Tire with tread of carbon black reinforced rubber composition containing specialized styrene/butadiene elastomer

Abstract

The invention relates to a tire having a tread of carbon black reinforced rubber composition containing a specialized styrene/butadiene elastomer with molecular weight profile containing a limited low molecular weight content and triglyceride vegetable oil.

Claims

1. A pneumatic rubber tire having a tread of a rubber composition containing, based on parts by weight per 100 parts by weight of the rubber (phr), (A) conjugated diene-based elastomers comprised of: (1) about 30 to about 60 phr of a specialized styrene/butadiene elastomer having a molecular weight profile comprised of a weight average molecular weight (Mw) in a range of from about 500,000 to about 800,000 with a low molecular weight content limited to a maximum of six percent of said styrene/butadiene elastomer having a weight average molecular weight (Mw) of up to 150,000, and correspondingly, (2) about 40 to about 70 phr of at least one additional conjugated diene-based elastomer, (B) about 40 to about 150 phr of reinforcing filler composed of rubber reinforcing carbon black and without precipitated silica, and (C) about 10 to about 50 phr of rubber processing oil comprised of triglyceride vegetable oil.

2. The tire of claim 1 wherein the rubber composition contains a combination of rubber processing oils comprised of petroleum based oil and triglyceride vegetable oil where greater than 50 weight percent of said rubber processing oil is said triglyceride vegetable oil.

3. The tire of claim 1 wherein said triglyceride vegetable oil is a freely added vegetable oil.

4. The tire of claim 1 wherein said triglyceride vegetable oil is comprised of at least one of soybean, sunflower, rapeseed, and canola oil.

5. The tire of claim 1 wherein said specialized styrene/butadiene elastomer has a heterogeneity index (Mw/Mn) in a range of from about 1.5/1 to about 1.8/1.

6. The tire of claim 1 wherein said rubber composition of said tire tread is sulfur cured.

7. The tire of claim 1 wherein said additional conjugated diene-based elastomer is comprised of a polymer of at least one of isoprene and 1,3-butadiene and of styrene and at least one of isoprene and 1,3-butadiene.

8. The tire of claim 7 wherein said additional styrene/butadiene elastomer is tin or silicon coupled.

9. The tire of claim 1 wherein said additional conjugated diene-based elastomer is at least one of cis 1,4-polybutadiene, cis 1,4-polyisoprene and styrene/butadiene elastomers other than said specialized styrene/butadiene elastomer having said molecular weight profile.

10. The tire of claim 1 wherein said specialized styrene/butadiene elastomer is tin or silicon coupled.

11. The tire of claim 1 wherein said specialized styrene/butadiene elastomer has a bound styrene content in a range of from about 10 to about 40 percent and a vinyl 1,2-content in a range of from about 10 to about 60 percent.

12. The tire of claim 1 wherein said specialized styrene/butadiene elastomer has a molecular weight profile comprised of a weight average molecular weight (Mw) in a range of from about 500,000 to about 800,000 with a low molecular weight content limited to a maximum of 5.5 percent of said styrene/butadiene elastomer having a weight average molecular weight (Mw) of up to 150,000.

13. The tire of claim 1 wherein said tread is provided as a sulfur cured rubber composition.

14. The tire of claim 1 wherein said low molecular weight content of said specialized styrene/butadiene elastomer is in a range of from about 1 to about 5.5 percent thereof of a weight average molecular weight in a range of from about 1,000 up to 150,000.

Description

EXAMPLE

(1) Rubber compositions were prepared to evaluate specialized solvent solution polymerization prepared styrene/butadiene elastomers (specialized styrene/butadiene elastomer as a specialized SSBR) which contain reinforcing filler composed of rubber reinforcing carbon black without precipitated silica and therefore without silica coupler and to further evaluate an inclusion of freely added triglyceride vegetable oil in a form of soybean oil.

(2) Comparative rubber Samples A and B contained a conventional aqueous emulsion polymerization prepared styrene/butadiene/styrene rubber prepared by polymerization of styrene and 1,3-butadiene monomers (ESBR) having a bound styrene content of about 23.5 percent and vinyl content (based on the butadiene portion) of about 12.5 percent.

(3) Experimental rubber Samples C and D contained a specialized styrene/butadiene rubber prepared by organic solution polymerization of styrene and 1,3-butadiene monomers (specialized SSBR) having a bound styrene content of about 30 percent and vinyl content (based on the butadiene portion) of about 41 percent with a molecular weight profile comprised of an overall weight average molecular weight (Mw) of about 683,000 wherein about 3 percent thereof had a weight average molecular weight (Mw) of only up to 150,000.

