CN108329549B - Modified diolefin rubber and preparation method thereof - Google Patents
Modified diolefin rubber and preparation method thereof Download PDFInfo
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Abstract
The invention provides a modified diolefin rubber, which is prepared from diolefin rubber, an initiator, an amino modifier, a stabilizer and an antioxidant; the amino modifier comprises one or more of formamide, acetamide, propionamide, N-dimethyl amide, benzamide, succinimide, phthalimide, acrylamide and polyacrylamide; the mass ratio of the diolefin rubber, the initiator, the amino modifier, the stabilizer and the antioxidant is 100: (0.1-1.0): (1-50): (1-10): (1-5). Compared with the prior art, the invention uses the amino modifier to change the chain structure of the diolefin rubber, so that the wet skid resistance of the diolefin rubber vulcanized rubber is improved, and the diolefin rubber vulcanized rubber has better physical mechanical properties and dynamic mechanical properties. The invention also provides a preparation method of the modified diolefin rubber.
Description
Technical Field
The invention belongs to the technical field of rubber, and particularly relates to modified diolefin rubber and a preparation method thereof.
Background
Diene rubber is a generic name for rubber materials prepared by catalytic polymerization of diolefins (butadiene, isoprene, etc. and derivatives thereof). The diene rubber has excellent characteristics of high elasticity, low modulus and the like, so that the diene rubber is widely applied to the fields of automobiles, buildings and electric appliances. Automobile tires are the main consumption source of diolefin rubber, and the high wet skid resistance, low oil consumption and high performance of the diolefin rubber are always the subjects pursued by rubber materials for tires. According to the actual vibration frequency of running of the tire, the relation between the loss tangent value (tan delta) of the vulcanized rubber and the rolling resistance and the time-temperature equivalent WLF equation are derived: under the condition of 10-20 HZ, the tan delta value of vulcanized rubber at 0 ℃ represents the wet skid resistance of the tire, the tan delta value at 60 ℃ represents the rolling resistance (oil consumption) of the tire, and the tensile strength and the tear strength represent the basic service performance of the tire.
The performance of the diene rubber determines the performance of vulcanized rubber, and further reflects the service performance of the tire. In general, the wet skid resistance, rolling resistance and wear resistance of a tire cannot be improved at the same time, and this phenomenon is also called "magic triangle" in the form of images by researchers. Therefore, it is an urgent problem to improve the wet skid resistance, rolling resistance and mechanical properties of diene rubber at the same time.
Disclosure of Invention
The invention aims to provide a modified diolefin rubber and a preparation method thereof, and the modified diolefin rubber has better wet skid resistance, rolling resistance and mechanical property.
The invention provides a modified diolefin rubber, which is prepared from diolefin rubber, an initiator, an amino modifier, a stabilizer and an antioxidant;
the amino modifier comprises one or more of formamide, acetamide, propionamide, N-dimethyl amide, benzamide, succinimide, phthalimide, acrylamide and polyacrylamide;
the mass ratio of the diolefin rubber, the initiator, the amino modifier, the stabilizer and the antioxidant is 100: (0.1-1.0): (1-50): (1-10): (1-5).
Preferably, the diene rubber is butadiene rubber, styrene-butadiene rubber, isoprene rubber or nitrile rubber.
Preferably, the initiator is one or more of benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, N-tetramethyldithiobisthiocarboxamide, tetramethylthiodicarbamide, tetraethyl thioperoxydicarbonate and dipentamethylenethiuram tetrasulfide.
Preferably, the stabilizer is one or more of magnesium oxide, lead oxide, dibutyltin dilaurate, barium stearate and lead stearate.
preferably, the antioxidant is one or more of 2, 2' -methylenebis- (4-methyl-6-tert-butylphenol), β -octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and 2, 4-bis (β -octylthiomethylene) -6-methylphenol.
The invention provides a preparation method of modified diolefin rubber, which comprises the following steps:
diene rubber, an initiator, an amino modifier, a stabilizer and an antioxidant are mixed according to the mass ratio of 100: (0.1-1.0): (1-50): (1-10): (1-5) carrying out mixing reaction in an internal mixer to obtain modified diolefin rubber;
the amine-based modifier comprises one or more of formamide, acetamide (TAA), propionamide, N-dimethyl amide (DMF), benzamide, succinimide, phthalimide, Acrylamide (AM) and Polyacrylamide (PAM).
