CN112409662A - Composition for preparing rubber compound, rubber compound and preparation method thereof, and tire - Google Patents
Composition for preparing rubber compound, rubber compound and preparation method thereof, and tire Download PDFInfo
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- CN112409662A CN112409662A CN202011281740.9A CN202011281740A CN112409662A CN 112409662 A CN112409662 A CN 112409662A CN 202011281740 A CN202011281740 A CN 202011281740A CN 112409662 A CN112409662 A CN 112409662A
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- butadiene rubber
- polymerized styrene
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- 239000005060 rubber Substances 0.000 title claims abstract description 108
- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 150000001875 compounds Chemical class 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 97
- 239000006229 carbon black Substances 0.000 claims abstract description 61
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 59
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000004073 vulcanization Methods 0.000 claims abstract description 38
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 28
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
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- 239000004594 Masterbatch (MB) Substances 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
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- 239000003921 oil Substances 0.000 claims description 13
- 239000012620 biological material Substances 0.000 claims description 12
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 230000003712 anti-aging effect Effects 0.000 claims description 8
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000010692 aromatic oil Substances 0.000 claims description 7
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- STSDHUBQQWBRBH-UHFFFAOYSA-N n-cyclohexyl-1,3-benzothiazole-2-sulfonamide Chemical compound N=1C2=CC=CC=C2SC=1S(=O)(=O)NC1CCCCC1 STSDHUBQQWBRBH-UHFFFAOYSA-N 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- -1 fatty acid ester Chemical class 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 claims description 2
- 229960004029 silicic acid Drugs 0.000 claims description 2
- 229920001890 Novodur Polymers 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical class [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 7
- 238000010074 rubber mixing Methods 0.000 description 7
- 238000002444 silanisation Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
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- 239000006185 dispersion Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
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- 239000010959 steel Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
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- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000000829 suppository Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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
- 241000227425 Pieris rapae crucivora Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
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- 238000004220 aggregation Methods 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- UEZWYKZHXASYJN-UHFFFAOYSA-N cyclohexylthiophthalimide Chemical compound O=C1C2=CC=CC=C2C(=O)N1SC1CCCCC1 UEZWYKZHXASYJN-UHFFFAOYSA-N 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 230000002035 prolonged effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application provides a composition for preparing rubber compound, the rubber compound, a preparation method of the rubber compound and a tire, and belongs to the technical field of rubber modification. The composition for preparing the rubber compound comprises 70-130 parts by weight of modified oil-extended solution-polymerized styrene-butadiene rubber A, 5-55 parts by weight of modified oil-extended solution-polymerized styrene-butadiene rubber B, 60-100 parts by weight of white carbon black, 5-15 parts by weight of carbon black, 3-7 parts by weight of vulcanization activator, 1-2 parts by weight of vulcanizing agent and 3.8-5.5 parts by weight of vulcanization accelerator. The styrene content in the modified oil-extended solution-polymerized styrene-butadiene rubber B is 20-35%, and the vinyl content is 40-60%. The modified oil-extended solution-polymerized styrene-butadiene rubber A, the modified oil-extended solution-polymerized styrene-butadiene rubber B and the white carbon black have higher affinity and can be better and fully combined, so that the rubber material prepared from the rubber compound has excellent ground gripping performance and lower rolling resistance.
Description
Technical Field
The application relates to the technical field of rubber modification, in particular to a composition for preparing rubber compound, the rubber compound, a preparation method of the rubber compound and a tire.
Background
With the development of semi-steel radial tires, the tire grip performance and fuel performance are required to be higher and higher from the aspects of safety and comfort. However, improving grip performance and reducing rolling resistance is usually a pair of spears, which tend to be longer than each other and longer than each other, and this presents a significant challenge to existing formulation technology. The grip safety, fuel economy and environmental protection are the two most important control links of the green tire, and the two large performance indexes are usually controlled at a higher level, so that the formula technology needs to be changed greatly.
Disclosure of Invention
Provided are a composition for preparing a rubber compound, a method for preparing the same, and a tire, which can improve the grip performance of the tire and, at the same time, reduce rolling resistance.
The embodiment of the application is realized as follows:
in a first aspect, the present application provides a composition for preparing a mix, comprising: 70-130 parts of modified oil-extended solution-polymerized styrene-butadiene rubber A, 5-55 parts of modified oil-extended solution-polymerized styrene-butadiene rubber B, 60-100 parts of white carbon black, 5-15 parts of carbon black, 3-7 parts of vulcanization activator, 1-2 parts of vulcanizing agent and 3.8-5.5 parts of vulcanization accelerator.
Wherein the styrene content in the modified oil-extended solution-polymerized styrene-butadiene rubber A is 25-40%, and the vinyl content is 25-40%.
The styrene content in the modified oil-extended solution-polymerized styrene-butadiene rubber B is 20-35%, and the vinyl content is 40-60%.
In the technical scheme, the modified oil-extended solution-polymerized styrene-butadiene rubber A, the modified oil-extended solution-polymerized styrene-butadiene rubber B and the white carbon black have higher affinity and can be well and fully combined, so that the rubber material prepared from the rubber compound has excellent ground gripping performance and lower rolling resistance.
The styrene content of the modified oil-extended solution-polymerized styrene-butadiene rubber A is controlled to be 25-40%, so that the rubber material is ensured to have excellent ground gripping performance, and the rolling resistance is not obviously improved; the vinyl content is controlled to be 25-40% so as to balance better rolling resistance. The styrene content of the modified oil-extended solution-polymerized styrene-butadiene rubber B is controlled to be 20-35%, and the vinyl content is controlled to be 40-60%, so that the rubber material has low hysteresis loss and low rolling resistance. The modified oil-extended solution-polymerized styrene-butadiene rubber A and the modified oil-extended solution-polymerized styrene-butadiene rubber B have better compatibility. And the cooperation of the modified oil-extended solution-polymerized styrene-butadiene rubber A and the modified oil-extended solution-polymerized styrene-butadiene rubber B can improve the conflict of the single modified oil-extended solution-polymerized styrene-butadiene rubber in the directions of ground gripping, rolling resistance and processing performance.
