CN114891286A - High-grip-ability and high-cold-resistance tread rubber and preparation method thereof - Google Patents
High-grip-ability and high-cold-resistance tread rubber and preparation method thereof Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 100
- 239000005060 rubber Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000006229 carbon black Substances 0.000 claims abstract description 35
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 20
- 229920005557 bromobutyl Polymers 0.000 claims abstract description 20
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 16
- 230000009477 glass transition Effects 0.000 claims abstract description 15
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 14
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 14
- 229920001194 natural rubber Polymers 0.000 claims abstract description 14
- CSIJXJQDPBJLMG-UHFFFAOYSA-N [Nd].C=CC=C Chemical compound [Nd].C=CC=C CSIJXJQDPBJLMG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 241000872198 Serjania polyphylla Species 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 230000003712 anti-aging effect Effects 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- 239000005011 phenolic resin Substances 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 150000001206 Neodymium Chemical class 0.000 claims description 3
- GSFXLBMRGCVEMO-UHFFFAOYSA-N [SiH4].[S] Chemical compound [SiH4].[S] GSFXLBMRGCVEMO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 238000010074 rubber mixing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 8
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000001993 wax Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 238000007551 Shore hardness test Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- 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)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
The invention discloses a tread rubber with high grip ability and high cold resistance and a preparation method thereof, wherein a rubber mixture with super wear resistance and high grip ability is obtained by applying natural rubber with better comprehensive performance, the low temperature resistance of neodymium butadiene rubber, high styrene-based butadiene styrene rubber with better grip ability, brominated butyl rubber 3745 and brominated butyl reclaimed rubber, and super wear-resistant carbon black and white carbon black with high specific surface area. The formula with high grip performance prepared by the invention has the most remarkable characteristics of excellent grip performance and wear resistance equivalent to that of tires in the existing market. The glass transition temperature of the rubber material is reduced from minus 20 ℃ to minus 50 ℃, and the manufactured tire has no brittle fracture when being used at the temperature of minus 40 ℃. The product of the invention improves the passing property and low temperature resistance on wet and slippery road surfaces.
Description
Technical Field
The invention relates to a tread rubber with high grip ability and high cold resistance and a preparation method thereof, in particular to a rubber mixture with high grip ability and high cold resistance, which is obtained by using natural rubber, neodymium cis-butadiene, butyl bromide rubber 3745 and butyl bromide reclaimed rubber.
Background
Most tires with high grip force (high grip tires for short) still pay attention to wear resistance and high grip performance, and the low temperature resistance of the tires is insufficient, so that the tires are easy to frost crack when placed outdoors in a low temperature area and cannot be ridden due to the fact that the produced products are not resistant to low temperature (-20 ℃) in the using process. The tire is grabbed to height on the market mostly fails to solve the low temperature frost crack problem, and the tire is frost crack easily under extremely cold condition, if need solve the tire frost crack problem, needs to reduce tire grip to cause the security and the comfort level of tire riding to reduce, consequently the high tire of grabbing must solve its not low temperature resistant problem under the condition of guaranteeing good riding.
Some researchers have noticed the low temperature resistance of tires, for example, CN102634088A discloses an anti-aging and anti-cracking engineering tire tread rubber composition, which comprises the following components in parts by weight: 50-70 parts of styrene-butadiene rubber, 1-3 parts of tear-resistant resin, 20-30 parts of natural rubber, 50-70 parts of medium and super wear-resistant carbon black, 10-20 parts of butadiene rubber, 5-10 parts of aromatic oil, 3-6 parts of nano zinc oxide, 1-3 parts of stearic acid, 1-3 parts of p-phenylenediamine antioxidant, 1-3 parts of ketoamine antioxidant, 0.5-1.5 parts of paraffin, 1-2 parts of microcrystalline wax, 1.5-2.5 parts of sulfur, 1-2 parts of sulfenamide accelerator and 1-2 parts of post-vulcanization stabilizer. The technology improves the aging resistance of the tread rubber by changing a protection system, adjusts a crude rubber system to reduce the glass transition temperature of the tread rubber to (-40 ℃), and improves the low-temperature elasticity of the tread rubber. However, the tire tread rubber compound with high grip and high cold resistance has less formula and does not meet the use requirements in the field.
