CN110283365B - Tire sidewall rubber and preparation method thereof - Google Patents
Tire sidewall rubber and preparation method thereof Download PDFInfo
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- CN110283365B CN110283365B CN201910660876.1A CN201910660876A CN110283365B CN 110283365 B CN110283365 B CN 110283365B CN 201910660876 A CN201910660876 A CN 201910660876A CN 110283365 B CN110283365 B CN 110283365B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
- B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
- B29B7/18—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft
- B29B7/183—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft having a casing closely surrounding the rotors, e.g. of Banbury type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/22—Component parts, details or accessories; Auxiliary operations
- B29B7/28—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/52—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices with rollers or the like, e.g. calenders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/82—Heating or cooling
- B29B7/823—Temperature control
-
- 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
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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
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- 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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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to the field of rubber processing, in particular to a tire sidewall rubber and a preparation method thereof. The tire sidewall rubber comprises the following components in parts by weight: 30-80 parts of natural rubber; 20-70 parts of TBIR-BR master batch; 2-7 parts of zinc oxide; 1-3.5 parts of stearic acid; 3-7 parts of an anti-aging agent; 40-60 parts of a filler; 2-8 parts of operating oil; 0-3 parts of a filler dispersant; 0.8-2 parts of an accelerator; 0.6-2 parts of sulfur; 0-0.4 part of anti-vulcanization reversion agent. According to the invention, the natural rubber and the TBIR-BR master batch are matched with other components for synergistic action, so that the compatibility and the co-vulcanization characteristic of the natural rubber and the butadiene rubber are further improved, the filler is more uniformly distributed in the natural rubber and the butadiene rubber, and finally, the obtained tire sidewall rubber has the advantages of better fatigue resistance, lower rolling resistance and lower compression heat generation.
Description
Technical Field
The invention relates to the field of rubber processing, in particular to a tire sidewall rubber and a preparation method thereof.
Background
During the running process of the tire, the tire side part is easy to generate cracks due to repeated bending deformation, and the fatigue failure of the tire side caused by the generation and the propagation of the cracks is an important reason for influencing the service life of the tire. In the general rubber material, the natural rubber has very excellent mechanical strength and fatigue crack propagation resistance, and the butadiene rubber has excellent fatigue crack initiation resistance; however, the conventional radial tire sidewall rubber cannot have both excellent fatigue crack initiation resistance and fatigue crack propagation resistance due to poor compatibility and co-vulcanization characteristic of natural rubber and butadiene rubber and the fact that the filler is preferentially dispersed in a phase region of the butadiene rubber.
With the rapid development of the automobile industry, people pay more and more attention to the use safety of tires, and the fatigue resistance of the sidewall rubber is improved. The tire side part accounts for about 14% of the rolling resistance distribution of the whole tire, so that the reduction of the rolling resistance of the tire side part is also beneficial to the reduction of the oil consumption of an automobile.
Trans-1, 4-polyisoprene and natural rubber/butadiene rubber are introduced in 2002 and 2010 of the synthetic rubber industry and 2004 and 2010 of the rubber industry to be applied to sidewall rubber in combination, the influence of a vulcanization system on the application performance is researched, and the sidewall rubber containing the trans-1, 4-polyisoprene has excellent fatigue resistance. However, trans-1, 4-polyisoprene is a crystalline rubber-plastic dual material at normal temperature, and the rubber compound containing trans-1, 4-polyisoprene has poor viscosity and is not beneficial to processing. Therefore, it is necessary to study a sidewall rubber having superior properties.
The trans-butadiene-isoprene rubber produced by adopting the technology of the patent CN103387641A has good processability, good fatigue resistance, wear resistance and tear resistance, and lower rolling resistance and heat generation, but the application and development of multiple fields are still lack of research. The team also researches that trans-butyl-pentyl rubber replaces natural rubber or cis-butyl rubber to be applied to sidewall rubber of a passenger car tire (synthetic rubber industry, 3(2018): 313-317), finds that the fatigue crack propagation resistance of the sidewall rubber of the passenger car tire containing the trans-butyl-pentyl rubber is better, and needs to research on a mixing formula and a method for better improving the application performance.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a tire sidewall rubber and a preparation method thereof, and the tire sidewall rubber provided by the present invention has the advantages of excellent fatigue resistance, low rolling resistance and low heat generation under compression.
The invention provides a tire sidewall rubber, which comprises the following components in parts by weight:
preferably, the TBIR-BR master batch is prepared by banburying and blending trans-butyl amyl rubber and cis-butyl rubber;
the mass ratio of the trans-butadiene rubber to the cis-butadiene rubber is 10-90: 1-90;
the temperature of the banburying and blending is 40-80 ℃, the rotating speed of the banburying and blending is 30-90 rpm, the feeding coefficient of the banburying and blending is 0.7-0.85, and the banburying and blending time is 1-5 min.
Preferably, in the trans-butadiene rubber, the molar content of a butadiene unit is 5-45%, the molar content of an isoprene unit is 55-95%, the molar content of a trans-1, 4-structure is more than 90%, and the Mooney viscosity ML is3+4 100℃45 to 100.
Preferably, the anti-aging agent is selected from one or more of anti-aging agent 4020, anti-aging agent RD, anti-aging agent 4010NA, anti-aging agent 4010 and paraffin.