In combination with the first aspect, in a first possible example of the first aspect of the present application, the modified oil-extended solution-polymerized styrene-butadiene rubber a has a styrene content of 30 to 40% and a vinyl content of 30 to 40%, and the modified oil-extended solution-polymerized styrene-butadiene rubber B has a styrene content of 20 to 30% and a vinyl content of 40 to 50%.
Optionally, the modified oil-extended solution-polymerized styrene-butadiene rubber A has a weight-average molecular weight Mw≥106The weight average molecular weight of the modified oil-extended solution-polymerized styrene-butadiene rubber B is 4 x 105～6*105。
Optionally, 35 to 40phr of modified oil-extended solution polymerized styrene-butadiene rubber A is oil-extended, and 3 to 7phr of modified oil-extended solution polymerized styrene-butadiene rubber B is oil-extended.
In the above examples, the high molecular weight modified oil-extended solution-polymerized styrene-butadiene rubber A enables the rubber material to have better grip performance, abrasion resistance, mechanical properties, and reduced rolling resistance.
In a second possible example of the first aspect of the present application, in combination with the first aspect, the white carbon black is precipitated hydrated silica, and the BET specific surface area is 140 to 180cm2/g。
Optionally, the nitrogen adsorption specific surface area of the carbon black is more than or equal to 80cm2/g。
Optionally, the composition for preparing the rubber compound comprises 2-4 parts by weight of white carbon black dispersing agent, and the white carbon black dispersing agent comprises a mixture of zinc stearate and fatty acid ester.
Optionally, the composition for preparing the rubber compound comprises 6-15 parts by weight of the silane coupling agent.
Alternatively, the silane coupling agent comprises Si-69 solid silicon.
In the above examples, the white carbon black of the present application has better dispersibility, and such white carbon black can be dispersed to the level of primary particles, thereby shortening the required mixing time.
The silane coupling agent can reduce the generation of ethanol, reduce the discharge of VOC and improve the performance of sizing material.
In a third possible example of the first aspect of the present application in combination with the first aspect, the vulcanizing agent includes sulfur, and the vulcanization accelerator includes N-cyclohexyl-2-benzothiazolesulfenamide, diphenylguanidine, and tetrabenzylthiuram disulfide.
Optionally, the vulcanization accelerator comprises 1.5-2 parts by weight of N-cyclohexyl-2-benzothiazole sulfonamide, 2-3 parts by weight of diphenyl guanidine and 0.3-0.5 part by weight of tetrabenzylthiuram disulfide.
In a fourth possible example of the first aspect of the present application in combination with the first aspect, the above composition for preparing a rubber compound includes 4 to 7 parts by weight of a grip resin.
Alternatively, the grip resin comprises a modified alpha-methyl styrene resin.
In the above examples, the grip resin has good compatibility with the modified oil-extended solution-polymerized styrene-butadiene rubber A and the modified oil-extended solution-polymerized styrene-butadiene rubber B, and the grip performance of the rubber material obtained from the rubber compound can be improved without increasing the rolling resistance.
In a fifth possible example of the first aspect of the present application, in combination with the first aspect of the present application, the composition for preparing a rubber composition includes 4 to 7 parts by weight of the biological material KSH-1, wherein the biological material KSH-1 has a molecular formula C9H8.83(OCH3)0.95。
In the above examples, the combination of the biomaterial with the modified oil-extended solution-polymerized styrene-butadiene rubber A and the modified oil-extended solution-polymerized styrene-butadiene rubber B can improve the grip performance of the rubber material prepared from the rubber compound and reduce the rolling resistance.
In a sixth possible example of the first aspect of the present application, in combination with the first aspect, the composition for preparing a rubber compound includes 2 to 9 parts by weight of the eco-friendly aromatic oil, 4 to 7 parts by weight of the anti-aging agent, and 0.1 to 0.3 part by weight of the scorch retarder.
In a second aspect, the present application provides a method for preparing a rubber compound, which comprises a first-stage masterbatch mixing, a second-stage masterbatch mixing, a third-stage masterbatch mixing and a fourth-stage masterbatch mixing which are sequentially performed.
The first-stage master batch mixing comprises the step of mixing 70-130 parts by weight of modified oil-extended solution-polymerized styrene-butadiene rubber A, 5-55 parts by weight of modified oil-extended solution-polymerized styrene-butadiene rubber B, 60-100 parts by weight of white carbon black, 2-4 parts by weight of white carbon black dispersing agent, 6-15 parts by weight of silane coupling agent, 4-7 parts by weight of ground-grabbing resin, 4-7 parts by weight of biological material KSH-1, 2-4 parts by weight of vulcanization activator, 2-3 parts by weight of vulcanization accelerator, 1-3 parts by weight of anti-aging agent and 2-9 parts by weight of environment-friendly aromatic hydrocarbon oil to prepare the first master batch.
The two-stage masterbatch mixing comprises the step of mixing the prepared first masterbatch, 5-15 parts by weight of carbon black, 1-3 parts by weight of vulcanization activator and 2-4 parts by weight of anti-aging agent to prepare second masterbatch in a masterbatch manner.
And the three-stage master batch mixing comprises the step of carrying out remilling on the prepared second master batch to prepare a third master batch.
The four-stage masterbatch mixing comprises the step of mixing the prepared third masterbatch, 1-2 parts by weight of vulcanizing agent, 1.8-2.5 parts by weight of vulcanization accelerator and 0.1-0.3 part by weight of scorch retarder for final rubber mixing to prepare the rubber compound.
In the technical scheme, a specific four-stage mixing process is adopted, and the four-stage mixing process can ensure that the white carbon black can be fully dispersed and is fully combined with the modified oil-extended solution-polymerized styrene-butadiene rubber A and the modified oil-extended solution-polymerized styrene-butadiene rubber B.