Disclosure of Invention
The invention aims to use a special crude rubber system to solve the problems that the glass transition temperature of the tread rubber of the conventional high-grip tire is higher (about-20 ℃), the rubber is changed from a high elastic state to a glassy state in the temperature range and loses the use performance, and the tire tread is brittle and cracked and cannot be used, so that the cold resistance of the high-grip tire is improved, and the tire can still be normally used at the temperature of-40 ℃.
In order to achieve the above purpose, one embodiment of the present invention adopts the following technical solutions:
the rubber mixture with super wear resistance and high grip power is obtained by applying natural rubber with better comprehensive performance, the low temperature resistance of neodymium butadiene rubber, high styrene-based styrene butadiene rubber with better grip power, brominated butyl rubber 3745 and brominated butyl reclaimed rubber, and then adding super wear-resistant carbon black and white carbon black with high specific surface area (oil absorption value of 200Ml/100g to 300Ml/100 g).
More specifically, the invention provides a tread rubber material with high grip ability and high cold resistance, which contains 5-10 PHR of natural rubber, 30-50 PHR of high styrene butadiene rubber, 10-20 PHR of brominated butyl rubber, 10-20 PHR of neodymium butadiene rubber, 10-20 PHR of brominated butyl reclaimed rubber, 20-40 PHR of high specific surface area white carbon black, 1-3 PHR of low-sulfur silane coupling agent, 20-50 PHR of super wear-resistant carbon black, 2-5 PHR of zinc oxide, 3-5 PHR of phenolic resin, 3-5 PHR of anti-aging agent, 2-5 PHR of protective wax, 1.8-2.0 PHR of sulfur, 1.0-1.2 PHR of accelerator and 1.4-1.6 PHR of stearic acid.
The main component of natural rubber is cis-isoprene polymer, which is widely used due to its good overall properties.
The high styrene butadiene rubber adopts SBR1739 with the styrene content of 40-42 percent, ensures good ground gripping performance, and also has good wear resistance, the styrene content is limited to 40-42 percent, the higher the styrene content is, the better the ground gripping force is, and the glass transition temperature is higher, so the styrene butadiene rubber with the styrene content of 40 percent is preferably adopted, and meanwhile, neodymium series butadiene rubber, brominated butyl rubber and brominated butyl reclaimed rubber with low glass transition temperature are required to be matched, so that the glass transition temperature of the whole rubber material is reduced. Preferably, in the formula, the total amount of the brominated butyl rubber, the neodymium butadiene rubber and the brominated butyl reclaimed rubber is 1.0-2.0 times of the dosage of the high styrene butadiene styrene rubber, including but not limited to 1.1 times, 1.2 times, 1.3 times, 1.5 times, 1.7 times and 1.9 times.
The neodymium cis-butadiene rubber can adopt Langsheng rare earth neodymium cis-butadiene rubber CB22, has good low temperature resistance, has a glass transition temperature of-109 ℃, and has good wear resistance on the premise of ensuring good low temperature resistance.
The brominated butyl rubber uses American Exxon brominated butyl rubber 3745, has super-good grip performance, and is also excellent in low-temperature resistance and physical performance, meanwhile, the brominated butyl rubber 3745 and the brominated butyl reclaimed rubber are used together to ensure good grip performance, low-temperature resistance and environmental protection performance, the grip rolling resistance of the brominated butyl rubber 3745 and the brominated butyl reclaimed rubber is excellent, and the vitrification temperature is slightly low, so that the effects of high grip performance and low vitrification temperature are taken into consideration in the formula, but the abrasion is poor, and therefore, the emulsion polymerized styrene-butadiene rubber with excellent abrasion and the high-abrasion-resistant carbon black are matched.
