CN115716940A - Rubber composition, vulcanized rubber, and preparation method and application thereof - Google Patents
Rubber composition, vulcanized rubber, and preparation method and application thereof Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 172
- 239000005060 rubber Substances 0.000 title claims abstract description 172
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 239000004636 vulcanized rubber Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 71
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000006229 carbon black Substances 0.000 claims abstract description 50
- 239000011159 matrix material Substances 0.000 claims abstract description 41
- 238000004073 vulcanization Methods 0.000 claims abstract description 37
- 239000003607 modifier Substances 0.000 claims abstract description 36
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 35
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 30
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 30
- 229920001194 natural rubber Polymers 0.000 claims abstract description 30
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 29
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 29
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 29
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 28
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical group CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000003213 activating effect Effects 0.000 claims abstract description 9
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 43
- 235000010215 titanium dioxide Nutrition 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- 239000012190 activator Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000004902 Softening Agent Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 239000010692 aromatic oil Substances 0.000 claims description 5
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 5
- 229960002447 thiram Drugs 0.000 claims description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 239000005662 Paraffin oil Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 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 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims 2
- 229910052623 talc Inorganic materials 0.000 claims 2
- 235000012222 talc Nutrition 0.000 claims 2
- 238000012545 processing Methods 0.000 abstract description 12
- 238000005452 bending Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 34
- 239000011787 zinc oxide Substances 0.000 description 17
- 235000021355 Stearic acid Nutrition 0.000 description 15
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 15
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 15
- 239000008117 stearic acid Substances 0.000 description 15
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 12
- 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 11
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical group C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 238000011056 performance test Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 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 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000005063 High cis polybutadiene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- HNWAHFPYJHAAJE-UHFFFAOYSA-N n-tert-butyl-1,3-benzothiazole-2-sulfonamide Chemical compound C1=CC=C2SC(S(=O)(=O)NC(C)(C)C)=NC2=C1 HNWAHFPYJHAAJE-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- 235000013878 L-cysteine Nutrition 0.000 description 1
- 206010039203 Road traffic accident Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical group [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of rubber materials, and discloses a rubber composition, vulcanized rubber and a preparation method of the vulcanized rubber, wherein the rubber composition contains a rubber matrix, a rubber modifier, white carbon black, titanium dioxide, superfine talcum powder, an activating agent, an anti-aging agent, a softener, an accelerator and a vulcanizing agent; the rubber modifier is L-cysteine, and the rubber matrix is a mixture of butadiene rubber and natural rubber. The rubber composition can obviously improve the processing safety and the vulcanization efficiency of the rubber composition on the premise of ensuring that vulcanized rubber has higher strength and dynamic bending flexibility.
Description
Technical Field
The invention relates to the field of rubber, in particular to a rubber composition, vulcanized rubber, and a preparation method and application thereof.
Background
In recent years, in order to adapt to the development trend of safety, environmental protection and green of automobile tires, white carbon black type non-petroleum resources are more and more emphasized in the field of tires due to the characteristics of reducing the rolling resistance of tires, saving the fuel consumption of automobiles and the like, but the white carbon black has stronger surface polarity, so that the white carbon black is extremely difficult to disperse in a rubber matrix, and the application of the white carbon black is limited to a certain extent.
The white carbon black is easy to adsorb zinc oxide on the surface due to high polarity, silicon complex zinc is easy to form in the vulcanization process, and the silicon complex zinc can not activate the accelerator. Therefore, the activation of zinc oxide is reduced, which causes a delay in vulcanization of the rubber, reducing the vulcanization efficiency of the rubber in production.
CN104530501A discloses a rubber composition for color tire sidewall discoloration resistance, wherein the rubber composition comprises, by weight, 100 parts of a base rubber, 30-40 parts of an active filler, 20-30 parts of a coloring filler, 5-7 parts of paraffin oil, 5-7 parts of an active agent, 2-3 parts of a silane coupling agent, 1-2 parts of a light-colored tackifying resin, 4-6 parts of a non-polluting anti-aging agent, 1-2 parts of a vulcanizing agent, 3-5 parts of an accelerator, 3-6 parts of an organic colorant and 1-2 parts of an ultraviolet absorber. The rubber prepared by the composition has bright color and better discoloration resistance, the dark color sidewall tire does not have discoloration phenomenon within one year in the environment of strong illumination and damp heat, the formula has higher tearing resistance, and the rubber shows excellent discoloration resistance when used in the severe environment of strong illumination and damp heat.
