CN104311932A - Rubber composite for treads of semi-steel radial tyres - Google Patents
Rubber composite for treads of semi-steel radial tyres Download PDFInfo
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- CN104311932A CN104311932A CN201410665049.9A CN201410665049A CN104311932A CN 104311932 A CN104311932 A CN 104311932A CN 201410665049 A CN201410665049 A CN 201410665049A CN 104311932 A CN104311932 A CN 104311932A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 60
- 239000005060 rubber Substances 0.000 title claims abstract description 60
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 17
- 239000010959 steel Substances 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title abstract 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000006229 carbon black Substances 0.000 claims abstract description 25
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- 229920005557 bromobutyl Polymers 0.000 claims abstract description 21
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005864 Sulphur Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 5
- 238000010057 rubber processing Methods 0.000 claims abstract description 5
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 4
- 239000002270 dispersing agent Substances 0.000 claims abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 14
- 229960001866 silicon dioxide Drugs 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000002174 Styrene-butadiene Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 12
- 229920006978 SSBR Polymers 0.000 description 16
- 239000003921 oil Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000004513 sizing Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000284 extract Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 229920002266 Pluriol® Polymers 0.000 description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 241001441571 Hiodontidae Species 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 4
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 2
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- WJAKXPUSJAKPHH-UHFFFAOYSA-N buta-1,3-diene;ethene;styrene Chemical compound C=C.C=CC=C.C=CC1=CC=CC=C1 WJAKXPUSJAKPHH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- CMKDPNYJYNDKQH-UHFFFAOYSA-N n,n-dicyclohexyl-1,3-benzothiazole-2-sulfonamide Chemical compound N=1C2=CC=CC=C2SC=1S(=O)(=O)N(C1CCCCC1)C1CCCCC1 CMKDPNYJYNDKQH-UHFFFAOYSA-N 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of rubber, in particular to a rubber composite for treads of semi-steel radial tyres. On the standard of 100 parts of a rubber component by weight, the rubber composite further comprises, by weight, 60-85 parts of silicon dioxide, 5-25 parts of carbon black, 15-45 parts of rubber processing softeners, 5-10 parts of silane coupling agents, 5-15 parts of white carbon black dispersing agents, 3-10 parts of anti-aging agents, 1-5 parts of sulphur, and 1.5-6.5 parts of accelerants, wherein the rubber component comprises, by weight, 50-85 parts of modified solution-polymerized styrene-butadiene rubber, 5-25 parts of brominated butyl rubber and 15-35 parts of emulsion-polymerized styrene-butadiene rubber. The rubber composite is filled with an appropriate quantity of high-dispersion white carbon black, meanwhile, a small quantity of the brominated butyl rubber is used in the rubber composite so as to improve wet skid resistance of the rubber composite, wet skid resistance of the semi-steel radial tyres made of the rubber composite is improved remarkably, and therefore high-speed driving safety performance is improved.
Description
Technical field
The present invention relates to a kind of field of rubber technology, specifically a kind of very-high performance semi-steel radial tire tread rubber composition.
Background technology
Along with the fast development of automotive industry and motorway, people require more and more higher to the safety performance of tire, tire is when highway driving, particularly export to some countries of Europe to motorway not speed limit, when tire occurs to bring threat to navigating mate life when breakking away or manipulate unstable in the process of moving, the Serious Accident of car crash especially may be there is under the condition of running at high speed.For this reason, each giant tyre company all actively drops into exploitation superelevation earth-grasping force and handling exsertile high-performance semi-steel radial tire.
The crown of tire is the position of mere contact track, and the anti-slippery handling therefore improving tread rubber is most important to the safety performance improving tire.Improve the wet and slippery handling of tread glue formula, what generally adopt in the industry is the tread mix formula of modified styrene-butadiene's rubber in conjunction with high filler loading capacity white carbon black.
Have in the industry solution styrene-divinyl rubber is applied to tire tread technical report in conjunction with the white carbon black of high filler loading capacity, but the processing performance that the white carbon black of high filler loading capacity causes declines and the safety problem such as accumulation of electrostatic in tire running process.
