CN-121975187-A - Silane coupling agent combination and application thereof, and rubber composition

CN121975187ACN 121975187 ACN121975187 ACN 121975187ACN-121975187-A

Abstract

The invention relates to the technical field of rubber manufacturing, and discloses a silane coupling agent combination, application thereof and a rubber composition. The silane coupling agent combination for rubber formula provided by the invention takes sulfur-containing silane as main silane and n-octyl hexaethoxy silane as auxiliary silane, and the n-octyl hexaethoxy silane cooperates with the sulfur-containing silane to better improve the dispersibility of white carbon black in rubber, and effectively improve the tensile strength, abrasion performance and hysteresis loss of the rubber composition. The rubber composition provided by the invention can be used for preparing rubber materials such as tire tread rubber, base rubber and the like.

Inventors

REN HUIMING
ZHANG LEI
HUANG DAYE
CHEN LI
LIU HUI
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. A silane coupling agent combination for a rubber composition is characterized by comprising a silane coupling agent I and a silane coupling agent II, wherein the silane coupling agent I is sulfur-containing silane, the silane coupling agent II is n-octyl hexaethoxy silane, the structural formula of the silane coupling agent is C 8 H 17 −Si(OC 2 H 5 ) 6 , the addition amount of the silane coupling agent I is 5-10% of the addition amount of white carbon black, and the addition amount of the silane coupling agent II is 0.5-5 parts by weight based on 100 parts by weight of raw rubber of the rubber composition.
2. The combination of claim 1, wherein the silane coupling agent I is selected from the group consisting of bis- [ gamma- (triethoxysilyl) propyl ] -tetrasulfide (TESPT) and bis- [ gamma- (triethoxysilyl) propyl ] -disulfide (TESPD).
3. The silane coupling agent combination for rubber composition according to claim 1, wherein the addition amount of the silane coupling agent I is 7-9% of the addition amount of white carbon black.
4. The silane coupling agent combination for rubber compositions according to claim 1, wherein the silane coupling agent II is added in an amount of 1 to 3 parts by weight.
5. Use of a silane coupling agent combination for rubber compositions as claimed in any one of claims 1 to 4 for the preparation of rubber compositions.
6. A rubber composition, characterized in that the rubber composition comprises the silane coupling agent combination for the rubber composition according to any one of claims 1 to 4, and the rubber composition is prepared by mixing the following raw materials in 100 parts by weight: 60-80 parts by weight of solution polymerized styrene-butadiene rubber, 20-40 Parts by weight of polybutadiene rubber, 70-90 Parts by weight of white carbon black, 3.5 To 9 parts by weight of silane coupling agent I, 0.5-5 Parts by weight of silane coupling agent II.
7. The rubber composition according to claim 6, wherein the white carbon black is a highly dispersed white carbon black having a specific surface area CTAB of 160m 2 /g or more, preferably 180-195m 2 /g.
8. The rubber composition according to claim 6, wherein the raw materials for mixing the rubber composition further comprise an activator, an anti-aging agent, a vulcanizing agent and a vulcanization accelerator, preferably the activator comprises 2-5 parts by weight of zinc oxide, 1-3 parts by weight of stearic acid, 1-4 parts by weight of the anti-aging agent, 1.0-3.0 parts by weight of the vulcanizing agent and 1.0-4.0 parts by weight of the vulcanization accelerator.