Preferably, the reaction temperature is 70-150 ℃;
the reaction time is 1-10 min.
Preferably, the rotor speed of the internal mixer is 20-80 rpm.
The invention provides a modified diolefin rubber, which is prepared from diolefin rubber, an initiator, an amino modifier, a stabilizer and an antioxidant; the amine-based modifier comprises one or more of formamide, acetamide (TAA), propionamide, N-dimethyl amide (DMF), benzamide, succinimide, phthalimide, Acrylamide (AM) and Polyacrylamide (PAM); the mass ratio of the diolefin rubber, the initiator, the amino modifier, the stabilizer and the antioxidant is 100: (0.1-1.0): (1-50): (1-10): (1-5). Compared with the prior art, the invention uses the amino modifier to change the chain structure of the diolefin rubber, so that the wet skid resistance of the diolefin rubber vulcanized rubber is improved, and the networking structure and interaction of the diolefin rubber and the carbon black/white carbon black can be improved, thereby realizing the purposes of designing and regulating the hysteresis loss of the diolefin rubber molecular structure, and ensuring that the modified diolefin rubber has better physical mechanical property and dynamic mechanical property. On the other hand, the diolefin rubber, the initiator, the amino modifier, the stabilizer and the antioxidant are mixed in the internal mixer, so that the filler can be uniformly dispersed in the diolefin rubber, the problem of agglomeration of the filler in the rubber is avoided, and the performance of diolefin rubber products is effectively improved. The experimental result shows that the tensile strength of the modified diene rubber is improved by 6.4-16.4%, the tear strength is improved by 10.1-38.4%, the tan delta value at 60 ℃ is basically unchanged, and the tan delta value at 0 ℃ is improved by 13.3-31.8%.
Detailed Description
The invention provides a modified diolefin rubber, which is prepared from diolefin rubber, an initiator, an amino modifier, a stabilizer and an antioxidant;
the amine-based modifier comprises one or more of formamide, acetamide (TAA), propionamide, N-dimethyl amide (DMF), benzamide, succinimide, phthalimide, Acrylamide (AM) and Polyacrylamide (PAM);
the mass ratio of the diolefin rubber, the initiator, the amino modifier, the stabilizer and the antioxidant is 100: (0.1-1.0): (1-50): (1-10): (1-5).
In the invention, in order to improve the wet skid resistance and the physical and mechanical properties of the modified diene rubber on the basis of keeping the original rolling resistance performance, the diene rubber is preferably one or more of styrene-butadiene rubber, isoprene rubber, butadiene rubber and nitrile rubber.
In the present invention, the initiator is a specific auxiliary agent for promoting the activation of the double bonds of the diene rubber, and generally contains peroxide groups or polysulfide groups. The initiator is preferably one or more of Benzoyl Peroxide (BPO), Lauroyl Peroxide (LPO), dicumyl peroxide (DCP), Azobisisobutyronitrile (AIBN), Azobisisoheptonitrile (ABVN), N-tetramethyldithiobisthiocarboxamide (TMTD), tetramethylthiodicarbonamide (TMTM), tetraethylthioperoxydicarbonate (TETD), dipentamethylenethiuram tetrasulfide (DPTT). In the present invention, the mass ratio of the diolefin rubber to the initiator is preferably 100: (0.1 to 1.0), more preferably 100: (0.2 to 0.8), most preferably 100: (0.2-0.5), specifically, it may be 100:0.1, 100:0.2 or 100: 0.5.
The invention uses the amino modifier in the aspect of modifying the diolefin rubber, can increase the interaction between the diolefin rubber and the filler, and improves the wet skid resistance and the physical and mechanical properties of the modified diolefin rubber on the basis of keeping the original excellent performance. The amine-based modifier comprises one or more of formamide, acetamide (TAA), propionamide, N-dimethyl amide (DMF), benzamide, succinimide, phthalimide, Acrylamide (AM) and Polyacrylamide (PAM). The mass ratio of the diolefin rubber to the amine modifier is preferably 100: (1 to 50), more preferably 100: (5-30), most preferably 100: (5-10), specifically, the ratio may be 100:1, 100:5 or 100: 10.
