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CN-121975197-A - Double-network crosslinked base rubber composition for cracking carbon black-bio-based liquid rubber and preparation method thereof

CN121975197ACN 121975197 ACN121975197 ACN 121975197ACN-121975197-A

Abstract

The invention relates to the technical field of tire rubber manufacturing, and discloses a base rubber composition for double-network crosslinking of cracked carbon black-bio-based liquid rubber and a preparation method thereof. The invention adopts the biological base liquid rubber to adjust delta SP (solubility difference between filler and raw rubber) and sulfur/peroxide (DCP) composite crosslinking technology, so as to improve the content of the biological base filler in the base rubber sizing material as much as possible, and effectively reduce the Paen effect of the sizing material and reduce the rolling resistance of the sizing material under the condition of adding the biological base filler.

Inventors

  • CHEN LI
  • LU XIAOQI
  • CHEN XIDONG
  • Ba Shihao
  • GU YING
  • SUN XUEFENG
  • HUANG DAYE
  • WANG DANLING

Assignees

  • 中策橡胶集团股份有限公司
  • 杭州海潮橡胶有限公司

Dates

Publication Date
20260505
Application Date
20260310

Claims (10)

  1. 1. The base rubber composition for cracking carbon black-bio-based liquid rubber double-network crosslinking is characterized by being prepared by mixing the following raw materials in parts by weight: 75 to 85phr of natural rubber, 15 To 25phr of butadiene rubber, 10 To 40phr of semi-reinforcing carbon black, 10 To 40phr of cracked carbon black, 10 To 35phr of a biobased liquid rubber, 1.0 To 5.0phr of sulfur, Dicumyl peroxide 0.5-1.0phr, Accelerators 1.0 to 2.5phr, 1To 4phr of nano zinc oxide, 1 To 3phr of stearic acid, 1-5Phr of an anti-aging agent; Solubility difference between total carbon black (semi-reinforcing carbon black and cracked carbon black) and raw rubber (natural rubber and butadiene rubber) 。
  2. 2. The double-network crosslinked base rubber composition of the cracked carbon black-bio-based liquid rubber according to claim 1, wherein the rubber composition is prepared by mixing the raw materials comprising the following components in 100 parts by weight of raw rubber: 75 to 85phr of natural rubber, 15 To 25phr of butadiene rubber, 30 To 40phr of semi-reinforcing carbon black, 10 To 20phr of a carbon black to be cracked, 25 To 35phr of a biobased liquid rubber, 2.0 To 3.0phr of sulfur, Dicumyl peroxide 0.5-1.0phr, Accelerators 1.4 to 1.8phr, 2 To 4phr of nano zinc oxide, 1 To 2phr of stearic acid, 3-5Phr of anti-aging agent.
  3. 3. The double network crosslinked base rubber composition of claim 1 or 2, wherein the solubility difference between the carbon black and the raw rubber Preferably, the hydroxyl value of the bio-based liquid rubber is more than or equal to 0.8 mmol/g, and Mn=2000-8000.
  4. 4. The double network crosslinked base rubber composition of a cracked carbon black-bio-based liquid rubber according to claim 1 or 2, wherein the mass ratio of the bio-based liquid to the total carbon black is (1-3.5): 5, the mass ratio of the semi-reinforcing carbon black to the cracked carbon black is (0.25-4): 1, and preferably the total amount of the bio-based liquid and the semi-reinforcing carbon black added is 45-50 parts by weight.
  5. 5. The double network crosslinked base rubber composition of claim 1 or 2, wherein the Bio-based liquid rubber is Bio-IBR 6600 of new polymer materials limited in tokyo, shandong.
  6. 6. The double network crosslinked base rubber composition of claim 1 or 2, wherein the rubber composition further comprises 1-5phr of a tackifying resin, preferably resorcinol formaldehyde resin.
  7. 7. The double network cross-linked base rubber composition of a cracked carbon black-biobased liquid rubber according to claim 1 or 2, wherein said rubber composition stock further comprises 8-12phr of an environmental friendly oil.
