CN115637049A - High-conductivity oil-resistant fluorine-silicon composite rubber and preparation method thereof - Google Patents
High-conductivity oil-resistant fluorine-silicon composite rubber and preparation method thereof Download PDFInfo
- Publication number
- CN115637049A CN115637049A CN202211330387.8A CN202211330387A CN115637049A CN 115637049 A CN115637049 A CN 115637049A CN 202211330387 A CN202211330387 A CN 202211330387A CN 115637049 A CN115637049 A CN 115637049A
- Authority
- CN
- China
- Prior art keywords
- rubber
- parts
- fluorosilicone
- resistant
- composite rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses high-conductivity oil-resistant fluorosilicone composite rubber and a preparation method thereof, wherein the fluorosilicone composite rubber comprises the following raw materials in parts by weight: 10 to 30 portions of master batch, 60 to 80 portions of conductive filler, 3 to 15 portions of white carbon black, 1 to 5 portions of structural control agent, 0.3 to 1.5 portions of vulcanizing agent, 1 to 4 portions of heat-resistant auxiliary agent and 0.1 to 0.5 portion of antioxidant; the master batch is a blended rubber of fluorosilicone rubber and methyl vinyl silicone rubber, and the mass percentage of the methyl vinyl silicone rubber in the master batch is 10-50%; the high-conductivity oil-resistant fluorosilicone composite rubber prepared by the invention has excellent conductivity, oil resistance, aging resistance and resilience, meanwhile, the conductivity and aging resistance of the fluorosilicone composite rubber can be improved by matching different conductive powder filling amounts with an antioxidant and a heat-resistant auxiliary agent, and the preparation method is simple, low in raw material cost and stable in source, and is widely applied to the fields of automobiles, aerospace and the like.
Description
Technical Field
The invention relates to the technical field of conductive fluorosilicone rubber, in particular to high-conductivity oil-resistant fluorosilicone composite rubber and a preparation method thereof.
Background
With the increasing demands of the market on fuel efficiency, energy conservation, emission reduction and cost reduction, the automobile technology develops more intelligent, safe, quiet and energy-saving and continuously reduces the development trend of the influence on the environment. Transmission design and Automatic Transmission Fluid (ATF) technology have made significant advances in powertrain technology improvements that increase fuel economy, improve vehicle performance and quality. The automobile oil seal isolates parts needing lubrication in the transmission parts from the output parts so as to prevent lubricating oil in a gearbox and an engine from leaking and prevent external impurities from entering the automobile oil seal. The automobile oil seal rubber material is required to have the performances of temperature resistance, oil resistance, aging resistance, small deformation, good rebound resilience, high tensile strength, wear resistance and the like.
At present, the high-conductivity oil-resistant fluorosilicone rubber can not meet the long-term reliability problem, the conductivity, the tensile property, the compression permanent deformation and other properties can be reduced along with the change of the product in oil immersion time, and the material sealing and conductivity can not meet the requirements easily, so that the conductivity, the tensile property, the compression permanent deformation and other properties can be improved by adding the blend rubber and the heat-resistant and antioxidant auxiliary agents.
The sealing ring for the automatic gearbox of the automobile has very strict performance requirements in all aspects, and not only can meet the requirements of high conductivity, long-term high-temperature oil resistance, but also can meet the requirements of low compression set. The large amount of the conductive filler can reduce the content of the fluorosilicone rubber and influence the oil resistance of the material.
Disclosure of Invention
The invention aims to solve the technical problem of providing high-conductivity oil-resistant fluorine-silicon composite rubber which can keep good conductivity, physical and mechanical properties and resilience when being applied to the condition of contacting mineral oil for a long time.
The invention provides high-conductivity oil-resistant fluorine-silicon composite rubber which comprises the following raw materials in parts by weight: 10 to 30 portions of master batch, 60 to 80 portions of conductive filler, 3 to 15 portions of white carbon black, 1 to 5 portions of structural control agent, 0.3 to 1.5 portions of vulcanizing agent, 1 to 4 portions of heat-resistant auxiliary agent and 0.1 to 0.5 portion of antioxidant; the master batch is a blended rubber of fluorosilicone rubber and methyl vinyl silicone rubber, and the mass percentage of the methyl vinyl silicone rubber in the master batch is 10-50%.
Further, the mol percentage of the vinyl in the methyl vinyl silicone rubber is preferably 0.1 to 0.5 percent
Further, the conductive filler is preferably at least one of silver powder, silver-coated copper powder, silver-coated aluminum powder, silver-coated glass beads, nickel powder and nickel-coated graphite, wherein the average particle size of the silver powder is 5-15 μm, the average particle size of the silver-coated copper powder is 10-80 μm, the average particle size of the silver-coated aluminum powder is 10-60 um, the average particle size of the silver-coated glass beads is 20-80 μm, the average particle size of the nickel powder is 25-100 μm, and the average particle size of the nickel-coated graphite is 25-100 μm.
Further, it is preferable that the structural control agent is at least one of dihydroxypolydimethylsiloxane, polyhydroxymethylsiloxane, diphenylsilanediol, dihydroxy (3, 3-trifluoropropyl) methylsiloxane, octamethyltetrasiloxane and hexamethyldisilazane.
Further, it is preferable that the vulcanizing agent is at least one of 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 4-dichlorobenzoyl peroxide, benzoyl peroxide, t-butyl peroxybenzoate, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane, di-t-butyl peroxide and dicumyl peroxide.
Further, the heat-resistant auxiliary is preferably at least one of iron oxide, cerium oxide, nickel oxide, zinc oxide, titanium dioxide, carbon black, a phenyl polyazo compound, and an indole compound.
Further, it is preferable that the antioxidant is at least one of 2, 4-dichlorobenzoic acid, p-chlorobenzoic acid, ammonium phenylate and 2, 4-dichlorobenzoyl peroxide.