In a third aspect, the present application provides a rubber composition prepared according to the method of preparing the rubber composition described above.
In the technical scheme, the rubber material prepared from the rubber compound has high ground-grasping performance and low rolling resistance.
In a fourth aspect, the present application provides a tire made using the above-described rubber composition.
In the technical scheme, the tire has high ground gripping performance and low rolling resistance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 is a schematic diagram of the synthesis reaction of a modified oil-extended solution-polymerized styrene-butadiene rubber of the present application;
FIG. 2 is a schematic view of the combination of a modified oil-extended solution-polymerized styrene-butadiene rubber and a filler according to the present application;
fig. 3 is a schematic diagram of a silylation reaction of white carbon black and rubber according to the present application.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following description is made specifically for the composition for preparing the rubber compound, the preparation method thereof and the tire according to the embodiments of the present application:
the present application provides a composition for preparing a rubber compound, comprising: 70-130 parts of modified oil-extended solution-polymerized styrene-butadiene rubber A (F-SSBR A), 5-55 parts of modified oil-extended solution-polymerized styrene-butadiene rubber B (F-SSBR B), 60-100 parts of white carbon black, 5-15 parts of carbon black, 3-7 parts of vulcanization activator, 1-2 parts of vulcanizing agent and 3.8-5.5 parts of vulcanization accelerator.
Wherein the styrene content in the modified oil-extended solution-polymerized styrene-butadiene rubber A is 25-40%, and the vinyl content is 25-40%;
the styrene content in the modified oil-extended solution-polymerized styrene-butadiene rubber B is 20-35%, and the vinyl content is 40-60%.
Optionally, the styrene content in the modified oil-extended solution-polymerized styrene-butadiene rubber A is 30-40%, and the vinyl content is 30-40%;
the styrene content in the modified oil-extended solution-polymerized styrene-butadiene rubber B is 20-30%, and the vinyl content is 40-50%.
Optionally, the styrene content in the modified oil-extended solution-polymerized styrene-butadiene rubber A is 32-36%, and the vinyl content is 35-40%;
the styrene content of the modified oil-extended solution-polymerized styrene-butadiene rubber B is 25-30%, and the vinyl content is 40-45%.
The synthetic reaction schemes of the modified oil-extended solution-polymerized styrene-butadiene rubber A and the modified oil-extended solution-polymerized styrene-butadiene rubber B are shown in figure 1, wherein the modified oil-extended solution-polymerized styrene-butadiene rubber A and the modified oil-extended solution-polymerized styrene-butadiene rubber B are both modified at the single end of 4,4 '-bis- (dialkylamino) -benzophenone, and the modified oil-extended solution-polymerized styrene-butadiene rubber at the single end of 4, 4' -bis- (dialkylamino) -benzophenone.
The oil charge of the modified oil-extended solution-polymerized styrene-butadiene rubber A is 35 to 40phr, and the oil charge of the modified oil-extended solution-polymerized styrene-butadiene rubber B is 3 to 7 phr.
Alternatively, the oil extension of the modified oil-extended solution-polymerized styrene-butadiene rubber A is 37.5phr and the oil extension of the modified oil-extended solution-polymerized styrene-butadiene rubber B is 5 phr.
The styrene content in the present application means the content of a styrene structure; vinyl content refers to the amount of vinyl bonds.
Weight average molecular weight M of modified oil-extended solution-polymerized styrene-butadiene rubber Aw≥106Weight average molecular weight M of modified oil-extended solution-polymerized styrene-butadiene rubber BwAt 4 x 105～6*105In the meantime.
Optionally, the modified oil-extended solution-polymerized styrene-butadiene rubber A has a weight-average molecular weight Mw≥1.15*106Weight average molecular weight M of modified oil-extended solution-polymerized styrene-butadiene rubber BwAt 4.5 x 105～5.5*105In the meantime.
The solubility parameter SP value of the modified oil-extended solution-polymerized styrene-butadiene rubber A is 17.83, and the solubility parameter SP value of the modified oil-extended solution-polymerized styrene-butadiene rubber A is 17.61.
The modified oil-extended solution-polymerized styrene-butadiene rubber A and the modified oil-extended solution-polymerized styrene-butadiene rubber B have higher affinity with white carbon black, and can be better and fully combined. Therefore, the rubber material prepared from the rubber compound has excellent ground gripping performance and lower rolling resistance.
As shown in FIG. 2, the comparison between the unmodified oil-extended solution-polymerized styrene-butadiene rubber and the modified oil-extended solution-polymerized styrene-butadiene rubber shows that: the molecular chain terminal functional group of the modified oil-extended solution-polymerized styrene-butadiene rubber can react with the filler (silicon dioxide), so that the free chain terminal is reduced and the rubber-filler interaction is better, thereby reducing the hysteresis loss and having better reinforcing effect. The amount of unmodified oil-extended solution-polymerized styrene-butadiene rubber capable of reacting with the filler is small.
The styrene content of the modified oil-extended solution-polymerized styrene-butadiene rubber A is not too high or too low, so that the rubber material is ensured to have excellent ground gripping performance, and the rolling resistance is not obviously improved; the vinyl content is controlled at a higher level in order to balance better rolling resistance properties. Meanwhile, the high molecular weight modified oil-extended solution-polymerized styrene-butadiene rubber A can enable the rubber material to have better ground-grasping performance, wear resistance and mechanical performance, and reduce the rolling resistance.
The styrene content of the modified oil-extended solution-polymerized styrene-butadiene rubber B is controlled to be 20-35%, the vinyl content is controlled to be 40-60%, and 4 x 10%5Weight average molecular weight M is less than or equal tow≤6*105The modified oil-extended solution-polymerized styrene-butadiene rubber B can ensure that the rubber material has small hysteresis loss and low rolling resistance.