In the present invention, the stabilizer enhances the thermal stability of the material, particularly the diene rubber, and the stabilizer is preferably one or more of magnesium oxide, lead oxide, dibutyltin dilaurate, barium stearate and lead stearate. The mass ratio of the diolefin rubber to the stabilizer is 100: (1-10), more preferably 100: (3-8), specifically, the ratio can be 100:1, 100:5 or 100: 10.
the antioxidant is preferably one or more of 2, 2' -methylenebis- (4-methyl-6-tert-butylphenol), β -octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 4-di (β -octylthiomethylene) -6-methylphenol, an antioxidant A and an antioxidant RD, and the mass ratio of the diolefin rubber to the antioxidant is preferably 100 (1-5).
The invention also provides a preparation method of the modified diolefin rubber, which comprises the following steps:
diene rubber, an initiator, an amino modifier, a stabilizer and an antioxidant are mixed according to the mass ratio of 100: (0.1-1.0): (1-50): (1-10): (1-5) carrying out mixing reaction in an internal mixer to obtain modified diolefin rubber;
the amine-based modifier comprises one or more of formamide, acetamide (TAA), propionamide, N-dimethyl amide (DMF), benzamide, succinimide, phthalimide, Acrylamide (AM) and Polyacrylamide (PAM).
In the present invention, the types, amounts and sources of the diene rubber, the initiator, the amine modifier, the stabilizer and the antioxidant are the same as those of the diene rubber, the initiator, the amine modifier, the stabilizer and the antioxidant, and thus are not described herein again.
In the invention, the reaction temperature is preferably 70-150 ℃, more preferably 100-120 ℃, and specifically can be 70 ℃, 100 ℃, 120 ℃ or 150 ℃; the reaction time is preferably 1-10 min, more preferably 2-8 min, and most preferably 3-5 min. The rotating speed of the rotor of the internal mixer is preferably 20-80 rpm, more preferably 30-70 rpm, and most preferably 40-60 rpm.
The invention also vulcanizes the modified diene rubber (crude rubber) so as to test the performance of the vulcanized rubber, and the vulcanizing method is different for different types of diene, and concretely, the following method can be referred:
wherein, the styrene-butadiene rubber is mixed and vulcanized according to the A series in GB/T8656-1998' evaluation method of emulsion and solution polymerization type styrene-butadiene rubber (SBR), the mixing formula comprises 100 parts by weight of styrene-butadiene rubber before/after modification, 1 part by weight of stearic acid, 3 parts by weight of zinc oxide, 1 part by weight of promoter TBBS, 50 parts by weight of carbon black for general industrial reference and 1.75 parts by weight of sulfur;
the isoprene rubber is mixed and vulcanized according to the method A of international standard ISO 2303-2000, and the mixing formula comprises 100 parts by weight of isoprene rubber before/after modification, 2 parts by weight of stearic acid, 5 parts by weight of zinc oxide, 0.7 part by weight of accelerator TBBS, 35 parts by weight of universal industrial reference carbon black and 2.25 parts by weight of sulfur;
cis-butadiene rubber is subjected to mixing vulcanization according to the method C2 of "solution polymerization type Butadiene Rubber (BR) evaluation method" in GB/T8660-2008, wherein the mixing formula comprises 100 parts by weight of cis-butadiene rubber before/after modification, 2 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 0.9 part by weight of accelerator TBBS, 60 parts by weight of general industrial reference carbon black, and 15 parts by weight of ASTM103#Process oil, 1.5 parts by weight of sulfurSulphur;
nitrile rubber according to standard test method for astm d3187-2006 rubber: evaluation method of NBR (acrylonitrile butadiene rubber) mixing vulcanization is carried out, and mixing formula comprises 100 weight parts of nitrile rubber before/after modification, 1 weight part of stearic acid, 3 weight parts of zinc oxide, 0.7 weight part of promoter TBBS, 40 weight parts of industrial reference IRB-7 carbon black and 1.5 weight parts of sulfur.