The invention also provides a preparation method of the high-conductivity oil-resistant fluorosilicone composite rubber, which comprises the following steps:
s1, taking 10-30 parts of masterbatch, 3-15 parts of white carbon black, 1-5 parts of a structural control agent and 1-4 parts of a heat-resistant auxiliary agent, and stirring and mixing to obtain a base material;
s2, gradually adding 60-80 parts of conductive filler into the base material obtained in the step S1, and uniformly mixing to obtain rubber compound;
s3, adding 0.1-0.5 part of antioxidant and 0.3-1.5 parts of vulcanizing agent into the rubber compound in the step S2, and uniformly mixing to obtain fluorine-silicon rubber compound;
and S4, placing the fluorosilicone rubber compound in the step S3 in a mold, and performing mold pressing to obtain the high-conductivity oil-resistant fluorosilicone composite rubber.
Further, in the step S1, heat treatment is preferably performed after the kneading, the heat treatment temperature is 160 to 190 ℃, and the heat treatment time is 1 to 4 hours;
in the step S2, the base material is cooled to the normal temperature of 25 ℃ and then the conductive filler is added;
in the step S4, the mould pressing pressure is 20000-100000 kg, the mould pressing temperature is 140-185 ℃, the mould pressing time is 5-10 min, the secondary vulcanization temperature is 180-200 ℃, and the vulcanization time is 2-4 h.
The invention has the beneficial effects that: according to the high-conductivity oil-resistant fluorosilicone composite rubber provided by the invention, the fluorosilicone rubber and the methyl vinyl silicone rubber are jointly used to form the blended master batch, the fluorosilicone rubber has good performances of resisting mineral oil and non-polar solvent, the addition of the methyl vinyl silicone rubber can improve the comprehensive mechanical properties of the fluorosilicone composite rubber product, reduce the compression set, enable the vulcanization to be more uniform, reduce the generation of bubbles, improve the vulcanization activity of the fluorosilicone composite rubber, use organic peroxide with lower activity for vulcanization crosslinking, greatly improve the heat resistance and high-temperature compression set resistance due to the improvement of the vulcanization activity, and the joint use of the fluorosilicone rubber and the methyl vinyl silicone rubber can improve the filling amount of a conductive filler, and improve the comprehensive mechanical properties of the fluorosilicone composite rubber under the condition of ensuring high conductivity. The fluorine-silicon composite rubber has excellent conductivity, long-term high temperature resistance, oil resistance and aging resistance, can continuously work at the temperature of-40-150 ℃, and the conductivity and the sealing performance can not be obviously reduced along with the time; the preparation method of the fluorine-silicon composite rubber is simple and easy to operate, improves the production efficiency and reduces the production cost.
Detailed Description
The technical scheme adopted by the invention for solving the technical problem is as follows: the high-conductivity oil-resistant fluorine-silicon composite rubber comprises the following raw materials in parts by mass: 10 to 30 portions of master batch, 60 to 80 portions of conductive filler, 3 to 15 portions of white carbon black, 1 to 5 portions of structural control agent, 0.3 to 1.5 portions of vulcanizing agent, 1 to 4 portions of heat-resistant auxiliary agent and 0.1 to 0.5 portion of antioxidant; the master batch is a blended rubber of fluorosilicone rubber and methyl vinyl silicone rubber, and the mass percentage of the methyl vinyl silicone rubber in the master batch is 10-50%.
Furthermore, the mol percentage of vinyl in the methyl vinyl silicone rubber is 0.1-0.5%, the fluorosilicone rubber and the methyl vinyl silicone rubber are jointly used to form a blended master batch, the fluorosilicone rubber has good performances of mineral oil resistance and nonpolar solvent resistance, the addition of the methyl vinyl silicone rubber can improve the comprehensive mechanical property of the fluorosilicone composite rubber of a product, reduce the compression permanent deformation, ensure uniform vulcanization, reduce the generation of bubbles, improve the vulcanization activity of the fluorosilicone composite rubber, use organic peroxide with smaller activity for vulcanization crosslinking, reduce the use amount, improve the vulcanization activity, greatly improve the heat resistance and the high-temperature compression permanent deformation resistance, jointly use the fluorosilicone rubber and the methyl vinyl silicone rubber, improve the filling amount of the conductive filler, and do not influence the physical property of the product under the condition of ensuring high conductivity.
The conductive filler is at least one of silver powder, silver-coated copper powder, silver-coated aluminum powder, silver-plated glass beads, nickel powder and nickel-coated graphite, and the conductive filler has good conductivity and dispersibility, so that the prepared fluorine-silicon composite rubber has excellent high conductivity; the average grain size of the silver powder is 5-15 mu m, the average grain size of the silver-coated copper powder is 10-80 mu m, the average grain size of the silver-coated aluminum powder is 10-60 mu m, the average grain size of the silver-coated glass beads is 20-80 mu m, the average grain size of the nickel powder is 25-100 mu m, and the average grain size of the nickel-coated graphite is 25-100 mu m.
The structural control agent is at least one of dihydroxy polydimethylsiloxane, polyhydroxy methyl siloxane, diphenyl silanediol, dihydroxy (3, 3-trifluoropropyl) methyl siloxane, octamethyl tetrasiloxane and hexamethyldisilazane. The structural control agent can improve the dispersibility of the filler in the mixed silicone rubber, and obviously improve the physical and mechanical properties after vulcanization, particularly the compression permanent deformation.
Further, the vulcanizing agent is at least one of 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 4-dichlorobenzoyl peroxide, benzoyl peroxide, t-butyl peroxybenzoate, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane, di-t-butyl peroxide and dicumyl peroxide.
The heat-resistant auxiliary agent is at least one of ferric oxide, cerium oxide, nickel oxide, zinc oxide, titanium dioxide, carbon black, phenyl polyazo compound and indole compound. The addition of the heat-resistant auxiliary agent enables the fluorosilicone composite rubber to be used for a long time in a high-temperature environment and used for a short time in an ultrahigh-temperature environment, so that the hot air aging performance of the fluorosilicone composite rubber can be improved, and the problems that the fluorosilicone composite rubber is hardened, the tensile strength and the elongation are reduced and the like after hot air aging are solved.