The modified oil-extended solution-polymerized styrene-butadiene rubber A and the modified oil-extended solution-polymerized styrene-butadiene rubber B have better compatibility. And the cooperation of the modified oil-extended solution-polymerized styrene-butadiene rubber A and the modified oil-extended solution-polymerized styrene-butadiene rubber B can improve the conflict of the single modified oil-extended solution-polymerized styrene-butadiene rubber in the directions of ground gripping, rolling resistance and processing performance.
It should be noted that, in order to fully exert the efficacy, the dry rubber of the modified oil-extended solution-polymerized styrene-butadiene rubber B of the present application should not be less than 20% in the whole crude rubber system.
Vulcanization activators include Stearic Acid (SA) and activated zinc oxide (ZnO).
Specifically, the 3-7 parts by weight of vulcanization activator comprises 1-3 parts by weight of active zinc oxide and 2-4 parts by weight of stearic acid.
The vulcanizing agent comprises sulfur powder.
Optionally, the composition for preparing the compound comprises 1.2-1.7 parts by weight of vulcanizing agent.
Vulcanization accelerators include N-cyclohexyl-2-benzothiazolesulfenamide (CZ), Diphenylguanidine (DPG) and tetrabenzylthiuram disulfide (TBzTD).
Alternatively, the vulcanization accelerator is a mixture of N-cyclohexyl-2-benzothiazolesulfenamide, diphenylguanidine, and tetrabenzylthiuram disulfide.
Specifically, the 3.8-5.5 parts by weight of the vulcanization accelerator comprises 1.5-2 parts by weight of N-cyclohexyl-2-benzothiazole sulfonamide, 2-3 parts by weight of diphenyl guanidine and 0.3-0.5 part by weight of tetrabenzylthiuram disulfide.
The application uses a moderate amount of vulcanizing agent to match with the vulcanization accelerator, and the 'semi-effective vulcanization system' is between an effective vulcanization system and a common vulcanization system. It can endow the rubber composition with good vulcanization flatness, long scorching time, high crosslinking density and crosslinking stability and high physical and mechanical properties.
The three accelerators of the present application mutually activate in a characteristic manner in terms of vulcanization speed and crosslinking degree, and they have a synergistic effect, but are absent, which ensures that the rubber composition has a suitable vulcanization speed and a prolonged scorch time. And because a large number of acidic groups on the surface of the white carbon black can adsorb the vulcanization accelerator, the vulcanization speed is delayed, the inventor of the application has made a long-term investigation on a vulcanization system, and the physical and mechanical properties of the rubber material can be greatly improved and the durability of the tire can be improved by increasing the using amounts of the accelerators N-cyclohexyl-2-benzothiazole sulfenamide and the diphenyl guanidine, particularly increasing the using amount of the diphenyl guanidine of the alkaline accelerator and reducing the using amount of the sulfur powder.
The white carbon black is precipitated hydrated silicon dioxide, and the BET specific surface area of the white carbon black is 140-180 cm2A D50 value of 2 to 5 μm, and a particle diameter of the primary particle of 5 to 15 nm;
optionally, the white carbon black is precipitated hydrated silicon dioxide, and the BET specific surface area of the white carbon black is 160-170 cm2A D50 value of 2-3 μm, and a particle diameter of the primary particle of 8-10 nm;
optionally, the white carbon black is sold under the trademark of Solvay
1165MP, of silicon
HD165MP。
This application replaces carbon black with white carbon black part or whole, can improve the relation between loss factor and the temperature, and greatly reduced rolling resistance improves and grabs ground performance.
The high-dispersion white carbon black has great difference in production process compared with common white carbon black, is specifically embodied in the control process of the silicon dioxide aggregate structure in the semi-finished product synthesis stage, and the production process of the high-dispersion white carbon black emphasizes the polymerization of primary particles and the depolymerization of secondary particles of silicon dioxide, so that a plurality of small particles exist stably with uniform particle size, the interaction between the white carbon black is reduced, the formation of a network structure between the silicon dioxide is reduced, and the appearance of flocculation aggregation is reduced.
The nitrogen adsorption specific surface area of the carbon black is more than or equal to 80cm2/g；
Optionally, the nitrogen adsorption specific surface area of the carbon black is more than or equal to 100cm2/g；
Optionally, the nitrogen adsorption specific surface area of the carbon black is 132-142 cm2The DBP oil absorption value is 108-118 mL/100 g.
Alternatively, the carbon black is CB N115.
The carbon black has excellent tear resistance and can endow rubber materials with better durability.
The composition for preparing the rubber compound comprises 2-4 parts by weight of white carbon black dispersing agent, wherein the white carbon black dispersing agent comprises a mixture (RF-70) of zinc stearate and fatty acid ester.
The composition for preparing the rubber compound comprises 6-15 parts by weight of a silane coupling agent, wherein the silane coupling agent comprises a novel silane coupling agent of Si-69 solid silicon, monosulfur or disulfide.
Alternatively, the silane coupling agent is Si-69 solid silicon.
The price of the Si-69 solid silicon is relatively low, and the manufacturing cost of the rubber material can be controlled. If the manufacturing cost of the rubber material is not considered, a novel silane coupling agent of mono-sulfur or disulfide can be selected.
The ethanol generated in the silanization reaction of the high-part white carbon black and the rubber cannot be completely discharged to delay the silanization reaction, dense air holes are possibly formed on the extruded section of the tire tread, and the silane coupling agent can reduce the generation of the ethanol, reduce the discharge of VOC and improve the performance of the rubber material.
The composition for preparing the rubber compound comprises 4-7 parts by weight of a grip resin, wherein the grip resin comprises a modified alpha-methyl styrene resin (CSR6200) and the softening point of the grip resin is 90-110 ℃.