The experimental result shows that the tensile strength of the modified diene rubber is improved by 6.4-16.4%, the tear strength is improved by 10.1-38.4%, the tan delta value at 60 ℃ is basically unchanged, and the tan delta value at 0 ℃ is improved by 13.3-31.8%.
The invention provides a modified diolefin rubber, which is prepared from diolefin rubber, an initiator, an amino modifier, a stabilizer and an antioxidant; the amine-based modifier comprises one or more of formamide, acetamide (TAA), propionamide, N-dimethyl amide (DMF), benzamide, succinimide, phthalimide, Acrylamide (AM) and Polyacrylamide (PAM); the mass ratio of the diolefin rubber, the initiator, the amino modifier, the stabilizer and the antioxidant is 100: (0.1-1.0): (1-50): (1-10): (1-5). Compared with the prior art, the invention uses the amino modifier to change the chain structure of the diolefin rubber, so that the wet skid resistance of the diolefin rubber vulcanized rubber is improved, and the networking structure and interaction of the diolefin rubber and the carbon black/white carbon black can be improved, thereby realizing the purposes of designing and regulating the hysteresis loss of the diolefin rubber molecular structure, and ensuring that the modified diolefin rubber has better physical mechanical property and dynamic mechanical property. On the other hand, the diolefin rubber, the initiator, the amino modifier, the stabilizer and the antioxidant are mixed in the internal mixer, so that the filler can be uniformly dispersed in the diolefin rubber, the problem of agglomeration of the filler in the rubber is avoided, and the performance of diolefin rubber products is effectively improved.
In order to further illustrate the present invention, the following examples are given to describe in detail a modified diene rubber and a method for preparing the same, but should not be construed as limiting the scope of the present invention.
The diene rubber adopted in the embodiment of the invention is styrene butadiene rubber, isoprene rubber, ternary butadiene rubber and nitrile butadiene rubber, and the detailed manufacturer brands are shown in table 1.
TABLE 1. production of diene rubber and its brand
Example 1
Styrene butadiene rubber, BPO, TAA, magnesium oxide and an antioxidant 2, 2' -methylene bis- (4-methyl-6-tert-butylphenol) are mixed according to the mass ratio of 100: 0.1: 1: 1: 1, mixing in an internal mixer at the mixing temperature of 100 ℃ for 5 minutes at the rotor speed of 40 rpm to obtain modified styrene-butadiene rubber;
mixing 100 parts by weight of modified styrene-butadiene rubber, 1 part by weight of stearic acid, 3 parts by weight of zinc oxide, 1 part by weight of accelerator TBBS, 50 parts by weight of carbon black and 1.75 parts by weight of sulfur in an open mill, and vulcanizing to obtain vulcanized rubber; physical and mechanical properties were measured, and as shown in Table 2, Table 2 is a table of physical and mechanical properties of the vulcanizate prepared in this example.
Example 2
mixing isoprene rubber, AIBN, DMF, dibutyltin dilaurate and β - (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate in an internal mixer according to the mass ratio of 100: 0.5: 5: 5, wherein the mixing temperature is 70 ℃, the rotor speed is 40 r/min, and the mixing time is 5 minutes to obtain modified isoprene rubber;
mixing 100 parts by weight of modified isoprene rubber, 2 parts by weight of stearic acid, 5 parts by weight of zinc oxide, 0.7 part by weight of accelerator TBBS, 35 parts by weight of carbon black and 2.25 parts by weight of sulfur in an open mill to obtain vulcanized rubber; physical and mechanical properties were measured, and as shown in Table 2, Table 2 is a table of physical and mechanical properties of the vulcanizate prepared in this example.
