CN114835959A - Ultralow rolling resistance rubber composition for four-season tire, mixing method thereof and tire - Google Patents
Ultralow rolling resistance rubber composition for four-season tire, mixing method thereof and tire Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 105
- 239000005060 rubber Substances 0.000 title claims abstract description 105
- 238000002156 mixing Methods 0.000 title claims abstract description 32
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000005096 rolling process Methods 0.000 title claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 136
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 58
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 28
- 239000005543 nano-size silicon particle Substances 0.000 claims description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 238000005299 abrasion Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 239000004200 microcrystalline wax Substances 0.000 claims description 7
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000012779 reinforcing material Substances 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 6
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 238000004513 sizing Methods 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000498 cooling water Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical group CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 2
- 229960002447 thiram Drugs 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims 2
- 239000010734 process oil Substances 0.000 claims 2
- 238000013329 compounding Methods 0.000 claims 1
- 238000009472 formulation Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000012855 volatile organic compound Substances 0.000 abstract description 7
- 238000002444 silanisation Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 9
- 230000004580 weight loss Effects 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000004636 vulcanized rubber Substances 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 3
- 241000872198 Serjania polyphylla Species 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 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 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of rubber tire manufacturing, in particular to an ultralow rolling resistance rubber composition for a four-season tire, a mixing method thereof and a tire. According to the invention, the silane coupling agent is adopted to pre-react the nano-silica, and then the modified nano-silica is mixed with other raw materials, so that VOC (volatile organic compounds) emission is effectively avoided, the useless cost in a mixing formula and the use cost of equipment and instruments are reduced, and the silane coupling agent pre-reacted nano-silica does not need to carry out a silanization reaction at a constant temperature, so that the mixing efficiency is further improved.
Description
Technical Field
The invention relates to the field of rubber tire manufacturing, in particular to an ultralow rolling resistance rubber composition for a four-season tire, a mixing method thereof and a tire.
Background
With the increasing exhaustion of the world fuel resources, the society pays more and more attention to energy conservation and emission reduction, and the fuel economy of the automobile becomes more and more important as a high-consumption individual of petrochemical fuel. The rolling resistance of tires is a key index affecting fuel consumption of automobiles, and the european union has issued labeling regulations for tires, which stipulate that tires having rolling resistance higher than F level are sold in grades as a key index of tires, and are not allowed to be sold in the european union market.
In order to reduce the rolling resistance of the tire, Michellin company replaces the traditional carbon black with nano silica to reinforce the rubber, and the rolling resistance of the tire using the nano silica is reduced by 30 percent compared with the rolling resistance of the tire using the traditional carbon black under the same reinforcing degree.
Although the tire using the nano-silica makes a prominent contribution to the fuel economy of an automobile, in the process of using the nano-silica, the nano-silica is a strong-polarity reinforcing material, the main rubber in the formula is nonpolar, the nano-silica and the rubber cannot be compatible, in order to uniformly mix the nano-silica and the rubber, the surface of the nano-silica needs to be modified by using a silane coupling agent, the silane coupling agent reacts with hydroxyl on the surface of the nano-silica to change the polarity of the hydroxyl into the nonpolar, the reaction process needs a certain temperature and time, and the conventional carbon black formula can be uniformly mixed when the mixing temperature reaches 150 ℃, so that rubber can be discharged. The formula using the nano silicon dioxide is required to perform constant temperature silanization reaction after the mixing temperature reaches 150 ℃, the constant temperature is generally required to be kept at 150 ℃ for more than two minutes, the constant temperature reaction is required to be performed in a specific internal mixer with a constant temperature function, the manufacturing cost of internal mixing equipment with the constant temperature function is higher than that of common equipment, and the rubber material mixing time and the equipment cost are invisibly increased greatly.
Meanwhile, a large amount of ethanol is generated in the reaction process of the silane coupling agent and hydroxyl on the surface of the nano silicon dioxide, and according to measurement and calculation, 8.6kg of ethanol is generated in each ton of nano silicon dioxide mixing, so that a large amount of VOC (volatile organic compounds) which is harmful to the environment is generated.