The grip resin has good compatibility with the modified oil-filled solution-polymerized styrene-butadiene rubber A and the modified oil-filled solution-polymerized styrene-butadiene rubber B, can interact with surface groups of white carbon black, improves the viscoelastic property of a rubber material, and endows the rubber material with excellent grip performance and traction performance.
The composition for preparing the rubber compound comprises 4-7 parts by weight of a biological material KSH-1, wherein the molecular formula of the biological material KSH-1 is C9H8.83(OCH3)0.95. The biological material is matched with the modified oil-filled solution-polymerized styrene-butadiene rubber A and the modified oil-filled solution-polymerized styrene-butadiene rubber B, so that the ground gripping performance of the rubber material can be improved, the rolling resistance can be reduced, and the vulcanization speed of the rubber material can be obviously reduced.
The composition for preparing the rubber compound comprises 2-9 parts by weight of environment-friendly aromatic oil, 4-7 parts by weight of anti-aging agent and 0.1-0.3 part by weight of anti-scorching agent.
The environment-friendly aromatic oil is used for improving the processing performance of rubber materials and improving the ground gripping performance of rubber materials.
Alternatively, the environmentally friendly aromatic oil comprises holy Vivatec500, han, germany.
Optionally, the 4 to 7 parts by weight of antioxidant comprises 1 to 3 parts by weight of rhine Wax 111(Wax) and 2 to 4 parts by weight of antioxidant 6PPD (N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine).
Optionally, the scorch retarder includes the scorch retarder CTP (N-cyclohexylthiophthalimide).
Alternatively, the composition for preparing a mix of the present application comprises: 95-115 parts of modified oil-extended solution-polymerized styrene-butadiene rubber A, 20-35 parts of modified oil-extended solution-polymerized styrene-butadiene rubber B, 65-85 parts of white carbon black, 5-10 parts of carbon black, 4-6 parts of a vulcanization activator, 1.2-1.7 parts of a vulcanizing agent, 4.5-5.5 parts of a vulcanization accelerator, 3-4 parts of a white carbon black dispersing agent, 8-13 parts of a silane coupling agent, 4-6 parts of a ground gripping resin, 4-6 parts of a biological material KSH-1, 3-8 parts of environment-friendly aromatic oil, 4-6 parts of an anti-aging agent and 0.1-0.3 part of a scorch retarder.
The application also provides a preparation method of the rubber compound, which comprises the steps of primary rubber mixing, secondary rubber mixing, tertiary rubber mixing and quaternary rubber mixing which are sequentially carried out.
It should be noted that although the silica as the filler can react with the functional groups at the molecular chain ends of the modified oil-extended solution-polymerized styrene-butadiene rubber a and the modified oil-extended solution-polymerized styrene-butadiene rubber B to realize the interaction, the whole reaction process has high requirements on the mixing equipment and the process, the white carbon black sizing material needs an additional mixing step to complete the reaction between the silanol of the white carbon black and the ethoxy group of the coupling agent, and the reaction schematic diagram is shown in fig. 3. Typically, this reaction has a minimum initiation temperature of about 130 ℃. Therefore, in actual production, the silanization reaction is usually controlled to be 145-150 ℃, which is a narrow temperature reaction window, and the reaction is only effective under the action of higher temperature treatment and longer constant-temperature mixing, so that activities such as chemical adsorption, grafting and the like can be generated. And the surface of the rubber material is flat, the Mooney is controlled in a proper range, the following extrusion process is met, which is difficult to control for a shearing rotor internal mixer, so the reaction temperature and time of the high white carbon black formula must be strictly controlled, sufficient silanization reaction is ensured, a plurality of mixing stages at 150 ℃ are formed, the excellent static physical property and dynamic mechanical property of the rubber material are ensured, and the excellent conversion capability and better durability between the gripping performance and the rolling resistance of the rubber material are realized.
The method adopts the measures of adjusting the initial rotating speed, adjusting the number of times of lifting the bolt, adjusting the rotating speed gradient, adjusting the heating speed, adjusting the rotating speed during constant-temperature mixing, and ensuring the constant-temperature mixing time to ensure that the silanization reaction is sufficient.
The preparation method of the rubber compound comprises the following steps:
mixing a first-stage master batch:
the filling factor is 0.65-0.8. 70-130 parts by weight of modified oil-extended solution-polymerized styrene-butadiene rubber A, 5-55 parts by weight of modified oil-extended solution-polymerized styrene-butadiene rubber B, 60-100 parts by weight of white carbon black, 2-4 parts by weight of white carbon black dispersing agent, 6-15 parts by weight of silane coupling agent, 4-7 parts by weight of ground-grabbing resin, 4-7 parts by weight of biological material KSH-1, 2-4 parts by weight of stearic acid, 2-3 parts by weight of diphenylguanidine and 1-3 parts by weight of rhinestone wax 111 are added into a GK400 internal mixer.
The initial rotating speed is higher than 50RPM, so that the heating speed in the gel breaking process reaches a higher level, the temperature of the plug is raised to 118-120 ℃ after 40-42 seconds of plug pressing, the plug is lifted, and the rotating speed is reduced to 45 RPM; then adding 9 parts by weight of environment-friendly aromatic oil, carrying out bolt pressing for 33-35 seconds, raising the temperature to 142-144 ℃, then extracting the bolt, and reducing the rotating speed to 30 RPM; then the plug is pressed for 68-70 seconds, the temperature is increased to 138-140 ℃, then the plug is lifted, and the rotating speed is reduced to 22 RPM; then the bolt is pressed for 48-50 seconds until the temperature rises to 139-141 ℃, and then the bolt is extracted; and finally, the temperature of the bolt is increased to 148-150 ℃ for 33-35 seconds for glue removal, the bolt is lifted, the discharging door is opened, and the rotating speed is recovered to 40 RPM. And (3) controlling the glue discharging by adopting time or temperature, wherein the set glue discharging technological parameter is 260 seconds or 150 ℃, and the glue discharging is started when one set parameter is reached, so that the first master batch is prepared.