The tread rubber material with high grip and cold resistance contains 5-10 PHR of natural rubber, which means that the dosage of the natural rubber can be selected from but not limited to 5PHR, 6PHR, 7PHR, 8PHR, 9PHR or 10 PHR.
The high-grip and high-cold-resistance tread rubber compound contains 30-50 PHR of high-styrene butadiene rubber, and the selectable dosage of the high-styrene butadiene rubber comprises, but is not limited to, 30PHR, 32PHR, 35PHR, 37PHR, 40PHR, 42PHR, 45PHR, 47PHR or 50 PHR.
The tread rubber compound with high grip ability and high cold resistance contains 10-20 PHR of brominated butyl rubber, and the optional value of the dosage of the brominated butyl rubber includes but is not limited to 10PHR, 12PHR, 14PHR, 16PHR, 18PHR or 20 PHR.
The tread rubber material with high grip ability and high cold resistance contains 10-20 PHR of neodymium butadiene rubber, and the selectable dosage of the neodymium butadiene rubber includes but is not limited to 10PHR, 12PHR, 14PHR, 16PHR, 18PHR or 20 PHR.
The tread rubber material with high grip ability and high cold resistance contains 10-20 PHR of brominated butyl reclaimed rubber, which means that the dosage of the brominated butyl reclaimed rubber can be selected from but not limited to 10PHR, 12PHR, 14PHR, 16PHR, 18PHR or 20 PHR. The brominated butyl reclaimed rubber is a component obtained by regenerating waste rubber of brominated butyl rubber.
Preferably, during processing, the total amount of the natural rubber, the high styrene butadiene rubber, the brominated butyl rubber, the neodymium butadiene rubber and the brominated butyl reclaimed rubber in the tread rubber compound with high grip ability and high cold resistance can be not 100PHR or can be set to be 100 PHR.
Preferably, the white carbon black with the high specific surface area is 165MP high-dispersion white carbon black which is easy to disperse, can reduce rolling resistance heat generation, and improves the ground gripping property and the wear resistance. The oil absorption value of the 165MP high-dispersion white carbon black is confirmed to be within the range of 200Ml/100 g-300 Ml/100 g. The selectable oil absorption value of the white carbon black with high specific surface area can be 200Ml/100g, 220Ml/100g, 250Ml/100g, 275Ml/100g, 280Ml/100g, 290Ml/100g, 300Ml/100g and the like. The tread rubber material with high grip ability and high cold resistance contains 20-40 PHR of high specific surface area white carbon black, and the selectable dosage of the high specific surface area white carbon black comprises but is not limited to 20PHR, 22PHR, 25PHR, 27PHR, 29PHR, 31PHR, 33PHR, 35PHR, 37PHR, 39PHR or 40 PHR.
The low-sulfur silane coupling agent preferably adopts one of NXT363, NXT245 and SI-75, and the coupling agent of the type has better processing safety and is easy to disperse with the white carbon black with high specific surface area. NXT363, NXT245 are NXT series silane coupling agents developed by Silicones division of GEAdvance materials, USA, and SI-75(C996) is manufactured by Ellipp. The tread rubber compound with high grip ability and high cold resistance contains 1-3 PHR of low-sulfur silane coupling agent, which means that the dosage of the low-sulfur silane coupling agent can be selected from but not limited to 1.0PHR, 1.2PHR, 1.5PHR, 1.8PHR, 2.0PHR, 2.3PHR, 2.5PHR, 2.8PHR or 3.0 PHR.
Preferably, the super wear-resistant carbon black is one or two of carbon black N234, carbon black N134 and carbon black N115, and has excellent wear resistance. The tread rubber material with high grip ability and high cold resistance contains 20-50 PHR of super wear-resistant carbon black, and the selectable dosage of the super wear-resistant carbon black comprises but is not limited to 20PHR, 25PHR, 30PHR, 35PHR, 40PHR, 45PHR or 50 PHR.