Preferably, the filler is selected from one or more of carbon black, white carbon black, calcium carbonate, argil and talcum powder;
the filler dispersant is selected from carbon black dispersant and/or white carbon black dispersant;
the operating oil is selected from environment-friendly aromatic oil.
Preferably, the promoter is selected from one or more of a promoter NS, a promoter NOBS and a promoter CZ;
the anti-reversion agent is selected from one or more of WK901, HTS and PK 900.
The invention also provides a preparation method of the tire sidewall rubber, which comprises the following steps:
A) mixing natural rubber, TBIR-BR masterbatch, zinc oxide, stearic acid, an anti-aging agent, a filler and operating oil to obtain a section of masterbatch;
B) banburying and mixing the primary masterbatch, the accelerator and sulfur to obtain secondary masterbatch;
C) the two-stage masterbatch is milled, and the obtained final masterbatch is placed for 4-168 hours under the conditions that the temperature is 21-25 ℃ and the humidity is 30-80%;
D) and vulcanizing the placed final rubber at the temperature of 140-180 ℃ and under the pressure of 10-35 MPa to obtain the tire sidewall rubber.
Preferably, in the step A), the temperature of the banburying mixing is 50-70 ℃, the rotating speed of the banburying blending is 30-90 rpm, the feeding coefficient of the banburying blending is 0.7-0.85, and the banburying blending time is 3-8 min; and the rubber discharge temperature after banburying and blending is 145-160 ℃.
Preferably, in the step B), the temperature of the banburying mixing is 50-70 ℃, the rotating speed of the banburying blending is 30-100 rpm, the feeding coefficient of the banburying blending is 0.7-0.85, and the banburying blending time is 1-5 min; the rubber discharge temperature after banburying and blending is less than 110 ℃.
Preferably, in the step C), the open milling temperature is 40-80 ℃, and the open milling rotating speed is 10-40 rpm.
The invention provides a tire sidewall rubber, which comprises the following components in parts by weight: 30-80 parts of natural rubber; 20-70 parts of TBIR-BR master batch; 2-7 parts of zinc oxide; 1-3.5 parts of stearic acid; 3-7 parts of an anti-aging agent; 40-60 parts of a filler; 2-8 parts of operating oil; 0-3 parts of a filler dispersant; 0.8-2 parts of an accelerator; 0.6-2 parts of sulfur; 0-0.4 part of anti-vulcanization reversion agent. According to the invention, the natural rubber and the TBIR-BR master batch are matched with other components for synergistic action, so that the compatibility and the co-vulcanization characteristic of the natural rubber and the butadiene rubber are further improved, the filler is more uniformly distributed in the natural rubber and the butadiene rubber, and finally, the obtained tire sidewall rubber has the advantages of better fatigue resistance, lower rolling resistance and lower compression heat generation.
The invention also provides a preparation method of the tire sidewall rubber, which comprises the following steps: A) mixing natural rubber, TBIR-BR masterbatch, zinc oxide, stearic acid, an anti-aging agent, a filler dispersant and operating oil to obtain a section of masterbatch; B) banburying and mixing the first-stage masterbatch, the accelerator, the sulfur and the anti-vulcanization reversion agent to obtain second-stage masterbatch; C) the two-stage masterbatch is milled, and the obtained final masterbatch is placed for 4-168 hours under the conditions that the temperature is 21-25 ℃ and the humidity is 30-80%; D) and vulcanizing the placed final rubber at the temperature of 140-180 ℃ and under the pressure of 10-35 MPa to obtain the tire sidewall rubber. In the sidewall rubber prepared by the method, the compatibility and the co-vulcanization characteristic of the natural rubber and the butadiene rubber are further improved, the filler is more uniformly distributed in the natural rubber and the butadiene rubber, and finally, the prepared sidewall rubber has better fatigue resistance and lower rolling resistance and compression heat generation.
Experimental results show that compared with the traditional tire sidewall rubber, the tire sidewall rubber provided by the invention has the advantages that the fatigue resistance is improved by 48-87%, the rolling resistance (tan delta @60 ℃) is reduced by 5-8%, and the heat generation under compression is reduced by about 10%.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a tire sidewall rubber, which comprises the following components in parts by weight:
the tire sidewall rubber provided by the invention comprises natural rubber. The weight portion of the natural rubber is 30-80. In certain embodiments of the present invention, the natural rubber is present in an amount of 40 parts by weight.
The type of the natural rubber is not particularly limited in the present invention, and the natural rubber may be generally commercially available. In certain embodiments of the invention, the natural rubber is selected from SMR 20 or SCR WF.
The tire sidewall rubber provided by the invention also comprises TBIR-BR master batch. The TBIR-BR master batch is 20-70 parts by weight. In certain embodiments of the invention, the TBIR-BR masterbatch is 60 parts by weight.
In the embodiment of the invention, the TBIR-BR master batch is prepared by banburying and blending trans-butyl rubber and cis-butyl rubber.
The temperature of banburying and blending is 40-80 ℃. In certain embodiments of the present invention, the temperature of the banbury blending is 60 ℃ or 40 ℃. The rotating speed of banburying and blending is 30-90 rpm. In certain embodiments of the present invention, the rotational speed of the banburying blending is 70rpm or 90 rpm. The feeding coefficient of the banburying and blending is 0.7-0.85. In certain embodiments of the present invention, the banbury blend has a feed factor of 0.75 or 0.85. And the banburying and blending time is 1-5 min. In certain embodiments of the present invention, the time for the banburying blending is 3min or 5 min.