CN104311918A discloses a rubber composition for sidewall part of car run-flat tire, the raw materials comprise, by weight, 10-30 parts of natural rubber, 70-90 parts of high cis-polybutadiene composite rubber, 20-50 parts of carbon black, 20-40 parts of white carbon black, 1.0-3.0 parts of stearic acid, and 1.0-5.0 parts of zinc oxide; wherein the 1, 2-polybutadiene content of the high cis-polybutadiene composite rubber is 1-10%. The rubber prepared by the composition can improve the safety performance of vehicles in running and reduce or eliminate traffic accidents caused by tire puncture and explosion.
However, in the above prior art, silane coupling agent Si75 is added to the silica to improve the dispersibility of the silica, and Si75 is a sulfur-containing compound, which has a high requirement on process control during high-temperature mixing, and may cause scorching due to improper control, thereby affecting the overall performance of the composite material. Si75 and the like are easy to generate ethanol in the processing process, and the existence of the ethanol brings hidden danger to the safety of the tire.
CN109384964A discloses a rubber composition for a tire side wall, which comprises a rubber matrix, a rubber modifier, white carbon black, an activator, an anti-aging agent, a softener, an accelerator and a vulcanizing agent, wherein the rubber modifier is a maleic acid monomer, and the rubber matrix is a mixture of butadiene rubber and natural rubber. The rubber prepared by the composition has the advantages of high strength, low rolling resistance and good dynamic bending flexibility, and the vulcanized rubber formed by the composition can be used for the tire side wall of a tire. But the composition generally performs in terms of vulcanization efficiency.
The prior art can not completely meet the requirements that when the rubber formula containing white carbon black is used as sidewall rubber, the rubber formula simultaneously has good processing safety and high vulcanization efficiency on the premise of ensuring high strength and dynamic bending flexibility.
Disclosure of Invention
The invention aims to solve the problem that the strength, dynamic flexibility, processing safety and vulcanization efficiency of white carbon black-containing rubber for the tire side cannot be simultaneously met in the prior art, and provides a rubber composition which can remarkably improve the processing safety and vulcanization efficiency of the rubber composition on the premise of ensuring that vulcanized rubber has higher strength and dynamic flexibility.
In order to achieve the above object, the first aspect of the present invention provides a rubber composition, which is characterized by comprising a rubber matrix, a rubber modifier, white carbon black, titanium dioxide, ultrafine talc powder, an activator, an anti-aging agent, a softener, an accelerator and a vulcanizing agent; the rubber modifier is L-cysteine, and the rubber matrix is butadiene rubber and natural rubber.
A second aspect of the present invention provides a method of preparing a vulcanized rubber, the method comprising:
(1) Carrying out first mixing on a component A containing a rubber matrix and a rubber modifier to obtain a section of master batch;
(2) Performing second mixing on the first-stage masterbatch and a component B containing white carbon black, titanium white, superfine talcum powder, an activating agent, an anti-aging agent and a softening agent to obtain a second-stage masterbatch;
(3) Performing third mixing on the second-stage masterbatch and a component C containing an accelerator and a vulcanizing agent to obtain final rubber;
(4) Vulcanizing the final rubber;
the rubber modifier is L-cysteine, and the rubber matrix is butadiene rubber and natural rubber.
In a third aspect, the present invention provides a vulcanized rubber prepared by the above-described method.
The invention provides a fourth aspect of the invention provides a use of the vulcanized rubber in a tire sidewall.
The rubber composition and the vulcanized rubber provided by the invention, and the preparation method and the application thereof have the following beneficial effects:
the rubber composition provided by the invention can obviously improve the processing safety and the vulcanization efficiency of the rubber composition on the premise of keeping the vulcanized rubber to have higher strength and dynamic flexibility.
Further, in the method for preparing vulcanized rubber, the rubber compound is obtained by adopting the modes of step-by-step feeding and multi-section mixing and then vulcanized, so that the bridge function of the rubber modifier in the rubber matrix and the white carbon black can be better exerted, the dispersion of the white carbon black in the rubber matrix is facilitated, the processing safety and the vulcanization efficiency of the rubber compound are improved, and the obtained vulcanized rubber has better strength and dynamic bending flexibility.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The first aspect of the invention provides a rubber composition which is characterized by comprising a rubber matrix, a rubber modifier, white carbon black, titanium dioxide, superfine talcum powder, an activating agent, an anti-aging agent, a softening agent, an accelerator and a vulcanizing agent; the rubber modifier is L-cysteine, and the rubber matrix is butadiene rubber and natural rubber.
According to the invention, butadiene rubber and natural rubber are used as rubber matrixes, L-cysteine is used as a modifier, and white carbon black, titanium dioxide, superfine talcum powder, an activating agent, an anti-aging agent, a softening agent, an accelerating agent and a vulcanizing agent are used in a matching manner, so that the dispersibility of white carbon black and the like in the rubber matrixes can be improved, and further, the processing safety and the vulcanizing efficiency of the rubber composition can be obviously improved on the premise that vulcanized rubber prepared from the composition has higher strength and dynamic flexibility.