The tread rubber material with high grip ability and high cold resistance contains 2-5 PHR of zinc oxide, and the dosage of the zinc oxide can be selected from but not limited to 2.0PHR, 2.3PHR, 2.5PHR, 2.8PHR, 3.0PHR, 3.5PHR, 4.0PHR, 4.5PHR or 5.0 PHR.
The high-grip high-cold-resistance tread rubber compound contains 3-5 PHR of phenolic resin, and the dosage of the phenolic resin can be selected from 3.0PHR, 3.5PHR, 4.0PHR, 4.5PHR or 5.0 PHR.
The high-grip high-cold-resistance tread rubber compound contains 3-5 PHR, which means that the amount of the anti-aging agent can be selected from the group consisting of but not limited to 3.0PHR, 3.5PHR, 4.0PHR, 4.5PHR and 5.0 PHR. The anti-aging agent is a conventional amine anti-aging agent, such as anti-aging agent 4020, anti-aging agent RD or a combination thereof, and the mutual substitution of the conventional anti-aging agents does not have a significant influence on the product performance.
The tread rubber compound with high grip ability and high cold resistance contains 2-5 PHR of protective wax, and the dosage of the protective wax can be selected from but not limited to 2.0PHR, 2.3PHR, 2.5PHR, 2.8PHR, 3.0PHR, 3.5PHR, 4.0PHR, 4.5PHR or 5.0 PHR. The protective wax adopts the conventional protective wax sold in the market.
The invention provides a preparation method of a tread rubber sizing material with high grip and high cold resistance, which comprises the following steps: the formula material is prepared by the linkage operation of an internal mixer F370+ an open mill (low-temperature one-step mixing process), and the mixing method of the internal mixer emphasizes the use of a constant-temperature mixing method, so that the time from the rubber temperature rising to 120 ℃ to the rubber material temperature of 145 ℃ is fixed, and the uniform mixing of the rubber material is ensured. And (3) uniformly smashing and mixing the mixed rubber obtained by the internal mixing operation by using an open mill with an automatic belt turning and cutting device, and then adding a sulfur accelerator to continuously turn and mix uniformly to finish final mixing.
More specifically, the detailed operation steps of the preparation method of the tread rubber compound with high grip and cold resistance are as follows:
all rubbers (natural rubber, high styrene butadiene styrene rubber, brominated butyl rubber, neodymium series butadiene rubber and brominated butyl reclaimed rubber) are put into an F370 internal mixer, the mixture is mixed for 20 seconds at the rotating speed of 55RPM, all weighed auxiliary agents (high specific surface area white carbon black, low sulfur silane coupling agent, super wear-resistant carbon black, zinc oxide, phenolic resin, anti-aging agent, protective wax and stearic acid) except sulfur and accelerating agent are respectively put into the internal mixer from a feeding door and a filler conveying pipe by lifting a top plug, and (3) when the temperature is increased to 120 ℃, rubber is mixed for 120 seconds by adopting a constant-temperature rubber mixing method, the mixed rubber is discharged from an internal mixer to an open mill with an automatic belt turning and cutting device for turning and mixing after the temperature of the rubber reaches 145 ℃, sulfur and an accelerator are added after the temperature of the rubber is reduced to about 90 ℃ (85-95 ℃) for turning and mixing uniformly, and then the obtained mixture is extruded and pressed into sheets, cooled and collected to obtain the tread rubber with high ground holding power and high cold resistance.
