CN110283365A - A kind of tire sidewall glue and preparation method thereof - Google Patents
A kind of tire sidewall glue and preparation method thereof Download PDFInfo
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- CN110283365A CN110283365A CN201910660876.1A CN201910660876A CN110283365A CN 110283365 A CN110283365 A CN 110283365A CN 201910660876 A CN201910660876 A CN 201910660876A CN 110283365 A CN110283365 A CN 110283365A
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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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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)
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention relates to rubber processings more particularly to a kind of tire sidewall glue and preparation method thereof.The tire sidewall glue, according to parts by weight, comprising: 30~80 parts of natural rubber；20~70 parts of TBIR-BR masterbatch；2~7 parts of zinc oxide；1~3.5 part of stearic acid；3~7 parts of anti-aging agent；40~60 parts of filler；2~8 parts of operation oil；0~3 part of filler dispersing agent；0.8~2 part of promotor；0.6~2 part of Sulfur；0~0.4 part of anti-recovery agent.The present invention acts synergistically natural rubber and TBIR-BR masterbatch cooperation other components, so that the compatibility and co-vulcanization characteristic of natural rubber and butadiene rubber further improve, filler is more evenly distributed in natural rubber and butadiene rubber, finally, the fatigue performance of the tire sidewall glue obtained is more excellent, rolling resistance and compression heat generation are lower.
Description
Technical field
The present invention relates to rubber processings more particularly to a kind of tire sidewall glue and preparation method thereof.
Background technique
In the process of moving, sidewall position is because being also easy to produce segmentation crack, the generation of segmentation crack by alternating bending deformation for tire
Sidewall fatigue failure is caused to be to influence the major reason of tire service life with extension.In general purpose rubber material, natural rubber
With very excellent mechanical strength and resistance to fatigue crack expansibility energy, butadiene rubber has excellent endurance crack initiation
Energy；But natural rubber and the poor compatibility of butadiene rubber and co-vulcanization characteristic and filler can preferentially be dispersed in butadiene rubber
Phase region causes existing radial sidewall rubber that cannot have both the excellent initiation of endurance crackle and fatigue crack growth energy.
With the rapid development of auto industry, people are higher and higher to the attention degree of tire used safety, improve tire
The fatigue performance of side glue is very urgent.Sidewall position accounts for 14% or so of entire tire drag distribution, therefore reduces tire
The rolling resistance of side is also beneficial to reduce automobile fuel consumption.
" China Synthetic Rubber Industry " 2002 and 2010, " rubber industry " introduce anti-form-1 for 2004 and 2010, and 4- is poly-
Isoprene and natural rubber/butadiene rubber and with applied to sidewall rubber, and influence of the vulcanizing system to application performance is had studied,
Preferably fatigue performance is presented in sidewall rubber containing trans-1,4-iroprene polymer.But trans-1,4-iroprene polymer room temperature
Under be a kind of crystalline rubber and plastic dual character material, contain anti-form-1, the mixing adhesivity of 4- polyisoprene too it is poor is unfavorable for plus
Work.Thus, studying, there is the sidewall rubber compared with dominance energy to be necessary.
Trans- butadiene-isoprene rubber using the production of patent CN103387641A technology has good processing performance, has simultaneously
Good fatigue performance, abrasion resistance and tearing-resistant performance and lower rolling resistance and heat, but multi-field application
Exploitation still lacks research.Team also once studied trans- butadiene-isoprene rubber and natural rubber or butadiene rubber is replaced to be applied to tyres for passenger cars tire
(3 (2018): China Synthetic Rubber Industry 313~317), finds the tyres for passenger cars sidewall rubber endurance containing trans- butadiene-isoprene rubber to side glue
Crack propagation performance is more excellent, and in order to preferably improve its application performance, mixing formula and method still require study.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of tire sidewall glue and preparation method thereof, this
Invent the tire sidewall glue provided fatigue performance is more excellent, rolling resistance and compression heat generation are lower.
The present invention provides a kind of tire sidewall glue, according to parts by weight, comprising:
Preferably, the TBIR-BR masterbatch is blended by trans- butadiene-isoprene rubber and butadiene rubber mixing and is made；
The mass ratio of the trans- butadiene-isoprene rubber and butadiene rubber is 10~90:1~90；
The temperature that the mixing is blended is 40~80 DEG C, and the revolving speed that the mixing is blended is 30~90rpm, and the mixing is total
Mixed batch charging coefficient is 0.7~0.85, and the time that the mixing is blended is 1~5min.
Preferably, in the trans- butadiene-isoprene rubber, the molar content of butadiene unit is 5~45%, isoprene unit
Molar content be 55~95%, anti-form-1, the molar content of 4- structure is greater than 90%, Mooney viscosity ML3+4 100℃For 45~
100。
Preferably, the anti-aging agent is selected from antioxidant 4020, anti-aging agent RD, antioxidant 4010NA, antioxidant 4010 and stone
One or more of wax.
Preferably, the filler is selected from one or more of carbon black, white carbon black, calcium carbonate, clay and talcum powder；
The filler dispersing agent is selected from carbon black disperser and/or White carbon black dispersant；
The operation oil is selected from environment-friendly aromatic oil.