The primary rubber mixing is the most important ring in the mixing process, the silanization reaction mainly occurs in the primary rubber mixing process, the mixing temperature is controlled by forming a rotating speed descending gradient and lifting bolts for multiple times, the silanization reaction is well completed in a shearing type rotor internal mixer, the full reaction is kept in a narrow temperature window, and the mixing effect at the stage plays a determining role in the performance of rubber materials.
Mixing the two-stage master batch:
the filling factor is 0.65-0.8. Adding the prepared first masterbatch, 5-15 parts by weight of carbon black, 1-3 parts by weight of active zinc oxide and 2-4 parts by weight of age inhibitor 6PPD into a GK400 internal mixer.
Producing the second-stage masterbatch at a constant rotating speed which is set to be 40RPM, and extracting the bolt after the temperature is raised to be 108-110 ℃ for 34-36 seconds after the bolt is pressed; then the suppository is pressed for 20-22 seconds, the temperature is raised to 118-120 ℃, and then the suppository is extracted; and then the bolt is pressed for 40-45 seconds, the temperature is raised to 140-145 ℃ for glue removal, and the bolt is lifted to open the discharging door. And (3) controlling the glue discharging by adopting time or temperature, wherein the set glue discharging technological parameter is time 130 seconds or temperature 145 ℃, and the glue discharging is started when one set parameter is reached, so that the second master batch is prepared.
The active zinc oxide is typically added to the primary masterbatch, but in the high white carbon black formulation, the scorch risk is reduced by selecting the secondary production formulation.
Three-stage master batch mixing:
the filling factor is 0.65-0.8. The second masterbatch was added to a GK400 internal mixer. The three-stage masterbatch adopts a remill process to reduce the mooney of rubber materials. Setting the initial rotating speed to be 40RPM, lifting the bolt after the temperature of the bolt is increased to 112-114 ℃ in 20-22 seconds after the bolt is pressed, and reducing the rotating speed to 35 RPM; and then the bolt is pressed for 68-70 seconds, the temperature is raised to 138-140 ℃, the glue is discharged, and the bolt is lifted to open the discharging door. And (3) controlling the glue discharging by adopting time or temperature, wherein the set glue discharging technological parameter is 110 seconds or 140 ℃, and the glue discharging is started when one set parameter is reached, so that the third master batch is prepared.
And (3) mixing the four sections of master batch:
the filling factor is 0.65-0.8. Adding the third master batch, 1-2 parts by weight of vulcanizing agent, 1.5-2 parts by weight of N-cyclohexyl-2-benzothiazole sulfonamide, 0.3-0.5 part by weight of tetrabenzylthiuram disulfide and 0.1-0.3 part by weight of scorch retarder into a GK255 internal mixer.
Setting the initial rotating speed to be 28RPM, lifting the bolt after the temperature of the bolt is increased to 90-92 ℃ for 40-42 seconds, and reducing the rotating speed to 25 RPM; and then the plug is pressed for 32-37 seconds, the temperature is raised to 100-105 ℃, the glue is discharged, and the plug is lifted to open the discharging door.
The application also provides a rubber compound prepared by the preparation method of the rubber compound.
The rubber material prepared from the rubber compound can improve the dynamic rigidity retentivity of the semi-steel radial tire under temperature change while ensuring the physical properties of the semi-steel radial tire such as hardness and elastic modulus of the tire tread and the matching requirements of an extrusion process, greatly improves the ground gripping performance of the rubber material, greatly reduces the rolling resistance, and simultaneously improves the breaking strength of rubber materials.
The application also provides a tire which is prepared by adopting the rubber compound.
The tire of the present application has high grip performance and low rolling resistance.
A composition for preparing a rubber composition, a rubber composition and a method for preparing the same according to the present application will be described in further detail with reference to examples.
It should be noted that the specific four-stage kneading process of the present application was employed in each of examples 1 to 7 and comparative examples 1 to 7.
The formulations of examples 1 to 7 are shown in Table 1, and the formulations of comparative examples 1 to 7 are shown in Table 2.
TABLE 1 formulation tables for examples 1-7
Wherein the weight average molecular weight of F-SSBR A-1 is 1.2%106The content of styrene is 25-40%, and the content of vinyl is 25-40%; the weight average molecular weight of F-SSBR B-1 is 5.2X 105The content of styrene is 25-40%, and the content of vinyl is 25-40%; the weight average molecular weight of F-SSBR A-2 was 0.9 x 106The content of styrene is 25-40%, and the content of vinyl is 25-40%; the weight average molecular weight of F-SSBR B-2 was 3.4X 105The content of styrene is 20-35%, and the content of vinyl is 40-60%; the weight average molecular weight of F-SSBR B-3 is 7.5X 105The styrene content is 20-35%, and the vinyl content is 40-60%.
TABLE 2 formulation tables for comparative examples 1 to 7
Wherein the weight average molecular weight of F-SSBR A-3 is 5.5 x 105The content of styrene is 10-24%, and the content of vinyl is 41-55%; the weight average molecular weight of F-SSBR B-4 is 5.2X 105The styrene content is 5-19%, and the vinyl content is 25-39%.
Test example 1
The curing time at 160 ℃ for 30min and the scorch time at 127 ℃ and the Mooney viscosity characteristics at 100 ℃ of the rubber compounds prepared according to the formulations of examples 1 to 7 and comparative examples 1 to 3 and 6 to 7 were measured, respectively, as shown in tables 3 and 4. And the physical and mechanical properties of the rubber compounds prepared by the formulations of examples 1 to 7 and comparative examples 1 to 3 and 6 to 7 after vulcanization at 160 ℃ for 20min were measured, as shown in tables 5 and 6.