Compared with the prior art, the invention has at least the following beneficial effects:
the formula with high grip performance prepared by the invention has the most remarkable characteristics of excellent grip performance and wear resistance equivalent to that of tires in the existing market. The glass transition temperature of the rubber material is reduced from minus 20 ℃ to minus 50 ℃, and the manufactured tire has no brittle fracture when being used at the temperature of minus 40 ℃. The product of the invention improves the passing property and low temperature resistance on wet and slippery road surfaces.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Tread rubber preparation method of examples and comparative examples:
firstly, mixing the raw materials according to the raw material proportion shown in the table 1, then putting all the rubbers (natural rubber, styrene-butadiene rubber, brominated butyl rubber, butadiene rubber and brominated butyl reclaimed rubber) into an F370 internal mixer, mixing for 20 seconds at the rotating speed of 55RPM, lifting a top bolt, respectively putting all the weighed auxiliary agents (high specific surface area white carbon black, low sulfur silane coupling agent, super wear-resistant carbon black, zinc oxide, phenolic resin, anti-aging agent, protective wax and stearic acid) except sulfur and accelerator into the internal mixer from a feeding door and a filler conveying pipe, mixing, and (3) when the temperature is increased to 120 ℃, rubber is mixed for 120 seconds by adopting a constant-temperature rubber mixing method, the mixed rubber is discharged from an internal mixer to an open mill with an automatic belt turning and cutting device for turning and mixing until the temperature reaches 145 ℃, after the temperature of the rubber material is reduced to about 90 ℃, sulfur and an accelerator are added for turning and mixing uniformly, and then the mixture is extruded, tabletted, cooled and collected to obtain the tread rubber.
TABLE 1 raw material compounding ratios of examples and comparative examples
Note: the sulfur 99 refers to industrial grade sulfur with the sulfur mass content reaching 99%.
The compounds obtained in the examples and comparative examples were subjected to DMA test using a thermal dynamic analyzer, the test items including glass transition temperature (Tg), Tan. delta. at 0 ℃; the Akron abrasion was tested using the method described in GB/T1689-1998. Testing the Shore hardness, the tensile strength, the stress at definite elongation and the elongation at break of the rubber material, wherein the test standards are as follows:
shore hardness test standard: GB/T531.1-2008/ISO 7619-1;
and (3) testing standards of tensile strength, stress at definite elongation and elongation at break: HB/T2198-2011.
The results of the sizing property tests of the examples and comparative examples are shown in table 2.
TABLE 2 sizing Properties of the examples and comparative examples
Comparative example 1 the styrene content of styrene-butadiene rubber is lower and the rubber Tan delta is lower, unlike example 2; comparative example 2 the glass transition temperature of the resulting rubber was increased by replacing a portion of the low glass transition temperature compound with natural rubber; compared with the example 2, the high styrene butadiene styrene rubber of the comparative example 3 has higher dosage, other rubbers have lower dosage, and the glass transition temperature of the obtained rubber is further improved; comparative example 4, using ordinary cis-butadiene rubber instead of neodymium cis-butadiene rubber, resulted in an increase in the glass transition temperature of the resulting rubber, compared to example 2. The data show that the glass transition temperature of the rubber is reduced by designing the crude rubber system, so that the tire has better low-temperature resistance, the rubber has higher Tan delta (0 ℃), the grip is high, and the wet skid resistance is good.
Although the invention has been described herein with reference to illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (10)
1. The tread rubber with high grip and cold resistance is characterized by comprising 5-10 PHR of natural rubber, 30-50 PHR of high styrene butadiene rubber, 10-20 PHR of brominated butyl rubber, 10-20 PHR of neodymium butadiene rubber, 10-20 PHR of brominated butyl reclaimed rubber, 20-40 PHR of high specific surface area white carbon black, 1-3 PHR of low-sulfur silane coupling agent, 20-50 PHR of super wear-resistant carbon black, 2-5 PHR of zinc oxide, 3-5 PHR of phenolic resin, 3-5 PHR of anti-aging agent, 2-5 PHR of protective wax, 1.8-2.0 PHR of sulfur, 1.0-1.2 PHR of accelerant and 1.4-1.6 PHR of stearic acid.
2. The tread rubber with high grip ability and high cold resistance as claimed in claim 1, wherein the high styrene butadiene rubber is styrene butadiene rubber with styrene content of 40-42%.
3. The tread rubber with high grip and cold resistance as claimed in claim 2, wherein SBR1739 is adopted as the high styrene butadiene styrene rubber.
4. The tread rubber with high grip ability and high cold resistance as claimed in claim 1, wherein the total amount of the brominated butyl rubber, the neodymium butadiene rubber and the brominated butyl reclaimed rubber is 1.0-2.0 times of the amount of the high styrene butadiene styrene rubber.