Further, the antioxidant is at least one of 2, 4-dichlorobenzoic acid, p-chlorobenzoic acid, ammonium phenylate and 2, 4-dichlorobenzoyl peroxide. The antioxidant is added to prevent the surface of the conductive powder coating from being oxidized, and the condition of gradual reduction of the conductivity is improved.
According to the high-conductivity oil-resistant fluorosilicone composite rubber provided by the invention, the fluorosilicone rubber and the methyl vinyl silicone rubber are jointly used to form the blended master batch, the fluorosilicone rubber has good performances of resisting mineral oil and non-polar solvent, the addition of the methyl vinyl silicone rubber can improve the comprehensive mechanical properties of the fluorosilicone composite rubber of a product, reduce the compression permanent deformation, realize more uniform vulcanization, reduce the generation of bubbles, improve the vulcanization activity of the fluorosilicone composite rubber, use organic peroxide with lower activity for vulcanization crosslinking, reduce the use amount, greatly improve the heat resistance and high-temperature compression permanent deformation due to the improvement of the vulcanization activity, improve the filling amount of a conductive filler by jointly using the fluorosilicone rubber and the methyl vinyl silicone rubber, and do not influence the physical properties of the product under the condition of ensuring high conductivity; the fluorine-silicon composite rubber HAs excellent conductivity, long-term high temperature resistance, oil resistance and aging resistance, can continuously work at the temperature of-40-150 ℃, the conductivity and the sealing performance cannot be remarkably reduced along with time, the fluorine-silicon composite rubber is soaked in 150 ℃ ATF oil for 1000 hours, the volume resistivity change rate after aging is not more than 15%, the hardness change is not more than 10HA, and the volume change is not more than 5%, and the fluorine-silicon composite rubber is suitable for the fields of automobiles, aerospace and the like; the preparation method of the fluorine-silicon composite rubber is simple and easy to operate, improves the production efficiency and reduces the production cost.
The invention also provides a preparation method of the high-conductivity oil-resistant fluorine-silicon composite rubber, wherein the masterbatch, the conductive filler, the white carbon black, the structural control agent, the vulcanizing agent, the heat-resistant auxiliary agent and the antioxidant adopt the raw materials disclosed above, and the preparation method comprises the following steps:
s1, putting 10-30 parts of master batch, 3-15 parts of white carbon black, 1-5 parts of structural control agent and 1-4 parts of heat-resistant auxiliary agent into a kneader, mixing under stirring, and performing heat treatment after mixing, wherein the heat treatment temperature is 160-190 ℃ and the heat treatment time is 1-4 hours, so as to obtain the base material.
And S2, after the base material in the step S1 is cooled to the normal temperature of 25 ℃, gradually adding 60-80 parts of conductive filler into the base material, mixing on an open mill for 30-40 min, and uniformly mixing to obtain the rubber compound.
And S3, adding 0.1-0.5 part of antioxidant and 0.3-1.5 parts of vulcanizing agent into the rubber compound in the step S2, and uniformly mixing to obtain the fluorine-silicon rubber compound.
S4, placing the fluorosilicone rubber compound in the step S3 into a mold, wherein the mold pressing pressure is 20000 kg-100000 kg, the mold pressing temperature is 160-185 ℃, the mold pressing time is 5-10 min, the high-conductivity oil-resistant fluorosilicone composite rubber is obtained by mold pressing, the secondary vulcanization temperature is 180 ℃, and the vulcanization time is as follows: 2 to 4 hours.
The invention is further illustrated by the following specific examples.
Example 1
The highly-conductive oil-resistant fluorosilicone composite rubber comprises the following raw materials in parts by mass: 10 parts of fluorosilicone rubber and 10 parts of methyl vinyl silicone rubber (the mol percentage of vinyl in the methyl vinyl silicone rubber is 0.1%), 70 parts of conductive filler silver-coated copper powder (the average particle size is 35 +/-5 mu m), 5 parts of white carbon black, 3.6 parts of structural control agent dihydroxy (3, 3-trifluoropropyl) methyl siloxane, 0.3 part of vulcanizing agent 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane, 1 part of heat-resistant auxiliary agent iron oxide powder and 0.1 part of antioxidant 2, 4-dichlorobenzoyl peroxide.
The fluorosilicone composite rubber can be prepared by blending fluorosilicone rubber and methyl vinyl silicone rubber, wherein the vinyl content of the methyl vinyl rubber is 0.1-0.5%, and the silver-coated copper powder can be replaced by at least one of silver powder, silver-coated aluminum powder, silver-coated glass beads, nickel powder and nickel-coated graphite or a mixture of the silver-coated copper powder; the dihydroxy (3, 3-trifluoropropyl) methylsiloxane may be replaced by at least one of dihydroxy polydimethylsiloxane, polyhydroxy methylsiloxane, diphenylsilanediol, octamethyltetrasiloxane and hexamethyldisilazane or a mixture with dihydroxy (3, 3-trifluoropropyl) methylsiloxane; 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane may be replaced with at least one of 2, 4-dichlorobenzoyl peroxide, benzoyl peroxide, t-butyl peroxybenzoate, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane, di-t-butyl peroxide and dicumyl peroxide or a mixture with 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane; the iron oxide can be replaced by at least one of cerium oxide, nickel oxide, zinc oxide, titanium dioxide, carbon black, phenyl polyazo compounds and indole compounds or a mixture of the iron oxide and the iron oxide; the 2, 4-dichlorobenzoyl peroxide can be replaced by at least one of 2, 4-dichlorobenzoic acid, p-chlorobenzoic acid and ammonium phenylate or a mixture of the 2, 4-dichlorobenzoyl peroxide and the 2, 4-dichlorobenzoyl peroxide.
