CN113831652A - Carbon-based modified high-conductivity foamed ethylene propylene diene monomer - Google Patents

Carbon-based modified high-conductivity foamed ethylene propylene diene monomer Download PDF

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CN113831652A
CN113831652A CN202111265321.0A CN202111265321A CN113831652A CN 113831652 A CN113831652 A CN 113831652A CN 202111265321 A CN202111265321 A CN 202111265321A CN 113831652 A CN113831652 A CN 113831652A
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ethylene propylene
propylene diene
diene monomer
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张伟
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Hebei Huami New Material Technology Co Ltd
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    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16Ethene-propene or ethene-propene-diene copolymers
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Abstract

The invention discloses a carbon-based modified high-conductivity foamed ethylene propylene diene monomer, which comprises the following raw materials in parts by weight: 100 parts of ethylene propylene diene monomer crude rubber, 5-10 parts of zinc oxide, 1-3 parts of stearic acid, 30-60 parts of carbon black, 20-40 parts of light calcium carbonate, 15-35 parts of paraffin oil, 3-6 parts of an accelerant, 0.5-1.0 part of sulfur, 5 parts of a foaming agent and 5-15 parts of a carbon composite component; the material prepared by the invention can realize good combination of foaming, low density and electric conduction, and is suitable for rubber sealing elements.