TABLE 3 curing and 127 ℃ scorch of the rubber mixtures of examples 1 to 7 at 160 ℃ for 30min and 100 ℃ Mooney viscosity characteristics
TABLE 4 rubber mixtures of comparative examples 1 to 3, 6 to 7 vulcanized at 160 ℃ for 30min and scorched at 127 ℃ and Mooney viscosity characteristics at 100 DEG C
| Test items | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 6 | Comparative example 7 |
| ML | 1.49 | 2.09 | 1.48 | 1.62 | 1.72 |
| MH | 11.45 | 15.09 | 11.88 | 9.27 | 12.46 |
| TS1 | 2:33 | 0:44 | 2:59 | 2:43 | 3:20 |
| TS2 | 3:07 | 2:25 | 3:27 | 3:19 | 3:45 |
| T10 | 2:33 | 1:28 | 2:53 | 2:50 | 3:18 |
| T50 | 3:47 | 3:23 | 4:21 | 4:16 | 4:38 |
| T90 | 8:49 | 9:25 | 9:55 | 9:38 | 10:27 |
| Ts5(127℃) | 22:21 | 19:05 | 20:52 | 23:19 | 27:11 |
| ML(1+4)100℃ | 70.43 | 76.98 | 73.42 | 69.24 | 78.85 |
TABLE 5 physical and mechanical properties of the rubber mixtures of examples 1 to 7 after vulcanization at 160 ℃ for 20min
TABLE 6 physical and mechanical properties of the rubber mixtures of comparative examples 1 to 3 and 6 to 7 after vulcanization at 160 ℃ for 20min
As can be seen from tables 3 to 4, the total amount of the two resin materials CSR6200 and KSH-1 is the same, the use ratio is different, and the vulcanization speed is different. The larger the amount of KSH-1 used, the slower the vulcanization rate, and the longer the corresponding scorch time, the slower the vulcanization rate in example 4 compared with examples 1-3.
As can be seen from tables 5 to 6, the formulations of examples 1 to 4 can better balance the contradiction between the grip performance and the rolling resistance performance when the raw rubber systems of F-SSBR A-1 and F-SSBRB-1 are adopted. Example 5 Using the crude rubber combination of F-SSBR A-2 and F-SSBRB-1, the tensile strength at break of the vulcanized rubber is reduced, and the grip performance and the rolling resistance performance of the rubber compound can be characterized to some extent by the resilience at high and low temperatures in the same frame formulation system, and both of them are reduced to some extent. Similarly, the grip performance of the embodiment 6 to 7 is also reduced to a certain extent. Comparative examples 4 to 5 were too slow in vulcanization rate and could not be vulcanized. In the comparative examples 1-2, the crude rubber systems (IR and BR) of the non-solution polymerized styrene-butadiene rubber are introduced, and the grip performance and the rolling resistance performance are obviously reduced. The physical and mechanical properties of comparative examples 3 and 6 were significantly reduced, the grip performance of comparative example 6 was significantly reduced, and the grip performance and rolling resistance performance of comparative example 7 were not well balanced.
Test example 2
The dynamic mechanical properties of the rubber compounds prepared by the formulations of examples 1 to 7 and comparative examples 1 to 3 and 6 to 7 after vulcanization at 160 ℃ for 20min were measured, respectively, as shown in tables 7 to 8.
TABLE 7 dynamic mechanical Properties of the rubber mixtures of examples 1 to 7 after vulcanization at 160 ℃ for 20min
Wherein, DMA test conditions Static 3%, Dynamic 0.25 x 10HzTemp. @3K/MIN-40- > +120 ℃.
TABLE 8 dynamic mechanical properties of the rubber mixtures of comparative examples 1 to 3 and 6 to 7 after vulcanization at 160 ℃ for 20min
| Test items | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 6 | Comparative example 7 |
| RPA,ΔG' | 0.76 | 0.65 | 0.32 | 0.28 | 0.41 |
| tanδ(@0℃) | 0.733 | 0.535 | 1.089 | 0.612 | 0.717 |
| tanδ(@20℃) | 0.275 | 0.222 | 0.406 | 0.287 | 0.266 |
| tanδ(@60℃) | 0.115 | 0.126 | 0.087 | 0.091 | 0.120 |
| E'(Mpa)(@0℃) | 57.711 | 65.546 | 47.231 | 39.127 | 49.562 |
| E'(Mpa)(@20℃) | 16.870 | 27.823 | 9.181 | 14.635 | 12.543 |
| E'(Mpa)(@60℃) | 7.942 | 15.443 | 4.245 | 6.316 | 5.827 |
| E'(Mpa)(20-60℃) | 8.93 | 12.38 | 4.94 | 8.32 | 6.72 |
| Tg℃(@Max tanδ) | -4.6 | -8.8 | -5.5 | -6.1 | -12.3 |
Wherein, DMA test conditions Static 3%, Dynamic 0.25 x 10HzTemp. @3K/MIN-40- > +120 ℃.
As can be seen from tables 7 and 8, the RPA represents the dispersion condition of the white carbon black in the sizing material, the dispersion is better when the value is smaller, and the mixing process adopted by the application can effectively improve the dispersibility of the sizing material, so that the dynamic performance of the sizing material is improved. tan delta (@20 ℃) represents the dry grip performance of the sizing material, and the higher the value of the tan delta, the better the grip performance; tan delta (@60 ℃) represents the rolling resistance performance of the sizing material, and the lower the value of the tan delta, the better the rolling resistance performance. The grip performance and the rolling resistance performance of the embodiments 2 to 4 are well balanced, and the performances are outstanding. E' (20-60 ℃) represents the dynamic rigidity retention rate of the sizing material under the temperature change, the lower the value is, the smaller the influence of the sizing material on the temperature change is represented, the influence of the temperature change on the dynamic performance of all the embodiments is controlled within a lower threshold value, and the excellent conversion capability of the gripping performance and the rolling resistance performance can be realized.
In the case of increasing sulfur by a single variable, the comparative example 3 hardly affects the dynamic performance of the rubber material, but has insufficient static physical property performance, and has insufficient balance of the grip performance and the rolling resistance performance of comparative examples 1-2 and 6-7.