Example 3
Mixing butadiene rubber, TMTD, AM, barium stearate and 2, 4-di (n-octyl sulfur methylene) -6-methylphenol according to the mass ratio of 100: 0.5: 5: 1: 1, mixing in an internal mixer at the mixing temperature of 120 ℃, the rotor speed of 40 r/m and the mixing time of 5 minutes to obtain modified butadiene rubber;
100 parts by weight of modified butadiene rubber, 2 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 0.9 part by weight of accelerator TBBS, 60 parts by weight of carbon black, 15 parts by weight of ASTM103#Mixing operating oil and 1.5 parts by weight of sulfur in an open mill to obtain vulcanized rubber; the physical and mechanical properties, wet skid resistance (tan. delta. value at 0 ℃) and rolling resistance (tan. delta. value at 60 ℃) were measured, and as shown in Table 2, Table 2 is a data table of the physical and mechanical properties, wet skid resistance (tan. delta. value at 0 ℃) and rolling resistance (tan. delta. value at 60 ℃) of the vulcanized rubber prepared in this example.
Example 4
Mixing nitrile butadiene rubber, DCP, PAM, lead stearate and 2, 4-di (n-octyl sulfur methylene) -6-methylphenol according to the mass ratio of 100: 0.2: 10: 10: 5, mixing in an internal mixer at the mixing temperature of 150 ℃, the rotor speed of 40 rpm for 5 minutes to obtain modified nitrile rubber;
mixing 100 parts by weight of modified nitrile rubber, 1 part by weight of stearic acid, 3 parts by weight of zinc oxide, 0.7 part by weight of accelerator TBBS, 40 parts by weight of industrial reference IRB-7 carbon black and 1.5 parts by weight of sulfur in an open mill to obtain vulcanized rubber; physical and mechanical properties were measured, and as shown in Table 2, Table 2 is a table of physical and mechanical properties of the vulcanizate prepared in this example.
Example 5
Styrene butadiene rubber, TMTM, AM, magnesium oxide and 2, 4-di (n-octyl sulfur methylene) -6-methylphenol are mixed according to the mass ratio of 80: 20: 0.5: 10: 1: 1, mixing, and other steps and formula are the same as in example 3; table 2 shows the data of the physical and mechanical properties, wet skid resistance (tan. delta. value at 0 ℃ C.) and rolling resistance (tan. delta. value at 60 ℃ C.) of the vulcanizate prepared in this example.
Example 6
Styrene butadiene rubber, TETD, PAM, barium stearate and 2, 2' -methylene bis- (4-methyl-6-tert-butylphenol) are mixed according to the mass ratio of 80: 20: 0.2: 20: 5: 2 mixing, other steps and formula are the same as in example 3; table 2 shows the data of the physical and mechanical properties, wet skid resistance (tan. delta. value at 0 ℃ C.) and rolling resistance (tan. delta. value at 60 ℃ C.) of the vulcanizate prepared in this example.
Comparative example 1
Taking styrene-butadiene rubber as raw rubber, mixing 100 parts by weight of styrene-butadiene rubber, 1 part by weight of stearic acid, 3 parts by weight of zinc oxide, 1 part by weight of promoter TBBS, 50 parts by weight of carbon black and 1.75 parts by weight of sulfur in an open mill to obtain vulcanized rubber; physical and mechanical properties were measured, and as shown in Table 2, Table 2 is a table of physical and mechanical properties of the vulcanizate prepared in this example.
Comparative example 2
Taking isoprene rubber as raw rubber, and mixing 100 parts by weight of isoprene rubber, 2 parts by weight of stearic acid, 5 parts by weight of zinc oxide, 0.7 part by weight of accelerator TBBS, 35 parts by weight of carbon black and 2.25 parts by weight of sulfur in an open mill to obtain vulcanized rubber; physical and mechanical properties were measured, and as shown in Table 2, Table 2 is a table of physical and mechanical properties of the vulcanizate prepared in this example.
Comparative example 3
Taking cis-butadiene rubber as raw rubber, 100 parts by weight of cis-butadiene rubber, 2 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 0.9 part by weight of promoter TBBS, 60 parts by weight of carbon black and 15 parts by weight of ASTM103#Mixing operating oil and 1.5 parts by weight of sulfur in an open mill to obtain vulcanized rubber; the physical and mechanical properties, wet skid resistance (tan. delta. value at 0 ℃) and rolling resistance (tan. delta. value at 60 ℃) were measured, and as shown in Table 2, Table 2 is a data table of the physical and mechanical properties, wet skid resistance (tan. delta. value at 0 ℃) and rolling resistance (tan. delta. value at 60 ℃) of the vulcanized rubber prepared in this example.