Description

Carbon-based modified high-conductivity foamed ethylene propylene diene monomer
Technical Field
The invention belongs to the technical field of rubber, and particularly relates to carbon-modified high-conductivity foamed ethylene propylene diene monomer.
Background
The traditional foamed sealing material has the characteristic that the integral part of the formed material is connected by loose cell walls due to the cell structure in the material, the ethylene propylene diene monomer material has high electrical insulation property, and the electrical conductivity of the foamed material is poorer in the foamed structure. When the specific gravity of the foamed ethylene propylene diene monomer rubber is controlled at 500kg/m3When it is within, its volume resistivity is generally higher than 1013Omega cm, the volume resistivity of the material with the conductive requirement can be generally 1010-1012Omega cm, and the volume resistivity can be 10 when the conductive requirement is higher8-1010Omega cm. In the application fields of rail vehicles and the like, the material has high antistatic capability while playing a sealing role, and the volume resistivity needs to reach 107Omega cm or less.
The volume resistivity needs to be achieved in materials with slightly good conductivity such as nitrile rubber, chloroprene rubber, fluororubber and the like and silicone rubber which is researched more in industry, and the replacement of the ethylene propylene diene monomer material cannot be realized due to the performance difference, so that the problem of conductivity of the ethylene propylene diene monomer material needs to be solved.
At present, the method for solving the problem is to improve the conductivity of the rubber material by the traditional means, mainly by adding carbon black or conductive metal, while the former has relatively weak capability of improving the conductivity, and excessive addition can cause higher hardness and difficult foaming of the material; although the latter can effectively improve the conductivity of the rubber material, the specific gravity of the material can be greatly improved due to the metal particles which have better conductivity, stable performance and easy addition, and the specific gravity of the material is not in accordance with the current development trend of light weight.
Disclosure of Invention
The invention solves the defects of the prior art and provides the carbon-based modified high-conductivity foamed ethylene propylene diene monomer rubber which realizes the combination of foaming, low density and good conductivity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a carbon-based modified high-conductivity foamed ethylene propylene diene monomer comprises the following raw materials in parts by weight: 100 parts of ethylene propylene diene monomer crude rubber, 5-10 parts of zinc oxide, 1-3 parts of stearic acid, 30-60 parts of carbon black, 20-40 parts of light calcium carbonate, 15-35 parts of paraffin oil, 3-6 parts of an accelerant, 0.5-1.0 part of sulfur, 5 parts of a foaming agent and 5-15 parts of a carbon composite component.
Further, the preparation raw materials comprise the following components in parts by weight: 100 parts of ethylene propylene diene monomer crude rubber, 6-8 parts of zinc oxide, 2-3 parts of stearic acid, 40-50 parts of carbon black, 25-35 parts of light calcium carbonate, 20-30 parts of paraffin oil, 3.5-5.5 parts of an accelerator, 0.7-0.9 part of sulfur, 5 parts of a foaming agent and 8-12 parts of a carbon composite component.
Further, the preparation raw materials comprise the following components in parts by weight: 100 parts of ethylene propylene diene monomer crude rubber, 7 parts of zinc oxide, 2.5 parts of stearic acid, 45 parts of carbon black, 30 parts of light calcium carbonate, 25 parts of paraffin oil, 5 parts of an accelerant, 0.8 part of sulfur, 5 parts of a foaming agent and 10 parts of a carbon-series composite component.
Further, the raw ethylene propylene diene monomer rubber is ethylene propylene diene monomer rubber 4045.
Further, the foaming agent comprises 4,4' -oxybis-benzenesulfonyl hydrazide, azodicarbonamide and a microsphere foaming agent.
Further, the microsphere foaming agent accounts for 50% of the total amount of the foaming agent.
Further, the accelerators are N-cyclohexyl-2-benzothiazolesulfenamide, zinc dibutyldithiocarbamate, tetramethylthiuram disulfide and pentamethylenethiuram tetrasulfide.
Further, the N-cyclohexyl-2-benzothiazole sulfonamide and the zinc dibutyl dithiocarbamate respectively account for 35% -45% of the total amount of the accelerator, and the tetramethylthiuram disulfide and pentamethylene thiuram tetrasulfide respectively account for 5% -15% of the total amount of the accelerator.
Further, the carbon-based composite component comprises a single-walled carbon nanotube and graphene oxide, wherein the graphene oxide accounts for 10% -30% of the total amount of the carbon-based composite component.
Further, the carbon black comprises N774 carbon black and conductive carbon black, and the conductive carbon black accounts for 50% -70% of the total amount of the carbon black.
As the invention adopts the invention, compared with the prior art, the invention has the technical progress that:
(1) the light calcium carbonate and the paraffin oil are added to improve the processing performance and the hardness of the material; stearic acid, zinc oxide, accelerator and vulcanizing agent are taken as a vulcanization system of the material and are mainly used for the cross-linking process of the material;
(2) the raw ethylene propylene diene monomer rubber of the invention is 4045, the ethylene content and the third monomer content of the raw ethylene propylene diene monomer rubber are moderate, the Mooney viscosity is low, and the raw ethylene propylene diene monomer rubber has good process performance;
(3) the consumption of the microsphere foaming agent accounts for 50 percent of the total amount of the foaming agent, so that the material has uniform and compact foam pores;
(4) the accelerators N-cyclohexyl-2-benzothiazole sulfonamide and zinc dibutyl dithiocarbamate of the invention respectively account for 35-45% of the total amount of the accelerator, and the tetramethyl thiuram disulfide and pentamethylene thiuram tetrasulfide respectively account for 5-15% of the total amount of the accelerator, and the matching ensures that the material has good processing safety and sufficient fluidization speed;
(5) the carbon nano material formed by the single-walled carbon nanotube and the graphene oxide is compounded and matched, so that the conductivity is well improved; the conductive carbon black accounts for 50-70% of the total amount of the carbon black, and the proportion ensures that the mechanical property and the conductivity of the material have good combination;
in conclusion, the material prepared by the invention can realize good combination of foaming, low density and electric conduction, and is suitable for rubber sealing elements.
Detailed Description
The following description is given in conjunction with preferred embodiments of the present invention. It should be understood that the preferred embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the present invention.
Example 1
Carbon-based modified high-conductivity foamed ethylene propylene diene monomer
The raw materials in parts by weight include: 4045100 parts of ethylene propylene diene monomer, 5 parts of zinc oxide, 1 part of stearic acid, 12 parts of N774 carbon black, 18 parts of conductive carbon black, 20 parts of light calcium carbonate, 15 parts of paraffin oil, 1.2 parts of N-cyclohexyl-2-benzothiazole sulfonamide, 1.2 parts of zinc dibutyl dithiocarbamate, 0.3 part of tetramethyl thiuram disulfide, 0.3 part of pentamethylene thiuram tetrasulfide, 0.5 part of sulfur, 1 part of 4,4' -oxybis benzenesulfonylhydrazide, 1.5 parts of azodicarbonamide, 2.5 parts of a microsphere foaming agent, 4.4 parts of single-walled carbon nanotubes and 0.6 part of graphene oxide.
Example 2
Carbon-based modified high-conductivity foamed ethylene propylene diene monomer
The raw materials in parts by weight include: 4045100 parts of ethylene propylene diene monomer, 6 parts of zinc oxide, 2 parts of stearic acid, 16 parts of N774 carbon black, 24 parts of conductive carbon black, 25 parts of light calcium cholate, 20 parts of paraffin oil, 1.4 parts of N-cyclohexyl-2-benzothiazole sulfonamide, 1.4 parts of zinc dibutyl dithiocarbamate, 0.35 part of tetramethyl thiuram disulfide, 0.35 part of pentamethylene thiuram tetrasulfide, 0.7 part of sulfur, 1 part of 4,4' -oxybis-benzenesulfonylhydrazide, 1.5 parts of azodicarbonamide, 2.5 parts of a microsphere foaming agent, 7 parts of a single-walled carbon nanotube and 1 part of graphene oxide.
Example 3
Carbon-based modified high-conductivity foamed ethylene propylene diene monomer
The raw materials in parts by weight include: 4045100 parts of ethylene propylene diene monomer, 8 parts of zinc oxide, 3 parts of stearic acid, 20 parts of N774 carbon black, 30 parts of conductive carbon black, 35 parts of light calcium carbonate, 30 parts of paraffin oil, 2.2 parts of N-cyclohexyl-2-benzothiazole sulfonamide, 2.2 parts of zinc dibutyl dithiocarbamate, 0.55 part of tetramethyl thiuram disulfide, 0.55 part of pentamethylene thiuram tetrasulfide, 0.9 part of sulfur, 1 part of 4,4' -oxybis benzenesulfonylhydrazide, 1.5 parts of azodicarbonamide, 2.5 parts of a microsphere foaming agent, 10.5 parts of single-walled carbon nanotubes and 1.5 parts of graphene oxide.
Example 4
Carbon-based modified high-conductivity foamed ethylene propylene diene monomer
The raw materials in parts by weight include: 4045100 parts of ethylene propylene diene monomer, 10 parts of zinc oxide, 3 parts of stearic acid, 24 parts of N774 carbon black, 36 parts of conductive carbon black, 40 parts of light calcium carbonate, 35 parts of paraffin oil, 2.4 parts of N-cyclohexyl-2-benzothiazole sulfonamide, 2.4 parts of zinc dibutyl dithiocarbamate, 0.6 part of tetramethyl thiuram disulfide, 0.6 part of pentamethylene thiuram tetrasulfide, 1 part of sulfur, 1 part of 4,4' -oxybis benzenesulfonylhydrazide, 1.5 parts of azodicarbonamide, 2.5 parts of a microsphere foaming agent, 13 parts of single-walled carbon nanotubes and 2 parts of graphene oxide.
Example 5
Carbon-based modified high-conductivity foamed ethylene propylene diene monomer
The raw materials in parts by weight include: 4045100 parts of ethylene propylene diene monomer, 7 parts of zinc oxide, 2.5 parts of stearic acid, 18 parts of N774 carbon black, 27 parts of conductive carbon black, 30 parts of light calcium carbonate, 25 parts of paraffin oil, 2 parts of N-cyclohexyl-2-benzothiazole sulfonamide, 2 parts of zinc dibutyl dithiocarbamate, 0.5 part of tetramethyl thiuram disulfide, 0.5 part of pentamethylene thiuram tetrasulfide, 0.8 part of sulfur, 1 part of 4,4' -oxybis benzenesulfonylhydrazide, 1.5 parts of azodicarbonamide, 2.5 parts of a microsphere foaming agent, 9 parts of single-walled carbon nanotubes and 1 part of graphene oxide.
Example 6
Carbon-based modified high-conductivity foamed ethylene propylene diene monomer
The raw materials in parts by weight include: 4045100 parts of ethylene propylene diene monomer, 7 parts of zinc oxide, 2.5 parts of stearic acid, 18 parts of N774 carbon black, 27 parts of conductive carbon black, 30 parts of light calcium carbonate, 25 parts of paraffin oil, 2 parts of N-cyclohexyl-2-benzothiazole sulfonamide, 2 parts of zinc dibutyl dithiocarbamate, 0.5 part of tetramethyl thiuram disulfide, 0.5 part of pentamethylene thiuram tetrasulfide, 0.8 part of sulfur, 1 part of 4,4' -oxybis benzenesulfonylhydrazide, 1.5 parts of azodicarbonamide and 2.5 parts of a microsphere foaming agent.
Example 7
Carbon-based modified high-conductivity foamed ethylene propylene diene monomer
The raw materials in parts by weight include: 4045100 parts of ethylene propylene diene monomer, 7 parts of zinc oxide, 2.5 parts of stearic acid, 22 parts of N774 carbon black, 33 parts of conductive carbon black, 30 parts of light calcium carbonate, 25 parts of paraffin oil, 2 parts of N-cyclohexyl-2-benzothiazole sulfonamide, 2 parts of zinc dibutyl dithiocarbamate, 0.5 part of tetramethyl thiuram disulfide, 0.5 part of pentamethylene thiuram tetrasulfide, 0.8 part of sulfur, 1 part of 4,4' -oxybis benzenesulfonylhydrazide, 1.5 parts of azodicarbonamide and 2.5 parts of a microsphere foaming agent.
The paraffin oil used in the above examples was an environmentally friendly paraffin oil.
The examples 1 to 7 are respectively vulcanized into standard samples, and the density and the volume resistivity of the test are tested and calculated according to GB/T6343-2009 and GB/T1692-2008 standards, and the detection results are shown in Table 1:
TABLE 1
Figure BDA0003326802580000051
Figure BDA0003326802580000061
The data from table 1 may show that:
the second embodiment, the third embodiment and the fifth embodiment can meet the requirements, but the volume resistivity of the second embodiment is insufficient compared with the target requirement, the third embodiment has a large risk of exceeding the apparent density, the fifth embodiment is comprehensively judged to be the optimal scheme, and the two performances are balanced.
Through comparative analysis of comparative examples one to seven, the larger the amount of the carbon-based composite component (single-walled carbon nanotubes and graphene oxide), the lower the volume resistivity, but the negative effect on the foaming of the material is achieved.
Comparing the data of the fifth embodiment with the data of the sixth and seventh embodiments, it can be seen that the carbon black (N774 carbon black and conductive carbon black) has much smaller influence on the conductivity than the carbon-based composite components (single-walled carbon nanotubes and graphene oxide).
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.