Object of the Invention
In order to solve the problems that a large amount of ethanol gas is generated by nano silicon dioxide and a silane coupling agent during mixing, the mixing efficiency is low and the equipment cost is high, the silane coupling agent is adopted to pre-react the nano silicon dioxide aiming at a filler system of a tread formula, and then the modified nano silicon dioxide is mixed with other raw materials, so that the VOC emission is effectively avoided, the useless cost in the mixing formula and the use cost of equipment and instruments are reduced, and the silane coupling agent pre-reacted nano silicon dioxide does not need to perform a silanization reaction at a constant temperature, so that the mixing efficiency is further improved.
In order to achieve the above object, the present invention adopts the following technical solutions:
the mixing formula of the rubber composition comprises a rubber component, a reinforcing material, a processing aid and a vulcanizing agent, wherein the rubber component and the reinforcing material comprise the following raw material components in parts by weight based on 100 parts by weight of the rubber component:
the mass of styrene in the solution polymerized styrene-butadiene rubber A accounts for 20-30% of the total weight of the polymer, the mass of vinyl accounts for 20-30% of the total weight of butadiene, and the tail end of a rubber molecular chain is modified aiming at silicon dioxide; the mass of styrene in the solution polymerized styrene-butadiene rubber B accounts for 30-40% of the total weight of the polymer, the mass of vinyl accounts for 35-45% of the total weight of butadiene, and the tail end of a rubber molecular chain is modified aiming at silicon dioxide; the silane coupling agent pre-reacted nano silicon dioxide is prepared by reacting a silane coupling agent with nano silicon dioxide, wherein the mass ratio of the silane coupling agent to the nano silicon dioxide is 1: 8-20.
The solution polymerized styrene-butadiene rubber A and the solution polymerized styrene-butadiene rubber B can adopt oil-extended rubber, preferably, the solution polymerized styrene-butadiene rubber A is extended with 20 to 30phr of oil, and the solution polymerized styrene-butadiene rubber B is extended with 32 to 40phr of oil.
Preferably, the rubber component and the reinforcing material are composed of the following raw material components in parts by weight, based on 100 parts by weight of the rubber component:
preferably, the nitrogen adsorption specific surface area (BET) of the nano-silica is 130-200m 2 (ii)/g; the silane coupling agent is Si69 or Si 747.
Preferably, the carbon black is super wear-resistant carbon black with the particle size of 11-19 nm.
Preferably, the mixing formula of the rubber composition also comprises rubber operating oil and anti-slippery resin, wherein the rubber operating oil accounts for 2.0-10.0 parts, and the anti-slippery resin accounts for 2.0-10.0 parts; preferably, the anti-slippery resin is an alpha-methylstyrene modified resin, and the structural formula is as follows:
preferably, the processing aid comprises a silica dispersing agent, a rubber active agent and a rubber anti-aging agent, wherein the silica dispersing agent accounts for 3.0-8.0 parts, and the rubber active agent adopts zinc oxide and stearic acid: 2.0 to 4.0 parts by weight of zinc oxide and 1.0 to 3.0 parts by weight of stearic acid; the rubber antioxidant adopts antioxidant 6PPD, RD and microcrystalline wax: 1.0 to 3.0 parts by weight of 6PPD, 1.0 to 3.0 parts by weight of RD, and 1.0 to 3.5 parts by weight of microcrystalline wax.