Preferably, the promotor is selected from one or more of accelerator NS, accelerant NOBS and accelerant CZ；
The anti-recovery agent is selected from the one or more of WK901, HTS and PK900.
The present invention also provides a kind of preparation methods of tire sidewall glue described above, comprising the following steps:
A) natural rubber, TBIR-BR masterbatch, zinc oxide, stearic acid, anti-aging agent, filler and the oily mixing of operation are mixed,
Obtain one section of masterbatch；
B) one section of masterbatch, promotor and Sulfur mixing are mixed, obtain two sections of masterbatch；
C two sections of masterbatch) are subjected to mills, obtained finished composition is temperature is 21~25 DEG C, humidity is 30~80%
Under the conditions of place 4~168h；
D the finished composition after placement is vulcanized in the case where temperature is 140~180 DEG C, pressure is 10~35MPa), obtains tire
Side glue.
Preferably, step A) in, the temperature of mixing mixing is 50~70 DEG C, the revolving speed that the mixing is blended is 30~
90rpm, the batch charging coefficient that the mixing is blended are 0.7~0.85, and the time that the mixing is blended is 3~8min；The mixing
Dump temperature after blending is 145~160 DEG C.
Preferably, step B) in, the temperature of mixing mixing is 50~70 DEG C, the revolving speed that the mixing is blended is 30~
100rpm, the batch charging coefficient that the mixing is blended are 0.7~0.85, and the time that the mixing is blended is 1~5min；The mixing
Dump temperature after blending is less than 110 DEG C.
Preferably, step C) in, the temperature of the mill is 40~80 DEG C, and the revolving speed of mill is 10~40rpm.
The present invention provides a kind of tire sidewall glue, according to parts by weight, comprising: 30~80 parts of natural rubber；TBIR-BR
20~70 parts of masterbatch；2~7 parts of zinc oxide；1~3.5 part of stearic acid；3~7 parts of anti-aging agent；40~60 parts of filler；Operation oil 2
~8 parts；0~3 part of filler dispersing agent；0.8~2 part of promotor；0.6~2 part of Sulfur；0~0.4 part of anti-recovery agent.This hair
It is bright by natural rubber and TBIR-BR masterbatch cooperation other components synergistic effect so that natural rubber and butadiene rubber is compatible
Property and co-vulcanization characteristic further improve, and filler is more evenly distributed in natural rubber and butadiene rubber, finally, obtained tire
The fatigue performance of sidewall rubber is more excellent, rolling resistance and compression heat generation are lower.
The present invention also provides a kind of preparation methods of tire sidewall glue described above, comprising the following steps: A) it will be natural
Rubber, TBIR-BR masterbatch, zinc oxide, stearic acid, anti-aging agent, filler, filler dispersing agent and the oily mixing mixing of operation, obtain
One section of masterbatch；B) one section of masterbatch, promotor, Sulfur and anti-recovery agent mixing are mixed, obtain two sections of masterbatchings
Glue；C two sections of masterbatch) are subjected to mill, obtained finished composition is under conditions of temperature is 21~25 DEG C, humidity is 30~80%
Place 4~168h；D the finished composition after placement is vulcanized in the case where temperature is 140~180 DEG C, pressure is 10~35MPa), is taken turns
Tire sidewall rubber.In sidewall rubber using the method preparation, the compatibility and co-vulcanization characteristic of natural rubber and butadiene rubber are into one
Step improves, and filler is more evenly distributed in natural rubber and butadiene rubber, finally, the fatigue performance of tire sidewall glue obtained
More excellent, rolling resistance and compression heat generation are lower.
The experimental results showed that comparing conventional tire sidewall rubber, tire sidewall glue fatigue performance provided by the invention improves
48~87%, rolling resistance (60 DEG C of tan δ@) reduces by 5~8%, and compression heat generation reduces about 10%.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair
The range of bright protection.
The present invention provides a kind of tire sidewall glue, according to parts by weight, comprising:
Tire sidewall glue provided by the invention includes natural rubber.The parts by weight of the natural rubber are 30~80 parts.
In certain embodiments of the present invention, the parts by weight of the natural rubber are 40 parts.
The present invention has no special limitation to the type of the natural rubber, can be general commercially available.In certain of the invention
In a little embodiments, the natural rubber is selected from SMR 20 or SCR WF.
Tire sidewall glue provided by the invention further includes TBIR-BR masterbatch.The parts by weight of the TBIR-BR masterbatch
It is 20~70 parts.In certain embodiments of the present invention, the parts by weight of the TBIR-BR masterbatch are 60 parts.
In an embodiment of the present invention, the TBIR-BR masterbatch is blended by trans- butadiene-isoprene rubber and butadiene rubber mixing
It is made.
The temperature that the mixing is blended is 40~80 DEG C.In certain embodiments of the present invention, the temperature that the mixing is blended
Degree is 60 DEG C or 40 DEG C.The revolving speed that the mixing is blended is 30~90rpm.In certain embodiments of the present invention, the mixing
The revolving speed of blending is 70rpm or 90rpm.The batch charging coefficient that the mixing is blended is 0.7~0.85.In certain implementations of the invention
In example, the batch charging coefficient that the mixing is blended is 0.75 or 0.85.The time that the mixing is blended is 1~5min.In the present invention
Some embodiments in, the time that the mixing is blended is 3min or 5min.