Comparative example 4
Taking nitrile rubber as raw rubber, mixing 100 parts by weight of nitrile rubber, 1 part by weight of stearic acid, 3 parts by weight of zinc oxide, 0.7 part by weight of promoter TBBS, 40 parts by weight of industrial reference IRB-7 carbon black and 1.5 parts by weight of sulfur in an open mill to obtain vulcanized rubber; physical and mechanical properties were measured, and as shown in Table 2, Table 2 is a table of physical and mechanical properties of the vulcanizate prepared in this example.
Comparative example 5
Taking styrene butadiene rubber and butadiene rubber as raw rubber, 80 parts by weight of styrene butadiene rubber, 20 parts by weight of butadiene rubber, 2 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 0.9 part by weight of promoter TBBS, 60 parts by weight of carbon black, 15 parts by weight of ASTM103#Mixing operating oil and 1.5 parts by weight of sulfur in an open mill to obtain vulcanized rubber; the physical and mechanical properties, wet skid resistance (tan. delta. value at 0 ℃) and rolling resistance (tan. delta. value at 60 ℃) were measured, and as shown in Table 2, Table 2 is a data table of the physical and mechanical properties, wet skid resistance (tan. delta. value at 0 ℃) and rolling resistance (tan. delta. value at 60 ℃) of the vulcanized rubber prepared in this example.
TABLE 2 Table of Property data of vulcanizates in inventive examples 1 to 6 and comparative examples 1 to 5
In general, the wet skid resistance (tan delta value at 0 ℃) of automobile tires is improved by 10%, and as can be seen from table 2, the wet skid resistance of the present invention is improved by 13.3% to 31.8%, which indicates that the modified diolefin rubber of the present invention has good wet skid resistance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A modified diolefin rubber is prepared from diolefin rubber, an initiator, an amino modifier, a stabilizer and an antioxidant;
the amine modifier comprises one or more of formamide, acetamide, propionamide, N-dimethyl amide, benzamide, succinimide and phthalimide;
the mass ratio of the diolefin rubber, the initiator, the amino modifier, the stabilizer and the antioxidant is 100: (0.1-1.0): (1-50): (1-10): (1-5).
2. The modified diene rubber of claim 1, wherein the diene rubber is butadiene rubber, styrene-butadiene rubber, isoprene rubber or nitrile rubber.
3. The modified diene rubber of claim 1, wherein the initiator is one or more of benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, N-tetramethyldithiobisthiocarboxamide, tetramethylthiodicarbodiamide, tetraethylthioperoxydicarbonatediamide, and dipentamethylenethiuram tetrasulfide.
4. The modified diene rubber of claim 1, wherein the stabilizer is one or more of magnesium oxide, lead oxide, dibutyltin dilaurate, barium stearate and lead stearate.
5. the modified diene rubber of claim 1, wherein the antioxidant is one or more of 2, 2' -methylenebis- (4-methyl-6-tert-butylphenol), n-octadecyl- β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and 2, 4-di (n-octylthiomethylene) -6-methylphenol.
6. A preparation method of modified diolefin rubber comprises the following steps:
diene rubber, an initiator, an amino modifier, a stabilizer and an antioxidant are mixed according to the mass ratio of 100: (0.1-1.0): (1-50): (1-10): (1-5) carrying out mixing reaction in an internal mixer to obtain modified diolefin rubber;
the amine modifier comprises one or more of formamide, acetamide, propionamide, N-dimethyl amide, benzamide, succinimide, phthalimide, acrylamide and polyacrylamide.
7. The preparation method according to claim 6, wherein the reaction temperature is 70-150 ℃;
the reaction time is 1-10 min.
8. The preparation method according to claim 6, wherein the rotor speed of the internal mixer is 20-80 rpm.
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| EP2787033B1 (en) * | 2011-12-19 | 2016-09-14 | Sumitomo Rubber Industries, Ltd. | Rubber composition for tyre, and pneumatic tyre |
| CN103509159B (en) * | 2013-09-23 | 2018-12-18 | 北京石油化工学院 | The graft-modification method of low gel fraction solution polymerized butadiene styrene rubber |
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