5. The high-grip high-cold-resistant tread rubber according to claim 1, wherein the brominated butyl rubber is brominated butyl rubber 3745 of Exxon, USA.
6. The tread rubber with high grip and cold resistance as claimed in claim 1, wherein the neodymium-based butadiene rubber is neodymium-based butadiene rubber CB22 with a glass transition temperature of-109 ℃.
7. The tread rubber with high grip ability and high cold resistance of claim 1, wherein the white carbon black with high specific surface area is white carbon black with an oil absorption value in a range of 200Ml/100 g-300 Ml/100 g.
8. The tread rubber with high grip and cold resistance as claimed in claim 1, wherein the low-sulfur silane coupling agent is preferably one of NXT363, NXT245 and SI-75.
9. The tread rubber with high grip and cold resistance as claimed in claim 1, wherein the super wear-resistant carbon black is one or two of carbon black N234, carbon black N134 and carbon black N115.
10. The preparation method of the tread rubber with high grip and cold resistance as claimed in any one of claims 1 to 9, characterized by comprising the following steps: adding natural rubber, high styrene butadiene styrene rubber, brominated butyl rubber, neodymium series butadiene rubber and brominated butyl reclaimed rubber into an internal mixer, mixing, lifting a top bolt, adding weighed high specific surface area white carbon black, low sulfur silane coupling agent, super wear-resistant carbon black, zinc oxide, phenolic resin, anti-aging agent, protective wax and stearic acid into the internal mixer from a feeding door and a filler conveying pipe respectively, mixing, adopting a constant temperature rubber mixing method to mix rubber when the temperature is increased to 120 ℃, discharging the mixed rubber from the internal mixer to an open mill with an automatic belt turning and cutting device to be turned and refined when the temperature of a rubber material is reduced to 85-95 ℃, adding sulfur and the accelerator to be turned and refined uniformly, extruding tablets, cooling and collecting rubber to obtain the tread rubber with high grip and high cold resistance.
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| FI841808A0 (en) * | 1983-05-09 | 1984-05-07 | Bridgestone Corp | LUFTRING LAEMPLIG FOER KOERNING PAO SNOE- OCH ISVAEGAR. |
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| CN111944209A (en) * | 2020-08-06 | 2020-11-17 | 正道轮胎有限公司 | Winter tire tread rubber with high wet-skid performance and preparation method thereof |
| CN112812388A (en) * | 2020-12-30 | 2021-05-18 | 山东兴鸿源轮胎有限公司 | Low-temperature-resistant and high-wet-skid-resistance snow tire tread rubber and preparation method thereof |
| WO2021126628A1 (en) * | 2019-12-17 | 2021-06-24 | Exxonmobil Chemical Patents Inc. | Functionalized polymers tread additive to improve all-season tire performance |
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2022
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FI841808A0 (en) * | 1983-05-09 | 1984-05-07 | Bridgestone Corp | LUFTRING LAEMPLIG FOER KOERNING PAO SNOE- OCH ISVAEGAR. |
| JPS60213506A (en) * | 1984-04-10 | 1985-10-25 | Bridgestone Corp | Pneumatic tire having all-weather traveling performance |
| EP0161792A1 (en) * | 1984-04-10 | 1985-11-21 | Bridgestone Corporation | Pneumatic tire having all weather running performances |
| CN107216503A (en) * | 2017-07-21 | 2017-09-29 | 肇庆骏鸿实业有限公司 | A kind of tread rubber of environment-friendly type four seasons tire |
| WO2021126628A1 (en) * | 2019-12-17 | 2021-06-24 | Exxonmobil Chemical Patents Inc. | Functionalized polymers tread additive to improve all-season tire performance |
| CN111944209A (en) * | 2020-08-06 | 2020-11-17 | 正道轮胎有限公司 | Winter tire tread rubber with high wet-skid performance and preparation method thereof |
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Application publication date: 20220812 |