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CN-122011531-A - Nitrile rubber composite material and preparation method thereof

CN122011531ACN 122011531 ACN122011531 ACN 122011531ACN-122011531-A

Abstract

The invention discloses a nitrile rubber composite material which comprises, by weight, 100 parts of nitrile rubber, 0.5-3 parts of stearic acid, 1.5-3.5 parts of nano zinc oxide, 1-4 parts of a vulcanization aid or accelerator, 2-6 parts of a vulcanizing agent, 15-30 parts of white carbon black, 20-80 parts of a carbon black reinforcing agent, a silane coupling agent with the amount of 1% -3% of the mass of the white carbon black, and 0.2-4 parts of an anti-aging agent, wherein the content of acrylonitrile-butadiene rubber is 29% -42%, and a vulcanizing system is a peroxide vulcanizing system or a composite vulcanizing system formed by mixing a peroxide vulcanizing system and a sulfur vulcanizing system. The invention also discloses a preparation method of the nitrile rubber composite material, which comprises the steps of mixing raw material components to form a rubber compound, and vulcanizing the rubber compound. The nitrile rubber composite material has the advantages of high rebound resilience and low compression set under high hardness.

Inventors

  • GAO YAN
  • Yuan Jiyao
  • WANG FENGLE
  • CHENG JIN
  • LI CHANGWEI
  • CAO XIAOLONG
  • SONG WEI
  • LIU LI
  • LI TIEZHU
  • ZHANG BAOGANG
  • LIU ZHIQIN
  • ZHAO JIZHONG
  • LIU HEPING
  • FENG XU
  • WANG JIGANG

Assignees

  • 中国石油天然气股份有限公司

Dates

Publication Date
20260512
Application Date
20241112

Claims (13)