Preferably, the vulcanizing agent comprises sulfur and an accelerator, 0.5-1.0 part of sulfur, and the accelerator comprises 1.0-2.0 parts of accelerator A, 1.0-2.5 parts of accelerator B and 1.0-2.5 parts of accelerator C, wherein:
the accelerator A is N-cyclohexyl-2-benzothiazole sulfonamide, and the structural formula is as follows:
accelerator B is a thiuram tetrakis- (2-ethylhexyl) disulfide having the following structural formula:
the accelerator C is zinc dialkyl dithiophosphate, and the structural formula of the accelerator C is as follows:
further, the application also discloses a mixing method of the rubber composition, which uses a tandem one-time method internal mixer; controlling the rotor speed of the internal mixer to be 40-60rpm and the upper ram pressure to be 50-60N/cm 2 The temperature of the cooling water of the internal mixer is 30-40 ℃, and the method comprises the following steps:
firstly, an upper auxiliary machine process:
firstly, adding a rubber component and a silane coupling agent to pre-react nano silicon dioxide, carbon black and a processing aid, and lowering the top plug and keeping for 25-35 seconds;
lifting the top bolt, and keeping for 8-12 seconds;
lowering the top bolt to raise the temperature of the rubber material to 95-105 deg.c;
fourthly, lifting the top plug, adding rubber operating oil and anti-slippery resin, and keeping for 4-8 seconds;
lowering the upper top plug to heat the rubber material to 135-142 ℃;
lowering the top plug to mix the rubber material at the constant temperature of 138-142 ℃ for 100-150 seconds;
and discharging the rubber material to a lower auxiliary machine.
II, auxiliary machine process:
firstly, heating the sizing material to 135-142 ℃;
② mixing at constant temperature of 138-142 ℃ for 250-350 seconds;
thirdly, rubber discharging to an open mill: turning and cooling the rubber material to 90-100 ℃, adding sulfur and a vulcanization accelerator on an open mill, uniformly dispersing, and cooling the lower piece to room temperature.
Further, the application also discloses application of the rubber composition in preparing tread rubber of an ultra-low rolling resistance four-season tire.
Further, the application also discloses an ultra-low rolling resistance four-season tire, and the tread rubber of the tire is prepared by vulcanizing the rubber composition.
The beneficial effect of adopting above-mentioned technical scheme is: the silicon dioxide modified solution polymerized butadiene styrene rubber used in the invention can promote the dispersion of silicon dioxide, thereby improving the performance of the formula, and simultaneously, the wear resistance of the formula can be improved by using part of high molecular weight neodymium cis-butadiene rubber. The invention uses silane coupling agent to pre-react silicon dioxide, the traditional silane coupling agent and silicon dioxide react in the rubber viscous state, the reaction efficiency is low, in order to improve the reaction efficiency, excessive silane coupling agent (10% of the weight of silicon dioxide is generally used) is generally used, which also causes the increase of the formula cost, the silane coupling agent is already reacted with the silicon dioxide in the manufacturing process of the silane coupling agent pre-reacted silicon dioxide, the reaction efficiency of the silane coupling agent and the silicon dioxide is greatly improved due to the direct reaction of the silane coupling agent and the silicon dioxide, the silicon dioxide can be modified by using 5% of the weight of the silicon dioxide, 5% of the silane coupling agent is saved, and the unnecessary cost of the formula is reduced. The silane coupling agent is used for pre-reacting silicon dioxide, so that the formula performance is ensured, the formula mixing time is greatly shortened, the mixing efficiency is improved, and the use cost of banburying equipment is reduced. Meanwhile, the silane coupling agent is used for pre-reacting the silicon dioxide, so that VOC emission is avoided, and the method is environment-friendly.
In the rubber composition of the present invention, in addition to the above components, various additives such as other fillers, vulcanizing agents, vulcanization accelerators, various types of oils, antioxidants, plasticizers, and the like, which are generally used in tires and other rubber compositions, may be blended. These additives are mixed in a conventional manner to obtain a rubber composition which can be used for vulcanization. The amounts of these additives may also be conventional and customary mixing amounts, provided that the object of the invention is not adversely affected.
Detailed Description
The technical solutions in the embodiments of the present invention will be examined and completely described below with reference to the embodiments of the present invention, so as to further explain the invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. Given the embodiments of the present invention, all other embodiments that can be obtained by a person of ordinary skill in the art without any inventive step are within the scope of the present invention.