The mass ratio of the trans- butadiene-isoprene rubber and butadiene rubber is 10~90:1~90.In certain embodiments of the present invention
In, the mass ratio of the trans- butadiene-isoprene rubber and butadiene rubber is 50:10 or 50:50.
In certain embodiments of the present invention, in the trans- butadiene-isoprene rubber, the molar content of butadiene unit is 5~
45%, preferably 5~25%；The molar content of isoprene unit is 55~95%, preferably 75~95%；Anti-form-1,4- structure
Molar content be greater than 90%, Mooney viscosity ML3+4 100℃It is 45~100.In certain embodiments of the present invention, the trans- fourth
Penta rubber is selected from TBIR-0963 or TBIR-2063.The butadiene content of the TBIR-0963 is 9.7mol%, isoprene knot
Structure unit anti-form-1,4- structural content are 97.1mol%, and butadiene structural units anti-form-1,4- content is 95.8mol%, door
Buddhist nun's viscosity ML3+4 100℃=60.5.The butadiene content of the TBIR-2063 is 16.8mol%, and isoprene structures unit is anti-
Formula-Isosorbide-5-Nitrae-structural content is 96.5mol%, and butadiene structural units anti-form-1,4- content is 95.1mol%, Mooney viscosity
ML3+4 100℃=59.7.
The present invention has no special limitation to the type of the butadiene rubber, can be general commercially available.In certain of the invention
In a little embodiments, the butadiene rubber is selected from BR 9000.
The present invention is blended using TBIR-BR masterbatch with natural rubber and other components, is prepared in this way
The compatibility and co-vulcanization excellent of sidewall rubber, filler good dispersion, natural rubber and butadiene rubber, it is more excellent resistance to for obtaining
Fatigue behaviour and lower rolling resistance and compression heat generation play very crucial effect.
Tire sidewall glue provided by the invention further includes zinc oxide.The parts by weight of the zinc oxide are 2~7 parts.At this
In some embodiments of invention, the parts by weight of the zinc oxide are 3.5 parts.Zinc oxide can be with the vulcanization body in activating recipe
System, improves the crosslink density and heat aging property of vulcanizate.
Tire sidewall glue provided by the invention further includes stearic acid.The stearic parts by weight are 1~3.5 part.?
In certain embodiments of the present invention, the stearic parts by weight are 1.2 parts.Zinc oxide can be improved in rubber in stearic acid
Solubility.
Tire sidewall glue provided by the invention further includes anti-aging agent.The parts by weight of the anti-aging agent are 3~7 parts.At this
In some embodiments of invention, the parts by weight of the anti-aging agent are 6 parts.Anti-aging agent can improve the heat-proof aging of rubber and smelly
Oxidative aging energy.In certain embodiments of the present invention, the anti-aging agent is selected from antioxidant 4020, anti-aging agent RD, anti-aging agent
One or more of 4010NA, antioxidant 4010 and paraffin.
Tire sidewall glue provided by the invention further includes filler.The parts by weight of the filler are 40~60 parts.In this hair
In bright some embodiments, the parts by weight of the filler are 50 parts.The mechanical strength and modulus of vulcanizate can be improved in filler.
In certain embodiments of the present invention, the filler be selected from one of carbon black, white carbon black, calcium carbonate, clay and talcum powder or
It is several.
Tire sidewall glue provided by the invention further includes operation oil.The parts by weight of the operation oil are 2~8 parts.At this
In some embodiments of invention, the parts by weight of the operation oil are 6 parts.The processing performance of rubber compound can be improved in operation oil,
Improve dispersion effect of the filler in rubber matrix.In certain embodiments of the present invention, the operation oil is selected from environment-friendly aromatic
Oil.The present invention has no special limitation to the type of the environment-friendly aromatic oil, can be general commercially available.In certain realities of the invention
It applies in example, the environment-friendly aromatic oil is selected from the VIVATEC 500 of German Chinese sage.
Tire sidewall glue provided by the invention further includes filler dispersing agent.The parts by weight of the filler dispersing agent are 0~3
Part.In certain embodiments of the present invention, the parts by weight of the filler dispersing agent are 3 parts.Filler dispersing agent can obviously change
Dispersion effect of the filler in rubber matrix in kind recipe ingredient.In certain embodiments of the present invention, the filler dispersing agent
Selected from carbon black disperser and/or White carbon black dispersant.The present invention to the type of the carbon black disperser and White carbon black dispersant simultaneously
It can be general commercially available without special limitation.
Tire sidewall glue provided by the invention further includes promotor.The parts by weight of the promotor are 0.8~2 part.?
In certain embodiments of the present invention, the parts by weight of the promotor are 0.8 part.The vulcanization effect of Sulfur can be improved in promotor
Rate.In certain embodiments of the present invention, the promotor is selected from one of accelerator NS, accelerant NOBS and accelerant CZ
Or it is several.
Tire sidewall glue provided by the invention further includes Sulfur.The parts by weight of the Sulfur are 0.6~2 part.In this hair
In bright some embodiments, the parts by weight of the Sulfur are 1.6 parts.Sulfur is the crosslinking agent in recipe ingredient.The present invention couple
The type of the Sulfur has no special limitation, can be general commercially available.In certain embodiments of the present invention, the Sulfur choosing
From common sofril, oil-filled Sulfur, it is granulated one or more of Sulfur or insoluble sulfuy.