(4) Experimental rubber Sample D contained freely added vegetable oil in a form of soybean oil to replace the freely added petroleum based oil of rubber Sample C.

(5) The reinforcing filler for rubber Samples A, B, C and D was rubber reinforcing carbon black without precipitated silica and thereby also without silica coupler.

(6) The basic formulation is illustrated in the following Table 1 which is presented in terms of parts per 100 parts by weight of rubber (phr).

(7) As previously indicated, the rubber compositions may be prepared by mixing the elastomers(s) without sulfur and sulfur cure accelerators in a first non-productive mixing stage (NP-1) in an internal rubber mixer for about 4 minutes to a temperature of about 160 C. If desired, the rubber mixture may then be mixed in a second non-productive mixing stage (NP-2) in an internal rubber mixer for about 4 minutes to a temperature of about 160 C. while additional ingredients may optionally be added. The resulting rubber mixture may then be mixed in a productive mixing stage (PR) in an internal rubber mixer with sulfur and sulfur cure accelerator(s) for about 2 minutes to a temperature of about 110 C. The rubber composition may be sheeted out and cooled to below 50 C. between each of the non-productive mixing steps and prior to the productive mixing step. Such rubber mixing procedure is well known to those having skill in such art.

(8) TABLE-US-00001 TABLE 1 Parts (phr) Non-Productive Mixing Step (NP) - Mixed to 160 C. Emulsion polymerization prepared styrene/butadiene rubber 60, 43 & 0 (ESBR).sup.1 Specialized styrene/butadiene rubber (specialized SSBR).sup.2 0, 43 Cis 1,4-polybutadiene rubber.sup.3 20 & 37 Synthetic cis 1,4-polyisooprene rubber.sup.4 20 Fatty acid.sup.5 2 Total extension petroleum based oil in oil extended elastomers 23, 16 & 9 Freely added soybean oil.sup.6 0 & 27 Freely added petroleum based oil (naphthenic oil) 20, 27 & 0 Zinc oxide 1.8 Carbon black (N120).sup.7 85 Wax, microcrystalline and/or paraffinic 3.8 & 1.5 Antioxidant(s) 2.3 & 2.8 Productive Mixing Step (PR) - Mixed to 110 C. Sulfur 1.4 & 1.8 Accelerator(s).sup.8 1.6 & 1.4 .sup.1Aqueous emulsion polymerization prepared styrene/butadiene rubber (ESBR) as PLF1763 from The Goodyear Tire and Rubber Company having a bound styrene content of about 23.5 percent and vinyl-1,2-content of about 12.5 percent, an overall weight average molecular weight (Mw) of about 9,600,000 and a heterogeneity (polydispersity) index, (Mw/Mn), of about 2.3/1. The elastomer was petroleum oil extended with 37.5 parts by weight oil per 100 parts by weight of the elastomer and is reported in the Table in parts by weight of the elastomer. .sup.2Specialized organic solvent solution polymerization derived styrene/butadiene rubber (specialized SSBR) having a bound styrene of about 30 percent and vinyl content of about 41 percent and a molecular weight profile comprised of an overall weight average molecular weight (Mw) of about 535,000 with about four percent thereof having a weight average Mw of up to about 150,000 and a heterogeneity (polydispersity) index (Mw/Mn) of about 1.49/1. The elastomer was petroleum oil extended with about 20 parts by weight oil per 100 parts by weight of the elastomer and is reported in the Table in parts by weight of the elastomer. .sup.3Cis-1,4-polybutadiene rubber as BUD1207 from The Goodyear Tire and Rubber Company having a Tg of about 105 C. .sup.4Synthetic cis 1,4-polyisoprene rubber .sup.5Fatty acid comprised of stearic, palmitic and oleic acids .sup.6Soybean oil as Cargill Master Chef soybean oil 22393 .sup.7Rubber reinforcing carbon black as N120, an ASTM characterization .sup.8Sulphenamide and diphenyl guanidine sulfur cure accelerators

(9) The following Table 2 represents the uncured and cure behavior and various physical properties of the rubber compositions. Test samples were cured for about 14 minutes at about 160 C.