  8. 8. The double network crosslinked base rubber composition of claim 1 or 2, wherein said accelerator is selected from the group consisting of N-cyclohexyl-2-benzothiazolyl sulfenamide, N-t-butyl-2-benzothiazolyl sulfenamide, N-dicyclohexyl-2-benzothiazolyl sulfenamide, N-oxydiethylene-2-benzothiazolyl sulfenamide, N, N-diisopropyll-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole, dibenzothiazyl disulfide, zinc salt of 2-mercaptobenzothiazole, N-cyclohexyl-2-benzothiazole sulfenamide, N-oxybisethylene-2-benzothiazole sulfenamide, derivatives of dibenzothiazyl disulfide, sodium salt of 2-mercaptobenzothiazole, tetramethylthiuram disulfide, tetramethylthiuram monosulfide, tetraethylthiuram disulfide, tetraisobutylthiuram disulfide, tetrabenzylthiuram disulfide, dipentylthiuram disulfide, bis (1, 5-pentylidene) thiuram tetrasulfide, dipentamethylenethiuram hexasulfide, tetrakis (2-ethylhexyl) thiuram disulfide, dipentamethylenethiuram monosulfide, thiocarbamide, diethylthiourea, dibutylthiourea, trimethylthiourea, diphenylhydrazide, diphenylguanidine, diphenylhydrotoluene, triphenylguanidine, o-toluene, diphenylguanidine phthalate, zinc diphenylguanidine sulfide, zinc dithiocarbamate, zinc dimethylguanidine sulfide, zinc dithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dipentyldithiocarbamate, zinc dipropyldithiocarbamate coordination salt of zinc pentamethylene dithiocarbamic acid and piperidine, zinc hexadecyl isopropyl dithiocarbamic acid, zinc octadecyl isopropyl dithiocarbamic acid one or more of zinc dibenzyl dithiocarbamate, sodium diethyl dithiocarbamate, piperidine pentamethylene dithiocarbamate, selenium dimethyl dithiocarbamate, tellurium diethyl dithiocarbamate, cadmium dipentyl dithiocarbamate, acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde-ammonia reactant; preferably one or more of N-cyclohexyl-2-benzothiazole sulfenamide, N-tert-butyl-2-benzothiazole sulfenamide.
  9. 9. The double network crosslinked base rubber composition of claim 1 or 2, wherein the anti-aging agent is selected from one or more of N-phenyl-N ' -isopropyl-p-phenylenediamine, N-1, 3-dimethylbutyl-N ' -phenyl-p-phenylenediamine (4020), 4' -bis (α, α -dimethylbenzyl) diphenylamine, N-cyclohexyl-N ' -phenyl-p-phenylenediamine, N- (1-methylheptyl) -N ' -phenyl-p-phenylenediamine, 2, 6-di-tert-butyl-4-methylphenol, tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris [2, 4-di-tert-butylphenyl ] phosphite, 2-mercaptobenzimidazole, zinc salts of 2, 4-trimethyl-1, 2-dihydroquinoline polymer, 2- (2-hydroxyphenyl) benzimidazole, preferably N-1, 3-dimethylbutyl-4-hydroxyphenyl-p-phenylenediamine, hydrogenated one or more of 2, 2-dimethylbutyl-2, 4-dihydroquinoline.
  10. 10. A process for the preparation of a rubber composition according to any one of claims 1 to 9, comprising the steps of: 1) Mixing, namely adopting a tangential internal mixer, setting the rotor speed of the internal mixer to be 40-55rpm, the upper bolt pressure to be 4.2+/-0.2 bar, and the cooling water temperature of the internal mixer to be 25-40 ℃; a. Adding raw rubber, pressing a top bolt, and keeping for 10-20 seconds; b. lifting a top plug, adding the cracking carbon black, the bio-based liquid rubber, the processing aid except the vulcanizing agent and the accelerator, and lifting the top plug to heat the rubber to 100-110 ℃; c. Raising the top plug and keeping for 6-10 seconds; d. pressing a top bolt to heat the sizing material to 130-140 ℃, lifting the top bolt, discharging the sizing material and tabletting to obtain the master batch; 2) Final smelting and vulcanizing, namely, adopting a tangential internal mixer, setting the rotor speed of the internal mixer to be 15-30rpm, the upper ram pressure to be 4.2+/-0.2 bar, and the cooling water temperature of the internal mixer to be 25-40 ℃; a. Adding the mixed masterbatch, adding a vulcanizing agent and an accelerator, and pressing a top bolt to heat the sizing material to 70-80 ℃; b. raising the top plug and keeping for 6-10 seconds; c. pressing a top bolt to heat the sizing material to 80-90 ℃; d. raising the top plug and keeping for 6-8 seconds; e. pressing the top bolt to heat the rubber material to 90-95 ℃, discharging the rubber material and tabletting.

