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CN-121975201-A - Low-Pane effect tread rubber composition and preparation method thereof

CN121975201ACN 121975201 ACN121975201 ACN 121975201ACN-121975201-A

Abstract

The invention relates to the technical field of tire rubber manufacturing, and discloses a tread rubber composition with low Paen effect and a preparation method thereof. The rubber composition is prepared by mixing the following raw materials, by weight, 100 parts of raw rubber, namely 60-80 parts of solution polymerized styrene-butadiene rubber, 20-40 parts of butadiene rubber, 50-100 parts of white carbon black, 5.0-30 parts of maleic anhydride modified liquid regenerated rubber and 1.0-2.0 parts of sulfur. The invention adopts maleic anhydride modified liquid regenerated rubber to replace silane coupling agent Si-69 in tread rubber material to control The payon effect, rolling resistance and wet grip performance of the tread rubber composition are effectively improved, the emission of volatile organic compounds is effectively reduced, and the environmental protection is promoted.

Inventors

  • CHEN LI
  • Ba Shihao
  • LU XIAOQI
  • 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 tread rubber composition with the low Pane effect is characterized by being prepared by mixing the following raw materials in parts by weight: 60-80 parts by weight of solution polymerized styrene-butadiene rubber, 20-40 Parts by weight of butadiene rubber, 50-100 Parts by weight of white carbon black, 8.0 To 20 parts by weight of maleic anhydride modified liquid reclaimed rubber, 1.0 To 2.0 parts by weight of sulfur; The maleic anhydride modified liquid regenerated rubber is obtained by grafting maleic anhydride with liquid regenerated rubber; The maleic anhydride modified liquid regenerated rubber and the solution polymerized styrene-butadiene rubber meet the solubility parameter difference 。
  2. 2. The low-payne-effect tread rubber composition as claimed in claim 1, wherein the rubber composition is prepared by mixing the following raw materials in 100 parts by weight of raw rubber: 65-75 parts by weight of solution polymerized styrene-butadiene rubber, 25-35 Parts of butadiene rubber, 70-90 Parts by weight of white carbon black, 8.0 To 20 parts by weight of maleic anhydride modified liquid reclaimed rubber, 1.0 To 2.0 parts by weight of sulfur, 1.0 To 5.0 parts by weight of accelerator, 1.0 To 4.0 parts by weight of zinc oxide, 1.0 To 3.0 parts by weight of stearic acid, 1.0 To 5.0 parts by weight of an anti-aging agent.
  3. 3. The low-payne tread rubber composition according to claim 1 or 2, wherein the molar ratio of the acid anhydride to the acid anhydride/hydroxyl groups of the surface hydroxyl groups of the white carbon black is 0.20 to 0.40.
  4. 4. The low-payne tread rubber composition as claimed in claim 1 or 2, wherein the difference in solubility parameter is preferably satisfied between the maleic anhydride-modified liquid reclaimed rubber and the solution polymerized styrene-butadiene rubber 。
  5. 5. The low-payne effect tread rubber composition according to claim 1 or 2, wherein the maleic anhydride-modified liquid reclaimed rubber has an anhydride content of 1.0 to 2.5 wt.%, an iodine value of 15 to 25g i 2 /100 g and a number average molecular weight of 4000 to 6000g/mol.
  6. 6. The low-Pahn effect tread rubber composition according to claim 1 or 2, wherein the rubber composition stock further comprises 18 to 25phr of a tackifying resin, preferably an alpha-methylstyrene monomer resin; and/or, the rubber composition raw material further comprises 5-15phr of environment-friendly oil.
  7. 7. A low-payne effect tread rubber composition according to 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 2-mercaptobenzothiazole, N-cyclohexyl-2-benzothiazole sulfenamide, N-tert-butyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, derivatives of dibenzothiazyl disulfide, sodium 2-mercaptobenzothiazole, 2-benzothiazolyl disulfide, tetramethylthiuram monosulfide, tetraethylthiuram disulfide, thiuram disulfide Tetraisobutylthiuram disulfide, tetrabenzylthiuram disulfide, dipentylthiuram disulfide, bis (1, 5-pentylidene) thiuram tetrasulfide, dipentamethylenethiuram hexasulfide, tetra (2-ethylhexyl) thiuram disulfide, dipentamethylenethiuram monosulfide, thiocarbamide, diethylthiourea, dibutylthiourea, trimethylthiourea, di-o-tolylthiourea, diphenylguanidine, di-o-tolylguanidine, triphenylguanidine, o-tolylguanidine, diphenylguanidine phthalate, zinc ethylphenyl dithiocarbamate, zinc octadecyl isopropyl dithiocarbamic acid, zinc dibenzyl dithiocarbamic acid, sodium diethyl dithiocarbamic acid pentamethylene dithiocarbamic acid piperidine, dimethyl dithiocarbamic acid selenium zinc octadecyl isopropyl dithiocarbamic acid, zinc dibenzyl dithiocarbamic acid, sodium diethyl dithiocarbamic acid, piperidine pentamethylene dithiocarbamic acid, selenium dimethyl dithiocarbamic acid one or more of tellurium diethyldithiocarbamate, cadmium dipentyldithiocarbamate, acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde-ammonia reactant; preferably one or more of N-cyclohexyl-2-benzothiazole sulfenamide and diphenylguanidine.
  8. 8. A low payne effect tread rubber composition according to claim 1 or 2, characterized in that said anti-aging agent is selected from N-phenyl-N ' -isopropyl-p-phenylenediamine, N-1, 3-dimethylbutyl-N ' -phenyl-p-phenylenediamine, 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, β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl-p-phenylenediamine, tris [2, 4-di-tert-butylphenyl ] phosphite, 2-mercaptobenzimidazole zinc salt, 2, 4-trimethyl-1, 2-dihydroquinoline polymer, 2- (2-hydroxyphenyl) benzimidazole, 2, 4-trimethyl-1, 2-dihydroquinoline polymer, N-diphenyl-N ' -sec-butyl-p-phenylenediamine, N ' -diphenyl guanidine, or one or more thereof, preferably N-sec-butyl-p-phenylenediamine.
  9. 9. The low-Pahn effect tread rubber composition according to claim 1, wherein the method for preparing the maleic anhydride modified liquid reclaimed rubber comprises the steps of adding the reclaimed liquid rubber, maleic anhydride and dicumyl peroxide into a double-screw extruder, reacting and extruding under vacuum, granulating and drying to obtain a particle sample.
  10. 10. A process for the preparation of a rubber composition according to any one of claims 1 to 8, 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 white carbon black, maleic anhydride modified liquid regenerated rubber, auxiliary materials except a vulcanizing agent and an 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