According to the present invention, the natural rubber is contained in the rubber matrix in an amount of 40 to 60 parts by weight and the butadiene rubber is contained in an amount of 40 to 60 parts by weight, relative to 100 parts by weight of the rubber matrix.
In the present invention, the natural rubber may be a natural rubber of a kind conventional in the art, for example, SMR-20.
According to the invention, the cis-1, 4-structure content of the butadiene rubber is 90 to 99% by weight.
According to the invention, relative to 100 parts by weight of the rubber matrix, the content of the rubber modifier is 8-15 parts by weight, the content of the white carbon black is 40-60 parts by weight, the content of the titanium dioxide is 10-30 parts by weight, the content of the superfine talcum powder is 10-20 parts by weight, the content of the activator is 5-10 parts by weight, the content of the anti-aging agent is 1-3 parts by weight, the content of the softener is 5-15 parts by weight, the content of the accelerator is 1-5 parts by weight, and the content of the vulcanizing agent is 0.5-4 parts by weight.
In the present invention, when the amount of each component in the rubber composition satisfies the above range, the composition can significantly improve the processing safety and vulcanization effect of the rubber composition while maintaining the high strength and dynamic bending flexibility of the vulcanized rubber prepared from the composition.
Further, relative to 100 parts by weight of the rubber matrix, the rubber modifier is 10-14 parts by weight, the white carbon black is 45-55 parts by weight, the titanium dioxide is 10-20 parts by weight, the superfine talcum powder is 10-20 parts by weight, the activator is 5-10 parts by weight, the anti-aging agent is 1.5-3 parts by weight, the softener is 10-13 parts by weight, the accelerator is 2-4 parts by weight, and the vulcanizing agent is 1-3 parts by weight.
According to the invention, the white carbon black is fumed white carbon black and/or precipitated white carbon black, preferably precipitated white carbon black; more preferably, the nitrogen adsorption specific surface area of the white carbon black is 10-200m 2 (iv) g. Specifically, the white carbon black is 165GR (Rodiya, france).
According to the invention, the titanium dioxide content in the titanium dioxide is greater than 98 wt%, preferably 99-100 wt%.
According to the invention, the activator is selected from at least one of a mixture of metal oxides and fatty acids, a fatty acid metal soap salt and zinc borate. The metal oxide is preferably zinc oxide and/or magnesium oxide; the fatty acid is preferably stearic acid; the fatty acid metal soap salt is zinc stearate.
In one embodiment of the present invention, the activating agents are zinc oxide and stearic acid, wherein the content of the zinc oxide is 3 to 5 parts by weight, and the content of the stearic acid is 2 to 5 parts by weight.
According to the present invention, the accelerator is selected from at least one of sulfenamide accelerators, thiazole accelerators, thiuram accelerators and guanidine accelerators.
In the present invention, preferably, the accelerator is selected from N-tert-butyl-2-benzothiazolesulfenamide (accelerator TBBS) and/or diphenylguanidine (accelerator D).
In one embodiment of the invention, the accelerator comprises N-tertiary butyl-2-benzothiazole sulfonamide (accelerator TBBS) and diphenyl guanidine (accelerator D), wherein the content of the N-tertiary butyl-2-benzothiazole sulfonamide is 1-2 parts by weight, and the content of the diphenyl guanidine is 2-3 parts by weight.
According to the invention, the anti-aging agent is at least one selected from amine anti-aging agents, quinoline anti-aging agents and benzimidazole anti-aging agents. For example, the antioxidant is N- (1, 3-dimethyl) butyl-N' -phenyl-p-phenylenediamine (antioxidant 4020).
According to the present invention, the softening agent is at least one selected from the group consisting of aromatic oil, paraffin oil, naphthenic oil, petroleum resin, and polyethylene glycol. The aromatic oil may be, for example, aromatic oil TDAEV500.
According to the invention, the vulcanizing agent is a sulfur donor. In the present invention, the sulfur donor refers to a substance capable of providing sulfur. Preferably, the sulphur donor is selected from at least one of insoluble sulphur, soluble sulphur and oil-extended sulphur. For example, the vulcanizing agent IS ordinary sulfur S, oil-extended insoluble sulfur IS, or the like.
In a second aspect, the present invention provides a process for preparing a vulcanized rubber, characterized in that the process comprises:
(1) Carrying out first mixing on a component A containing a rubber matrix and a rubber modifier to obtain a section of master batch;
(2) Performing second mixing on the first-stage masterbatch and a component B containing white carbon black, titanium white, superfine talcum powder, an activating agent, an anti-aging agent and a softening agent to obtain a second-stage masterbatch;
(3) Performing third mixing on the second-stage masterbatch and a component C containing an accelerator and a vulcanizing agent to obtain a final rubber compound;
(4) Vulcanizing the final rubber;
the rubber modifier is L-cysteine, and the rubber matrix is butadiene rubber and natural rubber.