9. The rubber composition according to claim 8, wherein the antioxidant is one or more selected from the group consisting of amine antioxidants, phenolic antioxidants, heterocyclic antioxidants, and particularly selected from the group consisting of N-phenyl-N ' -isopropyl-p-phenylenediamine, N-phenyl-N ' -sec-butyl-p-phenylenediamine, N-1, 3-dimethylbutyl-N ' -phenyl-p-phenylenediamine, N-cyclohexyl-N ' -phenyl-p-phenylenediamine, a condensate of p-phenylenediamine with diphenylamine, a condensate of p-phenylenediamine with acetone, 4-aminodiphenylamine, N- (1-methylheptyl) -N ' -phenyl-p-phenylenediamine, N- (1-methylheptyl) -N ' - (4-chlorophenyl) -p-phenylenediamine, N- (1-methylheptyl) -N ' - (3-chlorophenyl) -p-phenylenediamine, 2, 6-di-tert-butyl-4-methylphenol, tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester, tris [2, 4-di-tert-butylphenyl ] phosphite, 2- (2-hydroxy-phenyl) -2-triazol-2-hydroxy-2-phenyl-triazol, mercapto-2-mercapto-benzoimidazole, mercapto-2-mercapto-benzoimidazole, and zinc salt thereof, one or more of 2- (2-hydroxyphenyl) benzimidazole, 2- (2-aminophenyl) benzimidazole, 2- (2-methoxyphenyl) benzimidazole, 2- (2-dodecyloxyphenyl) benzimidazole, 2- (2-benzyloxyphenyl) benzimidazole, 2- (2-phenoxyphenyl) benzimidazole; The vulcanizing agent is selected from sulfur powder, insoluble sulfur, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dimorphine disulfide, dipentamethylenethiuram tetrasulfide, 2-mercaptobenzothiazole disulfide, alkylphenol sulfide, tetrabenzylthiuram disulfide, tetramethylthiuram monosulfide, dibenzyl disulfide, di-t-butyl peroxide, benzoyl peroxide, t-butylbenzoyl peroxide, dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 1-bis (t-butylperoxy) cyclohexane one or more of 2, 4-dichlorobenzoyl peroxide, t-butyl perbenzoate, t-butyl hydroperoxide, di-t-butyl hydroperoxide, cumyl hydroperoxide, lauroyl peroxide, cyclohexanone peroxide, 1, 4-bis-t-butylperoxyisopropyl benzene, p-t-butylphenol formaldehyde resin, p-t-octylphenol formaldehyde resin, alkylphenol formaldehyde resin, phenol formaldehyde resin, brominated p-t-butylphenol formaldehyde resin, hexamethoxymethyl melamine resin, epoxy resin, novolac epoxy resin, o-cresol formaldehyde epoxy resin, bismaleimide resin, urea formaldehyde resin, furfural resin, cashew phenol resin, resorcinol formaldehyde resin; The vulcanization accelerator is selected from N-cyclohexyl-2-benzothiazolyl sulfenamide, N-tertiary butyl-2-benzothiazolyl sulfenamide, N-dicyclohexyl-2-benzothiazolyl sulfenamide, N-oxydiethylene-2-benzothiazolyl sulfenamide and 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-benzothiazole disulfide, tetramethylthiuram monosulfide, tetraethylthiuram disulfide, tetraisobutylthiuram disulfide, tetrabenzylthiuram disulfide dipentylthiuram disulfide, bis (1, 5-pentylidene) thiuram tetrasulfide, dipentylenethiuram hexasulfide, tetrakis (2-ethylhexyl) thiuram disulfide, dipentylenethiuram monosulfide, thiocarbamide, diethylthiourea, dibutylthiourea, trimethylthiourea, di-o-tolylthiourea, diphenylguanidine, di-o-tolylguanidine, triphenylguanidine, o-tolylguanidine, diphenylguanidine phthalate, zinc ethylphenyl dithiocarbamate, zinc butylphenyl dithiocarbamate, sodium dimethyl dithiocarbamate, zinc dimethyl dithiocarbamate, zinc diethyl dithiocarbamate, zinc dibutyl dithiocarbamate zinc dipentyldithiocarbamic acid, zinc dipropyldithiocarbamic acid coordination salt of zinc pentamethylene dithiocarbamic acid and piperidine, zinc cetyl isopropyl dithiocarbamic acid, zinc stearyl isopropyl dithiocarbamic acid, zinc dibenzyl dithiocarbamic acid sodium diethyldithiocarbamate, piperidine pentamethylene dithiocarbamate selenium dimethyldithiocarbamate, tellurium diethyldithiocarbamate cadmium dipentyldithiocarbamate, acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde-ammonia reactant.
10. The rubber composition according to claim 8, wherein the anti-aging agent is one or more selected from the group consisting of N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine, 2, 4-trimethyl-1, 2-dihydroquinoline polymer, poly (1, 2-dihydro-2, 4-trimethylquinoline), N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine; The vulcanizing agent is selected from insoluble sulfur; The vulcanization accelerator is selected from one or more of N-tertiary butyl-2-benzothiazole sulfenamide or N-cyclohexyl-2-benzothiazole sulfenamide, diphenyl guanidine accelerator, hexamethylenetetramine, 4' -dithiodimorpholine and biscaprolactam disulfide.