The foregoing is illustrative of the present application and is not to be construed as limiting thereof, as numerous modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A composition for the preparation of a mix, characterized in that it comprises: 70-130 parts of modified oil-extended solution-polymerized styrene-butadiene rubber A, 5-55 parts of modified oil-extended solution-polymerized styrene-butadiene rubber B, 60-100 parts of white carbon black, 5-15 parts of carbon black, 3-7 parts of vulcanization activator, 1-2 parts of vulcanizing agent and 3.8-5.5 parts of vulcanization accelerator;
wherein the modified oil-extended solution-polymerized styrene-butadiene rubber A contains 25-40% of styrene and 25-40% of vinyl;
the styrene content in the modified oil-extended solution-polymerized styrene-butadiene rubber B is 20-35%, and the vinyl content is 40-60%.
2. A composition for preparing a rubber compound as claimed in claim 1, wherein said modified oil-extended solution-polymerized styrene-butadiene rubber A has a styrene content of 30 to 40% and a vinyl content of 30 to 40%, and said modified oil-extended solution-polymerized styrene-butadiene rubber B has a styrene content of 20 to 30% and a vinyl content of 40 to 50%;
optionally, the modified oil-extended solution-polymerized styrene-butadiene rubber A has a weight-average molecular weight Mw≥106The weight average molecular weight of the modified oil-extended solution-polymerized styrene-butadiene rubber B is 4 x 105～6*105；
Optionally, the modified oil-extended solution-polymerized styrene-butadiene rubber A is extended with 35 to 40phr of oil, and the modified oil-extended solution-polymerized styrene-butadiene rubber B is extended with 3 to 7phr of oil.
3. A composition for the preparation of a rubber compound as claimed in claim 1, wherein said white carbon black is precipitated hydrated silica and has a BET specific surface area of 140 to 180cm2/g；
Optionally, the nitrogen adsorption specific surface area of the carbon black is more than or equal to 80cm2/g；
Optionally, the composition for preparing the rubber compound comprises 2-4 parts by weight of white carbon black dispersing agent, and the white carbon black dispersing agent comprises a mixture of zinc stearate and fatty acid ester;
optionally, the composition for preparing the rubber compound comprises 6-15 parts by weight of a silane coupling agent;
optionally, the silane coupling agent comprises Si-69 solid silicon.
4. A composition for use in preparing a mix as claimed in claim 1, characterised in that said vulcanisation agent comprises sulphur and said vulcanisation accelerator comprises N-cyclohexyl-2-benzothiazolesulfenamide, diphenylguanidine and tetrabenzylthiuram disulphide;
optionally, the vulcanization accelerator comprises 1.5-2 parts by weight of N-cyclohexyl-2-benzothiazole sulfonamide, 2-3 parts by weight of diphenyl guanidine and 0.3-0.5 part by weight of tetrabenzylthiuram disulfide.
5. A composition for the preparation of a rubber mix as claimed in claim 1, characterized in that it comprises 4 to 7 parts by weight of a grip resin;
optionally, the grip resin comprises a modified alpha-methyl styrenic resin.
6. A composition for the preparation of a rubber mix as claimed in any one of claims 1 to 5, characterized in that it comprises 4 to 7 parts by weight of said biological material KSH-1, said biological material KSH-1 having the formula C9H8.83(OCH3)0.95。
7. A composition for the preparation of rubber compounds as claimed in any of claims 1 to 5, wherein said composition for the preparation of rubber compounds comprises 2 to 9 parts by weight of environmentally friendly aromatic oil, 4 to 7 parts by weight of anti-aging agent and 0.1 to 0.3 part by weight of scorch retarder.
8. The preparation method of the rubber compound is characterized by comprising the steps of sequentially carrying out first-stage master batch mixing, second-stage master batch mixing, third-stage master batch mixing and fourth-stage master batch mixing;
the first-stage master batch mixing comprises the steps of mixing 70-130 parts by weight of modified oil-extended solution-polymerized styrene-butadiene rubber A, 5-55 parts by weight of modified oil-extended solution-polymerized styrene-butadiene rubber B, 60-100 parts by weight of white carbon black, 2-4 parts by weight of white carbon black dispersing agent, 6-15 parts by weight of silane coupling agent, 4-7 parts by weight of ground-grabbing resin, 4-7 parts by weight of biological material KSH-1, 2-4 parts by weight of vulcanization activator, 2-3 parts by weight of vulcanization accelerator, 1-3 parts by weight of anti-aging agent and 2-9 parts by weight of environment-friendly aromatic hydrocarbon oil to prepare a first master batch;
the two-stage masterbatch mixing comprises the step of mixing the prepared first masterbatch, 5-15 parts by weight of carbon black, 1-3 parts by weight of vulcanization activator and 2-4 parts by weight of anti-aging agent to prepare second masterbatch;
the three-stage master batch mixing comprises the step of carrying out back mixing on the prepared second master batch to prepare a third master batch;
the four-stage masterbatch mixing comprises the step of mixing the prepared third masterbatch, 1-2 parts by weight of vulcanizing agent, 1.8-2.5 parts by weight of vulcanization accelerator and 0.1-0.3 part by weight of anti-scorching agent for final mixing to prepare the rubber compound.
9. A rubber composition, characterized in that it is obtained by the method for preparing a rubber composition according to claim 8.
10. A tire, characterized in that the tread of said tire is made using the mix of claim 9.
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| CN114656699A (en) * | 2022-03-15 | 2022-06-24 | 中策橡胶集团股份有限公司 | Low rolling resistance and high grip ground tread rubber compound composition, mixing method thereof and tire |
| CN115322460A (en) * | 2022-09-16 | 2022-11-11 | 中策橡胶集团股份有限公司 | High-performance tire tread rubber composition, mixing method thereof and prepared tire |
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