The raw materials for preparing the vulcanized rubber in the second aspect of the invention adopt the composition described in the first aspect of the invention, and the component A, the component B and the component C which are involved in the second aspect together form the rubber composition described in the first aspect of the invention, so the types of the raw materials in the second aspect of the invention are all completely the same as the types described in the first aspect of the invention, the invention is not described in detail in the second aspect in order to avoid repetition, and the person skilled in the art should not be understood as limiting the invention.
According to the method for preparing the vulcanized rubber, the rubber compound is obtained by adopting a mode of step-by-step feeding and multi-section mixing and then vulcanized, so that the bridge action of the rubber modifier in the rubber matrix and the white carbon black can be better exerted, the dispersion of the white carbon black in the rubber matrix is facilitated, the processing safety and the vulcanization efficiency of the rubber compound are improved, and the obtained vulcanized rubber has better strength and dynamic flexibility.
Specifically, the component A containing the rubber matrix and the rubber modifier is subjected to first mixing to obtain a section of master batch, and then the subsequent process steps of the invention are carried out, so that the obtained vulcanized rubber has more excellent properties such as strength, dynamic bending flexibility and the like.
According to the present invention, the natural rubber is contained in the rubber matrix in an amount of 40 to 60 parts by weight and the butadiene rubber is contained in an amount of 40 to 60 parts by weight, relative to 100 parts by weight of the rubber matrix.
In the present invention, the natural rubber may be a natural rubber of a kind conventional in the art, for example, SMR-20.
According to the invention, the cis-1, 4-structure content of the butadiene rubber is 90 to 99 wt.%.
According to the invention, relative to 100 parts by weight of the rubber matrix, the content of the rubber modifier is 8-15 parts by weight, the content of the white carbon black is 40-60 parts by weight, the content of the titanium dioxide is 10-30 parts by weight, the content of the superfine talcum powder is 10-20 parts by weight, the content of the activator is 5-10 parts by weight, the content of the anti-aging agent is 1-3 parts by weight, the content of the softener is 5-15 parts by weight, the content of the accelerator is 1-5 parts by weight, and the content of the vulcanizing agent is 0.5-4 parts by weight.
In the present invention, the mixing may be carried out in mixing equipment conventional in the art, such as an open mill and/or an internal mixer, preferably an internal mixer.
According to the invention, the conditions of the first mixing include: the first mixing temperature is 80-120 ℃, and the first mixing time is 1-5min.
According to the invention, the conditions of the second mixing comprise: the second mixing temperature is 100-140 deg.C, and the second mixing time is 2-6min.
According to the present invention, the conditions of the third mixing include: the third mixing temperature is not more than 120 ℃, and the third mixing time is 4-6min.
According to the invention, the conditions of the vulcanization include: the vulcanization temperature is 150-170 ℃, the vulcanization pressure is 10-20MPa, and the vulcanization time is 20-50min.
In a preferred embodiment of the present invention, the first mixing conditions include: the first mixing temperature is 90-100 ℃, and the first mixing time is 2-3min; preferably, the conditions of the second mixing include: the second mixing temperature is 120-130 ℃, and the second mixing time is 3-5min; preferably, the conditions of the third mixing include: the third mixing temperature is not more than 115 ℃, and the third mixing time is 4-6min; preferably, the conditions of the vulcanization include: the vulcanizing temperature is 150-170 ℃, the vulcanizing pressure is 10-20MPa, and the vulcanizing time is 30-50min. The rubber compound prepared by the preferred embodiment has better processing safety and vulcanization efficiency, and the mechanical property of vulcanized rubber is better (the strength is improved, and the bending resistance is good).
To specifically illustrate the process of the present invention for preparing a vulcanizate, a preferred embodiment is provided below for illustration:
(1) Placing the rubber matrix in an internal mixer, plasticating at the rotation speed of 50-120rpm, the initial mixing temperature of 70-90 ℃ and the raw rubber plasticating time of 0.1-1 min; then introducing the component A containing the rubber modifier into the internal mixer for first mixing to obtain a section of master batch;
(2) Adding the first-stage masterbatch and a component B containing white carbon black, titanium white, superfine talcum powder, an activating agent, an anti-aging agent and a softening agent into an internal mixer for second mixing, discharging and standing for 3-5 hours to obtain a second-stage masterbatch;
(3) Setting the rotation speed of an internal mixer to be 50-100rpm, setting the initial mixing temperature to be 25-50 ℃, plasticating the two-stage master batch for 0.5-1.5min, and adding a component C containing an accelerator and a vulcanizing agent to perform third mixing to obtain final mixed rubber;
(4) Putting the final rubber compound into a vulcanizing press for vulcanization;
the rubber modifier is L-cysteine, and the rubber matrix is a mixture of butadiene rubber and natural rubber.