Tire sidewall glue provided by the invention further includes anti-recovery agent.The parts by weight of the anti-recovery agent are
0~0.4 part.In certain embodiments of the present invention, the parts by weight of the anti-recovery agent are 0 part.Anti-recovery agent
It can inhibit the generation in sulfurating stage recovery phenomenon.In certain embodiments of the present invention, the anti-recovery agent
One or more selected from WK901, HTS and PK900.
The present invention also provides a kind of preparation methods of tire sidewall glue described above, comprising the following steps:
A) natural rubber, TBIR-BR masterbatch, zinc oxide, stearic acid, anti-aging agent, filler and the oily mixing of operation are mixed,
Obtain one section of masterbatch；
B) one section of masterbatch, promotor and Sulfur mixing are mixed, obtain two sections of masterbatch；
C two sections of masterbatch) are subjected to mills, obtained finished composition is temperature is 21~25 DEG C, humidity is 30~80%
Under the conditions of place 4~168h；
D the finished composition after placement is vulcanized in the case where temperature is 140~180 DEG C, pressure is 10~35MPa), obtains tire
Side glue.
In the preparation method, the component and proportion of the raw material are same as above, and details are not described herein.
In an embodiment of the present invention, the TBIR-BR masterbatch is blended by trans- butadiene-isoprene rubber and butadiene rubber mixing
It is made.
The temperature that the mixing is blended is 40~80 DEG C.In certain embodiments of the present invention, the temperature that the mixing is blended
Degree is 60 DEG C or 40 DEG C.The revolving speed that the mixing is blended is 30~90rpm.In certain embodiments of the present invention, the mixing
The revolving speed of blending is 70rpm or 90rpm.The batch charging coefficient that the mixing is blended is 0.7~0.85.In certain implementations of the invention
In example, the batch charging coefficient that the mixing is blended is 0.75 or 0.85.The time that the mixing is blended is 1~5min.In the present invention
Some embodiments in, the time that the mixing is blended is 3min or 5min.
The mass ratio of the trans- butadiene-isoprene rubber and butadiene rubber is 10~90:1~90.In certain embodiments of the present invention
In, the mass ratio of the trans- butadiene-isoprene rubber and butadiene rubber is 50:10,50:50 or 60:40.
In certain embodiments of the present invention, in the trans- butadiene-isoprene rubber, the molar content of butadiene unit is 5~
45%, preferably 5~25%；The molar content of isoprene unit is 55~95%, preferably 75~95%；Anti-form-1,4- structure
Molar content be greater than 90%, Mooney viscosity ML3+4 100℃It is 45~100.In certain embodiments of the present invention, the trans- fourth
Penta rubber is selected from TBIR-0963 or TBIR-2063.The butadiene content of the TBIR-0963 is 9.7mol%, isoprene knot
Structure unit anti-form-1,4- structural content are 97.1mol%, and butadiene structural units anti-form-1,4- content is 95.8mol%, door
Buddhist nun's viscosity ML3+4 100℃=60.5.The butadiene content of the TBIR-2063 is 16.8mol%, and isoprene structures unit is anti-
Formula-Isosorbide-5-Nitrae-structural content is 96.5mol%, and butadiene structural units anti-form-1,4- content is 95.1mol%, Mooney viscosity
ML3+4 100℃=59.7.
The present invention has no special limitation to the type of the butadiene rubber, can be general commercially available.In certain of the invention
In a little embodiments, the butadiene rubber is selected from BR 9000.
The present invention is first blended using trans- butadiene-isoprene rubber and butadiene rubber mixing and TBIR-BR masterbatch is made, then again with
Other components are blended, the sidewall rubber prepared in this way, filler good dispersion, the compatibility of natural rubber and butadiene rubber
With co-vulcanization excellent, played very for obtaining more excellent fatigue performance and lower rolling resistance and compression heat generation
Crucial effect.
After obtaining TBIR-BR masterbatch, by natural rubber, TBIR-BR masterbatch, zinc oxide, stearic acid, anti-aging agent, fill out
Material and the oily mixing mixing of operation, obtain one section of masterbatch.When containing filler dispersing agent in raw material, by natural rubber, TBIR-BR
Masterbatch, zinc oxide, stearic acid, anti-aging agent, filler, filler dispersing agent and the oily mixing mixing of operation, obtain one section of masterbatch.
In certain embodiments of the present invention, the temperature of the mixing mixing is 50~70 DEG C.In certain embodiments, institute
The temperature for stating mixing blending is 70 DEG C or 60 DEG C.The revolving speed that the mixing is blended is 30~90rpm.In certain embodiments, institute
The revolving speed for stating mixing blending is 60rpm, 70rpm or 80rpm.The batch charging coefficient that the mixing is blended is 0.7~0.85.Certain
In embodiment, the batch charging coefficient that the mixing is blended is 0.75 or 0.85.The time that the mixing is blended is 3~8min.At certain
In a little embodiments, the time that the mixing is blended is 4min or 5min.Dump temperature after the mixing is blended is 145~160
℃.In certain embodiments, the dump temperature after the mixing is blended is 155 DEG C or 150 DEG C.