Examples 1 to 3 are specifically shown in Table 1 (parts by weight):
table 1 examples 1-3 formulaic details
Note:
*1: HS256, 25.0% of the total weight of styrene mass station polymer, 25.0% of vinyl group of the total weight of butadiene, modification of rubber molecular chain end to silica, product of asahi chemicals co., ltd, batch process, oil charge 25 phr;
*2: e581, styrene quality station polymer gross weight 35.5%, vinyl accounts for butadiene gross weight 40.0%, rubber molecular chain end to silica modification, Asahi chemical company products, batch process production, oil extended 37.5 phr;
*3: CB24, a product of alurniaceae;
*4: 200MP, Cetyl Trimethyl Ammonium Bromide (CTAB) 200m2/g, Solvay chemical products;
*5: agilon 458, silane coupling agent pre-reacted nanosilica, cetyltrimethylammonium bromide (CTAB) 200m 2 (iv)/g, PPG chemical products;
*6: si69, product of flood and wave corp, Jiangxi;
*7: si747, a product of Jiangsu Qi Xiang high-new materials Co., Ltd;
*8: n134, cabot chemical products;
*9: v700, Ningbo Han Sheng chemical products;
*10: SYLVATRAXX 4401, a product of kraton chemical ltd;
*11: SPA, product of dada nanomaterials, wilhon;
*12: S200-10S Fufang Fuhong chemical industry Limited company product;
*13: CZ, langson chemical ltd;
*14: TBzTD, product of Wuhan Yuehe chemical Co., Ltd;
*15: TPZ, a product of Kyoho Kagaku Co., Ltd;
16 other 2.0 weight parts of zinc oxide and 1.0 weight part of stearic acid; 1.0 part by weight of 6PPD, 1.0 part by weight of RD and 2.5 parts by weight of microcrystalline wax;
the rest raw materials are commercial industrial products.
Preparation of example 1, comparative example 1: (the process uses a tandem one-shot internal mixer)
Controlling the rotor speed of the internal mixer to be 40-60rpm and the upper ram pressure to be 50-60N/cm 2 The temperature of the cooling water of the internal mixer is 30-40 ℃, and the method comprises the following steps:
firstly, an upper auxiliary machine process:
adding rubber, silicon dioxide, a silane coupling agent, zinc oxide, stearic acid, an anti-aging agent, microcrystalline wax and the like, and lowering the top plug and keeping for 30 seconds;
lifting the top bolt, and keeping for 10 seconds;
lowering the top bolt to raise the temperature of the rubber material to 100 deg.c;
fourthly, lifting the top plug, adding softening oil, and keeping for 5 seconds;
lowering the upper top bolt to raise the temperature of the rubber material to 138 ℃;
lowering the upper plug to mix the rubber material at the constant temperature of 138-142 ℃ for 120 seconds;
and discharging the rubber material to a lower auxiliary machine.
II, auxiliary machine process:
firstly, heating the sizing material to 138 ℃;
② mixing at constant temperature of 138-142 ℃ for 300 seconds;
thirdly, rubber discharging to an open mill: turning and cooling the rubber material to 90-100 ℃, adding sulfur and a vulcanization accelerator on an open mill, uniformly dispersing, and cooling the lower piece to room temperature.
Preparation of comparative example 2: (shear type Banbury mixer used in the process)
Controlling the rotor speed of the internal mixer to be 40-60rpm and the upper ram pressure to be 50-60N/cm 2 The temperature of the cooling water of the internal mixer is 30-40 ℃, and the method comprises the following steps:
adding rubber, silicon dioxide, zinc oxide, stearic acid, an anti-aging agent, microcrystalline wax and the like, and lowering the top plug and keeping for 30 seconds;
lifting the top bolt, and keeping for 10 seconds;
lowering the top bolt to raise the temperature of the rubber material to 100 deg.c;
fourthly, lifting the top plug, adding softening oil, and keeping for 5 seconds;
lowering the upper top bolt to heat the rubber material to 140 ℃;
sixthly, discharging the rubber to an open mill: turning and cooling the rubber material to 90-100 ℃, adding sulfur and a vulcanization accelerator on an open mill, uniformly dispersing, and cooling the lower piece to room temperature.