The pressures used in the present invention are gage pressures.
A third aspect of the present invention provides a vulcanized rubber prepared by the above-described method.
A fourth aspect of the present invention provides the use of the above-described vulcanized rubber in a tire sidewall.
The present invention will be described in detail below by way of examples.
Unless otherwise specified, various commercial products used below are commercially available.
The following examples and comparative examples the apparatus for preparing vulcanizates are shown in Table 1.
The apparatus for testing the vulcanized rubbers obtained in the examples and comparative examples is shown in Table 2, and the test conditions are shown in Table 3.
The chemicals used in the examples and comparative examples are commercially available as follows:
natural rubber: SMR-20, qingdao Seritet International Logistics, inc.;
butadiene rubber: BR9000, a Yanshan petrochemical (wherein the content of cis-1, 4-structures is 97.8% by weight);
white carbon black: 165GR, rodiya, france, nitrogen adsorption specific surface area 170m 2 /g；
Titanium dioxide: titanium dioxide content 98 wt%, medium to high chemical limited;
superfine talcum powder: 3000 mesh, chemical Limited, jinan Yubang;
rubber modifier: l-cysteine, aladdin Chemicals;
softening agent: environmental aromatic oil TDAEV500 (TDAE for short), xindayang (ningbo) limited;
activating agent: zinc oxide, stearic acid, weifang Hehenfeng chemical industry Co., ltd;
an anti-aging agent: n- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine (antioxidant 4020) Jiangsu san Oao chemical Co., ltd;
vulcanizing agent: sulfur, heicheng Hechenghuai chemical Limited;
accelerator (b): n-tert-butyl-2-benzothiazolesulfenamide (TBBS), diphenylguanidine (accelerator D), tetramethylthiuram disulfide (TMTD), shanghai Yongyan chemical science and technology Co., ltd.
The components in the following examples and comparative examples were used in parts by weight, each representing 1g.
The examples are intended to illustrate the rubber compositions, vulcanizates, and methods of making the same of the present invention.
TABLE 1
| Serial number | Device name | Type number | Manufacturer of the product |
| 1 | Internal mixer | BR1600 | Farrel America Ltd |
| 2 | Flat vulcanizing machine | XLB-D400*400*2 | Shanghai first rubber machinery plant |
TABLE 2
TABLE 3
Example 1
The rubber composition formula comprises: 60 parts of natural rubber, 40 parts of butadiene rubber, 8 parts of L-cysteine, 40 parts of white carbon black, 30 parts of titanium dioxide, 10 parts of superfine talcum powder, 15 parts of TDAE, 4 parts of zinc oxide, 1 part of stearic acid, 0.5 part of sulfur, 5 parts of TBBS and 1 part of anti-aging agent 4020.
The preparation process of the vulcanized rubber comprises the following steps:
(1) Performing first mixing on a rubber matrix and a rubber modifier to obtain a section of master batch; concretely, adding natural rubber and butadiene rubber into an internal mixer, setting the rotating speed to be 80rpm, the raw rubber plasticating temperature to be 80 ℃, and the raw rubber plasticating time to be 0.5min; adding a rubber modifier into the internal mixer for mixing, wherein the first mixing temperature is 90 ℃, and the first mixing time is 3min, so as to obtain a section of master batch;
(2) Performing second mixing on the primary masterbatch, the white carbon black, the titanium dioxide, the superfine talcum powder, the activator, the anti-aging agent and the softener to obtain secondary masterbatch; specifically, adding white carbon black, titanium dioxide, talcum powder, TDAE, zinc oxide, stearic acid and an anti-aging agent 4020 into an internal mixer, and performing second mixing with the first-stage masterbatch for 5min at a second mixing temperature of 120 ℃, discharging and standing for 4 hours to obtain a second-stage masterbatch;
(3) Performing third mixing on the second-stage masterbatch, an accelerator and a vulcanizing agent to obtain final rubber; specifically, setting the rotation speed of an internal mixer to be 80rpm, setting the initial mixing temperature to be 40 ℃, plasticating the two-stage masterbatch for 1min, adding a vulcanizing agent and an accelerator to perform third mixing, setting the third mixing temperature to be 105 ℃, setting the third mixing time to be 6min, and discharging to obtain final mixed rubber;
(4) And (3) putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 150 ℃, the vulcanization pressure is 20MPa, and the vulcanization time is 40min, so as to obtain a vulcanized rubber sample S1.