Low-Pane effect tread rubber composition and preparation method thereof Technical Field The invention relates to the technical field of tire rubber manufacturing, in particular to a tread rubber composition with low Pane effect and a preparation method thereof. Background In the field of tire manufacturing, the rolling resistance, the payne effect and the environmental protection performance of tread rubber are core indexes for measuring the comprehensive quality of tires. In the prior art, in order to reduce rolling resistance, a high-dispersion white carbon black and silane coupling agent (such as Si-69) compound system is commonly adopted in the industry. However, si-69 is prone to hydrolysis reaction during mixing, and releases a large amount of ethanol and Volatile Organic Compounds (VOCs), which not only increases the investment and operation cost of tail gas treatment equipment in factories, but also causes early scorching risks of sizing materials in the later mixing stage, and affects production stability. More importantly, the residual free ethanol after the silane hydrolysis can slowly migrate and separate out in the use process of the tire, destroy the bonding interface between the white carbon black and rubber molecules, and cause secondary agglomeration of the white carbon black, thereby leading to the Paeonia effect) Significantly elevated. The dynamic mechanical property of the rubber material is deteriorated due to the aggravation of the Paen effect, the rebound of rolling resistance is increased, the wear resistance and fatigue resistance of the tread rubber are reduced, and the service life of the tire is shortened. At the same time, annual output of global waste tires continues to increase, and recycling thereof becomes an important subject in the field of environmental protection. In the prior art, the thermal cracking of the waste tires can prepare liquid regenerated rubber, and the regenerated rubber molecular chain contains a large number of reactive double bonds and has chemical modification potential, but is only used as a low-cost filler at present, and the reactivity of the double bonds is not effectively developed into a coupling function, so that the additional value of the waste tire resources is low. The Chinese patent No. 202510682183.8 discloses a tread rubber composition containing modified liquid rubber, wherein the modified liquid rubber is added into the rubber system, the modified liquid rubber is prepared by melt grafting unsaturated regenerated liquid rubber prepared from waste tires and maleic anhydride in the presence of a free radical initiator, the addition of the modified liquid rubber improves the interface binding force of white carbon black and the rubber composition, weakens Payne effect, enhances the wear resistance of the rubber composition, does not influence the rolling resistance and the wet skid resistance of the rubber composition, and meets the low energy consumption requirement of new energy automobiles. In this invention, however, si-69 is still used. Therefore, development of a novel coupling material which takes waste tire self resources as raw materials, can completely replace Si-69 and can form a stable combination structure with white carbon black is needed to be developed, and the synergistic promotion of low VOC emission, low Paen effect and high dynamic mechanical property is realized, so that the development of the tire industry to the green and high performance is promoted. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a low-Paen effect tread rubber composition and a preparation method thereof, which effectively improve the Paen effect, rolling resistance and wet grip performance of the tread rubber composition and effectively reduce the emission of volatile organic compounds. In order to achieve the above purpose, the present invention adopts the following technical scheme: The tread rubber composition with the low Pane effect is prepared by mixing the following raw materials in 100 parts by weight of raw rubber: 60-80 parts by weight of solution polymerized styrene-butadiene rubber, 20-40 Parts by weight of butadiene rubber, 50-100 Parts by weight of white carbon black, 8.0 To 20 parts by weight of maleic anhydride modified liquid reclaimed rubber, 1.0 To 2.0 parts by weight of sulfur; The maleic anhydride modified liquid regenerated rubber is obtained by grafting maleic anhydride with liquid regenerated rubber; The maleic anhydride modified liquid regenerated rubber and the solution polymerized styrene-butadiene rubber meet the solubility parameter difference 。 Preferably, the rubber composition is prepared by mixing the raw materials comprising the following components in parts by weight (100 parts by weight): 65-75 parts by weight of solution polymerized styrene-butadiene rubber, 25-35 Parts of butadiene rubber, 70-90 Parts by weight of white carbon black, 8.0 To 20 parts by weight of maleic a