The mass ratio of the trans-butadiene rubber to the cis-butadiene rubber is 10-90: 1 to 90. In certain embodiments of the invention, the mass ratio of trans-butadiene rubber to cis-butadiene rubber is 50: 10 or 50: 50.
in certain embodiments of the invention, the trans-butadiene rubber has a molar content of butadiene units of 5 to 45%, preferably 5 to 25%; the molar content of the isoprene unit is 55-95%, preferably 75-95%; trans-1, 4-structure molar content of more than 90%, Mooney viscosity ML3+4 100℃45 to 100. In certain embodiments of the invention, the trans-butyl rubber is selected from TBIR-0963 or TBIR-2063. The TBIR-0963 had a butadiene content of 9.7 mol%, an isoprene structural unit trans-1, 4-structure content of 97.1 mol%, a butadiene structural unit trans-1, 4-content of 95.8 mol%, and a Mooney viscosity ML3+4 100℃60.5. The content of butadiene in the TBIR-2063 is 16.8 mol%, and an isoprene structural unit is a trans-1, 4-junctionA structure content of 96.5 mol%, a trans-1, 4-content of butadiene structural units of 95.1 mol%, a Mooney viscosity ML3+4 100℃＝59.7。
In the present invention, the kind of the butadiene rubber is not particularly limited, and may be generally commercially available. In certain embodiments of the present invention, the butadiene rubber is selected from BR 9000.
The TBIR-BR master batch is blended with the natural rubber and other components, and the sidewall rubber prepared by the method has good filler dispersibility, excellent compatibility and co-vulcanization characteristic of the natural rubber and the butadiene rubber, and plays a very key role in obtaining better fatigue resistance, lower rolling resistance and heat generation under compression.
The tire sidewall rubber provided by the invention also comprises zinc oxide. The zinc oxide is 2-7 parts by weight. In certain embodiments of the present invention, the zinc oxide is present in an amount of 3.5 parts by weight. The zinc oxide can activate a vulcanization system in the formula, and the crosslinking density and the heat aging resistance of the vulcanized rubber are improved.
The tire sidewall rubber provided by the invention also comprises stearic acid. The stearic acid accounts for 1-3.5 parts by weight. In certain embodiments of the present invention, the stearic acid is present in an amount of 1.2 parts by weight. Stearic acid may increase the solubility of zinc oxide in the rubber.
The tire sidewall rubber provided by the invention further comprises an anti-aging agent. The anti-aging agent is 3-7 parts by weight. In certain embodiments of the invention, the antioxidant is present in an amount of 6 parts by weight. The anti-aging agent can improve the heat aging resistance and ozone aging resistance of the rubber. In certain embodiments of the invention, the anti-aging agent is selected from one or more of anti-aging agent 4020, anti-aging agent RD, anti-aging agent 4010NA, anti-aging agent 4010, and paraffin.
The tire sidewall rubber provided by the invention also comprises a filler. The filler accounts for 40-60 parts by weight. In certain embodiments of the present invention, the filler is present in an amount of 50 parts by weight. The filler can improve the mechanical strength and modulus of the vulcanized rubber. In certain embodiments of the present invention, the filler is selected from one or more of carbon black, white carbon, calcium carbonate, china clay, and talc.
The tire sidewall rubber provided by the invention further comprises operating oil. The weight part of the operating oil is 2-8 parts. In certain embodiments of the present invention, the process oil is present in an amount of 6 parts by weight. The operating oil can improve the processing performance of the rubber compound and improve the dispersion effect of the filler in the rubber matrix. In certain embodiments of the invention, the process oil is selected from environmentally friendly aromatic oils. The type of the environmentally friendly aromatic oil is not particularly limited, and the environmentally friendly aromatic oil can be generally commercially available. In certain embodiments of the invention, the environmentally friendly aromatic oil is selected from VIVATEC 500, hansen, germany.
The tire sidewall rubber provided by the invention also comprises a filler dispersant. The weight portion of the filler dispersant is 0-3. In certain embodiments of the present invention, the filler dispersant is present in an amount of 3 parts by weight. The filler dispersing agent can obviously improve the dispersing effect of the filler in the rubber matrix in the formula components. In certain embodiments of the present invention, the filler dispersant is selected from carbon black dispersants and/or white carbon black dispersants. The invention is not limited to the types of the carbon black dispersant and the white carbon black dispersant, and the carbon black dispersant and the white carbon black dispersant can be generally sold in the market.
The tire sidewall rubber provided by the invention also comprises an accelerator. The weight portion of the accelerant is 0.8-2. In certain embodiments of the present invention, the accelerator is present in an amount of 0.8 parts by weight. The accelerator can improve the vulcanization efficiency of sulfur. In certain embodiments of the invention, the promoter is selected from one or more of promoter NS, promoter NOBS and promoter CZ.
The tire sidewall rubber provided by the invention also comprises sulfur. The sulfur accounts for 0.6-2 parts by weight. In certain embodiments of the present invention, the sulfur is present in an amount of 1.6 parts by weight. Sulfur is a cross-linking agent in the formula components. The sulfur of the present invention is not particularly limited in kind, and may be generally commercially available. In certain embodiments of the invention, the sulfur is selected from one or more of common sulfur powder, oil-extended sulfur, granulated sulfur, or insoluble sulfur.