Summary of the invention
Object of the present invention is exactly to overcome above-mentioned existing technical deficiency, a kind of very-high performance semi-steel radial tire tread rubber composition is provided, appropriate high-dispersion white carbon black is filled in this formula, use a small amount of brominated butyl rubber to improve sizing material wet-sliding resistant performance in rubber combination simultaneously, the wet-sliding resistant performance of prepared semi-steel radial tire promotes obviously, thus reaches the lifting of safety performance of running at high speed.
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of semi-steel radial tire tread rubber composition, with the rubber components of 100 weight parts for benchmark, also comprises
The silicon-dioxide of 60-85 weight part,
The carbon black of 5-25 weight part,
The Rubber processing tenderizer of 15-45 weight part,
The silane coupling agent of 5 ~ 10 weight parts,
The White carbon black dispersant of 5 ~ 15 weight parts,
The anti-aging agent of 3 ~ 10 weight parts,
The sulphur of 1 ~ 5 weight part,
The promotor of 1.5 ~ 6.5 weight parts;
Wherein said rubber components comprises the part by weight modified solution styrene-divinyl rubber of 50-85,5-25 weight part brominated butyl rubber and 15-35 weight part Emulsion polymerized styrene-divinyl rubber.
Described solution styrene-divinyl rubber has the styrene butadiene rubbers of the combined styrene content of 20 ~ 40 quality % and the contents of ethylene of 30 ~ 65 quality %; SBR of emulsion polymerization requires the combined styrene content with 40 quality %; The bromine content of brominated butyl rubber requires about 2.0%.
The invention has the beneficial effects as follows, the cinnamic styrene-butadiene rubber(SBR) of a certain amount of high-content is used and in conjunction with a small amount of brominated butyl rubber in this formula, formula wet-sliding resistant performance will be made to promote obviously, the prepared stopping distance of semi-steel radial high-performance tire under wet and slippery condition is shorter, effectively raises the driving safety performance of semi-steel radial high-performance tire.Fill appropriate high-dispersion white carbon black in this formula, the processing performance of prepared semi-steel radial tire is good, avoids the technological problems that traditional high filling white carbon black brings.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
The rubber components that the present invention relates to comprises modified solution polymerizing styrene-divinyl rubber, Emulsion polymerized styrene-divinyl rubber and brominated butyl rubber.
Modified solution polymerizing styrene-divinyl rubber described in invention has the combined styrene content of 20 ~ 40 quality %, the contents of ethylene styrene butadiene rubbers simultaneously containing 30 ~ 65 quality %; The both-end base of modified solution polymerized sbr must carry out end coupling technology process, and such Butadiene-Styrene Rubber is just like the SSBR2438-HM of German Lang Sheng company limited; The HP-755B of Japan JSR synthetic rubber company, the SSBR-2466 etc. of Tai Xiang Synesis Company.
Solution styrene in invention-divinyl rubber SSBR, for ensureing certain processing characteristics, SSBR that can be preferably oil-filled; Non-oil-filled SSBR also can use, and suitably should adjust the usage quantity of corresponding Rubber processing tenderizer during use.
The extending oil type of oil-filled SSBR is the aromatic hydrocarbon oil after TDAE(Treated Distillate Aromatic Extract process) or RAE oil (Residual Aromatic Extracts residual aromatics extract); The loading level of oil product is 35-55 weight part.
The virgin rubber Mooney viscosity value of the solution styrene in the present invention-divinyl rubber SSBR is 45-85, for ensureing certain processing characteristics, the SSBR of low Mooney point can be selected, but for ensureing the abrasion resistance of tire, the SSBR of high Mooney should be selected as far as possible, therefore the selection of Mooney point is depending on processing conditions, is recommended as about 70.
The consumption of the solution styrene in the present invention-divinyl rubber SSBR is preferably not less than 50 weight parts, is more preferably not less than 60 weight parts, when the consumption of SSBR is lower than 50 weight part, not easily obtains enough wet-sliding resistant performances.In addition, the consumption of SSBR, preferably no more than 85 weight parts, is more preferably no more than 75 weight parts, when the consumption of SSBR is more than 85 weight part, brominated butyl rubber and unmodified styrene butadiene rubbers consumption will be caused to reduce, and this will be unfavorable for the improvement of wetland handling.