In certain embodiments of the present invention, after obtaining TBIR-BR masterbatch, first by natural rubber and TBIR-BR masterbatching
Glue mixing mixes 0.5~2min, and it is mixed to add zinc oxide, stearic acid, anti-aging agent, filler, filler dispersing agent and the oily mixing of operation
Close 3~6.5min.
The natural rubber and temperature, revolving speed and the batch charging coefficient of TBIR-BR masterbatch mixing mixing are same as above, herein no longer
It repeats.It adds zinc oxide, stearic acid, anti-aging agent, filler, filler dispersing agent and operates oily mixing mixing temperature, revolving speed and throwing
Material coefficient is same as above, and details are not described herein.
In certain embodiments, the time of natural rubber and TBIR-BR masterbatch mixing mixing is 1min or 2min.At certain
In a little embodiments, adds zinc oxide, stearic acid, anti-aging agent, filler, filler dispersing agent and operate time of oily mixing mixing and be
4min or 6min.
After obtaining one section of masterbatch, one section of masterbatch, promotor and Sulfur mixing are mixed, two sections of masterbatchings are obtained
Glue.When in raw material contain anti-recovery agent when, after obtaining one section of masterbatch, by one section of masterbatch, promotor, Sulfur and
Anti-recovery agent mixing mixing, obtains two sections of masterbatch.
In certain embodiments of the present invention, the temperature of the mixing mixing is 50~70 DEG C.In certain embodiments, institute
The temperature for stating mixing blending is 60 DEG C or 50 DEG C.The revolving speed that the mixing is blended is 30~100rpm.In certain embodiments, institute
The revolving speed for stating mixing blending is 30rpm or 50rpm.The batch charging coefficient that the mixing is blended is 0.7~0.85.In some embodiments
In, the batch charging coefficient that the mixing is blended is 0.75.The time that the mixing is blended is 1~3min.In certain embodiments, institute
The time for stating mixing blending is 3min or 2min.Dump temperature after the mixing blending is less than 110 DEG C.In some embodiments
In, the dump temperature after the mixing is blended is 100 DEG C or 105 DEG C.
After obtaining two sections of masterbatch, two sections of masterbatch are subjected to mills, obtained finished composition temperature be 21~25 DEG C, it is wet
Degree places 4~168h under conditions of being 30~80%.
In certain embodiments of the present invention, the temperature of the mill is 40~80 DEG C.In certain embodiments, described to open
The temperature of refining is 50 DEG C or 40 DEG C.The revolving speed of the mill is 10~40rpm.In certain embodiments, the revolving speed of the mill
For 30rpm or 40rpm.The time of the mill is 0.5~2.5min.In certain embodiments, the time of the mill is
0.5min, 1.5min or 1min.
The temperature that obtained finished composition is placed is 21~25 DEG C.In certain embodiments, the temperature that the finished composition is placed
It is 23 DEG C or 21 DEG C.The humidity that the finished composition is placed is 30~80%.In certain embodiments, what the finished composition was placed is wet
Degree is 50% or 40%.The time that the finished composition is placed is 4~168h.In certain embodiments, the finished composition is placed
Time is for 24 hours or 72h.It is eliminated in the internal stress of parking period, rubber macromolecule chain, the auxiliary agent in formula will disperse more
It is even, conducive to the improvement of cured properties.After the finished composition places 4~168h, by the finished composition after placement temperature be 140~
180 DEG C, pressure be 10~35MPa under vulcanize, obtain tire sidewall glue.
In the present invention, the temperature of the vulcanization is 140~180 DEG C.In certain embodiments of the present invention, the vulcanization
Temperature is 150 DEG C or 140 DEG C.The pressure of the vulcanization is 10~35MPa.In certain embodiments of the present invention, the vulcanization
Pressure be 15MPa or 20MPa.In certain embodiments of the present invention, the time of the vulcanization is 1 times of technique sulfurizing time
~3 times of technique sulfurizing times.In certain embodiments, the time of the vulcanization is 1.5 times of technique sulfurizing times.
The present invention is preferentially blended to obtain TBIR-BR masterbatch with butadiene rubber using trans- butadiene-isoprene rubber, then uses
TBIR-BR masterbatch, natural rubber and other components are blended.Also in that this mode, filler in the sidewall rubber of preparation
The compatibility and co-vulcanization characteristic of dispersibility, natural rubber and butadiene rubber rubber are more excellent, and application performance is more preferable.
The present invention has no special limitation to the source of the raw material used above, can be general commercially available.
The present invention provides a kind of tire sidewall glue, according to parts by weight, comprising: 30~80 parts of natural rubber；TBIR-BR
20~70 parts of masterbatch；2~7 parts of zinc oxide；1~3.5 part of stearic acid；3~7 parts of anti-aging agent；40~60 parts of filler；Operation oil 2
~8 parts；0~3 part of filler dispersing agent；0.8~2 part of promotor；0.6~2 part of Sulfur；0~0.4 part of anti-recovery agent.This hair
It is bright by natural rubber and TBIR-BR masterbatch cooperation other components synergistic effect so that natural rubber and butadiene rubber is compatible
Property further improves, and filler is more evenly distributed in natural rubber and butadiene rubber, finally, tire sidewall glue obtained it is resistance to tired
Labor performance is more excellent, rolling resistance and compression heat generation are lower.