The tire sidewall rubber provided by the invention also comprises an anti-reversion agent. The weight part of the anti-vulcanization reversion agent is 0-0.4 part. In certain embodiments of the present invention, the weight part of the anti-reversion agent is 0 parts. The anti-reversion agent can inhibit the reversion phenomenon in the vulcanization stage. In certain embodiments of the invention, the anti-reversion agent is selected from one or more of WK901, HTS and PK 900.
The invention also provides a preparation method of the tire sidewall rubber, which comprises the following steps:
A) mixing natural rubber, TBIR-BR masterbatch, zinc oxide, stearic acid, an anti-aging agent, a filler and operating oil to obtain a section of masterbatch;
B) banburying and mixing the primary masterbatch, the accelerator and sulfur to obtain secondary masterbatch;
C) the two-stage masterbatch is milled, and the obtained final masterbatch is placed for 4-168 hours under the conditions that the temperature is 21-25 ℃ and the humidity is 30-80%;
D) and vulcanizing the placed final rubber at the temperature of 140-180 ℃ and under the pressure of 10-35 MPa to obtain the tire sidewall rubber.
In the preparation method, the components and the proportion of the raw materials are the same as above, and are not described again.
In the embodiment of the invention, the TBIR-BR master batch is prepared by banburying and blending trans-butyl rubber and cis-butyl rubber.
The temperature of banburying and blending is 40-80 ℃. In certain embodiments of the present invention, the temperature of the banbury blending is 60 ℃ or 40 ℃. The rotating speed of banburying and blending is 30-90 rpm. In certain embodiments of the present invention, the rotational speed of the banburying blending is 70rpm or 90 rpm. The feeding coefficient of the banburying and blending is 0.7-0.85. In certain embodiments of the present invention, the banbury blend has a feed factor of 0.75 or 0.85. And the banburying and blending time is 1-5 min. In certain embodiments of the present invention, the time for the banburying blending is 3min or 5 min.
The mass ratio of the trans-butadiene rubber to the cis-butadiene rubber is 10-90: 1 to 90. In certain embodiments of the invention, the mass ratio of trans-butadiene rubber to cis-butadiene rubber is 50: 10. 50: 50 or 60: 40.
in certain embodiments of the invention, the trans-butadiene rubber has a molar content of butadiene units of 5 to 45%, preferably 5 to 25%; the molar content of the isoprene unit is 55-95%, preferably 75-95%; trans-1, 4-structure molar content of more than 90%, Mooney viscosity ML3+4 100℃45 to 100. In certain embodiments of the invention, the trans-butyl rubber is selected from TBIR-0963 or TBIR-2063. The TBIR-0963 had a butadiene content of 9.7 mol%, an isoprene structural unit trans-1, 4-structure content of 97.1 mol%, a butadiene structural unit trans-1, 4-content of 95.8 mol%, and a Mooney viscosity ML3+4 100℃60.5. The content of butadiene in the TBIR-2063 was 16.8 mol%, the content of trans-1, 4-structure as an isoprene structural unit was 96.5 mol%, the content of trans-1, 4-structure as a butadiene structural unit was 95.1 mol%, and the Mooney viscosity ML was3+4 100℃＝59.7。
In the present invention, the kind of the butadiene rubber is not particularly limited, and may be generally commercially available. In certain embodiments of the present invention, the butadiene rubber is selected from BR 9000.
The invention firstly adopts trans-butadiene rubber and cis-butadiene rubber to be banburied and blended to prepare TBIR-BR master batch, and then the TBIR-BR master batch is blended with other components, the sidewall rubber prepared by adopting the method has good filler dispersibility, excellent compatibility and co-vulcanization characteristic of natural rubber and cis-butadiene rubber, and plays a very key role in obtaining better fatigue resistance, lower rolling resistance and heat generation by compression.
And after TBIR-BR master batch is obtained, mixing natural rubber, TBIR-BR master batch, zinc oxide, stearic acid, an anti-aging agent, a filler and operating oil to obtain a first-stage master batch. When the raw materials contain the filler dispersing agent, the natural rubber, the TBIR-BR master batch, the zinc oxide, the stearic acid, the anti-aging agent, the filler dispersing agent and the operating oil are mixed by milling to obtain a section of master batch.
In certain embodiments of the present invention, the temperature of the banburying mixing is 50 to 70 ℃. In certain embodiments, the temperature of the banbury blending is 70 ℃ or 60 ℃. The rotating speed of banburying and blending is 30-90 rpm. In certain embodiments, the rotational speed of the banburying blend is 60rpm, 70rpm, or 80 rpm. The feeding coefficient of the banburying and blending is 0.7-0.85. In certain embodiments, the banbury blend has a feed factor of 0.75 or 0.85. And the banburying and blending time is 3-8 min. In certain embodiments, the time for the banburying blending is 4min or 5 min. And the rubber discharge temperature after banburying and blending is 145-160 ℃. In certain embodiments, the temperature of the rubber discharge after the banburying blending is 155 ℃ or 150 ℃.
In some embodiments of the invention, after the TBIR-BR master batch is obtained, the natural rubber and the TBIR-BR master batch are firstly banburied and mixed for 0.5-2 min, and then the zinc oxide, the stearic acid, the anti-aging agent, the filler dispersant and the process oil are added and banburied and mixed for 3-6.5 min.
The temperature, the rotating speed and the feeding coefficient of the banburying and mixing of the natural rubber and the TBIR-BR master batch are the same as those of the natural rubber and the TBIR-BR master batch, and are not described in detail herein. The temperature, the rotating speed and the feeding coefficient of the internal mixing and mixing of the zinc oxide, the stearic acid, the anti-aging agent, the filler dispersant and the operating oil are the same as above, and are not described again.
