared by mixing the components in parts by weight to obtain a mixture, and then adding the mixture into a double-screw extruder for blending and extrusion.

Comparative example 1

This example provides a conductive rubber material having substantially the same formulation and preparation as in example 1, except that: in which no hyperbranched polythiophene is added.

Comparative example 2

This example provides a conductive rubber material having substantially the same formulation and preparation as in example 1, except that: no epoxy rubber was added.

Comparative example 3

This example provides a conductive rubber material having substantially the same formulation and preparation as in example 1, except that: in which benzidine disulfonic acid was not added.

Comparative example 4

This example provides a conductive rubber material having substantially the same formulation and preparation as in example 1, except that: no graphene quantum dots were added.

The conductive rubber materials of examples 1-5 and comparative examples 1-4 above were subjected to the performance test, the test results are shown in table 1, and the test methods are as follows: measuring the volume resistivity according to the standard GB/T1692-2008, measuring the tensile strength according to the standard GB/T528-; the heat aging resistance is characterized by the change rate of tensile strength after aging at 70 ℃ for 96 hours, and the test standard is shown in GB-T3512-2001.

TABLE 1 results of Performance test of conductive rubber materials

As can be seen from table 1, the conductive rubber material disclosed in the embodiment of the present invention has excellent mechanical properties, electrical conductivity and thermal aging resistance, which are the result of the synergistic effect of the components.

The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.