  1. 1. The nitrile rubber composite material is characterized by comprising, by weight, 100 parts of nitrile rubber, 0.5-3 parts of stearic acid, 1.5-3.5 parts of nano zinc oxide, preferably 2-3 parts of auxiliary vulcanizing agent or accelerator, 1-4 parts of vulcanizing agent, 2-6 parts of white carbon black, preferably 15-20 parts of carbon black reinforcing agent, 20-80 parts of silane coupling agent with the amount of 1% -3% of the mass of the white carbon black, and 0.2-4 parts of anti-aging agent, wherein the content of bound acrylonitrile of the nitrile rubber is 29% -42%, preferably 31% -35%, and the vulcanizing system is a peroxide vulcanizing system or a composite vulcanizing system formed by mixing a peroxide vulcanizing system and a sulfur vulcanizing system, preferably a composite vulcanizing system formed by mixing a peroxide vulcanizing system and a sulfur vulcanizing system.
  2. 2. The nitrile rubber composite material according to claim 1, wherein the particle size of the nano zinc oxide is 20-100 nm, preferably the nano zinc oxide is modified nano zinc oxide, more preferably the nano zinc oxide is nano zinc oxide modified by a coupling agent.
  3. 3. The nitrile rubber composite material according to claim 1, wherein the carbon black reinforcing agent is one or a mixture of more than two carbon blacks selected from carbon black N220, carbon black N550 and carbon black N774, preferably the carbon black reinforcing agent is more than two carbon blacks, and the addition amount of the carbon black reinforcing agent is preferably 60-70 parts.
  4. 4. The nitrile rubber composite of claim 1, wherein the mooney viscosity of the nitrile rubber 65-90.
  5. 5. The nitrile rubber composite according to claim 1, characterized in that the silane coupling agent is one of KH560, KH580, si-69.
  6. 6. The nitrile rubber composite according to claim 1, characterized in that the vulcanizing agent is a peroxide vulcanizing agent or a mixture of peroxide vulcanizing agent and sulfur.
  7. 7. Nitrile rubber composite according to claim 1, characterized in that the peroxide curing agent in the peroxide curing system is a dialkyl peroxide, a diacyl peroxide, a peroxyester or dicumyl peroxide, preferably the peroxide curing agent is dicumyl peroxide.
  8. 8. The nitrile rubber composite material according to claim 1, wherein the vulcanization aid is one or a mixture of more of N, N' -m-phenylene bismaleimide HVA-2, zinc diacrylate ZDAA and zinc dimethacrylate ZDMA, and preferably 1-3 parts of vulcanization aid.
  9. 9. Nitrile rubber composite according to claim 1, characterized in that the accelerator is a thiazole and/or thiuram accelerator, preferably the accelerator is one or a mixture of more of N-cyclohexyl-2-benzothiazolesulfenamide, 4' -dithiodimorpholine, tetramethylthiuram disulfide.
  10. 10. The nitrile rubber composite of claim 1, wherein said anti-aging agent is a mixture of one or more of 2-mercaptobenzimidazole, 2, 4-trimethyl-1, 2-dihydroquinoline polymer, N-isopropyl-N' -phenyl-p-phenylenediamine.
  11. 11. The nitrile rubber composite material according to claim 1, which is characterized by comprising the following raw material components, by weight, 100 parts of nitrile rubber, 0.5-3 parts of stearic acid, 2-3 parts of nano zinc oxide, 2-4 parts of a vulcanization aid or accelerator, 2-6 parts of a vulcanizing agent, 15-30 parts of white carbon black, 20-80 parts of a carbon black reinforcing agent, a silane coupling agent with the amount of 1% -3% of the mass of the white carbon black, 0.2-4 parts of an anti-aging agent, wherein the content of bound acrylonitrile of the nitrile rubber is 29% -42%, preferably 31% -35%, and the Mooney viscosity of the nitrile rubber 65-90.
  12. 12. The method of preparing a nitrile rubber composite according to any one of claims 1 to 11, characterized in that the raw material components are kneaded to form a rubber compound, and the rubber compound is vulcanized.
  13. 13. The preparation method according to claim 12, characterized by comprising the steps of: One-stage mixing, namely, putting nitrile rubber into an internal mixer for plasticating for 2-8 min at the temperature of 50-60 ℃ and the rotating speed of 30-50 r/min, adding white carbon black, a silane coupling agent, carbon black, zinc oxide, stearic acid and an accelerator in proportion, driving a ram on the internal mixer, providing mixing pressure for a mixing chamber, and carrying out banburying for 3-9 min to obtain a master batch uniformly mixed; two-stage mixing, namely, carrying out back mixing on the masterbatch obtained by the first-stage mixing on an open mill, adding a vulcanizing agent, carrying out thin-pass triangular packing for 3-7 times, and adjusting the roll spacing and blanking to obtain the nitrile rubber compound; And (3) vulcanization shaping, namely standing the nitrile rubber compound obtained by two-stage mixing for 24-36 h, and vulcanizing in a flat vulcanizing machine at 175+/-10 ℃ and 15+/-5 MPa to obtain the product.