The virgin rubber second-order transition temperature of the solution styrene in the present invention-divinyl rubber SSBR is not higher than subzero 10 degree, more preferably not higher than subzero 15 degree, for ensureing the low temperature use properties of tire, the SSBR of slightly lower glass transition temperatures can be selected, consider that the styrene content of the wet and slippery performance requriements SSBR improving tire wants high relatively on the other hand, and styrene content directly affects the second-order transition temperature of sizing material, about therefore second-order transition temperature the present invention of Butadiene-Styrene Rubber is recommended as minus 20 degrees.
In rubber components except solution styrene-divinyl rubber SSBR, the second sizing material is Emulsion polymerized styrene-divinyl rubber ESBR, the styrene content of the present invention to emulsion polymerized styrene butadiene rubber has clear stipulaties, for improving wetland handling of the present invention, styrene content in butadiene-styrene rubber is required to be 40 quality %, higher technique is required to processing characteristics, the SBR1739 etc. filling 37.5 weight part TDAE oil can be selected.
In invention, the consumption of ESBR is preferably not less than 15 weight parts, is more preferably not less than 20 weight parts, when the consumption of ESBR rubber is lower than 15 weight part, not easily obtains enough rubber strengths and modulus.In addition, the consumption of ESBR rubber, preferably no more than 35 weight parts, is more preferably no more than 30 weight parts, when the consumption of ESBR rubber is more than 35 weight part, will the rolling resistance of tread mix be caused to increase, and this is by the fuel oil grade of impact outlet tire.
The third sizing material related in the present invention is brominated butyl rubber, the use of brominated butyl rubber is one of feature of the present invention, because brominated butyl rubber is polarity saturated rubber, the consistency of itself and conventional rubber is poor, molecular backbone chain close to saturated, side chain is intensive, therefore the air protection layer as tire is used in comparatively common in the industry, and related invention is also more.The molecular chain kindliness of isoprene-isobutylene rubber is poor, causes its delayed height, and the present invention utilizes its this feature to improve wet and slippery handling in the tread with it.
In invention, the consumption of brominated butyl rubber is preferably not less than 5 weight parts, is more preferably not less than 10 weight parts, when the consumption of brominated butyl rubber is lower than 5 weight part, not easily obtains enough wet-sliding resistant performances.In addition, the consumption of brominated butyl rubber, preferably no more than 25 weight parts, is more preferably no more than 20 weight parts, when the consumption of brominated butyl rubber is more than 25 weight part, the tensile strength and modulus that cause tread mix are reduced, this is by unfavorable to the abrasion resistance of tire.
The virgin rubber Mooney viscosity value of the brominated butyl rubber in the present invention is 40-55, and the selection of Mooney point is depending on processing conditions, and the present invention is recommended as about 45; In brominated butyl rubber, content of halogen the present invention is recommended as 1.7-2.3 quality %, and recommended products is the brominated butyl rubber 2244 of EXXON company.
In view of the carinogenicity of European Union environmental protection laws and regulations requirement and high viscosity aromatic hydrocarbon oil, the kind of the present invention to Rubber Softener explicitly calls for, the extending oil type of recommendation has the aromatic hydrocarbon oil after the German Chinese holy company's T DAE(Treated Distillate Aromatic Extract process), the RAE oil (Residual Aromatic Extracts residual aromatics extract) of company of Total France; Rubber Softener recommends consumption to be 15-45 weight part.
To the carbon black related in formula, the present invention allows to use hard(carbon)black general in tire industry in right amount, is preferably less than 30 weight parts, is more preferably and is less than 25 weight parts.
The silicon-dioxide related in the present invention, it can be any reinforcing silica that those skilled in the art know, particularly BET specific surface area and CTAB specific surface area are all less than 400 m2/g precipitated silica, preferably BET specific surface area and the highly dispersible precipitated silica of CTAB specific surface area equal 60-350 m2/g.
When the present invention is for the production of high-performance semi-steel radial tire, preferred BET specific surface area 100-250 m2/g, more preferably the highly dispersible precipitated silica of BET specific surface area 120-230 m2/g, if use common precipitated silica will cause its dispersed decline and processing performance instability.
The dispersible precipitated silica of the height related in the present invention, can purchased from the Aerosil 200 1165MP of the Aerosil 200 Ultrasil 7000GR of Degussa, French Rhodia1 company, domestic HCSIL-822MP and the HCSIL-833MP Aerosil 200 having Wuxi Heng Chenggui industry company limited.