In certain embodiments, the natural rubber and TBIR-BR masterbatch are banbury mixed for 1min or 2 min. In some embodiments, the time for banburying and mixing by adding zinc oxide, stearic acid, anti-aging agent, filler dispersant and process oil is 4min or 6 min.
And after the first-stage master batch is obtained, banburying and mixing the first-stage master batch, the accelerator and sulfur to obtain a second-stage master batch. When the raw materials contain the anti-reversion agent, a first-stage master batch is obtained, and then the first-stage master batch, the accelerator, the sulfur and the anti-reversion agent are subjected to banburying mixing to obtain a second-stage master batch.
In certain embodiments of the present invention, the temperature of the banburying mixing is 50 to 70 ℃. In certain embodiments, the temperature of the banbury blending is 60 ℃ or 50 ℃. The rotating speed of banburying and blending is 30-100 rpm. In certain embodiments, the rotational speed of the banbury blending is 30rpm or 50 rpm. The feeding coefficient of the banburying and blending is 0.7-0.85. In certain embodiments, the banbury blend has a feed factor of 0.75. And the banburying and blending time is 1-3 min. In certain embodiments, the time for the banburying blending is 3min or 2 min. The rubber discharge temperature after banburying and blending is less than 110 ℃. In certain embodiments, the temperature of the binder removal after the internal mixing and blending is 100 ℃ or 105 ℃.
And (3) after the second-stage masterbatch is obtained, open milling the second-stage masterbatch, and standing the obtained final masterbatch for 4-168 hours under the conditions that the temperature is 21-25 ℃ and the humidity is 30-80%.
In certain embodiments of the present invention, the open mill temperature is 40 to 80 ℃. In certain embodiments, the open mill temperature is 50 ℃ or 40 ℃. The rotation speed of the open mill is 10-40 rpm. In certain embodiments, the mill is operated at 30rpm or 40 rpm. The open milling time is 0.5-2.5 min. In certain embodiments, the open mill time is 0.5min, 1.5min, or 1 min.
The temperature of the final rubber is 21-25 ℃. In certain embodiments, the temperature at which the final batch is placed is 23 ℃ or 21 ℃. The humidity of the final rubber compound is 30-80%. In certain embodiments, the final batch is placed at a humidity of 50% or 40%. The final rubber compound is placed for 4-168 hours. In certain embodiments, the final batch is left for 24 hours or 72 hours. In the standing process, the internal stress of the macromolecular chains of the rubber is eliminated, and the auxiliary agent in the formula can be dispersed more uniformly, so that the improvement of the performance of the vulcanized rubber is facilitated. And (3) after the final rubber is placed for 4-168 hours, vulcanizing the placed final rubber at the temperature of 140-180 ℃ and under the pressure of 10-35 MPa to obtain the tire sidewall rubber.
In the invention, the vulcanization temperature is 140-180 ℃. In certain embodiments of the invention, the temperature of the vulcanization is 150 ℃ or 140 ℃. The vulcanization pressure is 10-35 MPa. In certain embodiments of the invention, the pressure of the sulfiding is 15MPa or 20 MPa. In certain embodiments of the invention, the time for the sulfidation is 1 to 3 process positive sulfidation times. In certain embodiments, the time for sulfiding is 1.5 times the process positive sulfiding time.
The invention adopts the prior blending of trans-butyl-pentyl rubber and butadiene rubber to obtain TBIR-BR master batch, and then adopts the blending of TBIR-BR master batch, natural rubber and other components. Also because of this way, the prepared sidewall rubber has more excellent dispersibility of the filler, compatibility and co-vulcanization characteristics of the natural rubber and the butadiene rubber, and better application performance.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
The invention provides a tire sidewall rubber, which comprises the following components in parts by weight: 30-80 parts of natural rubber; 20-70 parts of TBIR-BR master batch; 2-7 parts of zinc oxide; 1-3.5 parts of stearic acid; 3-7 parts of an anti-aging agent; 40-60 parts of a filler; 2-8 parts of operating oil; 0-3 parts of a filler dispersant; 0.8-2 parts of an accelerator; 0.6-2 parts of sulfur; 0-0.4 part of anti-vulcanization reversion agent. According to the invention, the natural rubber and the TBIR-BR masterbatch are matched with other components for synergistic action, so that the compatibility of the natural rubber and the butadiene rubber is further improved, the filler is more uniformly distributed in the natural rubber and the butadiene rubber, and finally, the prepared tire sidewall rubber has the advantages of excellent fatigue resistance, low rolling resistance and low compression heat generation.
Experimental results show that compared with the traditional tire sidewall rubber, the tire sidewall rubber provided by the invention has the advantages that the fatigue resistance is improved by 48-87%, the rolling resistance (tan delta @60 ℃) is reduced by 5-8%, and the heat generation under compression is reduced by about 10%.
In order to further illustrate the present invention, a tire side rubber and a method for preparing the same provided by the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
The starting materials used in the following examples are all generally commercially available.
Example 1
Preparation of TBIR-BR masterbatch:
mixing trans-butadiene rubber TBIR-0963 and cis-butadiene rubber BR 9000 in a mass ratio of 50: 10, carrying out banburying blending, wherein the temperature of the banburying blending is 60 ℃, the rotating speed of the banburying blending is 70rpm, the feeding coefficient of the banburying blending is 0.75, and the time of the banburying blending is 3 min.