Description

Nitrile rubber composite material and preparation method thereof Technical Field The invention belongs to the technical field of preparation of composite materials, and particularly relates to a nitrile rubber composite material and a preparation method of the nitrile rubber composite material. Background Nitrile rubber has excellent elasticity, chemical stability and other performances, so that the nitrile rubber is widely applied to the rubber tube manufacturing industry. In recent years, with the development of industrial economy, there is a high demand for elastic materials suitable for sports equipment, automobiles, vibration prevention, medical treatment and other fields in China, and not only is it required to have good mechanical properties, but also it is required to have high rebound resilience and low compression set properties at high hardness. Chinese patent publication No. CN102702588a, publication No. 2012, 10/3, discloses a damping rubber material with low hardness, high-temperature static torque and good durability and a preparation method thereof. The composition comprises the following components in parts by mass: 100 parts of nitrile rubber and styrene-butadiene rubber composite material, 40-70 parts of reinforcing filler, 5-10 parts of nano white carbon black, 1-3 parts of coupling agent and processing aid, 10-15 parts of softening plasticizer, 2-3 parts of anti-aging agent, and 8-10 parts of vulcanizing and auxiliary agent. The nitrile rubber is a copolymer of butadiene and acrylonitrile, the content of the acrylonitrile is 28-33%, the vulcanizing agent in the vulcanizing aid is one of organic peroxide DCP (dicumyl peroxide), odorless DCP (tert-butyl peroxide diisopropylbenzene) and bis (2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane), the dosage is at least 2 parts, the vulcanizing aid comprises an accelerator and an active agent, wherein the accelerator is any one of an accelerator TAIC and an accelerator HVA-2, the mass part is 1-2 parts, the active agent comprises inorganic active agent zinc oxide and organic active agent stearic acid, the zinc oxide is 4-6 parts, and the stearic acid is 1-2 parts. The technology obtains the low-hardness shock-absorbing rubber material. Chinese patent publication No. CN113402792a, 9 and 17 days of 2021 discloses a low pressure nitrile rubber material in IRM903 oil and a preparation method thereof, the rubber material includes 47-52wt.% of high mooney nitrile rubber 3370C, 2-3wt.% of zinc oxide, 0.3-0.7wt.% of stearic acid, 0.8-1.2wt.% of anti-aging agent 4010NA, 0.4-0.6wt.% of anti-aging agent RD, 1.5-2.5wt.% of peroxide vulcanizing agent Perkadox 14 (RTM: di (tert-butylperoxyisopropyl) benzene), 1.5-2.5wt.% of peroxide crosslinking agent Chemmix PMA-201, 26-30wt.% of ST1120 carbon black, 9-12wt.% of N774 semi-reinforcing carbon black, and 2-5wt.% of plasticizer W260S. The technology overcomes the defect that the volume increment of the nitrile rubber in IRM903# oil is large, and higher swelling occurs, and white carbon black and a coupling agent are not used. A Chinese patent with the publication number of CN115806701A and the publication number of 2023 and 3-17 proposes a high-hardness wear-resistant durable hydrogenated nitrile rubber compound and a preparation method thereof, wherein the compound comprises, by weight, 80-100 parts of hydrogenated nitrile rubber, 4-7 parts of zinc oxide, 0.5-2 parts of stearic acid, 30-60 parts of carbon black, 0-15 parts of white carbon black, 0-20 parts of filler, 1-3 parts of aniline anti-aging agent, 0-15 parts of processing aid and 3-6 parts of peroxide vulcanizing agent. The filler is silicate, the processing aid comprises saturated fatty acid ester and/or erucamide, a coupling agent is not used, but the white carbon black is white carbon black with surface grafted maleimide, and the preparation method comprises the steps of adding the white carbon black and N- (2-hydroxyethyl) maleimide into ethanol according to the mass ratio of 12:1, stirring and mixing uniformly, adding 1wt% of dibutyltin dilaurate of the white carbon black, heating to 60 ℃, stirring for 4 hours, and evaporating the ethanol to obtain the white carbon black with the surface grafted maleimide. The technology uses hydrogenated nitrile rubber and white carbon black with maleimide grafted on the surface, and has high raw material cost. Chinese patent publication No. CN107573556A, publication No. 2018, publication No.1 and 12 discloses a gasket rubber material for an automobile oil pan and a preparation method thereof, wherein the rubber material comprises 100 parts by weight of nitrile rubber, 6-8 parts by weight of zinc oxide, 1-2 parts by weight of stearic acid, 1-2 parts by weight of 2, 4-trimethyl-1, 2-dihydroquinoline polymer, 1-5 parts by weight of N-1, 3-dimethylbutyl-N' -phenyl-p-phenylenediamine, 80-95 parts by weight of spray carbon black, 5-10 parts by weight of dioctyl phthalate, 1.5-2.5 parts by weight of dicumyl peroxide, 1-