The preparation method of the high-conductivity oil-resistant fluorosilicone composite rubber comprises the following steps:
s1, putting 10 parts of fluorosilicone rubber, 10 parts of methyl vinyl silicone rubber, 5 parts of white carbon black, 3.6 parts of a structural control agent and 1 part of a heat-resistant auxiliary agent into a kneader, mixing under stirring, and performing heat treatment after mixing, wherein the heat treatment temperature is 160 ℃ and the heat treatment time is 4 hours, so as to obtain the base material.
And S2, after the base material in the step S1 is cooled to 25 ℃, gradually adding 70 parts of conductive filler into the base material, and mixing on an open mill for 30min to obtain the rubber compound.
And S3, adding 0.1 part of antioxidant and 0.3 part of vulcanizing agent into the rubber compound in the step S2, and uniformly mixing to obtain the fluorine-silicon rubber compound.
And S4, placing the fluorosilicone rubber compound in the step S3 in a mold, wherein the mold pressing pressure is 20000kg, the mold pressing temperature is 160 ℃, the mold pressing time is 10min, and performing mold pressing to obtain a highly conductive oil-resistant fluorosilicone composite rubber test piece with the thickness of 2mm, wherein the test piece is subjected to secondary vulcanization for 2 hours at 180 ℃.
Example 2
The high-conductivity oil-resistant fluorosilicone composite rubber comprises the following raw materials in parts by mass: 17 parts of fluorosilicone rubber, 3 parts of methyl vinyl silicone rubber (the mol percentage of vinyl in the methyl vinyl silicone rubber is 0.4 percent), 30 parts of conductive filler silver-coated copper powder (the average particle size is 35 +/-5 mu m), 40 parts of silver-coated aluminum powder (the average particle size is 40 +/-5 mu m), 5 parts of white carbon black, 1.2 parts of structural control agent dihydroxy polydimethylsiloxane, 1 part of vulcanizing agent 2, 4-dichlorobenzoyl peroxide, 2.5 parts of heat-resistant auxiliary agent cerium oxide and 0.3 part of antioxidant ammonium benzoate.
The preparation method comprises the following steps:
s1, putting 17 parts of fluorosilicone rubber, 3 parts of methyl vinyl silicone rubber, 5 parts of white carbon black, 1.2 parts of a structural control agent and 2.5 parts of a heat-resistant auxiliary agent into a kneader, mixing under stirring, and performing heat treatment after mixing, wherein the heat treatment temperature is 175 ℃ and the heat treatment time is 2 hours, so as to obtain the base material.
And S2, after the base material in the step S1 is cooled to 25 ℃, gradually adding 70 parts of conductive filler into the base material, mixing on an open mill for 35min, and uniformly mixing to obtain the rubber compound.
And S3, adding 0.3 part of antioxidant and 1 part of vulcanizing agent into the rubber compound in the step S2, and uniformly mixing to obtain the fluorosilicone rubber compound.
And S4, placing the fluorosilicone rubber compound in the step S3 in a mold, wherein the mold pressing pressure is 20000kg, the mold pressing temperature is 170 ℃, the mold pressing time is 7min, and performing mold pressing to obtain a high-conductivity oil-resistant fluorosilicone composite rubber test piece with the thickness of 2mm, wherein the test piece is subjected to secondary vulcanization for 2 hours at 180 ℃.
Example 3
The high-conductivity oil-resistant fluorosilicone composite rubber comprises the following raw materials in parts by mass: 18.4 parts of fluorosilicone rubber, 5 parts of methyl vinyl silicone rubber (the mol percentage of vinyl in the methyl vinyl silicone rubber is 0.4 percent), 68 parts of nickel-coated graphite (the average particle size is 100 +/-5 mu m), 5 parts of white carbon black, 1 part of a structural control agent dihydroxy (3, 3-trifluoropropyl) methyl siloxane, 1 part of a vulcanizing agent 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane, 1.4 parts of a heat-resistant auxiliary agent iron oxide powder and 0.2 part of an antioxidant 2, 4-dichlorobenzoyl peroxide.
The preparation method comprises the following steps:
s1, putting 18.4 parts of fluorosilicone rubber, 5 parts of methyl vinyl silicone rubber, 5 parts of white carbon black, 1 part of structural control agent and 1.4 parts of heat-resistant auxiliary agent into a kneader, mixing under stirring, and performing heat treatment after mixing, wherein the heat treatment temperature is 190 ℃ and the heat treatment time is 1h to obtain the base material.
And S2, after the base material in the step S1 is cooled to 25 ℃, adding 68 parts of conductive filler into the base material step by step, mixing on an open mill for 30min, and uniformly mixing to obtain the rubber compound.
And S3, adding 0.2 part of antioxidant and 1 part of vulcanizing agent into the rubber compound in the step S2, and uniformly mixing to obtain the fluorosilicone rubber compound.
And S4, placing the fluorosilicone rubber compound in the step S3 in a mold, wherein the mold pressing pressure is 20000kg, the mold pressing temperature is 185 ℃, the mold pressing time is 5min, and performing mold pressing to obtain a high-conductivity oil-resistant fluorosilicone composite rubber test piece with the thickness of 2mm, wherein the test piece is subjected to secondary vulcanization for 2 hours at 180 ℃.
Example 4
The highly-conductive oil-resistant fluorosilicone composite rubber comprises the following raw materials in parts by mass: 14.9 parts of fluorosilicone rubber, 8 parts of methyl vinyl silicone rubber (the mol percentage of vinyl in the methyl vinyl silicone rubber is 0.4 percent), 70 parts of silver-plated glass microspheres (the average particle size is 40 +/-5 mu m), 3 parts of white carbon black, 2 parts of a structural control agent dihydroxy (3, 3-trifluoropropyl) methyl siloxane, 0.5 part of a vulcanizing agent 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane, 1.5 parts of a heat-resistant auxiliary agent iron oxide powder and 0.1 part of an antioxidant 2, 4-dichlorobenzoyl peroxide.