The SiO2 content (butt) that the height related in the present invention dispersibles precipitated silica must be greater than 90%; The moisture content of 105 degree is 5-10%, is preferably 4-8%; PH is 6-8.
When the present invention is for the production of high-performance semi-steel radial tire, highly dispersible precipitated silica consumption must be greater than 60 weight parts, is preferably greater than 65 weight parts, the wet and slippery performance do not provided when white carbon black is less than 60 weight part; The research on maximum utilized quantity of high-dispersion white carbon black is recommended as and is less than 85 weight parts, is more preferably and is less than 80 weight parts, and too high white carbon black loading level is unfavorable to processing performance, is also unfavorable for the transmission of electrostatic in travelling simultaneously; Moderate dioxide-containing silica is one of feature of the present invention, and this will ensure the wetland earth-catching property that sizing compound formula has had, but turn avoid the disadvantageous effect of high filling white carbon black to processing characteristics simultaneously.
Use silicon-dioxide as in the formula of filler, coupler must be used, it can carry out connecting or bonding between macromolecular chain and silica sphere, carries out chemistry simultaneously and infiltrates, thus play the dispersion in rubber matrix promoting mineral filler to inorganic filler surface.
As many sulfurations silane coupling agent conventional in silica formulations, with triethoxysilicane polysulfide (being abbreviated as TESPT) for general types in the industry, wherein purchased from the Si75(triethoxysilicane based bisulfide of Degussa company) and the silica-based tetrasulfide of Si69(triethoxy) range of application is the widest.
Preferable amount according to coupler TESPT of the present invention is 5-10 weight part, and being more preferably usage quantity is 6-9 weight part, but the usage quantity of TESPT generally should be little as much as possible; If the composition of TESPT comprises a certain amount of inertia dispersion agent, the number that it uses suitably should be adjusted.
For improving the dispersing property of white carbon black in sizing material, the present invention advises using a kind of activation dispersion agent effectively to alleviate this problem, facilitates the dispersion of silicon-dioxide in rubber matrix.Activation dispersion agent is the PLURIOL E 4000 purchased from BASF Corp. of Germany.
Making PLURIOL E 4000 in the sizing material of filler using white carbon black, as when activating dispersion agent, the impact of white carbon black on sulfuration can be reduced or eliminated, make various auxiliary agent be uniformly dispersed and extend time of scorch, improving the physical and mechanical properties of rubber item.
The present invention advises that the preferred addition of activation dispersion agent is: 10-20 weight part white carbon black adds the PLURIOL E 4000 of 1 weight part; The scheme of being more preferably is the PLURIOL E 4000 that 12-18 weight part white carbon black adds 1 weight part.
In addition, should notice that the PLURIOL E 4000 used in the present invention must measure according to a certain percentage in rubber compounding process and add use with silicon-dioxide simultaneously.
Sulphur powder is not specified especially, can use for the sulphur powder in tire industry.
To the usage quantity of sulphur powder, the system based on 100 weight part synthetical glues, the usage quantity of sulphur powder is no more than 5.0 weight parts, preferably no more than 4.5 weight parts, when powder is more than 5.0 weight part, easily causes the material sulfuring up using this formula; Usage quantity is not less than 1.5 weight parts, is preferably not less than 2.0 weight parts, and when powder is lower than 1.5 weight part, it is abundant not that state of vulcanization is carried out, and will have a strong impact on physics and the dynamic property of sizing material.
The alternative chemical classes of vulcanization accelerator is more, wherein uses sulfenamide type accelerators can give the good process safety performance of sizing material and vulcanization rate.
The sulfenamide type accelerators used in the present invention has the N-tertiary butyl-2 benzothiazole sulphenamide (accelerator NS), N-oxygen diethylene-2-benzothiazole sulfonamide (accelerant NOBS), N, N-bis-cyclohexyl benzothiazole sulfonamide (accelerator DZ), N, N '-dicyclohexyl-2-[4-morpholinodithio sulphenamide (accelerant CZ), consider the friendly of environment and the requirement of vulcanization rate, preferred accelerators NS and accelerant CZ.