Description

Silane coupling agent combination and application thereof, and rubber composition Technical Field The invention relates to the technical field of rubber manufacturing, in particular to a silane coupling agent combination and application thereof, and a rubber composition. Background White carbon black has been widely used as a reinforcing filler in the manufacture of high performance rubber products, particularly green tires. However, the white carbon black has the problem of polar agglomeration in a rubber system, and the use of a silane coupling agent is important in order to improve the dispersibility of the white carbon black in rubber and improve the comprehensive performance of the composite material. The silane coupling agent combination can better play the role than a single silane coupling agent, and the comprehensive performance of the rubber composition is improved. For example, the Chinese patent invention No. CN2016611043643. X discloses an ultra-low rolling resistance and ultra-high wet grip performance tire tread rubber material, the tire tread rubber material uses two silane coupling agents, the addition amount of the silane coupling agent I is 8.0-15.0 parts, the addition amount of the silane coupling agent II is 2.0-8.0 parts, the silane coupling agent I is 3-mercaptopropyl ethoxy bis [ propoxypolyether ] silane, the silane coupling agent II is n-octyl triethoxy silane, the dispersibility of white carbon black in a rubber matrix is effectively improved, and the Payne effect of filler and the hysteresis loss of the rubber material are reduced. By using the tire tread formula with low rolling resistance and high wet grip performance, the rolling resistance of the tire can reach below 6.5 (A grade: RRC is less than or equal to 6.5), the wet grip performance can reach above 1.55 (A grade: G is more than or equal to 1.55), and meanwhile, various physical and mechanical properties of the rubber material, the high speed and the durability of the tire can meet the normal use requirements. However, the applicant found that n-Octyl Triethoxysilane (OTES) has a certain effect as a silane coupling agent II, but has limited improvement degree, so that n-octyl hexaethoxysilane is developed as a novel auxiliary silane, and the auxiliary silane is used together with sulfur-containing main silane, so that the comprehensive performance of the white carbon black filled rubber can be remarkably improved. Disclosure of Invention The invention provides a silane coupling agent combination, application thereof and a rubber composition aiming at the defects of the prior art. Sulfur-containing silanes such as TESPD (bis- [3- (triethoxysilyl) propyl ] disulfide) or TESPT (bis- [3- (triethoxysilyl) propyl ] tetrasulfide) as the main silane are effective in promoting the dispersion of white carbon black and enhancing the reinforcing effect of rubber by sulfur bonds. The n-octyl hexaethoxy silane is used as the auxiliary silane, and can cooperate with sulfur-containing silane to further optimize the dynamic performance, physical performance and wear resistance of the rubber product. In order to achieve the above purpose, the present invention adopts the following technical scheme: The silane coupling agent combination comprises a silane coupling agent I and a silane coupling agent II, wherein the silane coupling agent I is sulfur-containing silane, the silane coupling agent II is n-octyl hexaethoxy silane, the structural formula of the silane coupling agent is C 8H17−Si(OC2H5)6, the addition amount of the silane coupling agent I is 5-10% of the addition amount of white carbon black based on 100 parts by weight of raw rubber of the rubber composition, and the addition amount of the silane coupling agent II is 0.5-5 parts by weight. Preferably, the silane coupling agent I is selected from bis- [ gamma- (triethoxysilyl) propyl ] -tetrasulfide (TESPT) or bis- [ gamma- (triethoxysilyl) propyl ] -disulfide (TESPD). Preferably, the addition amount of the silane coupling agent I is 7-9% of the addition amount of the white carbon black. Preferably, the silane coupling agent II is added in an amount of 1 to 3 parts by weight. Further, the invention also provides application of the silane coupling agent combination for the rubber composition in preparation of the rubber composition, in particular to application of the rubber for tires. Further, the invention also provides a rubber composition, which comprises the silane coupling agent combination for the rubber composition, wherein the rubber composition is prepared by mixing the following raw materials in parts by weight (100 parts by weight) of raw rubber: 60-80 parts by weight of solution polymerized styrene-butadiene rubber, 20-40 Parts by weight of polybutadiene rubber, 70-90 Parts by weight of white carbon black, 3.5 To 9 parts by weight of silane coupling agent I, 0.5-5 Parts by weight of silane coupling agent II. The solution polymerized styrene-butadiene rubber (SSBR) is