The preparation method comprises the following steps:
s1, putting 14.9 parts of fluorosilicone rubber, 8 parts of methyl vinyl silicone rubber, 3 parts of white carbon black, 2 parts of a structural control agent and 1.5 parts of a heat-resistant auxiliary agent into a kneader, mixing under stirring, and performing heat treatment after mixing, wherein the heat treatment temperature is 175 ℃ and the heat treatment time is 2 hours, so as to obtain the base material.
And S2, after the base material in the step S1 is cooled to 25 ℃, gradually adding 70 parts of conductive filler into the base material, and mixing on an open mill for 35min uniformly to obtain the rubber compound.
And S3, adding 0.1 part of antioxidant and 0.5 part of vulcanizing agent into the rubber compound in the step S2, and uniformly mixing to obtain the fluorosilicone rubber compound.
And S4, placing the fluorosilicone rubber compound in the step S3 in a mold, wherein the mold pressing pressure is 20000kg, the mold pressing temperature is 175 ℃, the mold pressing time is 5min, and performing mold pressing to obtain a highly conductive oil-resistant fluorosilicone composite rubber test piece with the thickness of 2mm, wherein the test piece is subjected to secondary vulcanization for 2 hours at 180 ℃.
Example 5
The highly-conductive oil-resistant fluorosilicone composite rubber comprises the following raw materials in parts by mass: 29.4 parts of fluorine silicon rubber, 0.6 part of methyl vinyl silicone rubber (the mol percentage of vinyl in the methyl vinyl silicone rubber is 0.5 percent), 60 parts of conductive filler silver-coated copper powder (the average particle size is 35 +/-5 mu m), 5 parts of white carbon black, 3.6 parts of structural control agent dihydroxy (3, 3-trifluoropropyl) methyl siloxane, 0.3 part of vulcanizing agent 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane, 1 part of heat-resistant auxiliary agent ferric oxide and 0.1 part of antioxidant 2, 4-dichloro benzoyl peroxide.
The preparation method of the high-conductivity oil-resistant fluorosilicone composite rubber comprises the following steps:
s1, putting 29.4 parts of fluorosilicone rubber, 0.6 part of methyl vinyl silicone rubber, 5 parts of white carbon black, 3.6 parts of a structural control agent and 1 part of a heat-resistant auxiliary agent into a kneader, mixing under stirring, and then carrying out heat treatment at 160 ℃ for 4 hours to obtain the base material.
And S2, after the base material in the step S1 is cooled to 25 ℃, gradually adding 60 parts of conductive filler into the base material, and mixing on an open mill for 30min to obtain the rubber compound.
And S3, adding 0.1 part of antioxidant and 0.3 part of vulcanizing agent into the rubber compound in the step S2, and uniformly mixing to obtain the fluorosilicone rubber compound.
And S4, placing the fluorosilicone rubber compound in the step S3 in a mold, wherein the mold pressing pressure is 60000kg, the mold pressing temperature is 185 ℃, the mold pressing time is 5min, preparing a high-conductivity oil-resistant fluorosilicone composite rubber test piece with the thickness of 2mm by mold pressing, and carrying out secondary vulcanization on the test piece for 3 hours at 200 ℃.
Example 6
The high-conductivity oil-resistant fluorosilicone composite rubber comprises the following raw materials in parts by mass: 9 parts of fluorosilicone rubber, 1 part of methyl vinyl silicone rubber (the mole percentage of vinyl in the methyl vinyl silicone rubber is 0.3 percent), 20 parts of conductive filler silver-coated copper powder (the average particle size is 35 +/-5 mu m), 40 parts of nickel-coated graphite (the average particle size is 50 +/-5 mu m), 20 parts of silver-coated aluminum powder (the average particle size is 40 +/-5 mu m), 5 parts of white carbon black, 1 part of structural control agent dihydroxy (3, 3-trifluoropropyl) methyl siloxane, 1 part of vulcanizing agent 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane, 2.8 parts of heat-resistant auxiliary agent ferric oxide powder and 0.2 part of antioxidant 2, 4-dichlorobenzoyl peroxide.
The preparation method comprises the following steps:
s1, putting 9.3 parts of fluorosilicone rubber, 0.7 part of methyl vinyl silicone rubber, 5 parts of white carbon black, 1 part of structural control agent and 2.8 parts of heat-resistant auxiliary agent into a kneader, mixing under stirring, and performing heat treatment after mixing, wherein the heat treatment temperature is 190 ℃ and the heat treatment time is 1h to obtain the base material.
And S2, after the base material in the step S1 is cooled to 25 ℃, gradually adding 66.3 parts of conductive filler into the base material, and mixing on an open mill for 30min to obtain the rubber compound.
And S3, adding 0.2 part of antioxidant and 1 part of vulcanizing agent into the rubber compound in the step S2, and uniformly mixing to obtain the fluorine-silicon rubber compound.
And S4, placing the fluorosilicone rubber compound in the step S3 in a mold, wherein the mold pressing pressure is 100000kg, the mold pressing temperature is 140 ℃, the mold pressing time is 8min, mold pressing is carried out to obtain a high-conductivity oil-resistant fluorosilicone composite rubber test piece with the thickness of 2mm, and the test piece is subjected to secondary vulcanization for 4 hours at 190 ℃.
Example 7
The highly-conductive oil-resistant fluorosilicone composite rubber comprises the following raw materials in parts by mass: 11 parts of fluorosilicone rubber, 3 parts of methyl vinyl silicone rubber (the mol percentage of vinyl in the methyl vinyl silicone rubber is 0.4 percent), 60 parts of conductive filler silver-coated copper powder (the average particle size is 35 +/-5 mu m), 15 parts of white carbon black, 5 parts of structural control agent dihydroxy (3, 3-trifluoropropyl) methyl siloxane, 1.5 parts of vulcanizing agent 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane, 4 parts of heat-resistant auxiliary agent ferric oxide and 0.5 part of antioxidant 2, 4-dichlorobenzoyl peroxide.