Preparing tire sidewall rubber:
firstly, banburying and mixing natural rubber and TBIR-BR master batch for 1min, and then adding zinc oxide, stearic acid, an anti-aging agent (3 parts by weight of anti-aging agent 4020, 1.5 parts by weight of anti-aging agent RD and 1.5 parts by weight of paraffin), carbon black N330, a carbon black dispersing agent and environment-friendly aromatic oil VIVATEC 500 for banburying and mixing for 4 min; the temperature of the two internal mixing and blending processes is 70 ℃, the rotating speed is 70rpm, the feeding coefficient is 0.75, and the rubber discharge temperature after the internal mixing and blending processes is 155 ℃, so that a section of master batch is obtained;
putting the first-stage masterbatch into an internal mixer, adding an accelerator NS and sulfur powder, and mixing to obtain second-stage masterbatch; the temperature of the banburying and blending is 60 ℃, the rotating speed is 30rpm, the feeding coefficient is 0.75, the time is 2min, and the rubber discharge temperature after the banburying and blending is 105 ℃.
Carrying out open milling on the two-section masterbatch on an upper sheet and a lower sheet in an open mill; the open milling temperature is 50 ℃, the rotation speed is 30rpm, and the time is 0.5 min.
The final rubber compound obtained after the open milling was left to stand for 48 hours at a temperature of 23 ℃ and a humidity of 50%.
And then vulcanizing the placed final rubber under the conditions that the temperature is 150 ℃ and the pressure is 15MPa, wherein the vulcanization time is 1.5 times of the positive vulcanization time, and obtaining the tire sidewall rubber.
Example 2
Preparation of TBIR-BR masterbatch:
mixing trans-butadiene rubber TBIR-2063 and cis-butadiene rubber BR 9000 in a mass ratio of 50: 10, carrying out banburying blending, wherein the temperature of the banburying blending is 60 ℃, the rotating speed of the banburying blending is 70rpm, the feeding coefficient of the banburying blending is 0.75, and the time of the banburying blending is 3 min.
Preparing tire sidewall rubber:
firstly, mixing natural rubber and TBIR-BR master batch for 1min, adding zinc oxide, stearic acid, an anti-aging agent (3 parts by weight of anti-aging agent 4020, 1.5 parts by weight of anti-aging agent RD and 1.5 parts by weight of paraffin), carbon black N330, a carbon black dispersing agent and naphthenic oil, and mixing for 5 min; the temperature of the two internal mixing and blending processes is 70 ℃, the rotating speed is 70rpm, the feeding coefficient is 0.75, and the rubber discharge temperature after the internal mixing and blending processes is 155 ℃, so that a section of master batch is obtained;
putting the first-stage masterbatch into an internal mixer, adding an accelerator NS and sulfur powder, and mixing to obtain second-stage masterbatch; the temperature of the banburying and blending is 60 ℃, the rotating speed is 30rpm, the feeding coefficient is 0.75, the time is 3min, and the rubber discharge temperature after the banburying and blending is 105 ℃.
Carrying out open milling on the two-section masterbatch on an upper sheet and a lower sheet in an open mill; the open milling temperature is 50 ℃, the rotation speed is 30rpm, and the time is 0.5 min.
The final rubber compound obtained after the open milling was left to stand for 48 hours at a temperature of 23 ℃ and a humidity of 50%.
And then vulcanizing the placed final rubber under the conditions that the temperature is 150 ℃ and the pressure is 15MPa, wherein the vulcanization time is 1.5 times of the positive vulcanization time, and obtaining the tire sidewall rubber.
Example 3
Preparation of TBIR-BR masterbatch:
mixing trans-butadiene rubber TBIR-2063 and cis-butadiene rubber BR 9000 in a mass ratio of 50: 50, carrying out banburying blending, wherein the temperature of the banburying blending is 40 ℃, the rotating speed of the banburying blending is 90rpm, the feeding coefficient of the banburying blending is 0.85, and the time of the banburying blending is 5 min.
Preparing tire sidewall rubber:
firstly, mixing natural rubber and TBIR-BR master batch for 2min, adding zinc oxide, stearic acid, an anti-aging agent (3 parts by weight of anti-aging agent 4020, 1.5 parts by weight of anti-aging agent RD and 1.5 parts by weight of paraffin), carbon black N330, a carbon black dispersing agent and naphthenic oil, and mixing for 6 min; the temperature of the two internal mixing and blending processes is 60 ℃, the rotating speed is 80rpm, the feeding coefficient is 0.85, and the rubber discharge temperature after the internal mixing and blending processes is 150 ℃, so that a section of master batch is obtained;
putting the first-stage masterbatch into an internal mixer, adding an accelerator NS and sulfur powder, and mixing to obtain second-stage masterbatch; the temperature of the banburying and blending is 50 ℃, the rotating speed is 50rpm, the feeding coefficient is 0.85, the time is 4min, and the rubber discharge temperature after the banburying and blending is 105 ℃.
Carrying out open milling on the two-section masterbatch on an upper sheet and a lower sheet in an open mill; the open milling temperature is 40 ℃, the rotation speed is 40rpm, and the time is 1 min.
The final rubber compound obtained after the open milling was left for 60 hours at a temperature of 21 ℃ and a humidity of 40%.