The rubber compound weighing data before and after mixing of example 1, comparative example 1 and comparative example 2 are shown in table 2:
table 2 examples 1-3 weight loss on bicycle results
In the mixing process of the rubber compound, due to the fact that the temperature is high, some small molecular substances volatilize to cause weight loss, meanwhile, a large amount of ethanol gas is generated in the reaction process of the silicon dioxide and the silane coupling agent to cause weight loss, and due to the fact that the generated ethanol gas needs to be removed, an upper top plug needs to be lifted to establish an exhaust channel in the mixing process, and floating silicon dioxide particles also can be lost in the exhaust process.
It can be seen from the data of table 2 that the weight loss of comparative examples 1 and 2 is much greater than that of example 1 because the silane coupling agent pre-reacted silica used in example 1 has completed the chemical reaction and no ethanol gas is generated during the kneading, and the loss of silica particles during the kneading is also significantly reduced because no ethanol gas is generated and no vent passage is established, so the weight loss of comparative examples 1 and 2 is much greater than that of example 1.
The weight loss of comparative example 2 is smaller than that of comparative example 1 because the silane coupling agent used in comparative example 2 has a large molecular weight and a small amount of effective functional groups, and thus the amount of ethanol gas generated is small.
In conclusion, the weight loss of the rubber compound can be obviously reduced by using the silane coupling agent pre-reacted silica, and the weight loss is mainly based on ethanol gas, so that the VOC emission of the rubber compound can be obviously reduced by using the silane coupling agent pre-reacted silica.
The mixing process data of example 1, comparative example 1 and comparative example 2 are shown in table 3:
table 3 test results of example 1, comparative example 1, and comparative example 2
Note: the electric charge is 1.0577 yuan/kilowatt hour.
From the data in Table 3, it can be seen that the mixing cost of comparative examples 1 and 2 is much higher than that of example 1, i.e. the pre-reaction of silica with the silane coupling agent can significantly reduce the mixing cost of the rubber compound, and can save the mixing cost by 66%.
Test methods for evaluating rubber properties:
the rubber composition obtained by kneading was vulcanized in a mold prepared in advance under the conditions of 160 ℃ for 15min and a pressure of 15 MPa. Then, the properties of the vulcanized rubber were measured by the following test methods, and the measurement results are shown in Table 4.
Physical properties:
the hardness at room temperature was measured based on GB/T531.1-2008, and the larger the value, the higher the hardness.
The tensile strength determined based on GB/T528-. Further, the elongation at break during the same test period is shown as "elongation at break". The product of tensile strength and elongation at break is shown as the "tensile product". The larger the value, the higher the reinforcement and the better the physical properties. The aging condition of the physical property after aging is 100 ℃ for 48 hours, the ratio of the tensile product after aging to the tensile product before aging is the heat aging retention rate, and the larger the value is, the better the aging resistance is.
Abrasion resistance-Akron abrasion:
the attone abrasion determined based on GB/T1689-. The smaller the value, the less wear and the more excellent the wear resistance.
Dynamic performance-Dynamic thermo-mechanical analysis (DMA):
measured by using a dynamic thermomechanical analyzer model VR-7120 manufactured by UESHIMA corporation of Japan. The test conditions were: a stretching mode; frequency, 12 Hz; strain, 7% ± 0.25%; temperature rise is carried out at 2 ℃/min. The results are shown in table 4. The tan delta value at 0 ℃ represents the wet land holding capacity of the vulcanized rubber, and the larger the value is, the better the wet land holding capacity of the tire prepared by the vulcanized rubber is; the tan delta value at 60 ℃ characterizes the hysteresis loss of the vulcanized rubber, the smaller this value, the lower the hysteresis loss of the vulcanized rubber and the lower the rolling resistance of the tyre obtained; the temperature at which the maximum tan δ corresponds is the Tg of the vulcanizate, the lower the Tg, the better the winter performance of the vulcanizate.