The preparation method of the high-conductivity oil-resistant fluorosilicone composite rubber comprises the following steps:
s1, putting 11 parts of fluorosilicone rubber, 3 parts of methyl vinyl silicone rubber, 15 parts of white carbon black, 5 parts of a structural control agent and 4 parts of a heat-resistant auxiliary agent into a kneader, mixing under stirring, and then carrying out heat treatment at 160 ℃ for 4 hours to obtain the base material.
And S2, after the base material in the step S1 is cooled to 25 ℃, gradually adding 60 parts of conductive filler into the base material, and mixing on an open mill for 30min to obtain the rubber compound.
And S3, adding 0.1 part of antioxidant and 0.3 part of vulcanizing agent into the rubber compound in the step S2, and uniformly mixing to obtain the fluorosilicone rubber compound.
And S4, placing the fluorosilicone rubber compound in the step S3 in a mold, wherein the mold pressing pressure is 20000kg, the mold pressing temperature is 185 ℃, the mold pressing time is 5min, and performing mold pressing to obtain a highly conductive oil-resistant fluorosilicone composite rubber test piece with the thickness of 2mm, wherein the test piece is subjected to secondary vulcanization for 2 hours at 180 ℃.
Comparative example 1
The comparative example differs from examples 1-7 in that the masterbatch of the comparative example is fluorosilicone rubber, and no methyl vinyl silicone rubber is added.
The composite rubber comprises the following raw materials in parts by weight: 20 parts of fluorosilicone rubber, 70 parts of conductive filler silver-coated copper powder (the average particle size is 35 +/-5 mu m), 5 parts of white carbon black, 3.6 parts of structural control agent dihydroxy (3, 3-trifluoropropyl) methyl siloxane, 0.3 part of vulcanizing agent 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 1 part of heat-resistant auxiliary agent iron oxide powder and 0.1 part of antioxidant 2, 4-dichlorobenzoyl peroxide.
The preparation method is the same as in example 1.
Comparative example 2
The comparative example is different from examples 1 to 7 in that the master batch of the comparative example is methyl vinyl silicone rubber, and fluorosilicone rubber is not added.
The composite rubber comprises the following raw materials in parts by weight: 20 parts of methyl vinyl silicone rubber, 70 parts of conductive filler silver-coated copper powder (the average particle size is 35 +/-5 mu m), 5 parts of white carbon black, 3.6 parts of structural control agent dihydroxy (3, 3-trifluoropropyl) methyl siloxane, 0.3 part of vulcanizing agent 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 1 part of heat-resistant auxiliary agent ferric oxide powder and 0.1 part of antioxidant 2, 4-dichlorobenzoyl peroxide.
The preparation method is the same as that of example 1.
Comparative example 3
This comparative example differs from examples 1-7 in that no structuring control agent was added to the comparative example.
The composite rubber comprises the following raw materials in parts by mass: 10 parts of fluorine silicon rubber (13.6 parts of methyl vinyl silicone rubber (the mol percentage of vinyl in the methyl vinyl silicone rubber is 0.1 percent)), 70 parts of conductive filler silver-coated copper powder (the average grain diameter is 35 +/-5 mu m), 5 parts of white carbon black, 0.3 part of vulcanizing agent 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane, 1 part of heat-resistant auxiliary agent iron oxide powder and 0.1 part of antioxidant 2, 4-dichlorobenzoyl peroxide.
The preparation method is the same as that of example 1 except that no structured control agent is added in the step S1.
Comparative example 4
This comparative example differs from examples 1-7 in that no heat resistance aid was added.
The composite rubber comprises the following raw materials in parts by mass: 10 parts of fluorosilicone rubber, 11 parts of methyl vinyl silicone rubber (the mol percentage of vinyl in the methyl vinyl silicone rubber is 0.1 percent), 70 parts of conductive filler silver-coated copper powder (the average particle size is 35 +/-5 mu m), and 5 parts of white carbon black (the specific surface area is 200 m) 2 (g), 3.6 parts of structural control agent dihydroxy (3, 3-trifluoropropyl) methyl siloxane, 0.3 part of vulcanizing agent 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane and 0.1 part of antioxidant 2, 4-dichlorobenzoyl peroxide.
The preparation method was the same as that of example 1 except that the heat-resistant auxiliary was not added in the step S1.
Comparative example 5
This comparative example differs from examples 1-7 in that no antioxidant was added.
The highly-conductive oil-resistant fluorosilicone composite rubber comprises the following raw materials in parts by mass: 10 parts of fluorosilicone rubber, 10 parts of methyl vinyl silicone rubber (the mol percentage of vinyl in the methyl vinyl silicone rubber is 0.1 percent), 70 parts of conductive filler silver-coated copper powder (the average particle size is 35 +/-5 mu m), and 5 parts of white carbon black (the specific surface area is 200 m) 2 The raw materials comprise/g), 3.7 parts of structural control agent dihydroxy (3, 3-trifluoropropyl) methyl siloxane, 0.3 part of vulcanizing agent 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane and 1 part of heat-resistant auxiliary agent ferric oxide powder.
The preparation method was the same as that of example 1 except that no antioxidant was added in the step S3.
The fluorosilicone composite rubbers of examples 1 to 4 and the composite rubbers of comparative examples 1 to 5 were tested according to ASTM D2000 for basic and additional performance requirements of the fluorosilicone composite rubbers, and the mechanical properties, oil resistance and conductivity of the fluorosilicone composite rubbers were tested with specific reference to ASTM D412, ASTM D573, ASTM D471 and ASTM D395. The results of the measurements are shown in the following table:
TABLE 1 Performance test results of the fluorosilicone composite rubbers of examples 1 to 4
TABLE 2 test results of the properties of the compounded rubbers of comparative examples 1 to 5
As can be seen from table 1, the fluorosilicone composite rubber of embodiments 1 to 4 of the present invention uses fluorosilicone rubber and methyl vinyl silicone rubber together, so that the product has excellent high temperature oil aging resistance, heat resistance, and high temperature compression permanent set resistance, and the conductive powder, the antioxidant, the heat-resistant auxiliary, the antioxidant, and the vulcanizing agent can improve the conductive performance and the aging resistance of the fluorosilicone composite rubber, and the preparation method is simple and has good application prospects.