The experimental results showed that comparing conventional tire sidewall rubber, tire sidewall glue fatigue performance provided by the invention improves
48~87%, rolling resistance (60 DEG C of tan δ@) reduces by 5~8%, and compression heat generation reduces about 10%.
In order to further illustrate the present invention, below with reference to embodiment to a kind of tire sidewall glue provided by the invention and its system
Preparation Method is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Raw material used in following embodiment is general commercially available.
Embodiment 1
Prepare TBIR-BR masterbatch:
Trans- butadiene-isoprene rubber TBIR-0963 and butadiene rubber BR 9000 is carried out mixing according to mass ratio for 50:10 to be total to
It is mixed, wherein the temperature that mixing is blended is 60 DEG C, and the revolving speed that mixing is blended is 70rpm, and the batch charging coefficient that mixing is blended is 0.75,
The time that mixing is blended is 3min.
Prepare tire sidewall glue:
First by natural rubber and TBIR-BR masterbatch mixing mixing 1min, zinc oxide, stearic acid, anti-aging agent (3 are added
Parts by weight antioxidant 4020,1.5 parts by weight anti-aging agent RDs and 1.5 parts by weight paraffin), carbon black N330, carbon black disperser and environmental protection
500 mixing mixing 4min of aromatic naphtha VIVATEC；The temperature that mixing twice is blended is 70 DEG C, and revolving speed is 70rpm, and feeding intake is
Number is 0.75, and the dump temperature after the mixing is blended is 155 DEG C, obtains one section of masterbatch；
One section of masterbatch is put into mixer, accelerator NS and sofril mixing mixing is added, obtains two sections of masterbatch；Institute
The temperature for stating mixing blending is 60 DEG C, revolving speed 30rpm, batch charging coefficient 0.75, time 2min, after the mixing is blended
Dump temperature is 105 DEG C.
By two sections of masterbatch bottom sheet on a mill, mill is carried out；The temperature of mill is 50 DEG C, revolving speed 30rpm,
Time is 0.5min.
The finished composition obtained after mill places 48h under conditions of temperature is 23 DEG C, humidity is 50%.
Then, the finished composition after placement is vulcanized in the case where temperature is 150 DEG C, pressure is 15MPa, vulcanization time is 1.5 times
Technique sulfurizing time, obtain tire sidewall glue.
Embodiment 2
Prepare TBIR-BR masterbatch:
Trans- butadiene-isoprene rubber TBIR-2063 and butadiene rubber BR 9000 is carried out mixing according to mass ratio for 50:10 to be total to
It is mixed, wherein the temperature that mixing is blended is 60 DEG C, and the revolving speed that mixing is blended is 70rpm, and the batch charging coefficient that mixing is blended is 0.75,
The time that mixing is blended is 3min.
Prepare tire sidewall glue:
First by natural rubber and TBIR-BR masterbatch mixing mixing 1min, zinc oxide, stearic acid, anti-aging agent (3 are added
Parts by weight antioxidant 4020,1.5 parts by weight anti-aging agent RDs and 1.5 parts by weight paraffin), carbon black N330, carbon black disperser and cycloalkanes
Oily mixing mixing 5min；The temperature that mixing twice is blended is 70 DEG C, and revolving speed is 70rpm, and batch charging coefficient is 0.75, described
Dump temperature after mixing is blended is 155 DEG C, obtains one section of masterbatch；
One section of masterbatch is put into mixer, accelerator NS and sofril mixing mixing is added, obtains two sections of masterbatch；Institute
The temperature for stating mixing blending is 60 DEG C, revolving speed 30rpm, batch charging coefficient 0.75, time 3min, after the mixing is blended
Dump temperature is 105 DEG C.
By two sections of masterbatch bottom sheet on a mill, mill is carried out；The temperature of mill is 50 DEG C, revolving speed 30rpm,
Time is 0.5min.
The finished composition obtained after mill places 48h under conditions of temperature is 23 DEG C, humidity is 50%.
Then, the finished composition after placement is vulcanized in the case where temperature is 150 DEG C, pressure is 15MPa, vulcanization time is 1.5 times
Technique sulfurizing time, obtain tire sidewall glue.
Embodiment 3
Prepare TBIR-BR masterbatch:
Trans- butadiene-isoprene rubber TBIR-2063 and butadiene rubber BR 9000 is carried out mixing according to mass ratio for 50:50 to be total to
It is mixed, wherein the temperature that mixing is blended is 40 DEG C, and the revolving speed that mixing is blended is 90rpm, and the batch charging coefficient that mixing is blended is 0.85,
The time that mixing is blended is 5min.
Prepare tire sidewall glue:
First by natural rubber and TBIR-BR masterbatch mixing mixing 2min, zinc oxide, stearic acid, anti-aging agent (3 are added
Parts by weight antioxidant 4020,1.5 parts by weight anti-aging agent RDs and 1.5 parts by weight paraffin), carbon black N330, carbon black disperser and cycloalkanes
Oily mixing mixing 6min；The temperature that mixing twice is blended is 60 DEG C, and revolving speed is 80rpm, and batch charging coefficient is 0.85, described
Dump temperature after mixing is blended is 150 DEG C, obtains one section of masterbatch；
One section of masterbatch is put into mixer, accelerator NS and sofril mixing mixing is added, obtains two sections of masterbatch；Institute
The temperature for stating mixing blending is 50 DEG C, revolving speed 50rpm, batch charging coefficient 0.85, time 4min, after the mixing is blended
Dump temperature is 105 DEG C.