And then, vulcanizing the placed final rubber at the temperature of 140 ℃ and the pressure of 20MPa for 1.5 times of positive vulcanization time to obtain the tire sidewall rubber.
Comparative example 1
Mixing natural rubber and butadiene rubber BR 9000 according to a mass ratio of 45: 55 banburying and mixing for 1min, then adding zinc oxide, stearic acid, an anti-aging agent (3 parts by weight of anti-aging agent 4020, 1.5 parts by weight of anti-aging agent RD and 1.5 parts by weight of paraffin), carbon black N330, a carbon black dispersing agent and naphthenic oil, and banburying and mixing for 4 min; the temperature of the two internal mixing and blending processes is 70 ℃, the rotating speed is 70rpm, the feeding coefficient is 0.75, and the rubber discharge temperature after the internal mixing and blending processes is 155 ℃, so that a section of master batch is obtained;
putting the first-stage masterbatch into an internal mixer, adding an accelerator NS and sulfur powder, and mixing to obtain second-stage masterbatch; the temperature of the banburying and blending is 60 ℃, the rotating speed is 30rpm, the feeding coefficient is 0.75, the time is 3min, and the rubber discharge temperature after the banburying and blending is 100 ℃.
Carrying out open milling on the two-section masterbatch on an upper sheet and a lower sheet in an open mill; the open milling temperature is 50 ℃, the rotation speed is 30rpm, and the time is 0.5 min.
The final rubber compound obtained after the open milling was left to stand for 48 hours at a temperature of 23 ℃ and a humidity of 50%.
And then vulcanizing the placed final rubber under the conditions that the temperature is 150 ℃ and the pressure is 15MPa, wherein the vulcanization time is 1.5 times of the positive vulcanization time, and obtaining the tire sidewall rubber.
Comparative example 2
Mixing natural rubber, butadiene rubber BR 9000 and trans-butadiene rubber TBIR-0963 in a mass ratio of 40: 50: 10, mixing for 1min, adding zinc oxide, stearic acid, an anti-aging agent (3 parts by weight of anti-aging agent 4020, 1.5 parts by weight of anti-aging agent RD and 1.5 parts by weight of paraffin), carbon black N330, a carbon black dispersing agent and naphthenic oil, and mixing for 5 min; the temperature of the two internal mixing and blending processes is 70 ℃, the rotating speed is 70rpm, the feeding coefficient is 0.75, and the rubber discharge temperature after the internal mixing and blending processes is 155 ℃, so that a section of master batch is obtained;
putting the first-stage masterbatch into an internal mixer, adding an accelerator NS and sulfur powder, and mixing to obtain second-stage masterbatch; the temperature of the banburying and blending is 60 ℃, the rotating speed is 30rpm, the feeding coefficient is 0.75, the time is 3min, and the rubber discharge temperature after the banburying and blending is 100 ℃.
Carrying out open milling on the two-section masterbatch on an upper sheet and a lower sheet in an open mill; the open milling temperature is 50 ℃, the rotation speed is 30rpm, and the time is 0.5 min.
The final rubber compound obtained after the open milling was left to stand for 48 hours at a temperature of 23 ℃ and a humidity of 50%.
And then vulcanizing the placed final rubber under the conditions that the temperature is 150 ℃ and the pressure is 15MPa, wherein the vulcanization time is 1.5 times of the positive vulcanization time, and obtaining the tire sidewall rubber.
Comparative example 3
Mixing natural rubber, butadiene rubber BR 9000 and trans-butadiene rubber TBIR-2063 according to a mass ratio of 40: 50: 10, mixing for 1min, adding zinc oxide, stearic acid, an anti-aging agent (3 parts by weight of anti-aging agent 4020, 1.5 parts by weight of anti-aging agent RD and 1.5 parts by weight of paraffin), carbon black N330, a carbon black dispersing agent and naphthenic oil, and mixing for 5 min; the temperature of the two internal mixing and blending processes is 70 ℃, the rotating speed is 70rpm, the feeding coefficient is 0.75, and the rubber discharge temperature after the internal mixing and blending processes is 155 ℃, so that a section of master batch is obtained;
putting the first-stage masterbatch into an internal mixer, adding an accelerator NS and sulfur powder, and mixing to obtain second-stage masterbatch; the temperature of the banburying and blending is 60 ℃, the rotating speed is 30rpm, the feeding coefficient is 0.75, the time is 3min, and the rubber discharge temperature after the banburying and blending is 100 ℃.
Carrying out open milling on the two-section masterbatch on an upper sheet and a lower sheet in an open mill; the open milling temperature is 50 ℃, the rotation speed is 30rpm, and the time is 0.5 min.
The final rubber compound obtained after the open milling was left to stand for 48 hours at a temperature of 23 ℃ and a humidity of 50%.
And then vulcanizing the placed final rubber under the conditions that the temperature is 150 ℃ and the pressure is 15MPa, wherein the vulcanization time is 1.5 times of the positive vulcanization time, and obtaining the tire sidewall rubber.
Example 4
The raw materials and their formulation ratios in examples 1 to 3 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1 results of testing the properties of the side rubbers of the tires obtained in examples 1 to 3 and comparative examples 1 to 3 (raw material amounts in parts by weight)
The results of measuring the vulcanization characteristics and mechanical properties of the tire side rubbers obtained in examples 1 to 3 and comparative examples 1 to 3 are shown in table 2.