In invention, based on 100 weight part synthetical glues, the amount of the sulfenamide type accelerators that system uses is no more than 3.5 weight parts, and preferably no more than 3.0 weight parts, when powder is more than 3.5 weight part, the safety performance easily causing sizing material to process the initial stage reduces; Because the dispersible precipitated silica consumption of camber of the present invention is at 80 weight parts, the consumption of promotor is slightly higher than the consumption of ordinary carbon black formula system, minimum amount is not less than 2.0 weight parts, preferably be not less than 2.5 weight parts, when accelerator level is lower than 2.0 weight part, vulcanization rate will reduce, and affect the curing efficiency of finished tire.
In addition, except the sulfenamide type accelerators used is for except primary accelerator in the present invention, generally also need and use a certain amount of secondary accelerator, type has diphenyl disulfide a pair of horses going side by side thiazole (altax), diphenylguanidine (vulkacit D PG), consider the requirement to vulcanization rate, preferred accelerators DPG.
In addition, all the other chemical substances used in the present invention are the general in the industry rubber small powder of tire.
Table one is in conjunction with example, the present invention will be described, but the present invention is not limited to these examples.
Composition according to table one coordinates table, once-through method is carried out mixing in internal rubber mixer, first other material except sulphur, promotor and scorch retarder is carried out kneading mixing 12 minutes at 155 DEG C, by kneaded mixture after opening rubber mixing machine cooling, add whole sulphur, promotor and scorch retarder and mediate 6 minutes again, obtain unvulcanized rubber combination.
Table two is corresponding rubber stock physicals table.
Table one: invention formula coordinates table (unit: weight part)
| Composition no | 1 | 2 | 3 | 4 | 5 |
| SSBR | 65 | 65 | 60 | 65 | 55 |
| ESBR | 35 | 30 | 25 | 25 | 25 |
| BIIR | 0 | 5 | 15 | 10 | 20 |
| Carbon black | 20 | 25 | 25 | 25 | 25 |
| Silicon-dioxide | 70 | 65 | 65 | 65 | 65 |
| Rubber processing tenderizer | 35 | 38 | 38 | 38 | 38 |
| Activation dispersion agent | 5 | 5 | 5 | 5 | 5 |
| Silane coupling agent | 7 | 6.5 | 6.5 | 6.5 | 6.5 |
| Zinc oxide | 5 | 5 | 5 | 5 | 5 |
| Stearic acid | 3 | 3 | 3 | 3 | 3 |
| Resol | 3 | 3 | 3 | 3 | 3 |
| Antioxidant 4020 | 5 | 5 | 5 | 5 | 5 |
| Anti-aging agent RD | 2 | 2 | 2 | 2 | 2 |
| Protection wax | 2 | 2 | 2 | 2 | 2 |
| Sulphur | 2.5 | 2.3 | 2.0 | 2.2 | 1.9 |
| Promotor | 4.8 | 4.5 | 4.5 | 4.5 | 4.5 |
| Scorch retarder | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
Table two: formula physicals table
| 150 DEG C of sulfuration * 30min | 1 | 2 | 3 | 4 | 5 |
| 100% stress at definite elongation/Mpa | 2.72 | 3.05 | 2.57 | 2.44 | 3.23 |
| 300% stress at definite elongation/Mpa | 11.12 | 12.15 | 11.83 | 11.34 | 12.75 |
| Tensile strength/Mpa | 18.30 | 18.75 | 16.48 | 17.22 | 14.89 |
| Tensile yield/% | 469 | 453 | 440 | 485 | 408 |
| Shao Er A type hardness tester | 69 | 67 | 69 | 70 | 68 |
| DIN wear index | 135 | 123 | 120 | 131 | 113 |
| Rebound value/% | 35 | 33 | 31 | 33 | 30 |
| Tension set/% | 20 | 22 | 21 | 22 | 21 |
| The hysteretic properties of 0 DEG C | 0.702 | 0.721 | 0.745 | 0.813 | 0.747 |
| The hysteretic properties of 60 DEG C | 0.195 | 0.187 | 0.185 | 0.179 | 0.193 |
| Aging resistance 100 DEG C of * 24h | ? | ? | ? | ? | ? |
| 100% stress at definite elongation/Mpa | 3.25 | 3.44 | 2.92 | 3.09 | 3.87 |
| 300% stress at definite elongation/Mpa | 14.18 | 14.65 | 14.13 | 13.98 | 13.56 |
| Tensile strength/Mpa | 15.58 | 16.19 | 15.83 | 14.96 | 14.04 |
| Tensile yield/% | 348 | 336 | 359 | 320 | 323 |
| Shao Er A type hardness tester | 73 | 72 | 74 | 75 | 74 |
Claims (3)
1. a semi-steel radial tire tread rubber composition, with the rubber components of 100 weight parts for benchmark, also comprises
The silicon-dioxide of 60-85 weight part,
The carbon black of 5-25 weight part,
The Rubber processing tenderizer of 15-45 weight part,
The silane coupling agent of 5 ~ 10 weight parts,
The White carbon black dispersant of 5 ~ 15 weight parts,
The anti-aging agent of 3 ~ 10 weight parts,
The sulphur of 1 ~ 5 weight part,
The promotor of 1.5 ~ 6.5 weight parts;
Wherein said rubber components comprises the part by weight modified solution styrene-divinyl rubber of 50-85,5-25 weight part brominated butyl rubber and 15-35 weight part Emulsion polymerized styrene-divinyl rubber.