Description

Double-network crosslinked base rubber composition for cracking carbon black-bio-based liquid rubber and preparation method thereof Technical Field The invention relates to the technical field of tire rubber manufacturing, in particular to a base rubber composition for double-network crosslinking of cracked carbon black-bio-based liquid rubber and a preparation method thereof. Background The cracked carbon black can absorb waste tires, but has few surface functional groups and weak combination with rubber interfaces, so that Payne effect is high and rolling resistance rebounds. The bio-based liquid rubber is prepared from straw sugar and the like serving as raw materials, can form a hydrogen bond-covalent double network with the cracked carbon black, and is a sustainable raw material. However, the polarity difference between the bio-based liquid rubber and the cracked carbon black is large, and phase separation easily occurs in simple blending. Therefore, how to effectively utilize bio-based liquid rubber and cracked carbon black to increase sustainable material ratio in tire compounds without degrading compound performance is a problem to be solved. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a double-network crosslinked base rubber composition of a cracking carbon black-bio-based liquid rubber and a preparation method thereof. In order to achieve the above purpose, the present invention adopts the following technical scheme: The base rubber composition for cracking carbon black-biobased liquid rubber double-network crosslinking is prepared by mixing the following raw materials in parts by weight: 75 to 85phr of natural rubber, 15 To 25phr of butadiene rubber, 10 To 40phr of semi-reinforcing carbon black, 10 To 40phr of cracked carbon black, 10 To 35phr of a biobased liquid rubber, 1.0 To 5.0phr of sulfur, Dicumyl peroxide 0.5-1.0phr, Accelerators 1.0 to 2.5phr, 1To 4phr of nano zinc oxide, 1 To 3phr of stearic acid, 1-5Phr of an anti-aging agent; Solubility difference delta of total carbon black (semi-reinforcing carbon black and cracked carbon black) and raw rubber (natural rubber and butadiene rubber) 。 Preferably, the rubber composition is prepared by mixing the raw materials comprising the following components in parts by weight (100 parts by weight): 75 to 85phr of natural rubber, 15 To 25phr of butadiene rubber, 30 To 40phr of semi-reinforcing carbon black, 10 To 20phr of a carbon black to be cracked, 25 To 35phr of a biobased liquid rubber, 2.0 To 3.0phr of sulfur, Dicumyl peroxide 0.5-1.0phr, Accelerators 1.4 to 1.8phr, 2 To 4phr of nano zinc oxide, 1 To 2phr of stearic acid, 3-5Phr of anti-aging agent. Preferably, the solubility difference between the carbon black and the raw rubberPreferably, the hydroxyl value of the bio-based liquid rubber is more than or equal to 0.8 mmol/g, and Mn=2000-8000. Preferably, the mass ratio of the bio-based liquid to the total carbon black is (1-3.5): 5, the mass ratio of the semi-reinforcing carbon black to the cracking carbon black is (0.25-4): 1, and preferably, the total addition amount of the bio-based liquid and the semi-reinforcing carbon black is 45-50 parts by weight. Preferably, the Bio-based liquid rubber is Bio-IBR 6600 of New polymeric materials Co., ltd. Preferably, the rubber composition raw material further comprises 1-5phr of tackifying resin, and preferably, resorcinol formaldehyde resin is used as the tackifying resin. Preferably, the rubber composition stock further comprises 8-12phr of an environmental friendly oil. Preferably, the accelerator is selected from the group consisting of N-cyclohexyl-2-benzothiazolyl sulfenamide, N-tert-butyl-2-benzothiazolyl sulfenamide, N-dicyclohexyl-2-benzothiazolyl sulfenamide, N-oxydiethylene-2-benzothiazolyl sulfenamide, N, N-diisopropyll-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole, dibenzothiazyl disulfide, zinc 2-mercaptobenzothiazole, N-cyclohexyl-2-benzothiazole sulfenamide, derivatives of dibenzothiazyl disulfide, sodium salt of 2-mercaptobenzothiazole, tetramethylthiuram disulfide, tetramethylthiuram monosulfide, tetraethylthiuram disulfide, tetraisobutylthiuram disulfide, tetrabenzylthiuram disulfide, dipentylthiuram disulfide, bis (1, 5-pentylidene) thiuram tetrasulfide, bis (1, 5-pentylidene) thiuram disulfide, and bis-pentamethylene thiuram hexasulfide, bis (2-ethylhexyl) thiuram disulfide, bis-pentamethylene thiuram monosulfide, thiocarbamide, diethyl thiourea, dibutyl thiourea, trimethyl thiourea, di-o-tolylthiourea, diphenyl guanidine, di-o-tolylguanidine, triphenyl guanidine, o-tolylguanidine, diphenyl guanidine phthalate, zinc ethylphenyl dithiocarbamate, zinc butylphenyl dithiocarbamate, sodium dimethyl dithiocarbamate, zinc diethyl dithiocarbamate, zinc dibutyl dithiocarbamate, zinc, one or more of zinc dipentyl dithiocarbamate, zinc dipropyl dithiocarbamate, zinc pentamethylene dithiocarbamate and piperidine coordination salt, zinc cetyl