TABLE 2 Performance test results of the tire side rubbers obtained in examples 1 to 3 and comparative examples 1 to 3
As can be seen from Table 2, the 150% tensile fatigue life of the tire sidewall rubber prepared by the invention is not less than 58.5 ten thousand, and compared with the conventional general tire sidewall rubber (comparative example 1), the fatigue resistance is improved by 48-87%; the rolling resistance (tan delta @60 ℃) is not more than 0.172, and the rolling resistance is reduced by 5-8%; the heat generation under compression is less than 32.5 ℃ and the heat generation under compression is reduced by about 10%.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to 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 (9)
1. A tire sidewall rubber comprises the following components in parts by weight:
the TBIR-BR master batch is prepared by banburying and blending trans-butyl amyl rubber and cis-butyl rubber;
the mass ratio of the trans-butadiene rubber to the cis-butadiene rubber is 10-90: 1-90;
the temperature of the banburying and blending is 40-80 ℃, the rotating speed of the banburying and blending is 30-90 rpm, the feeding coefficient of the banburying and blending is 0.7-0.85, and the banburying and blending time is 1-5 min.
2. The tire sidewall rubber of claim 1, wherein the trans-butadiene rubber has a molar content of butadiene units of 5 to 45%, a molar content of isoprene units of 55 to 95%, a molar content of trans-1, 4-structures of more than 90%, and a Mooney viscosity ML3+4 100℃45 to 100.
3. The tire sidewall rubber of claim 1, wherein the antioxidant is selected from one or more of antioxidant 4020, antioxidant RD, antioxidant 4010NA, antioxidant 4010 and paraffin.
4. The tire sidewall rubber of claim 1, wherein the filler is selected from one or more of carbon black, white carbon black, calcium carbonate, china clay and talc;
the filler dispersant is selected from carbon black dispersant and/or white carbon black dispersant;
the operating oil is selected from environment-friendly aromatic oil.
5. The tire sidewall rubber of claim 1, wherein the accelerator is selected from one or more of accelerator NS, accelerator NOBS and accelerator CZ;
the anti-reversion agent is selected from one or more of WK901, HTS and PK 900.
6. A method of preparing a tire sidewall rubber as in claim 1, comprising the steps of:
A) mixing natural rubber, TBIR-BR masterbatch, zinc oxide, stearic acid, an anti-aging agent, a filler and operating oil to obtain a section of masterbatch;
B) banburying and mixing the primary masterbatch, the accelerator and sulfur to obtain secondary masterbatch;
C) the two-stage masterbatch is milled, and the obtained final masterbatch is placed for 4-168 hours under the conditions that the temperature is 21-25 ℃ and the humidity is 30-80%;
D) and vulcanizing the placed final rubber at the temperature of 140-180 ℃ and under the pressure of 10-35 MPa to obtain the tire sidewall rubber.
7. The preparation method according to claim 6, wherein in the step A), the temperature of the banburying mixing is 50-70 ℃, the rotation speed of the banburying blending is 30-90 rpm, the feeding coefficient of the banburying blending is 0.7-0.85, and the time of the banburying blending is 3-8 min; and the rubber discharge temperature after banburying and blending is 145-160 ℃.
8. The preparation method according to claim 6, wherein in the step B), the temperature of the banburying mixing is 50-70 ℃, the rotation speed of the banburying blending is 30-100 rpm, the feeding coefficient of the banburying blending is 0.7-0.85, and the banburying blending time is 1-5 min; the rubber discharge temperature after banburying and blending is less than 110 ℃.
9. The preparation method according to claim 6, wherein in the step C), the temperature of the open mill is 40-80 ℃, and the rotating speed of the open mill is 10-40 rpm.
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| JPH0912784A (en) * | 1995-06-29 | 1997-01-14 | Toyo Tire & Rubber Co Ltd | Rubber composition |
| CN104513411A (en) * | 2013-10-08 | 2015-04-15 | 固特异轮胎和橡胶公司 | Rubbery blend containing trans isoprene-butadiene copolymer |
| JP2017019917A (en) * | 2015-07-09 | 2017-01-26 | 東洋ゴム工業株式会社 | Rubber composition and pneumatic tire |
| CN109181027A (en) * | 2018-09-07 | 2019-01-11 | 山东华聚高分子材料有限公司 | A kind of high-performance tire tread rubber and preparation method thereof |
| CN109942910A (en) * | 2019-03-21 | 2019-06-28 | 山东华聚高分子材料有限公司 | A kind of high flexing fatigue service life aviation sidewall rubber, preparation method and application |
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|---|---|---|---|---|
| JPH0912784A (en) * | 1995-06-29 | 1997-01-14 | Toyo Tire & Rubber Co Ltd | Rubber composition |
| CN104513411A (en) * | 2013-10-08 | 2015-04-15 | 固特异轮胎和橡胶公司 | Rubbery blend containing trans isoprene-butadiene copolymer |
| JP2017019917A (en) * | 2015-07-09 | 2017-01-26 | 東洋ゴム工業株式会社 | Rubber composition and pneumatic tire |
| CN109181027A (en) * | 2018-09-07 | 2019-01-11 | 山东华聚高分子材料有限公司 | A kind of high-performance tire tread rubber and preparation method thereof |
| CN109942910A (en) * | 2019-03-21 | 2019-06-28 | 山东华聚高分子材料有限公司 | A kind of high flexing fatigue service life aviation sidewall rubber, preparation method and application |
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