(10) TABLE-US-00002 TABLE 2 Samples Comparative Experimental A B C D Styrene/butadiene rubber (ESBR) 60 43 0 0 Specialized Styrene/butadiene rubber (specialized SSBR) 0 0 43 43 Cis 1,4-polybutadiene rubber 20 37 37 37 Synthetic cis 1,4-polyisoprene rubber 20 20 20 20 Rubber reinforcing carbon black (N120) 85 85 85 85 Petroleum based oil (naphthenic oil) in oil extended rubber(s) 23 16 9 9 Freely added petroleum based oil (naphthenic oil) 20 20 27 0 Soybean oil addition (freely added, not rubber extended) 0 0 0 27 Total oil content (oil extended rubber and freely added oil) 43 36 36 36 Weight percent soybean oil of the rubber processing oil NA NA NA 75 Wax, microcrystalline and paraffinic 3.8 3.8 3.8 3.8 Antioxidants 2.3 2.3 2.3 2.3 Sulfur 1.4 1.4 1.4 1.4 Sulfur cure accelerators 1.6 1.6 1.6 1.6 Properties Rubber processing indication (RPA.sup.1), uncured storage 0.195 0.248 0.265 0.25 modulus G, 15% strain 0.83 Hertz, 100 C. (MPa) Rubber stiffness indication (RPA.sup.1), cured storage 2.17 2.78 2.92 2.45 modulus G at 1% strain, 1 Hertz, 100 C., MPa (higher is better) Rubber Hysteresis Indication Tan delta at 10% strain, 1 Hertz, 100 C. (lower is better) 0.27 026. 0.24 0.21 Rebound (Zwick), 100 C., % (higher is better) 46.5 47.8 48.1 45.1 Predictive Low Temperature Performance (ARES.sup.2) (lower is better) Cured storage modulus G at 20 C., 3% strain, 10 Hz (MPa) 1.32E7 1.27E7 1.51E7 8.58E6 Predictive Wet Traction Performance (ARES.sup.2) (higher is better) Cured tan delta at 0 C., 3% strain, 10 Hz 0.42 0.4 0.44 0.42 Rubber Abrasion Resistance Indication.sup.4 DIN abrasion relative volume loss (lower is better) 69 44 77 56 MDR.sup.3 test; 60 minutes at 150 C. Delta torque (dN-m) 9.58 11.75 11.71 9.39 T90 (minutes) 15.7 14.4 11.6 9.3 T25 (minutes) 6.9 7.0 5.9 4.8 Stress-strain Properties Tensile strength (MPa) 15.2 16.4 15.7 14.4 Elongation at break (%) 566 523 535 610 300% modulus, (MPa) 6.3 7.9 7.3 5.4 Toughness = (tensile strength* elongation)/ 1369 1088 1444 1640 300% modulus) (higher is tougher) NA = not applicable .sup.1Rubber process analyzer .sup.2ARES analytical instrument .sup.3Moving die rheometer .sup.4DIN 53516 rubber abrasion test. Lower values indicate increased (improved) abrasion resistance.

(11) From Table 2 it is observed that:

(12) (A) Uncured Rubber Sample Processing

(13) As expected, doubling the polybutadiene content to 37 phr for carbon black reinforced Comparative rubber Sample B from 20 phr for Comparative rubber Sample A increased the uncured rubber processing parameter for the carbon black reinforced rubber composition by 11.5 percent to a value of 0.25 MPa from 0.2 MPa which is still considered an acceptable uncured rubber processing value.

(14) For Experimental carbon black reinforced rubber Samples C and D containing the specialized styrene/butadiene rubber (specialized SSBR) with its specialized molecular weight profile, the uncured G storage modulus values of 0.265 and 0.25 MPa, respectively, was greater than the G values of 0.195 and 0.248 MPa, respectively, for Comparative rubber Samples A and B. This is an indication that the inclusion of the specialized styrene/butadiene rubbers in the rubber Samples C and D with their molecular weight profiles containing the reduced low molecular weight contents increased the energy needed for processing the rubber Samples.

(15) However, it was discovered that the inclusion of the freely added triglyceride vegetable oil in Experimental rubber Sample D beneficially reduced the energy needed for processing the Experimental rubber Sample D as compared to Experimental rubber Sample C which contained the freely added petroleum based oil. (The freely added triglyceride vegetable oil simply replaced the freely added petroleum based rubber processing oil.)

(16) While the discovered result of inclusion of the specialized styrene/butadiene elastomer is not entirely understood, it is envisioned that the reduction in the lower molecular weight content of the styrene/butadiene elastomer increased the content of the higher molecular weight molecules of the elastomer profiles so that their polymer chain entanglements within the elastomers becomes a greater factor and promotes a higher storage modulus G for the uncured elastomers and rubber compositions.