By two sections of masterbatch bottom sheet on a mill, mill is carried out；The temperature of mill is 40 DEG C, revolving speed 40rpm,
Time is 1min.
The finished composition obtained after mill places 60h under conditions of temperature is 21 DEG C, humidity is 40%.
Then, the finished composition after placement is vulcanized in the case where temperature is 140 DEG C, pressure is 20MPa, vulcanization time is 1.5 times
Technique sulfurizing time, obtain tire sidewall glue.
Comparative example 1
According to mass ratio it is 45:55 mixing mixing 1min by natural rubber and butadiene rubber BR 9000, adds oxidation
Zinc, stearic acid, anti-aging agent (3 parts by weight antioxidant 4020s, 1.5 parts by weight anti-aging agent RDs and 1.5 parts by weight paraffin), carbon black
N330, carbon black disperser and naphthenic oil mixing mixing 4min；The temperature that mixing twice is blended is 70 DEG C, and revolving speed is 70rpm,
Batch charging coefficient is 0.75, and the dump temperature after the mixing is blended is 155 DEG C, obtains one section of masterbatch；
One section of masterbatch is put into mixer, accelerator NS and sofril mixing mixing is added, obtains two sections of masterbatch；Institute
The temperature for stating mixing blending is 60 DEG C, revolving speed 30rpm, batch charging coefficient 0.75, time 3min, after the mixing is blended
Dump temperature is 100 DEG C.
By two sections of masterbatch bottom sheet on a mill, mill is carried out；The temperature of mill is 50 DEG C, revolving speed 30rpm,
Time is 0.5min.
The finished composition obtained after mill places 48h under conditions of temperature is 23 DEG C, humidity is 50%.
Then, the finished composition after placement is vulcanized in the case where temperature is 150 DEG C, pressure is 15MPa, vulcanization time is 1.5 times
Technique sulfurizing time, obtain tire sidewall glue.
Comparative example 2
By natural rubber, butadiene rubber BR 9000 and trans- butadiene-isoprene rubber TBIR-0963 according to mass ratio be 40:50:10
Mixing mixing 1min, add zinc oxide, stearic acid, anti-aging agent (3 parts by weight antioxidant 4020s, 1.5 parts by weight anti-aging agent RDs and
1.5 parts by weight paraffin), carbon black N330, carbon black disperser and naphthenic oil mixing mixing 5min；Mixing twice be blended temperature be
70 DEG C, revolving speed is 70rpm, and batch charging coefficient is 0.75, and the dump temperature after the mixing is blended is 155 DEG C, obtains one section
Masterbatch；
One section of masterbatch is put into mixer, accelerator NS and sofril mixing mixing is added, obtains two sections of masterbatch；Institute
The temperature for stating mixing blending is 60 DEG C, revolving speed 30rpm, batch charging coefficient 0.75, time 3min, after the mixing is blended
Dump temperature is 100 DEG C.
By two sections of masterbatch bottom sheet on a mill, mill is carried out；The temperature of mill is 50 DEG C, revolving speed 30rpm,
Time is 0.5min.
The finished composition obtained after mill places 48h under conditions of temperature is 23 DEG C, humidity is 50%.
Then, the finished composition after placement is vulcanized in the case where temperature is 150 DEG C, pressure is 15MPa, vulcanization time is 1.5 times
Technique sulfurizing time, obtain tire sidewall glue.
Comparative example 3
By natural rubber, butadiene rubber BR 9000 and trans- butadiene-isoprene rubber TBIR-2063 according to mass ratio be 40:50:10
Mixing mixing 1min, add zinc oxide, stearic acid, anti-aging agent (3 parts by weight antioxidant 4020s, 1.5 parts by weight anti-aging agent RDs and
1.5 parts by weight paraffin), carbon black N330, carbon black disperser and naphthenic oil mixing mixing 5min；Mixing twice be blended temperature be
70 DEG C, revolving speed is 70rpm, and batch charging coefficient is 0.75, and the dump temperature after the mixing is blended is 155 DEG C, obtains one section
Masterbatch；
One section of masterbatch is put into mixer, accelerator NS and sofril mixing mixing is added, obtains two sections of masterbatch；Institute
The temperature for stating mixing blending is 60 DEG C, revolving speed 30rpm, batch charging coefficient 0.75, time 3min, after the mixing is blended
Dump temperature is 100 DEG C.
By two sections of masterbatch bottom sheet on a mill, mill is carried out；The temperature of mill is 50 DEG C, revolving speed 30rpm,
Time is 0.5min.
The finished composition obtained after mill places 48h under conditions of temperature is 23 DEG C, humidity is 50%.
Then, the finished composition after placement is vulcanized in the case where temperature is 150 DEG C, pressure is 15MPa, vulcanization time is 1.5 times
Technique sulfurizing time, obtain tire sidewall glue.
Embodiment 4
Examples 1 to 3 and raw material in comparative example 1~3 and its proportion are as shown in table 1.