2. semi-steel radial tire tread rubber composition according to claim 1, is characterized in that described solution styrene-divinyl rubber has the styrene butadiene rubbers of the combined styrene content of 20 ~ 40 quality % and the contents of ethylene of 30 ~ 65 quality %; SBR of emulsion polymerization requires the combined styrene content with 40 quality %; The bromine content of brominated butyl rubber requires about 2.0%.
3. a semi-steel radial tire, is characterized in that comprising the tyre surface prepared by the rubber combination described in claim 1 to 2 any one claim.
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| CN201410665049.9A CN104311932A (en) | 2014-11-20 | 2014-11-20 | Rubber composite for treads of semi-steel radial tyres |
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| CN201410665049.9A CN104311932A (en) | 2014-11-20 | 2014-11-20 | Rubber composite for treads of semi-steel radial tyres |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672568A (en) * | 2015-01-29 | 2015-06-03 | 柳州市中配橡塑配件制造有限公司 | Novel antiskid high-elasticity automobile tire rubber |
| CN105400022A (en) * | 2015-12-22 | 2016-03-16 | 三角轮胎股份有限公司 | Semi-steel radial ply tire tread rubber composition |
| CN105801942A (en) * | 2016-04-21 | 2016-07-27 | 江苏华安橡胶科技有限公司 | Formula of tread rubber of low-rolling-resistance semi-steel radial tire |
| CN107619509A (en) * | 2016-07-14 | 2018-01-23 | 四川轮胎橡胶（集团）股份有限公司 | It is exclusively used in the tread mix of half steel ice and snow road special tyre |
| CN112126138A (en) * | 2020-08-07 | 2020-12-25 | 山东玲珑轮胎股份有限公司 | Antibacterial rubber composition and tire |
| CN114031828A (en) * | 2021-12-21 | 2022-02-11 | 四川远星橡胶有限责任公司 | Low-antioxidant tread rubber and preparation method thereof |
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| CN1365372A (en) * | 1999-07-29 | 2002-08-21 | 拜尔公司 | Rubber composition |
| CN102634090A (en) * | 2012-05-02 | 2012-08-15 | 三角轮胎股份有限公司 | Tread rubber composition of fuel-efficient type semi-steel radial tire |
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| CN1365372A (en) * | 1999-07-29 | 2002-08-21 | 拜尔公司 | Rubber composition |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672568A (en) * | 2015-01-29 | 2015-06-03 | 柳州市中配橡塑配件制造有限公司 | Novel antiskid high-elasticity automobile tire rubber |
| CN105400022A (en) * | 2015-12-22 | 2016-03-16 | 三角轮胎股份有限公司 | Semi-steel radial ply tire tread rubber composition |
| CN105801942A (en) * | 2016-04-21 | 2016-07-27 | 江苏华安橡胶科技有限公司 | Formula of tread rubber of low-rolling-resistance semi-steel radial tire |
| CN107619509A (en) * | 2016-07-14 | 2018-01-23 | 四川轮胎橡胶（集团）股份有限公司 | It is exclusively used in the tread mix of half steel ice and snow road special tyre |
| CN112126138A (en) * | 2020-08-07 | 2020-12-25 | 山东玲珑轮胎股份有限公司 | Antibacterial rubber composition and tire |
| CN114031828A (en) * | 2021-12-21 | 2022-02-11 | 四川远星橡胶有限责任公司 | Low-antioxidant tread rubber and preparation method thereof |
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