(17) (B) Predictive Cold Weather, Wet Traction, and Treadwear Performances

(18) (1) The storage modulus (G) at 20 C. is used an indicator of cold weather performance. Lower values are considered better for cold weather (snow) performance for a tire tread of such rubber composition.

(19) It is seen in Table 2 that cured Experimental carbon black reinforced rubber Samples C and D containing the specialized styrene/butadiene rubber with its molecular weight profile, reported a cured G storage modulus value measured at 20 C. of 1.51E7 for rubber Sample C and a significantly reduced value of 8.58E6 MPa for rubber Sample D where freely added soybean oil replaced the freely added petroleum based oil. Therefore, the storage modulus (G) for rubber Sample C was greater than the storage modulus (G) values of 1.32E7 and 1.27E7 MPa, respectively, for Comparative rubber Samples A and B. However, the storage modulus (G) for Experimental rubber Sample D (containing the free added soybean oil) was beneficially significantly lower than for Experimental rubber Sample C as well as for Comparative rubber Samples A and B.

(20) It is concluded that, with lower values of the G (at 20 C.) considered as being better for predictive cold weather performance for a tire having a tread of such rubber composition that: (a) Experimental rubber Sample C exhibited a reduced predictive cold weather performance (snow performance) compared to Comparative rubber Samples A and B, and (b) Experimental rubber Sample D containing the freely added soybean oil in addition to the specialized styrene/butadiene elastomer exhibited a significantly and beneficially reduced storage modulus (G), and therefore an improved predictive cold weather performance compared to Experimental rubber Sample C and also compared to Comparative rubber Samples A and B.

(21) Therefore, it is concluded that it was discovered that the inclusion of the freely added soybean oil for rubber Sample D enabled the rubber composition C containing the specialized styrene/butadiene rubber with its specialized molecular weight profile to achieve a beneficially improved predictive cold weather performance property.

(22) (2) The tangent delta (tan delta) value at 0 C. is used as an indicator of wet traction performance. Higher values are considered better for predictive wet traction performance for a tire tread of such rubber composition.

(23) From Table 2 is it seen that for cured Experimental rubber Samples C and D containing the specialized styrene/butadiene rubber with its molecular weight profile, where rubber Sample D also contained the freely added soybean oil, their tan delta values at 0 C. of 0.44 and 0.42, respectively, were substantially the same as the tan delta values of 0.42 and 0.40, respectively, for Comparative rubber Samples A and B.

(24) Therefore, it is concluded that it has been discovered that the inclusion of the freely added soybean oil of Experimental rubber Sample D enabled the specialized styrene/butadiene elastomer containing rubber Sample C to achieve a beneficially improved predictive cold weather performance without significantly affecting its predictive wet traction performance for a tire read of such rubber composition.

(25) (3) The din abrasion relative volume loss is used as an indicator of treadwear performance. Lower values are considered better for predictive beneficial treadwear resistance and therefore extended tread life (sometimes referred to as treadwear performance) for a tire tread of such rubber composition.

(26) It is concluded that, with lower values of the relative volume loss considered as being better for predictive treadwear performance for a tire having a tread of such rubber composition that: (a) Experimental rubber Sample C exhibited a reduced predictive treadwear performance compared to Comparative rubber Samples A and B, and (b) Experimental rubber Sample D containing the freely added soybean oil in addition to the specialized styrene/butadiene elastomer exhibited a significantly and beneficially reduced relative volume loss, and therefore an improved predictive treadwear performance compared to Experimental rubber Sample C and also compared to Comparative rubber Samples A and B.

(27) Therefore, it is concluded that it has been discovered that the inclusion of the freely added soybean oil of Experimental rubber Sample D enabled the specialized styrene/butadiene elastomer containing rubber Sample C to achieve a beneficially improved predictive treadwear performance without significantly affecting its predictive wet traction performance for a tire tread of such rubber composition.

(28) (C) Tensile Properties

(29) Rubber composition toughness is used as an indicator of chip/chunk performance with higher values being predictive of better chip/chunk performance in a sense of being more resistive to chipping and chunking of the tire tread of such rubber composition during tire service. It was therefore discovered that the inclusion of the freely added soybean oil in the specialized styrene/butadiene elastomer-containing rubber composition of Experimental rubber Sample D resulted in a rubber composition toughness of 1640 which is a significant improvement over the toughness values of Control rubber Samples A and B as well as Experimental rubber Sample C which have toughness of 1369, 1088 and 1144, respectively. While the discovered results are not entirely understood, it is envisioned that unsaturation in the soybean oil interacts with the cure of the rubber composition to result in more robust tensile properties.

(30) While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the spirit or scope of the invention.