The vulcanized rubber sample S1 was subjected to the performance test, and the results are shown in Table 4.
Example 2
The rubber composition formula comprises: 40 parts of natural rubber, 60 parts of butadiene rubber, 15 parts of L-cysteine, 60 parts of white carbon black, 20 parts of titanium dioxide, 15 parts of superfine talcum powder, 5 parts of TDAE, 4 parts of zinc oxide, 3 parts of stearic acid, 4 parts of sulfur, 1 part of TMTD and 2 parts of anti-aging agent 4020.
The preparation process of the vulcanized rubber comprises the following steps:
(1) Performing first mixing on a rubber matrix and a rubber modifier to obtain a section of master batch; concretely, adding natural rubber and butadiene rubber into an internal mixer, setting the rotating speed to be 80rpm, the raw rubber plasticating temperature to be 80 ℃, and the raw rubber plasticating time to be 0.5min; adding a rubber modifier into the internal mixer for mixing, wherein the first mixing temperature is 95 ℃, and the first mixing time is 2.5min, so as to obtain a section of master batch;
(2) Performing second mixing on the primary masterbatch, the white carbon black, the titanium dioxide, the superfine talcum powder, the activator, the anti-aging agent and the softener to obtain secondary masterbatch; specifically, adding white carbon black, titanium dioxide, superfine talcum powder, TDAE, zinc oxide, stearic acid and an anti-aging agent 4020 into an internal mixer, and carrying out second mixing with the primary rubber for 4min at 125 ℃, discharging and standing for 5 hours to obtain secondary rubber;
(3) Carrying out third mixing on the second-stage masterbatch, an accelerant and a vulcanizing agent to obtain final rubber; specifically, setting the rotation speed of an internal mixer to be 80rpm, setting the initial mixing temperature to be 40 ℃, plasticating the two-stage master batch for 1min, adding a vulcanizing agent and an accelerator to perform third mixing, setting the third mixing temperature to be 110 ℃, setting the third mixing time to be 5min, and discharging to obtain final mixed rubber;
(4) And (3) putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 10MPa, and the vulcanization time is 20min, so as to obtain a vulcanized rubber sample S2.
The vulcanized rubber sample S2 was subjected to the performance test, and the results are shown in Table 4.
Example 3
The rubber composition formula comprises the following components: 50 parts of natural rubber, 50 parts of butadiene rubber, 11 parts of L-cysteine, 50 parts of white carbon black, 10 parts of titanium dioxide, 20 parts of superfine talcum powder, 10 parts of TDAE, 3 parts of zinc oxide, 5 parts of stearic acid, 2 parts of sulfur, 1 part of TBBS, 2 parts of accelerator D and 3 parts of anti-aging agent 4020.
The preparation process of the vulcanized rubber comprises the following steps:
(1) Carrying out first mixing on a rubber matrix and a rubber modifier to obtain a section of master batch; specifically, adding natural rubber and butadiene rubber into an internal mixer, setting the rotating speed to be 80rpm, the raw rubber plasticating temperature to be 80 ℃, and the raw rubber plasticating time to be 0.5min; adding a rubber modifier into the internal mixer for mixing, wherein the first mixing temperature is 100 ℃, and the first mixing time is 2min, so as to obtain a section of master batch;
(2) Performing second mixing on the primary masterbatch, the white carbon black, the titanium dioxide, the superfine talcum powder, the activator, the anti-aging agent and the softener to obtain secondary masterbatch; specifically, adding white carbon black, titanium dioxide, superfine talcum powder, TDAE, zinc oxide, stearic acid and an anti-aging agent 4020 into an internal mixer, and carrying out second mixing with the primary rubber for 3min at a second mixing temperature of 130 ℃, discharging and standing for 4 hours to obtain secondary rubber;
(3) Performing third mixing on the second-stage masterbatch, an accelerator and a vulcanizing agent to obtain final rubber; specifically, setting the rotation speed of an internal mixer to be 80rpm, setting the initial mixing temperature to be 40 ℃, plasticating the two-stage masterbatch for 1min, adding a vulcanizing agent and an accelerator to perform third mixing, setting the third mixing temperature to be 115 ℃, setting the third mixing time to be 4min, and discharging to obtain final mixed rubber;
(4) And (3) putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 160 ℃, the vulcanization pressure is 15MPa, and the vulcanization time is 30min, so that a vulcanized rubber sample S3 is prepared.
The vulcanizate sample S3 was tested for properties and the results are shown in Table 4.