Table 4 test results of example 1, comparative example 1, and comparative example 2
It can be seen from the comparison of example 1 with comparative example 1 and comparative example 2 that, when the silane coupling agent pre-reacted silica is used to replace the ordinary silica, the physical properties of the sizing material are improved, especially the physical properties after aging are greatly improved, because the silane coupling agent pre-reacted silica is reacted with the silica in the manufacturing process, and because the silane coupling agent is directly reacted with the silica, the reaction efficiency of the silane coupling agent pre-reacted silica and the silica is greatly improved, the silylation reaction rate is high, and the dispersion of the silica is improved.
Meanwhile, the dynamic performance of the sizing material is improved more obviously by using the silane coupling agent to pre-react the silicon dioxide, and the wet slip and rolling resistance are greatly improved, which is also benefited by better dispersion of the silane coupling agent pre-reacted silicon dioxide.
The abrasion performance of the comparative example 1 is superior to that of other schemes, which is caused by different silane coupling agents, the mercaptosilane used in the scheme 3 has higher reactivity than sulfur-containing silane, the generated silica-silane coupling agent-rubber cross-linked structure is more, the flexibility of rubber is reduced, and the abrasion performance of rubber materials is reduced, and the silane coupling agent pre-reacted silica also uses mercaptosilane, but the abrasion performance of the silane coupling agent pre-reacted silica is improved to a certain extent compared with the abrasion performance of the mercaptosilane additionally used in the comparative example 2.
In conclusion, after the silane coupling agent pre-reacted silicon dioxide is used for replacing common silicon dioxide, all properties of the rubber material are improved to a certain extent, particularly the dynamic property of the rubber material is improved, and the heat generation of the rubber material is reduced by 36%.
A batch of 215/55R18 size tires were prepared from the compound of example 1 and tested for a full tire, the results of which are shown in Table 5.
Table 5 example 1 stock trial tire machine tool performance data
From the data in table 4, it can be seen that the high speed and durability performance of the tire trial-manufactured by the present invention meet the regulatory requirements, and the tire has a label grade rolling resistance coefficient of class a and a wet skid coefficient of class B.
Industrial applicability: according to the invention, the tire with high label grade, especially extremely low rolling resistance and greatly reduced mixing cost can be manufactured, the manufacturing cost of the tire is reduced while the high performance of the tire is ensured, the carbon emission is reduced, and the environment is protected in the using and manufacturing processes of the tire. The present invention is useful for, but not limited to, tire tread manufacture for all season tires.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention, including any reference to the above-mentioned embodiments. Various modifications to these embodiments will be readily apparent to those skilled in the art. The general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The ultra-low rolling resistance rubber composition for the four-season tire is characterized in that the rubber component and the reinforcing material consist of the following raw material components in parts by weight based on 100 parts by weight of the rubber component:
the mass of styrene in the solution polymerized styrene-butadiene rubber A accounts for 20-30% of the total weight of the polymer, the mass of vinyl accounts for 20-30% of the total weight of butadiene, and the tail end of a rubber molecular chain is modified aiming at silicon dioxide; the mass of styrene in the solution polymerized styrene-butadiene rubber B accounts for 30-40% of the total weight of the polymer, the mass of vinyl accounts for 35-45% of the total weight of butadiene, and the tail end of a rubber molecular chain is modified aiming at silicon dioxide; the silane coupling agent pre-reacted nano silicon dioxide is prepared by reacting a silane coupling agent and nano silicon dioxide, and the mass ratio of the silane coupling agent to the nano silicon dioxide is 1: 8-20.