As shown in Table 2, in comparative example 1, the fluorosilicone rubber was used as the base rubber, which resulted in a large compression set and a high hardness, and the material itself had poor elasticity. Comparative example 2 using methyl vinyl silicone rubber as a base rubber results in poor oil resistance of the product, and changes in volume resistivity, tensile strength and volume, and in an oil resistance test, a higher numerical value results in failure of sealing performance and conductivity of the product in the use process. Comparative example 3 no structuring control was added. The structured control agent is used for adjusting the hardness of the base rubber, the flowing state of the rubber material and the bonding property of the rubber material and the powder, so that the moderate hardness of the product is ensured, the compression permanent deformation amount is small, and the material performance test and the oil resistance test are good. The requirement of customer installation is met, so that the composite rubber of the comparative example 3 has large compression set, and the material performance test and the oil resistance test are poor. Comparative example 4 no heat-resistant agent was added, which resulted in oxidation of methyl groups in the raw rubber molecules during high temperature aging, especially hot air aging, which in turn resulted in crosslinking, which increased the hardness of the silicone rubber product, even lost elasticity and cracked, and finally resulted in product failure. And the antioxidant of the comparative example 5 causes that the conductive powder coating is easy to be oxidized and cannot be applied to products for a long time.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The high-conductivity oil-resistant fluorosilicone composite rubber is characterized by comprising the following raw materials in parts by mass: 10 to 30 portions of master batch, 60 to 80 portions of conductive filler, 3 to 15 portions of white carbon black, 1 to 5 portions of structural control agent, 0.3 to 1.5 portions of vulcanizing agent, 1 to 4 portions of heat-resistant auxiliary agent and 0.1 to 0.5 portion of antioxidant; the master batch is a blended rubber of fluorosilicone rubber and methyl vinyl silicone rubber, and the mass percentage of the methyl vinyl silicone rubber in the master batch is 10-50%.
2. The highly conductive oil-resistant fluorosilicone composite rubber according to claim 1, wherein one molecular end of the fluorosilicone rubber is terminated by a vinyl chain link, and the chain of the fluorosilicone rubber is a trifluoropropylmethylsiloxane chain link.
3. The highly conductive oil-resistant fluorosilicone composite rubber according to claim 1, wherein the molar percentage of vinyl groups in the methyl vinyl silicone rubber is 0.1 to 0.5%.
4. The highly-conductive oil-resistant fluorosilicone composite rubber according to claim 1, wherein the conductive filler is at least one of silver powder, silver-coated copper powder, silver-coated aluminum powder, silver-coated glass beads, nickel powder and nickel-coated graphite, wherein the average particle size of the silver powder is 5-15 μm, the average particle size of the silver-coated copper powder is 10-80 μm, the average particle size of the silver-coated aluminum powder is 10-60 μm, the average particle size of the silver-coated glass beads is 20-80 μm, the average particle size of the nickel powder is 25-100 μm, and the average particle size of the nickel-coated graphite is 25-100 μm.
5. The highly conductive oil resistant fluorosilicone composite rubber according to claim 1, wherein the structural control agent is at least one of dihydroxypolydimethylsiloxane, polyhydroxymethylsiloxane, diphenylsilanediol, dihydroxy (3, 3-trifluoropropyl) methylsiloxane, octamethyltetrasiloxane and hexamethyldisilazane.
6. The highly conductive oil resistant fluorosilicone composite rubber according to claim 1, wherein the vulcanizing agent is at least one of 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2, 4-dichlorobenzoyl peroxide, benzoyl peroxide, t-butyl peroxybenzoate, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane, di-t-butyl peroxide and dicumyl peroxide.
7. The highly-conductive oil-resistant fluorosilicone composite rubber as claimed in claim 1, wherein the heat-resistant auxiliary is at least one of iron oxide, cerium oxide, nickel oxide, zinc oxide, titanium dioxide, carbon black, phenyl polyazo compound and indole compound.
8. The highly conductive oil resistant fluorosilicone composite rubber according to claim 1, wherein the antioxidant is at least one of 2, 4-dichlorobenzoic acid, p-chlorobenzoic acid, ammonium benzoate, and 2, 4-dichlorobenzoyl peroxide.
9. A preparation method of high-conductivity oil-resistant fluorosilicone composite rubber is characterized by comprising the following steps:
s1, taking 10-30 parts of masterbatch, 3-15 parts of white carbon black, 1-5 parts of a structural control agent and 1-4 parts of a heat-resistant auxiliary agent, and stirring and mixing to obtain a base material;
s2, gradually adding 60-80 parts of conductive filler into the base material in the step S1, mixing, and uniformly mixing to obtain rubber compound;
s3, adding 0.1-0.5 part of antioxidant and 0.3-1.5 parts of vulcanizing agent into the rubber compound in the step S2, and uniformly mixing to obtain fluorine-silicon rubber compound;
and S4, placing the fluorosilicone rubber compound in the step S3 in a mold, and performing mold pressing to obtain the high-conductivity oil-resistant fluorosilicone composite rubber.