Example 4
The rubber composition formulation of this example was the same as in example 3, and a vulcanized rubber was prepared in a similar manner to example 3, except that:
the procedure for the preparation of the vulcanizates was similar to that in example 3, except that:
in the process of preparing the first-stage masterbatch, the temperature of first mixing is 110 ℃, and the time is 4.5min;
in the process of preparing the second-stage masterbatch, the temperature of second mixing is 140 ℃ and the time is 2min;
in the process of preparing the final rubber compound, the time of the third mixing is 4min, and the temperature of the third mixing is 120 ℃.
A vulcanized rubber sample S4 was obtained.
The vulcanized rubber sample S4 was subjected to the performance test, and the results are shown in Table 4.
Example 5
The rubber composition formula comprises: 55 parts of natural rubber, 45 parts of butadiene rubber, 13 parts of L-cysteine, 55 parts of white carbon black, 15 parts of titanium dioxide, 10 parts of superfine talcum powder, 13 parts of TDAE, 5 parts of zinc oxide, 5 parts of stearic acid, 3 parts of sulfur, 2 parts of TBBS, 1.5 parts of accelerator D and 2 parts of anti-aging agent 4020.
The procedure for the preparation of the vulcanizates was the same as in example 3. A vulcanized rubber sample S5 was obtained.
The vulcanized rubber sample S5 was subjected to the performance test, and the results are shown in Table 4.
Comparative example 1
50 parts of natural rubber, 50 parts of butadiene rubber, 4 parts of Si69, 50 parts of white carbon black, 10 parts of titanium dioxide, 20 parts of superfine talcum powder, 10 parts of TDAE, 3 parts of zinc oxide, 5 parts of stearic acid, 2 parts of sulfur, 1 part of TBBS, 2 parts of accelerator D and 3 parts of anti-aging agent 4020. The procedure for the preparation of the vulcanizates was the same as in example 3. A vulcanized rubber sample DS1 was obtained.
The cured rubber sample DS1 was subjected to the performance test, and the results are shown in Table 4.
Comparative example 2
The rubber composition formula comprises: 80 parts of natural rubber, 20 parts of butadiene rubber, 5 parts of L-cysteine, 70 parts of white carbon black, 40 parts of titanium dioxide, 5 parts of superfine talcum powder, 10 parts of TDAE, 3 parts of zinc oxide, 5 parts of stearic acid, 2 parts of sulfur, 1 part of TBBS, 2 parts of accelerator D and 3 parts of anti-aging agent 4020. The procedure for the preparation of the vulcanizates was the same as in example 3. A vulcanized rubber sample DS2 was prepared.
The cured rubber sample DS2 was subjected to performance testing and the results are shown in Table 4.
Comparative example 3
The rubber composition formula comprises: 50 parts of natural rubber, 50 parts of butadiene rubber, 11 parts of maleic acid, 50 parts of white carbon black, 10 parts of titanium dioxide, 20 parts of superfine talcum powder, 10 parts of TDAE, 3 parts of zinc oxide, 2 parts of stearic acid, 2 parts of sulfur, 1 part of TBBS, 2 parts of accelerator D and 3 parts of anti-aging agent 4020.
The procedure for the preparation of the vulcanizates was the same as in example 3. A vulcanized rubber sample DS3 was prepared.
The cured rubber sample DS3 was subjected to performance testing and the results are shown in Table 4.
Comparative example 4
The formulation of the rubber composition of this comparative example was the same as in example 3, and a vulcanized rubber was prepared by a method similar to example 3, except that:
in the process of preparing the first-stage masterbatch, no rubber modifier is added;
and in the process of preparing the second-stage masterbatch, performing second mixing on the first-stage masterbatch, the rubber modifier, the white carbon black, the titanium white, the superfine talcum powder, the activator, the anti-aging agent and the softener to obtain the second-stage masterbatch.
A vulcanized rubber sample DS4 was prepared.
The cured rubber sample DS4 was subjected to performance testing and the results are shown in Table 4.
TABLE 4
| Sample numbering | S1 | S2 | S3 | S4 | S5 | DS1 | DS2 | DS3 | DS4 |
| Scorching time t10 (min) | 1.90 | 1.87 | 1.98 | 1.76 | 1.95 | 1.02 | 0.67 | 1.62 | 1.38 |
| Vulcanization time t90 (min) | 14.5 | 14 | 15 | 16.7 | 14.6 | 19.8 | 26.7 | 17.4 | 18.7 |
| Tear strength (MPa) | 13.9 | 13.5 | 14 | 13 | 14.1 | 9.8 | 7.1 | 12.6 | 11.5 |
| Fatigue life (times) | 26521 | 26398 | 26785 | 25006 | 26903 | 15034 | 8921 | 18975 | 16458 |
As can be seen from Table 4, the rubber composition of the present invention can provide better dispersion of the components in the rubber composition in the rubber matrix, which further improves the processing safety and vulcanization efficiency of the rubber compound, and provides the resulting vulcanized rubber with better strength and dynamic bending flexibility.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A rubber composition is characterized by comprising a rubber matrix, a rubber modifier, white carbon black, titanium white, superfine talcum powder, an activator, an anti-aging agent, a softener, an accelerator and a vulcanizing agent; the rubber modifier is L-cysteine, and the rubber matrix is butadiene rubber and natural rubber.