Claims (10)

1. A carbon-based modified high-conductivity foamed ethylene propylene diene monomer is characterized in that: the preparation raw materials comprise the following components in parts by weight: 100 parts of ethylene propylene diene monomer crude rubber, 5-10 parts of zinc oxide, 1-3 parts of stearic acid, 30-60 parts of carbon black, 20-40 parts of light calcium carbonate, 15-35 parts of paraffin oil, 3-6 parts of an accelerant, 0.5-1.0 part of sulfur, 5 parts of a foaming agent and 5-15 parts of a carbon composite component.
2. The carbon-based modified high-conductivity foamed ethylene propylene diene monomer according to claim 1, wherein: the preparation raw materials comprise the following components in parts by weight: 100 parts of ethylene propylene diene monomer crude rubber, 6-8 parts of zinc oxide, 2-3 parts of stearic acid, 40-50 parts of carbon black, 25-35 parts of light calcium carbonate, 20-30 parts of paraffin oil, 3.5-5.5 parts of an accelerator, 0.7-0.9 part of sulfur, 5 parts of a foaming agent and 8-12 parts of a carbon composite component.
3. The carbon-based modified high-conductivity foamed ethylene propylene diene monomer according to claim 2, wherein: the preparation raw materials comprise the following components in parts by weight: 100 parts of ethylene propylene diene monomer crude rubber, 7 parts of zinc oxide, 2.5 parts of stearic acid, 45 parts of carbon black, 30 parts of light calcium carbonate, 25 parts of paraffin oil, 5 parts of an accelerant, 0.8 part of sulfur, 5 parts of a foaming agent and 10 parts of a carbon-series composite component.
4. The carbon-based modified high-conductivity foamed ethylene propylene diene rubber according to any one of claims 1 to 3, wherein: the raw ethylene propylene diene monomer rubber is ethylene propylene diene monomer rubber 4045.
5. The carbon-based modified high-conductivity foamed ethylene propylene diene rubber according to any one of claims 1 to 3, wherein: the foaming agent comprises 4,4' -oxybis-benzenesulfonyl hydrazide, azodicarbonamide and a microsphere foaming agent.
6. The carbon-based modified high-conductivity foamed ethylene propylene diene monomer according to claim 5, wherein: the microsphere foaming agent accounts for 50% of the total amount of the foaming agent.
7. The carbon-based modified high-conductivity foamed ethylene propylene diene rubber according to any one of claims 1 to 3, wherein: the accelerators are N-cyclohexyl-2-benzothiazole sulfonamide, zinc dibutyl dithiocarbamate, tetramethyl thiuram disulfide and pentamethylene thiuram tetrasulfide.
8. The carbon-based modified high-conductivity foamed ethylene propylene diene monomer according to claim 7, wherein: the N-cyclohexyl-2-benzothiazole sulfonamide and the zinc dibutyl dithiocarbamate respectively account for 35-45% of the total amount of the accelerator, and the tetramethyl thiuram disulfide and pentamethylene thiuram tetrasulfide respectively account for 5-15% of the total amount of the accelerator.
9. The carbon-based modified high-conductivity foamed ethylene propylene diene rubber according to any one of claims 1 to 3, wherein: the carbon-series composite component comprises a single-walled carbon nanotube and graphene oxide, wherein the graphene oxide accounts for 10% -30% of the total amount of the carbon-series composite component.
10. The carbon-based modified high-conductivity foamed ethylene propylene diene rubber according to any one of claims 1 to 3, wherein: the carbon black comprises N774 carbon black and conductive carbon black, and the conductive carbon black accounts for 50% -70% of the total amount of the carbon black.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114874630A (en) * 2022-05-25 2022-08-09 浙江恒业成有机硅有限公司 High-rate platinum heat-vulcanized foamed silicone rubber and preparation method thereof

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JPH0827300A (en) * 1994-07-14 1996-01-30 Kureha Elastomer Kk Electrically conductive foamed rubber and its production
CN110437546A (en) * 2019-08-07 2019-11-12 潍坊军涛化工有限公司 A kind of ethylene propylene diene rubber extruded foaming materials and preparation method thereof
CN110684286A (en) * 2019-10-23 2020-01-14 明治橡胶化成(深圳)有限公司 Foamed rubber and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0827300A (en) * 1994-07-14 1996-01-30 Kureha Elastomer Kk Electrically conductive foamed rubber and its production
CN110437546A (en) * 2019-08-07 2019-11-12 潍坊军涛化工有限公司 A kind of ethylene propylene diene rubber extruded foaming materials and preparation method thereof
CN110684286A (en) * 2019-10-23 2020-01-14 明治橡胶化成(深圳)有限公司 Foamed rubber and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114874630A (en) * 2022-05-25 2022-08-09 浙江恒业成有机硅有限公司 High-rate platinum heat-vulcanized foamed silicone rubber and preparation method thereof
CN114874630B (en) * 2022-05-25 2023-08-11 浙江恒业成有机硅有限公司 High-magnification platinum hot vulcanization foaming silicone rubber and preparation method thereof

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Application publication date: 20211224