The performance test results for the tire sidewall glue that 1 Examples 1 to 3 of table and comparative example 1~3 obtain (press by raw material dosage
Parts by weight meter)
The vulcanization characteristics and mechanical performance of the tire sidewall glue obtained to Examples 1 to 3 and comparative example 1~3 are examined
It surveys, the results are shown in Table 2.
The performance test results for the tire sidewall glue that 2 Examples 1 to 3 of table and comparative example 1~3 obtain
From Table 2, it can be seen that 150% tensile fatigue lifetime of tire sidewall glue prepared by the present invention is not less than 58.5
Ten thousand, compared to the tire sidewall glue (comparative example 1) of traditional common, fatigue performance improves 48~87%；Rolling resistance (tan δ@
60 DEG C) it is no more than 0.172, rolling resistance reduces by 5~8%；Compression heat generation is lower than 32.5 DEG C, and compression heat generation reduces about 10%.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of tire sidewall glue, according to parts by weight, comprising:
2. tire sidewall glue according to claim 1, which is characterized in that the TBIR-BR masterbatch is by trans- penta rubber of fourth
Glue and butadiene rubber mixing, which are blended, to be made；
The mass ratio of the trans- butadiene-isoprene rubber and butadiene rubber is 10~90: 1~90；
The temperature that the mixing is blended is 40~80 DEG C, and the revolving speed that the mixing is blended is 30~90rpm, what the mixing was blended
Batch charging coefficient is 0.7~0.85, and the time that the mixing is blended is 1~5min.
3. tire sidewall glue according to claim 2, which is characterized in that in the trans- butadiene-isoprene rubber, butadiene unit
Molar content be 5~45%, the molar content of isoprene unit is 55~95%, anti-form-1, the molar content of 4- structure
Greater than 90%, Mooney viscosity ML3+4 100℃It is 45~100.
4. tire sidewall glue according to claim 1, which is characterized in that the anti-aging agent is selected from antioxidant 4020, prevents always
One or more of agent RD, antioxidant 4010NA, antioxidant 4010 and paraffin.
5. tire sidewall glue according to claim 1, which is characterized in that the filler is selected from carbon black, white carbon black, carbonic acid
One or more of calcium, clay and talcum powder；
The filler dispersing agent is selected from carbon black disperser and/or White carbon black dispersant；
The operation oil is selected from environment-friendly aromatic oil.
6. tire sidewall glue according to claim 1, which is characterized in that the promotor is selected from accelerator NS, promotor
One or more of NOBS and accelerant CZ；
The anti-recovery agent is selected from the one or more of WK901, HTS and PK900.
7. the preparation method of tire sidewall glue described in claim 1, comprising the following steps:
A) natural rubber, TBIR-BR masterbatch, zinc oxide, stearic acid, anti-aging agent, filler and the oily mixing of operation are mixed, obtained
One section of masterbatch；
B) one section of masterbatch, promotor and Sulfur mixing are mixed, obtain two sections of masterbatch；
C two sections of masterbatch) are subjected to mill, obtained finished composition is in the condition that temperature is 21~25 DEG C, humidity is 30~80%
4~168h of lower placement；
D the finished composition after placement is vulcanized in the case where temperature is 140~180 DEG C, pressure is 10~35MPa), obtains tire sidewall
Glue.
8. preparation method according to claim 7, which is characterized in that step A) in, the temperature of the mixing mixing is 50
~70 DEG C, the revolving speed that the mixing is blended is 30~90rpm, and the batch charging coefficient that the mixing is blended is 0.7~0.85, described close
The time that refining is blended is 3~8min；Dump temperature after the mixing is blended is 145~160 DEG C.
9. preparation method according to claim 7, which is characterized in that step B) in, the temperature of the mixing mixing is 50
~70 DEG C, the revolving speed that the mixing is blended is 30~100rpm, and the batch charging coefficient that the mixing is blended is 0.7~0.85, described
The time that mixing is blended is 1~5min；Dump temperature after the mixing blending is less than 110 DEG C.
10. preparation method according to claim 7, which is characterized in that step C) in, the temperature of the mill is 40~80
DEG C, the revolving speed of mill is 10~40rpm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480495A (en) * | 2020-11-17 | 2021-03-12 | 山东华聚高分子材料有限公司 | All-steel radial tire bead protection rubber |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0912784A (en) * | 1995-06-29 | 1997-01-14 | Toyo Tire & Rubber Co Ltd | Rubber composition |
| US20150096654A1 (en) * | 2013-10-08 | 2015-04-09 | The Goodyear Tire & Rubber Company | Rubbery blend containing trans isoprene-butadiene copolymer |
| JP6496201B2 (en) * | 2015-07-09 | 2019-04-03 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition and pneumatic tire |
| CN109181027B (en) * | 2018-09-07 | 2021-10-26 | 山东华聚高分子材料有限公司 | High-performance tire tread rubber and preparation method thereof |
| CN109942910B (en) * | 2019-03-21 | 2021-09-24 | 山东华聚高分子材料有限公司 | Aviation sidewall rubber with long flexing fatigue life, and preparation method and application thereof |
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2019
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Cited By (1)
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| CN112480495A (en) * | 2020-11-17 | 2021-03-12 | 山东华聚高分子材料有限公司 | All-steel radial tire bead protection rubber |
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