2. The rubber composition according to claim 1, wherein the natural rubber is contained in the rubber matrix in an amount of 40 to 60 parts by weight and the butadiene rubber is contained in an amount of 40 to 60 parts by weight, relative to 100 parts by weight of the rubber matrix;
preferably, the cis-1, 4-structure content in the butadiene rubber is 90 to 99% by weight.
3. The rubber composition according to claim 1 or 2, wherein the rubber modifier is contained in an amount of 8 to 15 parts by weight, the white carbon black is contained in an amount of 40 to 60 parts by weight, the titanium dioxide is contained in an amount of 10 to 30 parts by weight, the ultrafine talc is contained in an amount of 10 to 20 parts by weight, the activator is contained in an amount of 5 to 10 parts by weight, the anti-aging agent is contained in an amount of 1 to 3 parts by weight, the softener is contained in an amount of 5 to 15 parts by weight, the accelerator is contained in an amount of 1 to 5 parts by weight, and the vulcanizing agent is contained in an amount of 0.5 to 4 parts by weight, relative to 100 parts by weight of the rubber matrix.
4. The rubber composition according to any one of claims 1 to 3, wherein the silica has a nitrogen adsorption specific surface area of 10 to 200m 2 /g；
Preferably, the titanium dioxide content in the titanium dioxide is more than 98 wt%;
preferably, the mesh number of the superfine talcum powder is 2500-3000 meshes;
preferably, the activator is selected from at least one of a mixture of metal oxides and fatty acids, a fatty acid metal soap salt, and zinc borate.
5. The rubber composition according to any one of claims 1 to 4, wherein the antioxidant is at least one selected from the group consisting of amine antioxidants, quinoline antioxidants and benzimidazole antioxidants;
preferably, the accelerator is selected from at least one of sulfenamide accelerators, thiazole accelerators, thiuram accelerators and guanidine accelerators;
preferably, the softening agent is selected from at least one of aromatic oil, paraffin oil, naphthenic oil, petroleum resin and polyethylene glycol;
preferably, the vulcanizing agent is a sulfur donor.
6. A method of preparing a vulcanizate, the method comprising:
(1) Performing first mixing on a component A containing a rubber matrix and a rubber modifier to obtain a section of masterbatch;
(2) Performing second mixing on the first-stage masterbatch and a component B containing white carbon black, titanium dioxide, superfine talcum powder, an activating agent, an anti-aging agent and a softening agent to obtain a second-stage masterbatch;
(3) Performing third mixing on the second-stage masterbatch and a component C containing an accelerator and a vulcanizing agent to obtain a final rubber compound;
(4) Vulcanizing the final rubber;
the rubber modifier is L-cysteine, and the rubber matrix is butadiene rubber and natural rubber.
7. The method according to claim 6, wherein the content of natural rubber in the rubber matrix is 40 to 60 parts by weight and the content of butadiene rubber is 40 to 60 parts by weight, relative to 100 parts by weight of the rubber matrix;
preferably, the cis-1, 4-structure content in the butadiene rubber is 90 to 99% by weight.
8. The method according to claim 6 or 7, wherein the rubber modifier is 8 to 15 parts by weight, the white carbon black is 40 to 60 parts by weight, the titanium dioxide is 10 to 30 parts by weight, the ultrafine talc is 10 to 20 parts by weight, the activator is 5 to 10 parts by weight, the anti-aging agent is 1 to 3 parts by weight, the softener is 5 to 15 parts by weight, the accelerator is 1 to 5 parts by weight, and the vulcanizing agent is 0.5 to 4 parts by weight, relative to 100 parts by weight of the rubber matrix.
9. The method of any of claims 6-8, wherein the conditions of the first mixing comprise: the first mixing temperature is 80-120 ℃, and the first mixing time is 1-5min;
preferably, the conditions of the second mixing include: the second mixing temperature is 100-140 ℃, and the second mixing time is 2-6min;
preferably, the conditions of the third mixing comprise: the third mixing temperature is not more than 120 ℃, and the third mixing time is 4-6min;
preferably, the conditions of the vulcanization include: the vulcanization temperature is 150-170 ℃, the vulcanization pressure is 10-20MPa, and the vulcanization time is 20-50min.
10. A vulcanized rubber produced by the method of any one of claims 6 to 9.
11. Use of the vulcanizate of claim 10 in a tire sidewall.
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