2. The rubber composition according to claim 1, wherein the rubber component and the reinforcing material are composed of the following raw material components in parts by weight, based on 100 parts by weight of the rubber component:
3. the rubber composition as claimed in claim 1, wherein the nitrogen adsorption specific surface area (BET) of the nanosilica is 130-200m 2 (ii)/g; the silane coupling agent is Si69 or Si 747.
4. The rubber composition according to claim 1, wherein the carbon black is super abrasion-resistant carbon black having a particle size of 11 to 19 nm.
5. The rubber composition according to claim 1, wherein the compounding formulation of the rubber composition further comprises a rubber process oil and a wet-skid resistant resin, the rubber process oil is 2.0 to 10.0 parts, and the wet-skid resistant resin is 2.0 to 10.0 parts; preferably, the anti-slippery resin is an alpha-methylstyrene modified resin, and the structural formula is as follows:
6. the rubber composition of claim 1, wherein the processing aid comprises a silica dispersant, a rubber activator and a rubber antioxidant, wherein the silica dispersant is 3.0-8.0 parts, and the rubber activator is selected from the group consisting of zinc oxide and stearic acid: 2.0 to 4.0 parts by weight of zinc oxide and 1.0 to 3.0 parts by weight of stearic acid; the rubber antioxidant adopts antioxidant 6PPD, RD and microcrystalline wax: 1.0 to 3.0 parts by weight of 6PPD, 1.0 to 3.0 parts by weight of RD, and 1.0 to 3.5 parts by weight of microcrystalline wax.
7. The rubber composition according to claim 1, wherein the vulcanizing agent comprises sulfur and an accelerator, the sulfur is 0.5-1.0 part, and the accelerator comprises 1.0-2.0 parts of accelerator A, 1.0-2.5 parts of accelerator B and 1.0-2.5 parts of accelerator C, wherein: the accelerator A is N-cyclohexyl-2-benzothiazole sulfonamide, and the structural formula is as follows:
accelerator B is a thiuram tetrakis- (2-ethylhexyl) disulfide having the following structural formula:
the accelerator C is zinc dialkyl dithiophosphate, and the structural formula of the accelerator C is as follows:
8. a method for kneading a rubber composition according to any one of claims 1 to 7, wherein a tandem one-shot internal mixer is used; controlling the rotor speed of the internal mixer to be 40-60rpm and the upper ram pressure to be 50-60N/cm 2 The temperature of the cooling water of the internal mixer is 30-40 ℃, and the method comprises the following steps:
firstly, an upper auxiliary machine process:
firstly, adding a rubber component and a silane coupling agent to pre-react nano silicon dioxide, carbon black and a processing aid, and lowering the top plug and keeping for 25-35 seconds;
lifting the top bolt, and keeping for 8-12 seconds;
lowering the top bolt to raise the temperature of the rubber material to 95-105 deg.c;
fourthly, lifting the top plug, adding rubber operating oil and anti-slippery resin, and keeping for 4-8 seconds;
lowering the upper top plug to heat the rubber material to 135-142 ℃;
lowering the top plug to mix the rubber material at the constant temperature of 138-142 ℃ for 100-150 seconds;
and discharging the rubber material to a lower auxiliary machine.
II, auxiliary machine process:
firstly, heating the sizing material to 135-142 ℃;
② mixing at constant temperature of 138-142 ℃ for 250-350 seconds;
thirdly, rubber discharging to an open mill: turning and cooling the rubber material to 90-100 ℃, adding sulfur and a vulcanization accelerator on an open mill, uniformly dispersing, and cooling the lower piece to room temperature.
9. Use of the rubber composition according to any one of claims 1 to 7 in a tread rubber for producing an ultra-low rolling resistance all season tire.
10. An ultra-low rolling resistance all season tire, characterized in that the tread rubber of the tire is prepared by vulcanizing the rubber composition according to any one of claims 1 to 7.
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