10. The preparation method of the highly conductive oil-resistant fluorosilicone composite rubber according to claim 9, wherein in the step S1, heat treatment is performed after mixing, wherein the heat treatment temperature is 160 to 190 ℃, and the heat treatment time is 1 to 4 hours;
in the step S2, the base material is cooled to the normal temperature of 25 ℃ and then is added with the conductive filler, and the mixing time is 30-40 min;
in the step S4, the mould pressing pressure is 20000-100000 kg, the mould pressing temperature is 140-185 ℃, the mould pressing time is 5-10 min, the secondary vulcanization temperature is 180-200 ℃, and the vulcanization time is 2-4 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211330387.8A CN115637049A (en) | 2022-10-27 | 2022-10-27 | High-conductivity oil-resistant fluorine-silicon composite rubber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211330387.8A CN115637049A (en) | 2022-10-27 | 2022-10-27 | High-conductivity oil-resistant fluorine-silicon composite rubber and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115637049A true CN115637049A (en) | 2023-01-24 |
Family
ID=84947070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211330387.8A Pending CN115637049A (en) | 2022-10-27 | 2022-10-27 | High-conductivity oil-resistant fluorine-silicon composite rubber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115637049A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250472A (en) * | 2011-05-18 | 2011-11-23 | 杨福河 | High-performance silicon-based conductive rubber and preparation method thereof |
| CN103436037A (en) * | 2013-09-17 | 2013-12-11 | 威海新元化工有限公司 | Preparation method of fluorosilicone rubber/silicon rubber blend rubber for automotive high-voltage ignition wire |
| CN106280493A (en) * | 2016-08-25 | 2017-01-04 | 北京化工大学 | A kind of low cost oil-resisting type conductive silicon rubber composite and preparation technology thereof |
| CN111087824A (en) * | 2020-01-07 | 2020-05-01 | 中国电子科技集团公司第三十三研究所 | Environment-resistant electromagnetic protection composite conductive rubber and preparation method thereof |
| CN113025056A (en) * | 2021-02-25 | 2021-06-25 | 浙江恒业成有机硅有限公司 | Conductive silicone rubber and preparation method thereof |
| CN114672171A (en) * | 2022-04-25 | 2022-06-28 | 东莞新东方科技有限公司 | Special heat-resistant corrosion-resistant silicon rubber for shielding electronic cabinet, filler thereof and preparation method thereof |
-
2022
- 2022-10-27 CN CN202211330387.8A patent/CN115637049A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250472A (en) * | 2011-05-18 | 2011-11-23 | 杨福河 | High-performance silicon-based conductive rubber and preparation method thereof |
| CN103436037A (en) * | 2013-09-17 | 2013-12-11 | 威海新元化工有限公司 | Preparation method of fluorosilicone rubber/silicon rubber blend rubber for automotive high-voltage ignition wire |
| CN106280493A (en) * | 2016-08-25 | 2017-01-04 | 北京化工大学 | A kind of low cost oil-resisting type conductive silicon rubber composite and preparation technology thereof |
| CN111087824A (en) * | 2020-01-07 | 2020-05-01 | 中国电子科技集团公司第三十三研究所 | Environment-resistant electromagnetic protection composite conductive rubber and preparation method thereof |
| CN113025056A (en) * | 2021-02-25 | 2021-06-25 | 浙江恒业成有机硅有限公司 | Conductive silicone rubber and preparation method thereof |
| CN114672171A (en) * | 2022-04-25 | 2022-06-28 | 东莞新东方科技有限公司 | Special heat-resistant corrosion-resistant silicon rubber for shielding electronic cabinet, filler thereof and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107446346B (en) | Carbon fiber reinforced wear-resistant high-temperature nylon composite material and preparation method thereof | |
| CN101412835B (en) | Blend of fluorubber and silastic, and preparation thereof | |
| CN106751889A (en) | A kind of high temperature resistance and high strength rubber composition and preparation method thereof | |
| CN106751911A (en) | Soft high-strength insulating silicon rubber and preparation method thereof | |
| CN108129850B (en) | High-resilience high-strength silicone rubber and preparation method thereof | |
| CN105801916B (en) | Heat-conductive composite material, rubber composition, cooling medium tubing and preparation method thereof | |
| CN114672101B (en) | Low-temperature-compression-resistant permanent deformation ethylene propylene diene monomer rubber material and preparation method thereof | |
| CN105482200A (en) | High abrasion-resistant low rolling resistance tread rubber material containing silicone rubber and preparation method thereof | |
| CN102010551A (en) | EPDM (ethylene-propylene-diene monomer) composition and hose | |
| CN111117257A (en) | Silicon rubber for automobile turbocharger tube and preparation method thereof | |
| CN105906950A (en) | High temperature resistant ethylene propylene rubber/silicon rubber blend and preparation method thereof | |
| CN107189148A (en) | Colored hydrogenated nitrile-butadiene rubber material of a kind of high temperature resistant and preparation method thereof | |
| CN112210215A (en) | Low-tensile permanent deformation conductive silicone rubber and preparation method thereof | |
| CN114395175B (en) | Wear-resistant rubber material and preparation method thereof | |
| CN114085534A (en) | High-elongation low-permanent-deformation high-temperature silicone rubber and preparation method thereof | |
| CN115637049A (en) | High-conductivity oil-resistant fluorine-silicon composite rubber and preparation method thereof | |
| CN102173066B (en) | Method for manufacturing steel wire hydraulic knitted rubber hose containing formaldehyde modified lignin | |
| CN116535755B (en) | Modified hydrogenated nitrile rubber composition and application thereof in sealing oil injection ring | |
| CN108659282B (en) | Wide-temperature-range high-damping oil-resistant damping rubber composite material and preparation method thereof | |
| CN114133745B (en) | Heat-resistant agent, high-temperature-resistant silicon rubber and preparation method thereof | |
| CN113150415A (en) | Shale oil and oil mine drilling mud pump piston and preparation method thereof | |
| CN113637267A (en) | Acid and alkali resistant ethylene propylene diene monomer rubber and preparation method thereof | |
| CN111763361A (en) | Rubber composition and preparation method thereof | |
| CN112625364A (en) | High-temperature-resistant low-voltage-variable high-resistance EPDM (ethylene-propylene-diene monomer) rubber compound | |
| CN107298803B (en) | Polysiloxane additive for improving aging resistance of ethylene propylene diene monomer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |