Resin-modified oil-extended rubber

Abstract

To provide an oil extended solution styrene-butadiene rubber composition that provides improved wet traction characteristics without compromising cured stiffness (dry traction) and ultimate properties (chip / chunk resistance).SOLUTION: There is provided an oil extended solution styrene-butadiene rubber composition comprising a solution styrene-butadiene rubber, at least 5 phr of an oil, and at least 5 phr of a resin, wherein the solution styrene-butadiene rubber has a bound styrene content which is within the range of 10 percent to 60 wt.% and a bound butadiene content which is within the range of 40 wt.% to 90 wt.%, wherein 25% to 55% of the bound butadiene repeat units in the solution styrene-butadiene rubber are of trans 1,4-microstructure, 25% to 50% of the bound butadiene repeat units in the solution styrene-butadiene rubber are of cis-microstructure, 5% to 45% of the bound butadiene repeat units in the solution styrene-butadiene rubber are of vinyl-microstructure, the solution styrene-butadiene rubber has a Mz molecular weight of at least 800 kDa, and the solution styrene-butadiene rubber has a ratio of Mz molecular weight to the number average molecular weight of at least 1.58.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin-modified, oil-extended rubber composition and a method for making such a resin-modified, oil-extended rubber composition. In a highly preferred embodiment of the present invention, the resin-modified, oil-extended rubber composition is made utilizing a vegetable oil, such as soybean oil or corn oil. [Background technology]

[0002] In 1949, Emert S. Pfau, Gilbert H. Swart, and Kermit V. Weinstock discovered that "oil extension" enabled high molecular weight rubbers that were too difficult to process using conventional mixing techniques to be processed without excessive degradation during the compounding procedure. Accordingly, oil extension enabled the use of higher molecular weight synthetic rubbers that could be pre-processed in the manufacture of rubber products such as tires, hoses, power transmission belts, and conveyor belts. The ability to use such higher molecular weight rubbers in the manufacture of such products resulted in improved product performance characteristics, such as reduced hysteresis, and lower manufacturing costs. In 1950, Pfau et al. filed a U.S. patent application covering their invention, which eventually issued as U.S. Patent No. 2,964,083 on December 13, 1960. Since then, oil extension has been used extensively, enabling the processing of higher molecular weight synthetic rubbers.

[0003] Oil-extended rubber is generally defined as a synthetic rubber or elastomer that incorporates 25-50% petroleum emulsion to reduce cost and improve low-temperature flexibility and elasticity. Synthetic rubbers made by emulsion or solution polymerization can be oil-extended to achieve desired benefits. For example, extender oil can be added to a solution-polymerized synthetic rubber cement before recovery from the solvent in which it was synthesized. Upon subsequent solvent removal, the extender oil remains in the synthetic rubber, providing the benefits of oil extension. Similarly, synthetic rubbers made by emulsion polymerization can be oil-extended by mixing an emulsion of extender oil into the emulsion rubber latex before solidification. Again, the extender oil remains in the rubber phase, allowing the synthetic rubber to be further processed using conventional equipment and techniques.

[0004] High molecular weight uncured synthetic rubbers have properties that make them highly desirable for use in the manufacture of a variety of rubber products, such as tires, power transmission belts, hoses, windshield wiper blades, shoe soles, and the like. To make such high molecular weight rubbers more easily processable or fully processable on commercial equipment, they are often oil-extended. As previously mentioned, oil-extended rubbers are less susceptible to degradation during the mixing procedure, which also provides better properties in the final product application. In either case, oil extension is traditionally used in formulating synthetic rubbers for a wide variety of applications to make them more easily processable (enabling them to be incorporated into other rubbers and rubber compounding materials) and to achieve a number of beneficial properties not otherwise achievable.

[0005] Since the 1960s, a wide variety of synthetic rubbers have been oil-extended to improve their processability and ultimately their performance in rubber products such as tires, power transmission belts, conveyor belts, trucks, air springs, asphalt-modified polymers, adhesives, shoe soles, windshield wiper blades, bowling balls, golf balls, and energy-absorbing foot pads. Oil extension has been applied to a wide variety of synthetic rubbers, and is particularly beneficial for high molecular weight rubbers (rubbers with high Mooney viscosity). For example, some representative examples of synthetic rubbers that have been oil-extended include high cis-1,4-polybutadiene rubber, emulsion styrene-butadiene rubber, solution styrene-butadiene rubber, synthetic polyisoprene rubber, and styrene-isoprene-butadiene rubber. Petroleum-based oils are traditionally used to prepare oil-extended rubber. These petroleum-based oils include aromatic oils, naphthenic oils, paraffinic oils, and mixtures thereof. These petroleum-based extended oils are classified under ASTM Designation D2226 as highly aromatic, aromatic, naphthenic, or paraffinic according to the following table:

[0006] [Table 1]

[0007] Recently, U.S. Patent Publication No. 2017 / 0058112(A1) reported that the use of a triglyceride oil, such as soybean oil, in extending high molecular weight solution styrene-butadiene rubber unexpectedly and significantly reduced the rubber's Mooney viscosity compared to when a petroleum-based extender oil was used. This resulted in a significant reduction in the viscosity of the uncured solution styrene-butadiene rubber (SSBR), thereby enabling the processing of SSBR with higher molecular weights (higher Mooney viscosities). The resulting low viscosity of the uncured SSBR is a significant benefit and appears to be essential for enabling suitable processing of SSBR in both rubber manufacturing facilities and rubber composition preparation facilities (such as tire manufacturing plants). Accordingly, it has been reported that the use of soybean oil instead of petroleum oil in oil-extended high molecular weight solution styrene-butadiene rubber results in better processing and promotes better physical properties of the resulting rubber product. In either case, the triglyceride oils can be used in oil-extended high molecular weight solution styrene butadiene rubbers for use in a variety of products such as tires, power transmission belts, conveyor belts, trucks, air springs, asphalt-modified polymers, adhesives, shoe soles, windshield wiper blades, bowling balls, golf balls, energy absorbing foot pads, damping pads, seals, gaskets, etc. Such oil-extended solution styrene butadiene rubbers are particularly important in producing rubber compounds for tire tread and tire sidewall applications.

[0008] U.S. Patent No. 8,044,188 discloses the use of vegetable oils with an iodine value of 135 or greater, such as linseed oil, tung oil, safflower oil, and terpenes (α-pinene, β-pinene, limonene, and turpentine), in the oil extension of certain modified natural rubber lattices. The use of these vegetable oils in place of petroleum-based oils is recommended in this patent as being beneficial for environmental reasons because they are renewable resources.

[0009] Historically, vegetable oils such as soybean oil and corn oil have been used to blend with various rubber compositions by adding free oil to the rubber composition at the time of manufacture in lieu of oil extending the elastomer. For example, the use of soybean oil in rubber compositions is described in U.S. Patent Nos. 7,919,553, 8,100,157, and 8,022,136. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] U.S. Patent No. 2,964,083 [Patent Document 2] U.S. Patent Publication No. 2017 / 0058112(A1) [Patent Document 3] U.S. Patent No. 8,044,188 [Patent Document 4] U.S. Patent No. 7,919,553 [Patent Document 5] U.S. Patent No. 8,100,157 [Patent Document 6] U.S. Patent No. 8,022,136 [Patent Document 7] U.S. Patent No. 6,713,565 [Patent Document 8] U.S. Patent No. 4,983,695 [Patent Document 9] Canadian Patent No. 1,284,545 [Patent Document 10] U.S. Patent No. 5,698,643 [Patent Document 11] U.S. Patent No. 5,451,646 [Patent Document 12] U.S. Patent No. 4,260,707 [Patent Document 13] U.S. Patent No. 4,444,903 [Patent Document 14] U.S. Patent No. 4,461,883 [Patent Document 15] U.S. Patent No. 4,533,711 [Patent Document 16] U.S. Patent No. 6,780,948 [Patent Document 17] U.S. Patent No. 6,242,534 [Patent Document 18] U.S. Patent No. 6,207,757 [Patent Document 19] U.S. Patent No. 6,133,364 [Patent Document 20] U.S. Patent No. 6,372,857 [Patent Document 21] U.S. Patent No. 5,395,891 [Patent Document 22] U.S. Patent No. 6,127,488 [Patent Document 23] U.S. Patent No. 5,672,639 [Patent Document 24] U.S. Patent No. 6,608,125 [Patent Document 25] U.S. Patent Publication No. 2006 / 0041063 [Patent Document 26] U.S. Patent Publication No. 2003 / 0130535 [Non-patent literature]

[0011] [Non-Patent Document 1] Journal of the American Chemical Society, Vol. 60, p. 304 (1930) [Non-patent document 2] The Vanderbilt Rubber Handbook (1978), pp. 344-346 Summary of the Invention

[0012] The present invention is based on the unexpected discovery that hydrocarbon traction resins can be dispersed in oils used to make oil-extended emulsion and solution rubbers to achieve improved performance characteristics. For example, this technique allows for the incorporation of hydrocarbon traction resins into rubber at higher levels than would normally be possible using conventional mixing techniques. This results in improved wet traction characteristics in tire tread compounds without compromising cure stiffness (dry traction) and final properties (chip / chunk resistance). This technique can be used to incorporate resins into virtually any synthetic rubber that could benefit from oil extension. More specifically, the present invention is applicable to the production of resin-modified, oil-extended rubbers, including solution styrene-butadiene rubber (SSBR), emulsion styrene-butadiene rubber (ESBR), polybutadiene rubber, synthetic polyisoprene rubber, ethylene-propylene-diene rubber (EPDM), isoprene-butadiene rubber, styrene-isoprene-butadiene rubber, silicone rubber, nitrile rubber, carboxylated nitrile rubber, and the like. It is particularly valuable in producing resin-modified solution styrene-butadiene rubber (SSBR), emulsion styrene-butadiene rubber (ESBR), high cis-1,4-polybutadiene rubber, and synthetic polyisoprene rubber, which are formulated for use in tire tread compounds.

[0013] More specifically, the present invention discloses a method for preparing a resin-modified, oil-extended rubber composition, the method comprising: (1) blending an oil composition into rubber cement, the resin-modified, oil-extended rubber composition comprising oil and a hydrocarbon resin; and (2) recovering the resin-modified, oil-extended rubber from the rubber cement.

[0014] The present invention also discloses a method for preparing a resin-modified emulsion rubber composition, the method comprising: (1) blending an oil composition into a rubber emulsion, the oil composition comprising an oil and a hydrocarbon resin; and (2) recovering the resin-modified rubber from the rubber emulsion.

[0015] The present invention further provides a high cis-1,4-polybutadiene rubber composition comprising a high cis-1,4-polybutadiene rubber having a cis microstructure content of at least 90%, at least 5 phr of oil, and at least 5 phr of resin, wherein the high cis-1,4-polybutadiene rubber has a M of at least 750,000 Da. z High molecular weight cis-1,4-polybutadiene rubber M z Disclosed is a high cis-1,4-polybutadiene rubber composition having a ratio of molecular weight to number average molecular weight of at least 5. Such high cis-1,4-polybutadiene rubbers are typically free of fillers, curatives, accelerators, and other rubber compounding agents, with the exception of antidegradants such as antioxidants and antiozonants.

[0016] Additionally, the present invention provides a synthetic polyisoprene rubber composition comprising a high cis-polyisoprene having a cis microstructure content of at least 90%, at least 5 phr of oil, and at least 5 phr of resin, wherein the high cis-polyisoprene rubber has an M of at least 750,000 Da. z High cis-isoprene rubber M z The rubber composition has a molecular weight to number average molecular weight ratio of at least 2.7. Such high cis-polyisoprene rubbers are typically free of fillers, curatives, accelerators, and other rubber compounding agents, with the exception of antidegradants such as antioxidants and antiozonants.

[0017] The present invention also provides an emulsion styrene-butadiene rubber composition comprising an emulsion styrene-butadiene rubber, at least 5 phr of oil, and at least 5 phr of resin, wherein the emulsion styrene-butadiene rubber has a bound styrene content in the range of 22% to 60% by weight and a bound butadiene content in the range of 40% to 78% by weight, wherein 60% to 70% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are trans 1,4-microstructure, 13% to 23% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are cis-microstructure, and 12% to 22% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are vinyl microstructure, and the emulsion styrene-butadiene rubber has an M z The molecular weight of emulsion styrene-butadiene rubber is z Disclosed is an emulsion styrene-butadiene rubber composition having a ratio of molecular weight to number average molecular weight of at least 150. Such emulsion styrene-butadiene rubber is typically free of fillers, curatives, accelerators, and other rubber compounding agents, with the exception of antidegradants such as antioxidants and antiozonants.

[0018] The present invention further provides a solution styrene-butadiene rubber composition comprising a solution styrene-butadiene rubber, at least 5 phr of oil, and at least 5 phr of resin, wherein the solution styrene-butadiene rubber has a bound styrene content in the range of 10% to 60% by weight and a bound butadiene content in the range of 40% to 90% by weight, 30% to 55% of the bound butadiene repeat units in the solution styrene-butadiene rubber are trans 1,4-microstructure, 25% to 50% of the bound butadiene repeat units in the solution styrene-butadiene rubber are cis-microstructure, and 5% to 45% of the bound butadiene repeat units in the solution styrene-butadiene rubber are vinyl microstructure, and the solution styrene-butadiene rubber has at least M of 800 kDa z The molecular weight of the solution styrene-butadiene rubber is zDisclosed is a solution styrene-butadiene rubber composition having a ratio of molecular weight to number average molecular weight of at least 1.58. Such solution styrene-butadiene rubbers are typically free of fillers, curatives, accelerators, and other rubber compounding agents, with the exception of antidegradants such as antioxidants and antiozonants.

[0019] The present invention also provides a tire including a generally toroidal carcass having a circumferential tread, two sidewalls, two spaced apart beads, at least one ply extending from bead to bead, and sidewalls extending radially from and connecting said tread to said beads, said tread adapted for ground contact, at least one component of said tire being comprised of a high cis-1,4-polybutadiene rubber composition comprising a high cis-1,4-polybutadiene rubber having a cis-microstructure content of at least 90%, at least 5 phr of oil, and at least 5 phr of resin, wherein the high cis-1,4-polybutadiene rubber has an M of at least 750,000 Da. z High molecular weight cis-1,4-polybutadiene rubber M z Tires are disclosed having a ratio of molecular weight to number average molecular weight of at least 5. It is particularly advantageous to include high cis-1,4-polybutadiene rubber in the tread and / or sidewalls of such tires.

[0020] The present invention further provides a tire including a generally toroidal carcass having a circumferential tread, two sidewalls, two spaced apart beads, at least one ply extending from bead to bead, and sidewalls extending radially from and connecting said tread to said bead, said tread adapted for ground contact, at least one component of said tire being comprised of a synthetic polyisoprene rubber having a high cis-polyisoprene rubber content of at least 90% cis-microstructure, at least 5 phr oil, and at least 5 phr resin, wherein the high cis-polyisoprene rubber has an M of at least 750,000 Da. z High molecular weight cis-polyisoprene rubber M zTires are disclosed having a ratio of molecular weight to number average molecular weight of at least 2.7. It is particularly advantageous to include high cis-polyisoprene rubber in the tread and / or sidewalls of such tires.

[0021] The present invention also provides a tire including a generally toroidal carcass having a circumferential tread, two sidewalls, two spaced apart beads, at least one ply extending from bead to bead, and sidewalls extending radially from and connecting said tread to said beads, said tread adapted for ground contact, and at least one component of said tire being comprised of an emulsion styrene-butadiene rubber composition including emulsion styrene-butadiene rubber, at least 5 phr of oil, and at least 5 phr of resin, and a bound styrene content in the range of 22% to 60% by weight and a bound butadiene content in the range of 40% to 78% by weight, wherein 60% to 70% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are trans 1,4-microstructure, 13% to 23% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are cis-microstructure, and 12% to 22% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are vinyl-microstructure, and the emulsion styrene-butadiene rubber has an M z The molecular weight of emulsion styrene-butadiene rubber is z Tires are disclosed having a ratio of molecular weight to number average molecular weight of at least 150. It is particularly advantageous to include emulsion styrene-butadiene rubber in the tread and / or sidewalls of such tires.

[0022] The present invention further provides a tire including a generally toroidal carcass having a circumferential tread, two sidewalls, two spaced apart beads, at least one ply extending from bead to bead, and sidewalls extending radially from and connecting said tread to said beads, said tread adapted to contact the ground, and at least one component of said tire. a solution styrene-butadiene rubber composition comprising a solution styrene-butadiene rubber, at least 5 phr of oil, and at least 5 phr of resin, wherein the solution styrene-butadiene rubber has a bound styrene content in the range of 10% to 60% by weight and a bound butadiene content in the range of 40% to 90% by weight, wherein 30% to 55% of the bound butadiene repeat units in the solution styrene-butadiene rubber are trans 1,4-microstructure, 25% to 50% of the bound butadiene repeat units in the solution styrene-butadiene rubber are cis-microstructure, and 5% to 45% of the bound butadiene repeat units in the solution styrene-butadiene rubber are vinyl-microstructure, and the solution styrene-butadiene rubber has an M z The molecular weight of the solution styrene-butadiene rubber is z A tire is disclosed having a ratio of molecular weight to number average molecular weight of at least 1.58. It is particularly advantageous to include solution styrene-butadiene rubber in the tread and / or sidewall of such a tire.

[0023] The present invention also provides a power transmission belt including a compression section, a tension section, and a load section, wherein at least one component of the power transmission belt is comprised of a high cis-1,4-polybutadiene rubber composition including a high cis-1,4-polybutadiene rubber having a cis-microstructure content of at least 90%, at least 5 phr of oil, and at least 5 phr of resin, wherein the high cis-1,4-polybutadiene rubber has an M of at least 750,000 Da. z High molecular weight cis-1,4-polybutadiene rubber M z A power transmission belt is disclosed having a ratio of molecular weight to number average molecular weight of at least 5.

[0024] The present invention also provides a power transmission belt including a compression section, a tension section, and a load section, wherein at least one component of the power transmission belt is comprised of a synthetic polyisoprene rubber composition including a high cis-polyisoprene rubber having a cis-microstructure content of at least 90%, at least 5 phr of oil, and at least 5 phr of resin, wherein the high cis-polyisoprene rubber has an M of at least 750,000 Da. z High molecular weight cis-polyisoprene rubber M z A power transmission belt is disclosed having a ratio of molecular weight to number average molecular weight of at least 2.7.

[0025] The present invention also provides a power transmission belt including a compression section, a tension section, and a load-bearing section, wherein at least one component of the power transmission belt is made of an emulsion styrene-butadiene rubber composition including emulsion styrene-butadiene rubber, at least 5 phr of oil, and at least 5 phr of resin, wherein the emulsion styrene-butadiene rubber has a bound styrene content in the range of 22% to 60% by weight and a bound butadiene content in the range of 40% to 78% by weight, wherein 60% to 70% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are trans 1,4-microstructure, 13% to 23% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are cis-microstructure, and 12% to 22% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are vinyl-microstructure, and the emulsion styrene-butadiene rubber has an M z The molecular weight of emulsion styrene-butadiene rubber is z A power transmission belt having a ratio of molecular weight to number average molecular weight of at least 150 is disclosed.

[0026] The present invention further provides a power transmission belt including a compression section, a tension section, and a load section, wherein at least one component of the power transmission belt is made from a solution styrene-butadiene rubber composition including a solution styrene-butadiene rubber, at least 5 phr of oil, and at least 5 phr of resin, wherein the solution styrene-butadiene rubber has a bound styrene content in the range of 10% to 60% by weight and a bound butadiene content in the range of 40% to 90% by weight, wherein 30% to 55% of the bound butadiene repeat units in the solution styrene-butadiene rubber have a trans 1,4-microstructure and 25% to 50% of the bound butadiene repeat units in the solution styrene-butadiene rubber have a cis-microstructure. Between 5% and 45% of the bound butadiene repeat units in the solution are vinyl-microstructured and the solution styrene-butadiene rubber has an M of at least 800 kDa. z The molecular weight of the solution styrene-butadiene rubber is z Disclosed is a power transmission belt having a ratio of molecular weight to number average molecular weight of at least 1.58.

[0027] The present invention also provides a conveyor belt comprising a carry cover layer, a reinforcing layer, and a pulley cover layer, wherein at least one component of the conveyor belt is comprised of a high cis-1,4-polybutadiene rubber composition comprising a high cis-1,4-polybutadiene rubber having a cis-microstructure content of at least 90%, at least 5 phr of oil, and at least 5 phr of resin, wherein the high cis-1,4-polybutadiene rubber has an M of at least 750,000 Da. z High molecular weight cis-1,4-polybutadiene rubber M z Conveyor belts are disclosed having a ratio of molecular weight to number average molecular weight of at least 5. It is particularly advantageous to include high cis-1,4-polybutadiene rubber in the tread and / or sidewalls of such tires.

[0028] The present invention also provides a conveyor belt comprising a carry cover layer, a reinforcing layer, and a pulley cover layer, wherein at least one component of the conveyor belt is comprised of a synthetic polyisoprene rubber composition comprising a high cis-polyisoprene rubber having a cis-microstructure content of at least 90%, at least 5 phr of oil, and at least 5 phr of resin, wherein the high cis-polyisoprene rubber has an M of at least 750,000 Da. z High molecular weight cis-polyisoprene rubber M z A conveyor belt is disclosed having a ratio of molecular weight to number average molecular weight of at least 2.7. It is particularly advantageous to include high cis-polyisoprene rubber in the tread and / or sidewall of such tires.

[0029] The present invention also provides a conveyor belt including a carry cover layer, a reinforcing layer, and a pulley cover layer, wherein at least one component of the conveyor belt is comprised of an emulsion styrene-butadiene rubber composition including emulsion styrene-butadiene rubber, at least 5 phr of oil, and at least 5 phr of resin, wherein the emulsion styrene-butadiene rubber has a bound styrene content in the range of 22% to 60% by weight and a bound butadiene content in the range of 40% to 78% by weight, wherein 60% to 70% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are trans 1,4-microstructure, 13% to 23% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are cis-microstructure, and 12% to 22% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are vinyl-microstructure, and the emulsion styrene-butadiene rubber has an M z The molecular weight of emulsion styrene-butadiene rubber is z Conveyor belts are disclosed having a ratio of molecular weight to number average molecular weight of at least 150. It is particularly advantageous to include emulsion styrene-butadiene rubber in the tread and / or sidewalls of such tires.

[0030] The present invention also provides a conveyor belt including a carry cover layer, a reinforcing layer, and a pulley cover layer, wherein at least one component of the conveyor belt is comprised of a solution styrene-butadiene rubber composition including a solution styrene-butadiene rubber, at least 5 phr of oil, and at least 5 phr of resin, wherein the solution styrene-butadiene rubber has a bound styrene content in the range of 10% to 60% by weight and a bound butadiene content in the range of 40% to 90% by weight, wherein 30% to 55% of the bound butadiene repeat units in the solution styrene-butadiene rubber are trans 1,4-microstructure, 25% to 50% of the bound butadiene repeat units in the solution styrene-butadiene rubber are cis-microstructure, and 5% to 45% of the bound butadiene repeat units in the solution styrene-butadiene rubber are vinyl-microstructure, and the solution styrene-butadiene rubber has an M z The molecular weight of the solution styrene-butadiene rubber is z The ratio of molecular weight to number average molecular weight is low Both are 1.58 and disclose a conveyor belt.

[0031] The present invention also provides a windshield wiper blade comprising a head, a body, a neck portion, a rotating portion, and an edge portion, wherein at least one component of said windshield wiper blade is comprised of a high cis-1,4-polybutadiene rubber composition comprising a high cis-1,4-polybutadiene rubber having a cis-microstructure content of at least 90%, at least 5 phr of oil, and at least 5 phr of resin, wherein the high cis-1,4-polybutadiene rubber has a M of at least 750,000 Da. z High molecular weight cis-1,4-polybutadiene rubber M z A windshield wiper blade is disclosed having a ratio of molecular weight to number average molecular weight of at least 5. By way of example, the high cis-1,4-polybutadiene rubber composition can be used in the head, body, neck, turning section, and / or edge of the windshield wiper blade.

[0032] The present invention also provides a windshield wiper blade comprising a head, a body, a neck portion, a rotating portion, and an edge portion, wherein at least one component of said windshield wiper blade is comprised of a synthetic polyisoprene rubber composition comprising a high cis-polyisoprene rubber having a cis-microstructure content of at least 90%, at least 5 phr of oil, and at least 5 phr of resin, wherein the high cis-polyisoprene rubber has an M of at least 750,000 Da. z High molecular weight cis-1,4-polybutadiene rubber M z A windshield wiper blade is disclosed, having a ratio of molecular weight to number average molecular weight of at least 2.7. By way of example, the synthetic polyisoprene rubber composition may be used in the head, body, neck, turning portion, and / or edge of the windshield wiper blade.

[0033] The present invention also provides a windshield wiper blade comprising a head, a body, a neck portion, a rotating portion, and an edge portion, wherein at least one component of said windshield wiper blade is comprised of an emulsion styrene-butadiene rubber composition comprising emulsion styrene-butadiene rubber, at least 5 phr of oil, and at least 5 phr of resin, wherein the emulsion styrene-butadiene rubber has a bound styrene content in the range of 22% to 60% by weight and a bound butadiene content in the range of 40% to 78% by weight, wherein 60% to 70% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are trans 1,4-microstructure, 13% to 23% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are cis-microstructure, and 12% to 22% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are vinyl-microstructure, and the emulsion styrene-butadiene rubber has an M z The molecular weight of emulsion styrene-butadiene rubber is zA windshield wiper blade is disclosed, having a ratio of molecular weight to number average molecular weight of at least 150. By way of example, the emulsion styrene-butadiene rubber composition can be used in the head, body, neck, turning section, and / or edge of the windshield wiper blade.

[0034] The present invention also provides a windshield wiper blade comprising a head, a body, a neck portion, a rotating portion, and an edge portion, wherein at least one component of the windshield wiper blade is made from a solution styrene-butadiene rubber composition comprising a solution styrene-butadiene rubber, at least 5 phr of oil, and at least 5 phr of resin, wherein the solution styrene-butadiene rubber has a bound styrene content in the range of 10% to 60% by weight and a bound butadiene content in the range of 40% to 90% by weight, wherein 30% to 55% of the bound butadiene repeat units in the solution styrene-butadiene rubber are of trans 1,4-microstructure, 25% to 50% of the bound butadiene repeat units in the solution styrene-butadiene rubber are of cis-microstructure, and 5% to 45% of the bound butadiene repeat units in the solution styrene-butadiene rubber are of vinyl-microstructure, and the solution styrene-butadiene rubber has a M z The molecular weight of the solution styrene-butadiene rubber is z molecular weight number average A windshield wiper blade is disclosed, wherein the solution styrene-butadiene rubber composition has a ratio of at least 1.58 to the average molecular weight of the windshield wiper blade. By way of example, the solution styrene-butadiene rubber composition can be used in the head, body, neck, turning section, and / or edge of the windshield wiper blade.

[0035] The present invention also provides a golf ball comprising a core and a cover, wherein the core is comprised of a high cis-1,4-polybutadiene rubber composition comprising a high cis-1,4-polybutadiene rubber having a cis-microstructure content of at least 90%, at least 5 phr of oil, and at least 5 phr of resin, wherein the high cis-1,4-polybutadiene rubber has an M of at least 750,000 Da. zHigh molecular weight cis-1,4-polybutadiene rubber M z A golf ball is disclosed having a ratio of molecular weight to number average molecular weight of at least 5.

[0036] The present invention also provides a golf ball comprising a core and a cover, wherein the core is comprised of a synthetic polyisoprene rubber composition comprising a high cis-polyisoprene rubber having a cis-microstructure content of at least 90%, at least 5 phr of oil, and at least 5 phr of resin, wherein the high cis-polyisoprene rubber has an M of at least 750,000 Da. z High molecular weight cis-polyisoprene rubber M z A golf ball is disclosed having a ratio of molecular weight to number average molecular weight of at least 2.7.

[0037] The present invention also provides a golf ball including a core and a cover, wherein the core is comprised of an emulsion styrene-butadiene rubber composition including emulsion styrene-butadiene rubber, at least 5 phr of oil, and at least 5 phr of resin, wherein the emulsion styrene-butadiene rubber has a bound styrene content within the range of 22% to 60% by weight and a bound butadiene content within the range of 40% to 78% by weight, wherein 60% to 70% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in a trans 1,4-microstructure, 13% to 23% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in a cis-microstructure, and 12% to 22% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in a vinyl-microstructure, and the emulsion styrene-butadiene rubber has an M z The molecular weight of emulsion styrene-butadiene rubber is z A golf ball is disclosed having a ratio of molecular weight to number average molecular weight of at least 150.

[0038] The present invention also provides a golf ball comprising a core and a cover, wherein the core is comprised of a solution styrene-butadiene rubber composition comprising a solution styrene-butadiene rubber, at least 5 phr of oil, and at least 5 phr of resin, wherein the solution styrene-butadiene rubber has a bound styrene content in the range of 10% to 60% by weight and a bound butadiene content in the range of 40% to 90% by weight, wherein 30% to 55% of the bound butadiene repeat units in the solution styrene-butadiene rubber are in a trans 1,4-microstructure, 25% to 50% of the bound butadiene repeat units in the solution styrene-butadiene rubber are in a cis-microstructure, and 5% to 45% of the bound butadiene repeat units in the solution styrene-butadiene rubber are in a vinyl-microstructure, and the solution styrene-butadiene rubber has an M z The molecular weight of the solution styrene-butadiene rubber is z A golf ball is disclosed having a ratio of molecular weight to number average molecular weight of at least 1.58.

[0039] Golf balls having cores made from the rubber compositions of the present invention are typically cured using a peroxide cure system. The peroxide used will typically be an organic peroxide such as dicumyl peroxide, t-butyl peroxybenzoate, or di-t-butyl peroxide. It is generally preferred to use dicumyl peroxide in such golf ball compounds. The peroxide is typically present in the rubber component of the golf ball at a level ranging from about 0.5 phr to about 3 phr. The peroxide is preferably present at a level ranging from about 1 phr to about 3 phr. It is present in the rubber component of the golf ball at a level in the range of 2.5 phr.

[0040] Golf balls can be made using the resin-modified emulsion rubber of the present invention in accordance with the teachings of U.S. Patent No. 6,713,565. Such solid golf balls generally include a core and a resin cover. The solid golf ball design may include a core obtained by integral molding, or it may be a multi-cavity design in which one or more layers are coated onto the core. In either case, such solid golf balls include an elastic portion formed by vulcanizing a cis-1,4-polybutadiene rubber-containing composition that also includes a co-crosslinking agent and a peroxide.

[0041] In addition to cis-1,4-polybutadiene rubber, the elastic portion of a golf ball may also contain additional rubbers such as styrene-butadiene rubber, natural rubber, synthetic polyisoprene rubber, and styrene-isoprene rubber. The amount of such additional rubber contained in the elastic portion of a golf ball is typically about 60 phr (parts per hundred parts by weight of rubber) or less, based on the total amount of rubber contained in the elastic portion of a golf ball. Therefore, the elastic portion of a golf ball typically contains about 40 phr to 100 phr of cis-1,4-polybutadiene and 0 phr to about 60 phr of the additional rubber. It is typically preferred that the additional rubber be present in the elastic portion of a golf ball at a level of about 30 phr or less. It is more typically preferred that the additional rubber be present in the elastic portion of a golf ball at a level of about 15 phr or less. The co-crosslinking agent used in the elastic portion of a golf ball is typically an unsaturated carboxylic acid or its metal salt. For example, the co-crosslinking agent may be acrylic acid, methacrylic acid, zinc acrylate, zinc methacrylate, or a mixture thereof. The co-crosslinking agent is typically present in the rubber component of the golf ball at a level ranging from about 15 phr to about 60 phr. The co-crosslinking agent is typically present in the resilient portion of the golf ball at a level ranging from about 25 phr to about 40 phr. The teachings of U.S. Patent No. 6,713,565 are incorporated herein by reference. DETAILED DESCRIPTION OF THE INVENTION

[0042] Both resin-modified, oil-extended solution rubber and resin-modified emulsion rubber can be prepared using the method of the present invention. It should be noted that solution rubber is a rubbery polymer prepared by solution polymerization in a suitable organic solvent, and emulsion rubber is a rubbery polymer prepared by emulsion polymerization in an aqueous medium. In either case, the resin-modified solution rubber composition can be prepared in accordance with the present invention by (1) blending an oil composition into a rubber cement, the oil composition comprising an oil and a hydrocarbon resin, and (2) recovering the resin-modified, oil-extended rubber from the rubber cement. On the other hand, the resin-modified emulsion rubber composition can be prepared in accordance with the present invention by (1) blending an oil composition into a rubber emulsion, the oil composition comprising an oil and a hydrocarbon resin, and (2) recovering the resin-modified rubber from the rubber emulsion.

[0043] The oil composition used in oil extending rubber will typically be used at a level within the range of about 5 phr to 100 phr (parts per 100 parts by weight of rubber). In other words, about 5 phr to about 100 phr of the oil composition is added to the rubber cement (in the case of a solution polymer) or rubber emulsion (in the case of an emulsion polymer). In most cases, the oil composition is added at a level within the range of 6 phr to 80 phr. In many cases, the oil composition is added at a level within the range of 8 phr to 60 phr. The oil composition is preferably added at a level within the range of 10 phr to 40 phr.

[0044] Typically, it is desirable for the oil composition to contain as much resin as possible so that it can be effectively dispersed in the oil. In any case, the resin level in the extended oil composition will usually be in the range of 10% to 60% by weight (based on the total weight of the resin and oil in the extended oil composition). In most cases, In this case, the resin is included in the extended oil composition at a level within the range of 20% to 55% by weight. The oil is typically heated to an elevated temperature to facilitate mixing of the resin into the oil. In many cases, it is convenient to heat the oil to a temperature within the range of 50°C to 130°C to facilitate mixing. Typically, it is convenient to heat the oil to a temperature within the range of 80°C to 110°C before mixing the resin into the oil.

[0045] The amount of extender oil composition added is typically sufficient to produce an oil-extended product containing at least 5 phr of oil and at least 5 phr of resin. The maximum total level of extender oil composition that can be added is about 100 phr (the total weight of oil and resin usually does not exceed 100 phr). In most cases, the extender oil composition is not added at a level greater than about 80 phr. In most cases, the extender oil composition is added at a level sufficient to provide 10 phr to 40 phr of oil and 5 phr to 30 phr of resin in the oil-extended rubber produced. Typically, the extender oil composition is added at a level sufficient to provide 15 phr to 35 phr of oil and 8 phr to 20 phr of resin in the oil-extended rubber produced. Typically, the extender oil composition is added at a level sufficient to provide 20 phr to 30 phr of oil and 10 phr to 15 phr of resin in the oil-extended rubber produced.

[0046] The oil used in the production of resin-modified oil-extended rubber may be a petroleum-based oil, such as a highly aromatic oil, an aromatic oil, a naphthenic oil, a paraffinic oil, or a mixture thereof. The petroleum-based oil utilized may be Type 101, Type 102, Type 103, or Type 104, as detailed in ASTM Designation D2226, or a mixture thereof. Low PCA oils, such as MES, TDAE, and heavy naphthenic oils, may also be used. Suitable low PCA oils include, but are not limited to, mild extraction solvates (mild extraction solvates). MES), treated residual aromatic extracts (TDAE), and heavy naphthenic oils are listed as being known in the art and are further described in U.S. Pat. Nos. 5,504,135, 6,103,808, 6,399,697, 6,410,816, 6,248,929, 6,146,520, U.S. Patent Publication Nos. 2001 / 00023307, 2002 / 0000280, 2002 / 0045697, 2001 / 0007049, European Patent No. 0839891, Japanese Patent No. 2002097369, and ES2122917, which are incorporated herein by reference for the purposes of disclosing suitable oils. Generally, suitable oils include low PCA oils, including those having a glass transition temperature, Tg, in the range of about −40° C. to about −80° C., MES oils, which generally have a Tg in the range of about −57° C. to about −63° C., TDAE oils, which generally have a Tg in the range of about −44° C. to about −50° C., and heavy naphthenic oils, which generally have a Tg in the range of about −42° C. to about −48° C. A suitable method for measuring the Tg of TDAE oils is by DSC according to ASTM E1356, or equivalent.

[0047] Suitable low PCA oils include those having less than 3% polyaromatic content as determined by the IP346 method. The IP346 method procedure is described in Standard Method for Analysis & Testing of Petroleum and Related Products and British Standard 2000 Parts, 2003, 62, published by the Institute of Petroleum. In one embodiment, the low PCA oil may be of the MES, TDAE, or heavy naphthenic type having the properties identified in the table below.

[0048] [Table 2]

[0049] In one embodiment, the low PCA oil is a C 12 oil obtained by (1) solvent extraction of heavy petroleum distillates or (2) solvent dewaxing after treatment of heavy petroleum distillates with hydrogen in the presence of a catalyst. 20 ~C 50 The low PCA oil may be of the MES type, which is a complex combination primarily composed of saturated hydrocarbons in the range of 1 mg / kg. In one embodiment, the low PCA oil contains 1 mg / kg or less of benzo(a)pyrene and 10 mg / kg or less of polycyclic aromatic hydrocarbons (benzo(a)pyrene, benzo(e)pyrene, benzo(a)anthracene, benzo(b)fluoranthene, benzo(j)fluoranthene, benzo(k)fluoranthene, dibenz(a,h)anthracene, and chrysene). Suitable TDAE oils are available as Tudalen SX500 from Klaus Dahleke KG, VivaTec 400 and VivaTec 500 from H&R Group, Enerthene 1849 from BP, and Extensoil 1996 from Repsol. The oil may be available alone or together with an elastomer in the form of an extended elastomer.

[0050] In the practice of the present invention, the oil is preferably a triglyceride oil such as a vegetable oil. The following table lists the number of available triglyceride oils and indicates the saturated, monounsaturated and polyunsaturated content of these vegetable oils (triglyceride oils). The vegetable oil used preferably has an iodine value of less than 135, preferably less than 130. Vegetable oil Saturated Monounsaturated Polyunsaturated Soybean 16% 45% 40% Canola (rapeseed) 7% 63% 28% Corn 13% 28% 55% Coconut 87% 6% 2% Cottonseed 26% 18% 52% Olive 14% 73% 11% Palm 49% 37% 9% Peanuts 17% 46% 32% Safflower 10% 45% 40% Generally, genetically modified soybeans may also be used as a source of soybean oil for use in the practice of the present invention. Such soybean oil has a higher oleic acid content and, in some cases, In either case, HOSBO typically contains about 74.5% oleic acid.

[0051] When an oil-extended emulsion polymer is prepared, the oil is usually emulsified into an oil-in-water emulsion. The water used to prepare the oil-in-water emulsion is preferably ion-exchanged water or distilled water with a low content of dissolved minerals. The surfactant used to prepare the emulsion should have good compatibility with the oil and water. In either case, it is preferable to use a nonionic surfactant because of its high affinity for oils such as triglyceride oils. Among nonionic surfactants, some have cloud points, and nonionic surfactants with relatively low cloud points are preferred in terms of their tendency to solidify. In this specification, the cloud point is considered to be the temperature at which the nonionic surfactant becomes insoluble in water, and the temperature at which the solution turns cloudy is called the cloud point.

[0052] The nonionic surfactant used in the present invention has a hydrophilic portion (A) and a lipophilic portion (B). For the hydrophilic portion (A), a polyoxyethylene compound having a repeating unit of an oxyethylene chain (-CH2-CH2-O-) is used in view of its high affinity for oils such as vegetable oils. The number n of repeating units of the oxyethylene chain in the hydrophilic portion (A) is preferably 2 or more, more preferably 4 or more, and even more preferably 5 or more. When the n of the hydrophilic portion (A) is less than 2, the compound tends to be insoluble in water. The number n of the hydrophilic portion (A) is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. When the n of the hydrophilic portion (A) is more than 40, the emulsifying ability decreases, and a stable emulsion tends to be difficult to prepare.

[0053] The lipophilic portion (B) is preferably an alkyl ether and / or alkenyl ether from the viewpoint of high affinity with oils, particularly vegetable oils. Examples of alkyl ethers include lauryl ether, cetyl ether, and stearyl ether. The alkyl ethers usable in the present invention are not limited to these examples. In addition, alkyl vinyl ethers with different numbers of carbon atoms may be blended. An example of an alkenyl ether is oleyl ether. Examples of surfactants that satisfy the above conditions include polyoxyethylene alkyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene hydrogenated castor oil. These surfactants may be used alone or in combination of at least two of them. Among the above surfactants, examples of sorbitan fatty acid esters include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, and polyoxyethylene sorbitol tetraoleate.

[0054] In order to enhance emulsion stability, anionic surfactants or cationic surfactants can be used in combination with nonionic surfactants.Examples of anionic surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, fatty acid salts, and formalin-naphthalene sulfonate condensates.The combination of a specific type of anionic surfactants or cationic surfactants and nonionic surfactants can be appropriately selected according to the type of oil to be used.These ratios can also be appropriately selected according to the type of oil and surfactant system to be used.

[0055] The content of the surfactant in the emulsion containing oil, water and surfactant is preferably 0.1% by weight or more, more preferably 0.3% by weight or more. When the surfactant content is less than 10% by weight, the emulsion tends to be insufficient in stability. The surfactant content is preferably 10% by weight or less, more preferably 8% by weight or less. When the surfactant content is more than 10% by weight, the surfactant easily remains in the rubber, and furthermore, the rubber tends to have water absorption, which reduces the physical properties of the rubber and increases its cost.

[0056] Oil-in-water emulsion can be prepared using standard equipment and conventional techniques known in the art.More specifically, oil, surfactant and water are typically mixed in a high-speed stirring device such as a homogenizer to disperse oil with fine particle diameter in water, thus preparing an oil-in-water emulsion.The rotation speed of the high-speed stirring device is preferably 1000 rpm or more, more preferably 2000 rpm or more.When the rotation speed of the high-speed stirring device is less than 1000 rpm, it tends to be difficult to obtain oil droplets with sufficiently fine particle diameter.

[0057] The mixing time using a high-speed agitator is preferably 3 minutes or more, more preferably 5 minutes or more. If the mixing time using a high-speed agitator is less than 3 minutes, it tends to be difficult to obtain a sufficiently stable emulsion. The mixing time using a high-speed agitator is preferably 5 hours or less, more preferably 3 hours or less. If the mixing time using a high-speed agitator exceeds 5 hours, it is difficult to obtain the desired effect by continuing the agitation, and therefore productivity tends to be low.

[0058] Resins used in the practice of the present invention typically have a Tg greater than 30°C. The resin can be selected from the group consisting of hydrocarbon resins, phenolic / acetylene resins, terpene phenolic resins, rosin-derived resins, and mixtures thereof. Representative hydrocarbon resins include coumarone-indene resins, petroleum resins, terpene polymers, alpha-methylstyrene resins, and mixtures thereof. Coumarone-indene resins are commercially available in many forms with melting points (measured by the ring and ball method) ranging from 10 to 160°C. Preferably, the melting point is within the range of 30 to 100°C. Coumarone-indene resins contain a large amount of polyindene. However, coumarone-indene resins typically contain random polymer units derived from methylindene, coumarone, methylcoumarone, styrene, and methylstyrene.

[0059] Petroleum resins are commercially available with softening points ranging from 10°C to 120°C. Preferably, the softening point of the petroleum resin is in the range of 30°C to 100°C. Suitable petroleum resins include both aromatic and non-aromatic types. Several types of petroleum resins are available. Some resins have low unsaturation and high aromatic content, while others have high unsaturation and still others contain no aromatic structures. The differences between resins are primarily due to the olefins in the feedstock from which they are derived. Conventional derivatives of such resins include dicyclopentadiene, cyclopentadiene, their dimers, and diolefins such as isoprene and piperylene.

[0060] Terpene polymers are typically commercially produced by polymerizing mixtures of alpha-pinene and beta-pinene in mineral spirits. Resins are usually supplied with a variety of melting points ranging from 10°C to 135°C. Phenol / acetylene resins can also be used. Phenol / acetylene resins may be derived by adding acetylene to butylphenol in the presence of zinc naphthenate. Additional examples are derived from alkylphenols and acetylene.

[0061] Terpene phenolic resins may also be used. Terpene phenolic resins may be derived by copolymerizing phenolic monomers with terpenes, limonene, and pinene. Resins derived from rosin and derivatives may also be used in the present invention. Rubber and wood rosins have roughly the same composition, although the amounts of various isomers can vary. They typically contain about 10% by weight neutrals, 53% by weight resin acids containing two double bonds, 13% by weight resin acids containing one double bond, 16% by weight fully saturated resin acids, and 2% dehydroabietic acids containing aromatic rings but no unsaturation. Approximately 6% oxygenated acids are also present. Representative examples of diunsaturated acids include abietic acid, levopimaric acid, and neoabietic acid. Representative examples of monounsaturated acids include dextroplmaris acid and dihydroabietic acid. A representative saturated rosin acid is tetrahydroabietic acid.

[0062] In one embodiment, the resin is derived from styrene and alpha-methylstyrene. In one aspect, its glass transition temperature (Tg) characteristics in combination with its molecular weight (Mn) and molecular weight distribution (Mw / Mn) are believed to provide suitable compatibility of the resin in the rubber composition, with the degree of compatibility directly related to the properties of the rubber composition. The presence of a styrene / alpha-methylstyrene resin in a rubber blend containing the presence of a styrene-butadiene elastomer is believed to be advantageous herein because of the observed viscoelastic properties of the tread rubber composition, such as the complex and storage moduli, loss modulus tan delta, and loss compliance at different temperatures / frequencies / strains, as broadly described below. It is understood that the properties of complex and storage modulus, loss modulus tan delta, and loss compliance are generally well known to those skilled in the art. These are broadly described below.

[0063] The molecular weight distribution of the resin, visualized as the ratio of the resin's molecular weight average (Mw) to the molecular weight number average (Mn), is believed herein to be in the range of about 1.5 / L to about 2.5 / L, which is believed to be a relatively narrow range, which is believed to be advantageous because of its selective compatibility with the polymer matrix and its intended use in tires under wet and dry conditions over a wide range of temperatures.

[0064] The glass transition temperature, Tg, of the copolymer resin is considered herein to be in the range of about 20° C. to about 100° C., or alternatively, about 30° C. to about 80° C., depending somewhat on the intended use of the particular resin-modified, oil-extended rubber. A suitable method for measuring the resin Tg is DSC according to ASTM D6604 or equivalent.

[0065] Styrene / alpha-methylstyrene resins are herein considered to be relatively short-chain copolymers of styrene and alpha-methylstyrene, having a styrene / alpha-methylstyrene molar ratio ranging from about 0.40 to about 1.50. In one embodiment, such resins can be conveniently prepared, for example, by cationic copolymerization of styrene and alpha-methylstyrene in a hydrocarbon solvent. Thus, contemplated styrene / alpha-methylstyrene resins can be characterized, for example, by their chemical structure, i.e., their styrene and alpha-methylstyrene content and softening point, and, optionally, by their glass transition temperature, molecular weight, and molecular weight distribution.

[0066] In one embodiment, the styrene / alpha-methylstyrene resin is comprised of about 40 to about 70% styrene-derived units, and correspondingly, about 60 to about 30% alpha-methylstyrene-derived units. In one embodiment, the styrene / alpha-methylstyrene resin has a softening point in the range of about 80° C. to about 145° C. per ASTM No. E-28. Suitable styrene / alpha-methylstyrene resins are commercially available from Eastman as Resin 2336 or from Arizona Chemical as Sylvares SA85.

[0067] Virtually any type of high molecular weight synthetic rubber can be oil-extended and resin-modified in accordance with the present invention. For example, solution styrene-butadiene rubber (SSBR), emulsion styrene-butadiene rubber (ESBR), polybutadiene rubber, synthetic polyisoprene rubber, ethylene-propylene-diene rubber (EPDM), isoprene-butadiene rubber, styrene-isoprene-butadiene rubber, silicone rubber, nitrile rubber, carboxylated nitrile rubber, and the like can be resin-modified and simultaneously oil-extended in accordance with the method of the present invention. Resin-modified solution styrene-butadiene rubber (SSBR), emulsion styrene-butadiene rubber (ESBR), high cis-1,4-polybutadiene rubber, and synthetic polyisoprene rubber are particularly valuable in producing these rubbers, which are formulated for use in tire tread compounds.

[0068] Resin-modified and oil-extended high cis-1,4-polybutadiene rubber according to the present invention can be synthesized using a nickel-based catalyst system in accordance with the teachings of U.S. Patent No. 4,983,695. This process involves polymerizing 1,3-butadiene in solution in an aliphatic and / or alicyclic solvent system using as a catalyst system a mixture of (1) an organonickel compound, (2) an organoaluminum compound, and (3) a fluorine-containing compound selected from the group consisting of hydrogen fluoride and hydrogen fluoride complexes prepared by complexing hydrogen fluoride with ketones, esters, ethers, alcohols, phenols, and water, said polymerization being carried out in the presence of a small amount of an alpha olefin (such as ethylene or propylene). More specifically, this technique involves synthesizing high cis-1,4-polybutadiene by polymerizing 1,3-butadiene in a solution of an aliphatic and / or alicyclic solvent system using a catalyst system consisting of a mixture of (1) a nickel salt of a carboxylic acid, (2) a trialkylaluminum compound, and (3) a fluorine-containing compound prepared by complexing hydrogen fluoride with an ether, wherein the molar ratio of the trialkylaluminum compound to the nickel salt of a carboxylic acid is in the range of about 0.3 / L to about 300 / L, the molar ratio of the fluorine-containing compound to the nickel salt of a carboxylic acid is in the range of about 0.5 / L to about 500 / L, and the molar ratio of the fluorine-containing compound to the trialkylaluminum compound is in the range of about 0.4 / L to about 15 / L, and the polymerization is carried out in the presence of 0.73 to 4.57 phm of propylene. A more detailed description of nickel-based catalyst systems that can be used in the synthesis of high cis-1,4-polybutadiene rubber is provided in Canadian Patent No. 1,284,545, the teachings of which are incorporated herein by reference for the purposes of disclosing said nickel-based catalyst systems.

[0069] High cis-1,4-polybutadiene can also be synthesized using the method described in U.S. Patent No. 5,698,643, which involves polymerizing 1,3-butadiene monomer in hexane solution at a temperature of about 65° C. using as a catalyst system a mixture of (1) nickel octoate, (2) triisobutylaluminum, and (3) a hydrogen fluoride complex prepared by complexing hydrogen fluoride with dibutyl ether, wherein the molar ratio of the triisobutylaluminum to the nickel octoate is about 40:1, the molar ratio of the hydrogen fluoride complex to the nickel octoate is about 105:1, and the molar ratio of the hydrogen fluoride complex to the triisobutylaluminum is about 2.6:1, and the polymerization is carried out in the presence of 2 to 15 phm of isobutene, which acts as a molecular weight regulator to reduce the molecular weight of the high cis-1,4-polybutadiene.

[0070] High cis-1,4-polybutadiene can also be synthesized according to the teachings of U.S. Patent No. 5,451,646. The method involves polymerizing 1,3-butadiene in the presence of (a) an organonickel compound, (b) an organoaluminum compound, (c) a fluorine-containing compound, and (d) para-styrenated diphenylamine, where the organoaluminum compound and the fluorine-containing compound are combined in the presence of para-styrenated diphenylamine. U.S. Patent Nos. 4,983,695, 5,698,643, and 5,451,646 disclose high cis-1,4-polybutadiene. The teachings of No. 1,646 are incorporated herein by reference.

[0071] High cis-1,4-polybutadiene can also be synthesized using rare earth metal catalyst systems. For example, U.S. Pat. No. 4,260,707 discloses the use of rare earth metal compounds as components of organometallic mixed catalyst systems for the stereoregular polymerization of 1,3-butadiene monomer to high cis-1,4-polybutadiene. The catalyst system disclosed in U.S. Pat. No. 4,260,707 includes a reaction mixture formed by reacting (a) a rare earth carboxylate with an aluminum compound having three hydrocarbon residues having 1 to 20 carbon atoms attached to the aluminum, (b) a trialkylaluminum and / or a dialkylaluminum hydride, and (c) a Lewis acid. An improved method for preparing conjugated diolefin polymers or copolymers with a high content of 1,4-cis units and high linearity is disclosed in U.S. Pat. No. 4,444,903. In this process, the catalyst system comprises (a) at least one carboxylate or alcoholate of a rare earth element, (b) a tertiary organic halide compound, and (c) a compound of formula R a R b AlR c (In the formula, R a and R b is an alkyl residue, and R cis a hydrogen atom or an alkyl group) and a halide ion-free organometallic aluminum compound. Another example of the use of an organometallic mixed catalyst system containing a rare earth compound for producing conjugated diene polymers is disclosed in U.S. Pat. No. 4,461,883. This process is characterized by the polymerization of at least one conjugated diene using a catalyst consisting of (A) the reaction product of a Lewis base and a carboxylate of a rare earth element of the lanthanum series, represented by AlR2R3R4 (where R2, R3, and R4 may be the same or different and represent hydrogen or alkyl substituents, but R2, R3, and R4 cannot all be hydrogen atoms), (C) an alkylaluminum, and (D) an optional conjugated diene. The lanthanum-based catalyst system may also be composed of (1) a compound of a rare earth metal of the lanthanum series, (2) an organoaluminum compound, and (3) a halogen-containing compound. Lanthanide series rare earth metal compounds include carboxylates, alkoxides, thioalkoxides, halides, amides, and the like of elements having an atomic number ranging from 57 to approximately 71, such as cerium, lanthanum, praseodymium, neodymium, and gadolinium. Some representative examples of sources include carboxylates, alkoxides, or thioalkoxides of octanoic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, benzoic acid, naphthenic acid, 2-ethylhexyl alcohol, oleyl alcohol, phenol, benzyl alcohol, and thiophenol. In each case, the rare earth metal may be used alone or in combination with two or more additional rare earth metals. To solubilize the lanthanide series rare earth metal compound in the polymerization catalyst system, the compound may be used as a mixture or reaction product with a Lewis base and / or a Lewis acid, as needed. Typically, the use of a Lewis base is preferred. Some representative examples of Lewis bases that can be used include acetylacetone, tetrahydrofuran, pyridine, N,N'-dimethylformamide, thiophene, diphenyl ether, triethylamine, organophosphorus compounds, monohydric or dihydric alcohols, and the like.The organoaluminum compound is typically a trialkylaluminum compound such as triethylaluminum, triisobutylaluminum, triisopropylaluminum, trihexylaluminum, etc. Among these, triethylaluminum, triisobutylaluminum, and trihexylaluminum are preferred. The halogen-containing compound is typically a fluorine- or chlorine-containing compound such as boron trifluoride, a hydrogen fluoride complex prepared by complexing hydrogen fluoride with a dialkyl ether, or an aluminum halide compound. The catalyst system is described in more detail in U.S. Pat. No. 4,533,711, the teachings of which are incorporated herein by reference for the purpose of disclosing useful catalyst systems.

[0072] In either case, the resin-modified and oil-extended high cis-1,4-polybutadiene rubber according to the present invention comprises a high cis-1,4-polybutadiene rubber having a cis-microstructure content of at least 90%, at least 5 phr of oil, and at least 5 phr of resin. and the high cis-1,4-polybutadiene rubber has a molecular weight of at least 750,000 Da. z High molecular weight cis-1,4-polybutadiene rubber M z High cis-1,4-polybutadiene rubber compositions can be characterized by a ratio of molecular weight to number average molecular weight of at least 5. High cis-1,4-polybutadiene rubber compositions typically have a M of at least 1,000,000 Da. z and more typically, an M of at least 1,500,000 Da. z It has a molecular weight.

[0073] The high cis-1,4-polybutadiene rubber composition is more typically z The ratio of molecular weight to number average molecular weight is at least 5.5, more typically M z The ratio of molecular weight to number average molecular weight is at least 6. High cis-1,4-polyisoprene rubber is M z The ratio of molecular weight to number average molecular weight may be at least 6.1, and M zThe ratio of molecular weight to number average molecular weight may be at least 6.2.

[0074] High cis-1,4-polybutadiene rubbers more typically have a cis-microstructure content of at least 94%, and more frequently at least 95%. Often, high cis-1,4-polybutadiene rubbers have a cis-microstructure content of at least 96%, at least 97%, or even at least 98%. Often, high cis-1,4-polybutadiene rubbers have a polydispersity of at least 2.3, and may have a polydispersity of at least 2.4.

[0075] The resin-modified oil-extended synthetic polyisoprene rubber composition made in accordance with the present invention is comprised of a high cis-polyisoprene rubber having a cis-microstructure content of at least 90%, at least 5 phr of oil, and at least 5 phr of resin, wherein the high cis-polyisoprene rubber has an M of at least 750,000 Da. z High molecular weight cis-polyisoprene rubber M z High cis-polyisoprene rubbers are often characterized by a ratio of molecular weight to number average molecular weight of at least 2.7. z having a molecular weight, typically an M of at least 1,200,000 Da z In most cases, high cis-polyisoprene rubber has a molecular weight of at least 1,400,000 Da. z having a molecular weight of at least 1,500,000 Da z It may have a molecular weight.

[0076] High cis-polyisoprene rubber M z The ratio of molecular weight to number average molecular weight is typically at least 2.8 or 2.9. In many cases, high cis-polyisoprene rubbers have a M z The ratio of molecular weight to number average molecular weight is at least 3.0, and frequently M zThe ratio of molecular weight to number average molecular weight is at least 3.1. High cis-1,4-polyisoprene rubber typically has a polydispersity of at least 1.8, more commonly at least 1.85. In many cases, high cis-1,4-polyisoprene rubber has a polydispersity of at least 1.9.

[0077] The high cis-polyisoprene rubber may be a neodymium polyisoprene rubber having a cis-microstructure content of at least 95% or at least 96%. Often, the neodymium polyisoprene rubber has a cis-microstructure content of 96% to 98%, a trans-microstructure content of less than 0.5%, and a 3,4-microstructure content of 2% to 4%. Neodymium polyisoprene rubber can be synthesized using a three-component catalyst system containing (1) an organoaluminum compound, (2) an organo-neodymium compound, and (3) at least one compound containing at least one labile halide ion. Such a neodymium catalyst system is described in U.S. Pat. No. 6,780,948, the teachings of which are incorporated herein by reference. This patent describes a method for synthesizing polyisoprene rubber, which includes polymerizing isoprene monomer in the presence of a neodymium catalyst system, the neodymium catalyst system being: (1) reacting a neodymium carboxylate with an organoaluminum compound in the presence of isoprene for about 10 minutes to about 30 minutes to form a neodymium-aluminum catalyst; and (2) subsequently reacting the neodymium-aluminum catalyst component with a dialkylaluminum chloride for at least 30 minutes to form a neodymium catalyst system.

[0078] The synthetic polyisoprene rubber may also be a titanium polyisoprene rubber having a cis-microstructure content of at least 96% or 97%. For example, the titanium polyisoprene rubber may have a cis-microstructure content of 97% to 99% and a trans-microstructure content of 1% to 3%. In some cases, the titanium polyisoprene rubber has a 3,4-microstructure content of 0.2% to 0.8%.

[0079] The synthetic polyisoprene rubber may also be a lithium polyisoprene rubber having a cis-microstructure content of at least 86%. Often, the lithium polyisoprene rubber has a cis-microstructure content of 88% to 92%, a trans-microstructure content of 5% to 8%, and a 3,4-microstructure content of 3% to 4%.

[0080] The resin-modified oil-extended emulsion styrene-butadiene rubber composition made in accordance with the present invention comprises an emulsion styrene-butadiene rubber, at least 5 phr of oil, and at least 5 phr of resin, wherein the emulsion styrene-butadiene rubber has a bound styrene content in the range of 22% to 60% by weight and a bound butadiene content in the range of 40% to 78% by weight, wherein 60% to 70% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are trans 1,4-microstructure, 13% to 23% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are cis-microstructure, and 12% to 22% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are vinyl-microstructure, and the emulsion styrene-butadiene rubber has an M of at least 25,000 kDa. z The molecular weight of emulsion styrene-butadiene rubber is z It may be characterized by a ratio of molecular weight to number average molecular weight of at least 150.

[0081] Emulsion styrene-butadiene rubbers typically have a bound styrene content of 22% to 60% by weight and a bound butadiene content of 40% to 78% by weight. Emulsion styrene-butadiene rubbers more typically have a bound styrene content of 24% to 32% by weight and a bound butadiene content of 68% to 76% by weight. Emulsion styrene-butadiene rubbers more typically have a bound styrene content of 27% to 30% by weight and a bound butadiene content of 70% to 73% by weight. Typically, 62% to 68% of the bound butadiene repeat units in emulsion styrene-butadiene rubbers are trans 1,4-microstructure, 15% to 21% of the bound butadiene repeat units in emulsion styrene-butadiene rubbers are cis-microstructure, and 14% to 20% of the bound butadiene repeat units in emulsion styrene-butadiene rubbers are vinyl-microstructure. More typically, 63% to 67% of the bound butadiene repeat units in emulsion styrene-butadiene rubber are trans 1,4-microstructure, 16% to 20% of the bound butadiene repeat units in emulsion styrene-butadiene rubber are cis-microstructure, and 15% to 19% of the bound butadiene repeat units in emulsion styrene-butadiene rubber are vinyl-microstructure. Often, 64% to 66% of the bound butadiene repeat units in emulsion styrene-butadiene rubber are trans 1,4-microstructure, 17% to 19% of the bound butadiene repeat units in emulsion styrene-butadiene rubber are cis-microstructure, and 16% to 18% of the bound butadiene repeat units in emulsion styrene-butadiene rubber are vinyl-microstructure.

[0082] Emulsion styrene-butadiene rubber typically has a M of at least 30,000 kDa. z More typically, emulsion styrene-butadiene rubber has a molecular weight of at least 34,000 kDa or at least 36,000 kDa. z In some cases, the emulsion styrene-butadiene rubber has a molecular weight of at least 38,000 kDa.z Emulsion styrene-butadiene rubber has a molecular weight of M z The ratio of molecular weight to number average molecular weight is usually at least 175. In many cases, the M z The ratio of molecular weight to number average molecular weight is at least 180, at least 190, at least 200, at least 210, or at least 215. Emulsion styrene-butadiene rubber typically has a polydispersity of at least 40. Often, emulsion styrene-butadiene rubber has a polydispersity of at least 45 or even at least 50.

[0083] The resin-modified, oil-extended solution styrene-butadiene rubber composition prepared in accordance with the present invention comprises a solution styrene-butadiene rubber composition comprising a solution styrene-butadiene rubber, at least 5 phr of oil, and at least 5 phr of resin, wherein the solution styrene-butadiene rubber has a bound styrene content in the range of 10% to 60% by weight and a bound butadiene content in the range of 40% to 90% by weight, 25% to 55% of the bound butadiene repeat units in the solution styrene-butadiene rubber are of trans 1,4-microstructure, 25% to 50% of the bound butadiene repeat units in the solution styrene-butadiene rubber are of cis-microstructure, 5% to 45% of the bound butadiene repeat units in the solution styrene-butadiene rubber are of vinyl-microstructure, and the solution styrene-butadiene rubber has an M z The molecular weight of the solution styrene-butadiene rubber is z It may be characterized by a ratio of molecular weight to number average molecular weight of at least 1.58.

[0084] Solution styrene-butadiene rubber compositions typically have a bound styrene content of 24% to 32% by weight and a bound butadiene content of 68% to 76% by weight. Solution styrene-butadiene rubbers frequently have a bound styrene content of 27% to 30% by weight and a bound butadiene content of 70% to 73% by weight. Typically, 38% to 52% of the bound butadiene repeat units in the solution styrene-butadiene rubber are trans 1,4-microstructure, 28% to 48% of the bound butadiene repeat units in the solution styrene-butadiene rubber are cis-microstructure, and 6% to 30% of the bound butadiene repeat units in the solution styrene-butadiene rubber are vinyl-microstructure. More typically, 40% to 50% of the bound butadiene repeat units in solution styrene-butadiene rubber are in the trans 1,4-microstructure, 30% to 46% of the bound butadiene repeat units in solution styrene-butadiene rubber are in the cis-microstructure, and 8% to 28% of the bound butadiene repeat units in solution styrene-butadiene rubber are in the vinyl-microstructure.

[0085] Solution styrene-butadiene rubber typically has a M of at least 810 kDa z Solution styrene-butadiene rubbers more typically have a molecular weight of at least 820 kDa. z Molecular weight, often at least 830 kDa z In many cases, solution styrene-butadiene rubber has a molecular weight of at least 835 kDa. z The solution styrene-butadiene rubber has a molecular weight of at least 840 kDa. z Having a molecular weight is sometimes preferred. M of solution styrene-butadiene rubber z The ratio of molecular weight to number average molecular weight is typically at least 1.60. In many cases, the M zThe ratio of molecular weight to number average molecular weight is at least 1.62. Solution styrene-butadiene rubbers typically have a polydispersity of at least 1.30. In many cases, solution styrene-butadiene rubbers have a polydispersity of at least 1.31. Solution styrene-butadiene rubbers frequently have a polydispersity of at least 1.32.

[0086] The resin-modified, oil-extended rubber can then be compounded with conventional rubber compounding ingredients and auxiliaries. Commonly used siliceous pigments may be used in the rubber compound, including conventional calcined and precipitated siliceous pigments (silica), with precipitated silica being preferred. Conventional siliceous pigments preferably used in the present invention include precipitated silicas, such as those obtained by the acidification of soluble silicates, e.g., sodium silicate.

[0087] Such conventional silicas can be characterized, for example, by having a BET surface area, measured using nitrogen gas, preferably in the range of about 40 to about 600, more typically in the range of about 50 to about 300 square meters per gram. The BET method for measuring surface area is described in Journal of the American Chemical Society, Vol. 60, p. 304 (1930). Conventional silicas can also be characterized by having a dibutyl phthalate (DBP) absorption value, typically in the range of about 100 to about 400, more typically in the range of about 150 to about 300. Conventional silicas can be expected to have an average ultimate particle size, for example, in the range of 0.01 to 0.05 microns as determined by electron microscopy, although silica particles can be smaller in size, or in some cases larger in size.

[0088] Various commercially available silicas may be used, such as, by way of example only and not limitation, silicas commercially available under the Hi-Sil trademark designations 210, 243, etc. from PPG Industries; silicas commercially available under the designations Z1165MP and Z165GR from Rhodia; and silicas commercially available under the designations VN2 and VN3 from Degussa AG.

[0089] The vulcanizable rubber composition may contain from about 5 to about 50 phr of carbon black. Commonly used carbon blacks can be used as conventional fillers. Representative examples of such carbon blacks include N110, N121, N134, N220, N231, N234, N242, N293, N299, N5315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990, and N991. These carbon blacks have iodine absorptions ranging from 9 to 145 g / kg and DBP numbers ranging from 34 to 150 cm.sup.3 / 100 g.

[0090] The vulcanizable rubber composition may contain both silica and carbon black at a combined concentration of about 50 to about 150 phr, in any weight ratio of silica to carbon black. In one embodiment, the vulcanizable rubber composition contains both silica and carbon black in approximately equal amounts by weight, i.e., in a weight ratio of about 1:1. Other fillers may be used in the resin-modified, oil-extended rubber composition, such as particulate fillers including ultra-high molecular weight polyethylene (UHMWPE), particulate polymer gels such as those disclosed in U.S. Pat. No. 6,242,534; U.S. Pat. No. 6,207,757; U.S. Pat. No. 6,133,364; U.S. Pat. No. 6,372,857; U.S. Pat. No. 5,395,891; or U.S. Pat. No. 6,127,488, and plasticized starch composite fillers such as those disclosed in U.S. Pat. No. 5,672,639. The teachings of U.S. Patent Nos. 6,242,534, 6,207,757, 6,133,364, 6,372,857, 5,395,891, 6,127,488, and 5,672,639 are incorporated herein by reference.

[0091] The resin-modified, oil-extended rubber composition of the present invention may additionally contain a conventional sulfur-containing organosilicon compound. Examples of suitable sulfur-containing organosilicon compounds that can be used in accordance with the present invention include 3,3'-bis(trimethoxysilylpropyl) disulfide, 3,3'-bis(trimethoxysilylpropyl) disulfide, ethoxysilylpropyl) disulfide, 3,3'-bis(triethoxysilylpropyl) tetrasulfide, 3,3'-bis(triethoxysilylpropyl) octasulfide, 3,3'-bis(trimethoxysilylpropyl) tetrasulfide, 2,2'-bis(triethoxysilylethyl) tetrasulfide, 3,3'-bis(trimethoxysilylpropyl) trisulfide, 3,3'-bis(triethoxysilylpropyl) trisulfide, 3,3'-bis(tributoxysilylpropyl) disulfide, 3,3'-bis(trimethoxysilylpropyl) hexasulfide, 3,3'-bis(trimethoxysilylpropyl) octasulfide, 3,3'-bis(trioctoxysilylpropyl) tetrasulfide, 3,3'-bis(trihexoxy silylpropyl) disulfide, 3,3'-bis(tri-2''-ethylhexoxysilylpropyl) trisulfide, 3,3'-bis(triisooctoxysilylpropyl) tetrasulfide, 3,3'-bis(tri-t-butoxysilylpropyl) disulfide, 2,2'-bis(methoxydiethoxysilylethyl) tetrasulfide, 2,2'-bis(tripropoxysilylethyl) pentasulfide, 3,3'-bis(tricyclonexoxysilylpropyl) tetrasulfide, 3,3'-bis(tricyclopentoxysilylpropyl) trisulfide, 2,2'-bis(tri-2''-methylcyclohexoxysilylethyl) tetrasulfide, bis(trimethoxysilylmethyl) tetrasulfide, 3-methoxyethoxypropoxysilyl 3' -diethoxybutoxy-silylpropyl tetrasulfide, 2,2'-bis(dimethylmethoxysilylethyl) disulfide, 2,2'-bis(dimethyl sec.butoxysilylethyl) trisulfide, 3,3'-bis(methylbutylethoxysilylpropyl) tetrasulfide, 3,3'-bis(di-t-butylmethoxysilylpropyl) tetrasulfide, 2,2'-bis(phenylmethylmethoxysilylethyl) trisulfide, 3,3'-bis(diphenylisopropoxysilylpropyl) tetrasulfide, 3,3'-bis(diphenylcyclohexoxysilylpropyl) disulfide, 3,3'-bis(dimethylethylmercaplayertosilylpropyl)tetrasulfide, 2,2'-bis(methyldimethoxysilylethyl) trisulfide silylethyl) trisulfide, 2,2'-bis(methylethoxypropoxysilylethyl) tetrasulfide, 3,3'-bis(diethylmethoxysilylpropyl) tetrasulfide, 3,3'-bis(ethyldi-sec-butoxysilylpropyl) disulfide, 3,3'-bis(propyldiethoxysilylpropyl) disulfide, 3,3'-bis(butyldimethoxysilylpropyl) trisulfide, 3,3'-bis(phenyldimethoxysilylpropyl) tetrasulfide, 3-phenylethoxybutoxysilyl 3'-trimethoxysilylpropyl tetrasulfide, 4,4'-bis(trimethoxysilylbutyl) tetrasulfide, 6,6'-bis(triethoxysilyl 12,12'-bis(triisopropoxysilyldodecyl)disulfide, 18,18'-bis(trimethoxysilyloctadecyl)tetrasulfide, 18,18'-bis(tripropoxysilyloctadecenyl)tetrasulfide, 4,4'-bis(trimethoxysilyl-buten-2-yl)tetrasulfide, 4,4'-bis(trimethoxysilylcyclohexylene)tetrasulfide, 5,5'-bis(dimethoxymethylsilylpentyl)trisulfide, 3,3'-bis(trimethoxysilyl-2-methylpropyl)tetrasulfide, 3,3'-bis(dimethoxyphenylsilyl-2-methylpropyl)disulfide.

[0092] The preferred sulfur-containing organosilicon compound is 3,3'-bis(trimethoxy or triethoxysilylpropyl) sulfide. The most preferred compounds are 3,3'-bis(triethoxysilylpropyl) disulfide and 3,3'-bis(triethoxysilylpropyl) tetrasulfide. In another embodiment, suitable sulfur-containing organosilicon compounds include those disclosed in U.S. Pat. No. 6,608,125. In one embodiment, the sulfur-containing organosilicon compound is 3-(octanoylthio)-1-propyltriethoxysilane, commercially available under the trademark NXT-Z from Momentive Performance Materials. This includes thoxysilane, CH3(CH2)6C(=O)-S-CH2CH2CH2Si(OCH2CH3)3.

[0093] In another embodiment, suitable sulfur-containing organosilicon compounds are disclosed in U.S. Patent Publication No. 2006 / 0041063. In one embodiment, the sulfur-containing organosilicon compound comprises the reaction product of a hydrocarbon-based diol (e.g., 2-methyl-1,3-propanediol) with S-[3-(triethoxysilyl)propyl]thiooctanoate. In one embodiment, the sulfur-containing organosilicon compound is NXT-Z™ manufactured by Momentive Performance Materials. In another embodiment, the sulfur-containing organosilicon compound includes those disclosed in U.S. Patent Publication No. 2003 / 0130535. In one embodiment, the sulfur-containing organosilicon compound is Si-363 manufactured by Degussa.

[0094] Those skilled in the art will readily understand that rubber compositions are generally compounded by methods commonly known in the rubber compounding art, such as blending various sulfur-vulcanizable component rubbers with various commonly used additives, such as sulfur donors, curing aids such as activators and inhibitors and processing additives, fillers, pigments, fatty acids, zinc oxide, waxes, antioxidants and antiozonants, and peptizers. As known to those skilled in the art, the additives are selected and generally used in conventional amounts depending on the intended use of the sulfur-vulcanizable and sulfur-vulcanized materials (rubbers). Representative examples of sulfur donors include elemental sulfur (free sulfur), amine disulfides, polymeric polysulfides, and sulfur-olefin adducts. Preferably, the sulfur-vulcanizing agent is elemental sulfur. Sulfur-vulcanizing agents may be used in amounts ranging from 0.5 to 8 phr, with a range of 1.5 to 6 phr being preferred. Typical amounts of antioxidants comprise from about 1 to about 5 phr. Representative antioxidants include, for example, diphenyl-p-phenylenediamine and others, such as those disclosed in The Vanderbilt Rubber Handbook (1978), pages 344-346. Typical amounts of antiozonants comprise about 1 to 5 phr. Typical amounts of fatty acids, which, if used, can include stearic acid, comprise about 0.5 to about 3 phr. Typical amounts of zinc oxide comprise about 2 to about 5 phr. Typical amounts of wax comprise about 1 to about 5 phr. Microcrystalline wax is often used. Typical amounts of peptizers comprise about 0.1 to about 1 phr. Typical peptizers may be, for example, pentachlorothiophenol and dibenzamidodiphenyl disulfide.

[0095] Accelerators are used to control the time and / or temperature required for vulcanization and to improve the properties of the vulcanizate. In one embodiment, a single accelerator system, i.e., a primary accelerator, may be used. The primary accelerator may be used in a total amount ranging from about 0.5 to about 4 phr, preferably from about 0.8 to about 1.5 phr. In another embodiment, a combination of primary and secondary accelerators may be used to activate and improve the properties of the vulcanizate, with the secondary accelerator used in a minor amount, such as from about 0.05 to about 3 phr. These accelerator combinations are expected to produce a synergistic effect on the final properties, somewhat superior to those produced by either accelerator alone. In addition, delayed-action accelerators may be used that are not affected by normal processing temperatures but produce a satisfactory cure at ordinary vulcanization temperatures. Vulcanization retarders may also be used. Suitable types of accelerators that can be used in the present invention are amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates, and xanthates. Preferably, the primary accelerator is a sulfenamide. If a second accelerator is used, the secondary accelerator is preferably a guanidine, dithiocarbamate or thiuram compound.

[0096] The mixing of the rubber composition can be accomplished by methods known to those skilled in the rubber mixing art. For example, the ingredients are typically mixed in at least two stages, i.e., at least one non-productive stage followed by a productive mix stage. The final rubber composition containing the sulfur vulcanizing agent is then mixed in a final stage. The curatives are typically mixed in a final stage, commonly referred to as the "productive" mix stage, where mixing is typically performed at a lower or final temperature than the mixing temperature of the preceding non-productive mix stage. The terms "non-productive" and "productive" mix stages are well known to those skilled in the rubber mixing art. The rubber composition may undergo a thermomechanical mixing process. The thermomechanical mixing process generally involves mechanical processing in a mixer or extruder for a time suitable to produce a rubber temperature between 140°C and 190°C. The appropriate duration of the thermomechanical processing varies depending on the operating conditions and the volume and nature of the ingredients. For example, the thermomechanical processing may be from 1 to 20 minutes.

[0097] The resin-modified, oil-extended rubbers of the present invention can be used in the manufacture of a wide variety of products, including tires, power transmission belts, conveyor belts, trucks, air springs, asphalt-modified polymers, adhesives, shoe soles, windshield wiper blades, bowling balls, golf balls, and energy-absorbing foot pads. These resin-modified rubbers can be incorporated into numerous tire components. For example, the resin-modified, oil-extended rubbers of the present invention can be used in tire treads (including outer and inner tread cap layers) and tire sidewalls. They can also be used in tire apexes, chafers, sidewall inserts, wire coats, and innerliner formulations.

[0098] The pneumatic tire of the present invention may be a race tire, passenger tire, aircraft tire, agricultural tire, earthmover tire, off-road tire, truck tire, etc. Typically, the tire is a passenger tire or a truck tire. Also, the tire may be radial or bias, although radial is preferred.

[0099] Vulcanization of the pneumatic tires of the present invention is generally carried out at conventional temperatures ranging from about 100°C to 200°C. Preferably, vulcanization is carried out at temperatures ranging from about 110°C to 180°C. Any of the conventional vulcanization processes may be used, such as heating in a press or mold, heating with superheated steam or hot air. Such tires can be built, shaped, molded, and cured by a variety of methods known and readily understood by those skilled in the art.

[0100] The following examples are presented for illustrative purposes and are not intended to limit the scope of the invention. All parts are by weight unless otherwise specified.

[0101] [Example 1] In this series of experiments, neodymium polybutadiene rubber (cis-polybutadiene rubber) was compounded using a "wet mix" technique according to the procedure of the present invention and a "dry mix" technique in which the oil-extended polymer and resin were added separately to a mixer. In the procedure used, the resin / oil extender used in making the "wet mix" was prepared by dissolving one part resin in two parts soybean oil at a temperature of 100°C. This mixing was carried out by vigorous mixing for approximately 30 minutes. The soybean oil / resin mixture was then blended into neodymium polybutadiene rubber cement at a level of 37.5 phr for approximately 30 minutes at room temperature. The cement was then drum dried to recover the resin-modified neodymium polybutadiene rubber.

[0102] A dry blend was also prepared by first extending the neodymium polybutadiene rubber cement with 25 phr of soybean oil. The soybean oil-extended neodymium polybutadiene rubber was then recovered by drum drying. The dried soybean oil-extended neodymium polybutadiene rubber was then mixed for 1 minute in a 70 cc Brabender mixer at 60°C and 60 rpm. 12.5 phr of polyterpene resin was then added to the mixer, and mixing was continued for 5 minutes to prepare a dry-blended resin-modified polybutadiene rubber.

[0103] The "wet mixed" and "dry mixed" rubbers were then characterized by asymmetric flow field flow fractionation to determine the number average, weight average, and z-average molecular weights. Three molecular weight measurements were made on both rubbers and the averages are recorded in the table below.

[0104] [Table 3]

[0105] As can be seen, the ratio of Mz to Mn molecular weights was much higher when the wet mixing procedure was used. This indicates less polymer degradation and retention of high molecular weight fractions for rubbers made by the "wet mixing" procedure of the present invention. This in turn translates into better properties in end products such as tire tread compounds.

[0106] [Example 2] In this series of experiments, neodymium polyisoprene rubber (cis-polybutadiene rubber) was compounded using a "wet mix" technique according to the procedure of the present invention and a "dry mix" technique in which the oil-extended polymer and resin were added separately to a mixer. In the procedure used, the resin / oil-extending agent used in making the "wet mix" was prepared by dissolving one part resin in two parts soybean oil at a temperature of 100°C. This mixture was carried out by vigorous mixing for approximately 30 minutes. The soybean oil / resin mixture was then blended into neodymium polyisoprene rubber cement at a level of 37.5 phr for approximately 30 minutes at room temperature. The cement was then drum dried to recover the resin-modified neodymium polyisoprene rubber.

[0107] A dry blend was also prepared by first extending the neodymium polyisoprene rubber cement with 25 phr of soybean oil. The soybean oil-extended neodymium polyisoprene rubber was then recovered by drum drying. The dried soybean oil-extended neodymium polyisoprene rubber was then mixed for 1 minute in a 70 cc Brabender mixer at 60°C and 60 rpm. 12.5 phr of polyterpene resin was then added to the mixer, and mixing was continued for 5 minutes to prepare a dry-blended resin-modified polyisoprene rubber.

[0108] The "wet mixed" and "dry mixed" rubbers were then characterized by asymmetric flow field flow fractionation to determine the number average, weight average, and z-average molecular weights. Three molecular weight measurements were made on both the "wet mixed" and "dry mixed" rubbers, and the averages are recorded in the table below.

[0109] [Table 4]

[0110] As can be seen, the ratio of Mz to Mn molecular weights was much higher when the wet mixing procedure was used. This indicates less polymer degradation and retention of high molecular weight fractions for rubbers made by the "wet mixing" procedure of the present invention. This in turn translates into better properties in end products such as tire tread compounds.

[0111] [Example 3] In this series of experiments, solution styrene-butadiene rubber was compounded using a "wet mix" technique according to the procedure of the present invention, as well as a "dry mix" technique in which the oil-extended polymer and resin were added separately to a mixer. In the procedure used, the resin / oil extender used in making the "wet mix" was prepared by dissolving one part resin in two parts soybean oil at a temperature of 100°C. This mixture was carried out by vigorous mixing for approximately 30 minutes. The soybean oil / resin mixture was then blended into the solution styrene-butadiene rubber cement at a level of 37.5 phr for approximately 30 minutes at room temperature. The cement was then drum dried to recover the resin-modified solution styrene-butadiene rubber.

[0112] A dry blend was also prepared by first extending the solution styrene-butadiene rubber cement with 25 phr of soybean oil. The soybean oil-extended solution styrene-butadiene rubber was then recovered by drum drying. The dried soybean oil-extended solution styrene-butadiene rubber was then mixed for 1 minute in a 70 cc Brabender mixer at 60°C and 60 rpm. 12.5 phr of polyterpene resin was then added to the mixer, and mixing was continued for 5 minutes to prepare the dry-blended resin-modified solution styrene-butadiene rubber.

[0113] The "wet mixed" and "dry mixed" rubbers were then characterized by asymmetric flow field flow fractionation to determine the number average, weight average, and z-average molecular weights. Duplicate molecular weight measurements were made on both the "wet mixed" and "dry mixed" rubbers, and the averages are recorded in the table below.

[0114] [Table 5]

[0115] As can be seen, the ratio of Mz to Mn molecular weights was higher when the wet mixing procedure was used. This indicates less polymer degradation and retention of high molecular weight fractions for rubbers made by the "wet mixing" procedure of the present invention. This in turn translates into better properties in end products such as tire tread compounds.

[0116] [Example 4] In this series of experiments, emulsion styrene-butadiene rubber was compounded using a "wet mix" technique according to the procedure of the present invention and a "dry mix" technique in which the oil-extended polymer and resin were added separately to a mixer. In the procedure used, the resin / oil-extender used in making the "wet mix" was prepared by dissolving one part resin in two parts soybean oil at a temperature of 100°C. This mixture was carried out by vigorous mixing for approximately 30 minutes. The soybean oil / resin mixture was emulsified with a rosin acid / fatty acid soap mixture at a temperature of 60°C (140°F). The emulsified soybean oil / resin mixture was then added to an emulsion styrene-butadiene rubber latex at a level of 37.5 phr for approximately 10 minutes at room temperature. The latex was then coagulated using a salt / acid coagulant to recover the resin-modified emulsion styrene-butadiene rubber, which was then oven-dried at a temperature of 60°C (140°F).

[0117] A dry mix was also prepared by first extending the emulsion styrene-butadiene rubber latex with 25 phr of soybean oil using the same procedure utilized in the wet mixing procedure. The soybean oil-extended emulsion styrene-butadiene rubber was then recovered by coagulation of the latex. The dried soybean oil-extended emulsion styrene-butadiene rubber was then The rubber was mixed for 1 minute in a 70 cc Brabender mixer at 60°C and 60 rpm. 12.5 phr of polyterpene resin was then added to the mixer and mixing continued for 5 minutes to prepare a dry-mixed resin-modified emulsion styrene-butadiene rubber.

[0118] The "wet mixed" and "dry mixed" rubbers were then characterized by asymmetric flow field flow fractionation to determine the number average, weight average, and z-average molecular weights. Duplicate molecular weight measurements were made on both the "wet mixed" and "dry mixed" rubbers, and the averages are recorded in the table below.

[0119] [Table 6]

[0120] As can be seen, the ratio of Mz to Mn molecular weights was much higher when the wet mixing procedure was used. This indicates less polymer degradation and retention of high molecular weight fractions for rubbers made by the "wet mixing" procedure of the present invention. This in turn translates into better properties in end products such as tire tread compounds.

[0121] [Examples 5 to 11] In this series of experiments, resin-modified, oil-extended rubbers prepared according to the technology of the present invention were cured, and the properties of the cured rubbers produced in the rubber state were compared with those of rubbers prepared using conventional techniques. In the procedure used, rubber samples were prepared by blending the ingredients, except for the sulfur vulcanizing agent, in an internal rubber mixer in a first non-productive mix stage for approximately 4 minutes at a temperature of 160°C. Subsequently, the resulting mixture was individually mixed in a second non-productive mix stage to a temperature of approximately 140°C. Subsequently, in a productive mix stage, the rubber composition was mixed with a sulfur vulcanizing agent, including sulfur and a sulfur vulcanization accelerator, for approximately 2 minutes to a temperature of approximately 115°C. After each mix, the rubber composition was removed from the internal mixer and cooled to below 40°C between each of the individual non-productive mix stages and before the final productive mix stage.

[0122] [Table 7-1]

[0123] [Table 7-2]

[0124] It is noted that tan delta at 0°C (3% strain at a frequency of 10 Hz) is a good indicator of the wet traction characteristics of a tire tread compound, with high tan delta values ​​being associated with better traction characteristics. G' at -20°C (3% strain at a frequency of 10 Hz) is a good indicator of studless tire performance, with lower values ​​being associated with better studless tire performance characteristics. It is also noted that for good tire rolling resistance, it is desirable to have high rebound at 100°C and low tan delta values ​​at 100°C (10% strain at a frequency of 1 Hz). The Grossche wheel abrasion test is a good predictor of tire abrasion characteristics, with lower values ​​being more desirable.

[0125] As can be seen from a review of the results obtained in Examples 5-11 (E5-E11), the cured rubber samples (E8 and E11) made with the resin-modified, oil-extended rubbers prepared in accordance with the present invention possessed a combination of properties more desirable than other rubbers for use in preparing tire tread rubber formulations. More specifically, these resin-modified, oil-extended rubbers exhibited excellent combinations of tensile strength, tan delta at 0°C, rebound at 100°C, tan delta at 100°C, and Gross Wheel Polishability. Correspondingly, these resin-modified, oil-extended rubbers possessed excellent tensile properties, wear resistance properties, predicted wet tire performance characteristics, and low levels of predicted tire rolling resistance (indicating better fuel economy).

[0126] While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the invention. [Embodiments of the present invention] 1. A high cis-1,4-polybutadiene rubber composition comprising a high cis-1,4-polybutadiene rubber having a cis-microstructure content of at least 90%, at least 5 phr of oil, and at least 5 phr of resin, wherein the high cis-1,4-polybutadiene rubber has a M of at least 750,000 Da. z a ratio of the Mz molecular weight to the number average molecular weight of the high cis-1,4-polybutadiene rubber of at least 5. 2. The high cis-1,4-polybutadiene rubber has a molecular weight of at least 1,000,000 Da. z 1. A high cis-1,4-polybutadiene rubber composition having a molecular weight as defined in claim 1. 3. The high cis-1,4-polybutadiene rubber has a molecular weight of at least 1,500,000 Da. z 1. A high cis-1,4-polybutadiene rubber composition having a molecular weight as defined in claim 1. 4. A high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the ratio of the Mz molecular weight to the number average molecular weight of the high cis-1,4-polybutadiene rubber is at least 5.5. 5. A high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the ratio of the Mz molecular weight to the number average molecular weight of the high cis-1,4-polybutadiene rubber is at least 6. 6. A high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the ratio of the Mz molecular weight to the number average molecular weight of the high cis-1,4-polybutadiene rubber is at least 6.1. 7. A high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the ratio of the Mz molecular weight to the number average molecular weight of the high cis-1,4-polybutadiene rubber is at least 6.2. 8. A high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the high cis-1,4-polybutadiene rubber has a cis-microstructure content of at least 94%. 9. A high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the high cis-1,4-polybutadiene rubber has a cis-microstructure content of at least 95%. 10. A high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the high cis-1,4-polybutadiene rubber has a cis-microstructure content of at least 96%. 11. A high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the high cis-1,4-polybutadiene rubber has a cis-microstructure content of at least 97%. 12. A high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the high cis-1,4-polybutadiene rubber has a cis-microstructure content of at least 98%. 13. A high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the high cis-1,4-polybutadiene rubber composition contains 5 phr to 100 phr of oil. 14. A high cis-1,4-polybutadiene rubber composition as defined in 13, wherein the high cis-1,4-polybutadiene rubber composition contains 5 phr to 100 phr of a resin. 15. A high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the high cis-1,4-polybutadiene rubber composition contains 10 phr to 80 phr of oil. 16. A high cis-1,4-polybutadiene rubber composition as defined in 15, wherein the high cis-1,4-polybutadiene rubber composition contains 6 phr to 80 phr of resin. 17. A high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the high cis-1,4-polybutadiene rubber composition contains 15 phr to 60 phr of oil. 18. A high cis-1,4-polybutadiene rubber composition as defined in paragraph 17, wherein the high cis-1,4-polybutadiene rubber composition contains 8 phr to 60 phr of resin. 19. A high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the high cis-1,4-polybutadiene rubber composition contains 20 phr to 40 phr of oil. 20. A high cis-1,4-polybutadiene rubber composition as defined in paragraph 19, wherein the high cis-1,4-polybutadiene rubber composition contains 10 phr to 35 phr of a resin. 21. A high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the high cis-1,4-polybutadiene rubber composition contains 20 phr to 30 phr of oil. 22. A high cis-1,4-polybutadiene rubber composition as defined in 21, wherein the high cis-1,4-polybutadiene rubber composition contains 10 phr to 15 phr of resin. 23. A high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the high cis-1,4-polybutadiene rubber composition contains 22 phr to 28 phr of oil. 24. A high cis-1,4-polybutadiene rubber composition as defined in 23, wherein the high cis-1,4-polybutadiene rubber composition contains 10 phr to 14 phr of resin. 25. The high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the oil is a petroleum extender oil selected from the group consisting of highly aromatic petroleum oils, aromatic petroleum oils, naphthenic petroleum oils, and paraffinic petroleum oils. 26. The high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the oil is a triglyceride oil. 27. A high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the oil is a vegetable oil. 28. The high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the oil is a triglyceride oil selected from the group consisting of soybean oil, sunflower oil, canola (rapeseed) oil, corn oil, coconut oil, cottonseed oil, olive oil, palm oil, peanut oil, and safflower oil. 29. The high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the triglyceride oil is soybean oil. 30. The high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the triglyceride oil is corn oil. 31. The high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the high cis-1,4-polybutadiene rubber has a polydispersity of at least 2.3. 32. The high cis-1,4-polybutadiene rubber composition as defined in 1, wherein the high cis-1,4-polybutadiene rubber has a polydispersity of at least 2.4. 33. A synthetic polyisoprene rubber composition comprising a high-cis polyisoprene rubber having a cis microstructure content of at least 90%, at least 5 phr of oil, and at least 5 phr of resin, wherein the high-cis polyisoprene rubber has an M z olecular weight of at least 750,000 Da and the ratio of the Mz molecular weight of the high-cis polyisoprene rubber to the number average molecular weight is at least 2.5. 34. The synthetic polyisoprene rubber composition as defined in 33, wherein the high-cis polyisoprene rubber has an M z olecular weight of at least 1,000,000 Da. 35. The synthetic polyisoprene rubber composition as defined in 33, wherein the high-cis polyisoprene rubber has an M z olecular weight of at least 1,200,000 Da. 36. The synthetic polyisoprene rubber composition as defined in 33, wherein the high-cis polyisoprene rubber has an M z olecular weight of at least 1,400,000 Da. 37. The synthetic polyisoprene rubber composition as defined in 33, wherein the high-cis polyisoprene rubber has an M z olecular weight of at least 1,500,000 Da. 38. The synthetic polyisoprene rubber composition as defined in 33, wherein the ratio of the Mz molecular weight of the high-cis polyisoprene rubber to the number average molecular weight is at least 2.8. 39. The synthetic polyisoprene rubber composition as defined in 33, wherein the ratio of the Mz molecular weight of the high-cis polyisoprene rubber to the number average molecular weight is at least 2.9. 40. The synthetic polyisoprene rubber composition as defined in 33, wherein the ratio of the Mz molecular weight of the high-cis polyisoprene rubber to the number average molecular weight is at least 3.0. 41. The synthetic polyisoprene rubber composition as defined in 33, wherein the ratio of the Mz molecular weight of the high-cis polyisoprene rubber to the number average molecular weight is at least 3.1. 42. The synthetic polyisoprene rubber composition as defined in 33, wherein the high-cis polyisoprene rubber is a neodymium polyisoprene rubber. 43. A synthetic polyisoprene rubber composition as defined in 42, wherein the neodymium polyisoprene rubber has a cis-microstructure content of at least 95%. 44. A synthetic polyisoprene rubber composition as defined in paragraph 42, wherein the neodymium polyisoprene rubber has a cis-microstructure content of at least 96%. 45. A synthetic polyisoprene rubber composition as defined in paragraph 42, wherein the neodymium polyisoprene rubber has a cis-microstructure content within the range of 96% to 98%. 46. ​​A synthetic polyisoprene rubber composition as defined in paragraph 45, in which the neodymium polyisoprene rubber has a trans-microstructure content of less than 0.5%. 47. A synthetic polyisoprene rubber composition as defined in 45, wherein the neodymium polyisoprene rubber has a 3,4-microstructure content within the range of 2% to 4%. 48. The synthetic polyisoprene rubber composition defined in 33, wherein the high cis-polyisoprene rubber is a titanium polyisoprene rubber. 49. A synthetic polyisoprene rubber composition as defined in paragraph 48, wherein the titanium polyisoprene rubber has a cis-microstructure content of at least 96%. 50. A synthetic polyisoprene rubber composition as defined in paragraph 48, wherein the titanium polyisoprene rubber has a cis-microstructure content of at least 97%. 51. A synthetic polyisoprene rubber composition as defined in paragraph 48, wherein the titanium polyisoprene rubber has a cis-microstructure content within the range of 97% to 99%. 52. A synthetic polyisoprene rubber composition as defined in 51, wherein the titanium polyisoprene rubber has a trans-microstructure content within the range of 1% to 3%. 53. A synthetic polyisoprene rubber composition as defined in paragraph 52, wherein the titanium polyisoprene rubber has a 3,4-microstructure content within the range of 0.2 to 0.8%. 54. The synthetic polyisoprene rubber composition as defined in 33, wherein the high cis-polyisoprene rubber is lithium polyisoprene rubber. 55. A synthetic polyisoprene rubber composition as defined in 54, wherein the lithium polyisoprene rubber has a cis-microstructure content of at least 86%. 56. A synthetic polyisoprene rubber composition as defined in 55, wherein the lithium polyisoprene rubber has a cis-microstructure content within the range of 88% to 92%. 57. A synthetic polyisoprene rubber composition as defined in paragraph 56, wherein the lithium polyisoprene rubber has a trans-microstructure content within the range of 5% to 8%. 58. A synthetic polyisoprene rubber composition as defined in 57, wherein the lithium polyisoprene rubber has a 3,4-microstructure content within the range of 3% to 4%. 59. The high cis-polyisoprene rubber composition as defined in paragraph 33, wherein the high cis-1,4-polybutadiene rubber composition contains 5 phr to 100 phr of oil. 60. The high cis-1,4-polybutadiene rubber composition is 5 phr to 100 phr 59, containing a high cis-1,4-polyisoprene rubber composition. 61. A high cis-polyisoprene rubber composition as defined in paragraph 33, wherein the high cis-1,4-polyisoprene rubber composition contains 10 phr to 80 phr of oil. 62. A high cis-1,4-polyisoprene rubber composition as defined in paragraph 61, wherein the high cis-1,4-polyisoprene rubber composition contains 6 phr to 80 phr of resin. 63. The high cis-1,4-polyisoprene rubber composition as defined in paragraph 62, wherein the high cis-1,4-polyisoprene rubber composition contains 15 phr to 60 phr of oil. 64. A high cis-1,4-polybutadiene rubber composition as defined in paragraph 33, wherein the high cis-1,4-polyisoprene rubber composition contains 8 phr to 60 phr of resin. 65. A high cis-1,4-polyisoprene rubber composition as defined in paragraph 64, wherein the high cis-1,4-polyisoprene rubber composition contains 20 phr to 40 phr of oil. 66. A high cis-1,4-polyisoprene rubber composition as defined in paragraph 33, wherein the high cis-1,4-polyisoprene rubber composition contains 10 phr to 35 phr of resin. 67. A high cis-1,4-polyisoprene rubber composition as defined in paragraph 66, wherein the high cis-1,4-polyisoprene rubber composition contains 20 phr to 30 phr of oil. 68. A high cis-1,4-polyisoprene rubber composition as defined in paragraph 33, wherein the high cis-1,4-polyisoprene rubber composition contains 10 phr to 15 phr of resin. 69. A high cis-1,4-polyisoprene rubber composition as defined in paragraph 68, wherein the high cis-1,4-polyisoprene rubber composition contains 22 phr to 28 phr of oil. 70. A high cis-1,4-polyisoprene rubber composition as defined in paragraph 33, wherein the high cis-1,4-polybutadiene rubber composition contains 10 phr to 14 phr of resin. 71. The high cis-1,4-polyisoprene rubber composition as defined in paragraph 33, wherein the oil is a petroleum extender oil selected from the group consisting of highly aromatic petroleum, aromatic petroleum, naphthenic petroleum, and paraffinic petroleum. 72. A high cis-1,4-polyisoprene rubber composition as defined in paragraph 33, wherein the oil is a triglyceride oil. 73. The high cis-1,4-polyisoprene rubber composition as defined in paragraph 33, wherein the oil is a vegetable oil. 74. The high cis-1,4-polyisoprene rubber composition as defined in paragraph 33, wherein the oil is a triglyceride oil selected from the group consisting of soybean oil, sunflower oil, canola (rapeseed) oil, corn oil, coconut oil, cottonseed oil, olive oil, palm oil, peanut oil, and safflower oil. 75. A high cis-1,4-polyisoprene rubber composition as defined in paragraph 72, wherein the triglyceride oil is soybean oil. 76. The high cis-1,4-polyisoprene rubber composition defined in paragraph 72, wherein the triglyceride oil is corn oil. 77. A high cis-1,4-polyisoprene rubber composition as defined in paragraph 33, wherein the high cis-1,4-polyisoprene rubber has a polydispersity of at least 1.8. 78. The high cis-1,4-polyisoprene rubber composition as defined in paragraph 33, wherein the high cis-1,4-polyisoprene rubber has a polydispersity of at least 1.85. 79. A high cis-1,4-polyisoprene rubber composition as defined in paragraph 33, wherein the high cis-1,4-polyisoprene rubber has a polydispersity of at least 1.9. 80. An emulsion styrene-butadiene rubber composition comprising an emulsion styrene-butadiene rubber, at least 5 phr of oil, and at least 5 phr of resin, wherein the emulsion styrene-butadiene rubber has a bound styrene content in the range of 22% to 60% by weight and a bound butadiene content in the range of 40% to 78% by weight, 60% to 70% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are trans 1,4-microstructure, 13% to 23% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are cis-microstructure, and 12% to 22% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are vinyl-microstructure, and the emulsion styrene-butadiene rubber has an M z Molecular weight Styrene-butadiene rubber emulsion z An emulsion styrene-butadiene rubber composition having a ratio of molecular weight to number average molecular weight of at least 150. 81. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the emulsion styrene-butadiene rubber has a bound styrene content within the range of 23% to 32% by weight and a bound butadiene content within the range of 68% to 77% by weight. 82. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the emulsion styrene-butadiene rubber has a bound butadiene content in the range of 27% to 30% by weight and a bound styrene content in the range of 70% to 73% by weight. 83. An emulsion styrene-butadiene rubber composition as defined in paragraph 80, wherein 62% to 68% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in the trans 1,4-microstructure, 15% to 21% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in the cis-microstructure, and 14% to 20% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in the vinyl-microstructure. 84. An emulsion styrene-butadiene rubber composition as defined in paragraph 80, wherein 63% to 67% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in the trans 1,4-microstructure, 16% to 20% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in the cis-microstructure, and 15% to 19% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in the vinyl-microstructure. 85. An emulsion styrene-butadiene rubber composition as defined in paragraph 80, wherein 64% to 66% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in the trans 1,4-microstructure, 17% to 19% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in the cis-microstructure, and 16% to 18% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in the vinyl-microstructure. 86. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the emulsion styrene-butadiene rubber has an Mz molecular weight of at least 30,000 kDa. 87. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the emulsion styrene-butadiene rubber has an Mz molecular weight of at least 34,000 kDa. 88. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the emulsion styrene-butadiene rubber has an Mz molecular weight of at least 36,000 kDa. 89. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the emulsion styrene-butadiene rubber has an Mz molecular weight of at least 38,000 kDa. 90. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the ratio of the Mz molecular weight of the emulsion styrene-butadiene rubber to the number average molecular weight is at least 175. 91. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the ratio of the Mz molecular weight of the emulsion styrene-butadiene rubber to the number average molecular weight is at least 180. 92. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the ratio of the Mz molecular weight of the emulsion styrene-butadiene rubber to the number average molecular weight is at least 190. 93. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the ratio of the Mz molecular weight of the emulsion styrene-butadiene rubber to the number average molecular weight is at least 200. 94. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the ratio of the Mz molecular weight of the emulsion styrene-butadiene rubber to the number average molecular weight is at least 210. 95. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the ratio of the Mz molecular weight of the emulsion styrene-butadiene rubber to the number average molecular weight is at least 215. 96. The emulsion styrene-butadiene rubber composition as defined in 80, which contains 5 phr to 100 phr < of oil. 97. The emulsion styrene-butadiene rubber composition as defined in 80, which contains 5 phr to 100 phr of resin. 98. The emulsion styrene-butadiene rubber composition as defined in 80, which contains 10 phr to 8 phr of oil. 99. The emulsion styrene-butadiene rubber composition as defined in 98, which contains 6 phr to 80 phr of resin. 100. An emulsion styrene-butadiene rubber composition as defined in paragraph 80, wherein the emulsion styrene-butadiene rubber composition contains 15 phr to 60 phr of oil. 101. An emulsion styrene-butadiene rubber composition as defined in 100, wherein said emulsion styrene-butadiene rubber composition contains 8 phr to 60 phr of resin. 102. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the emulsion styrene-butadiene rubber composition contains 20 phr to 40 phr of oil. 103. An emulsion styrene-butadiene rubber composition as defined in paragraph 102, wherein said emulsion styrene-butadiene rubber composition contains 10 phr to 35 phr of resin. 104. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the emulsion styrene-butadiene rubber composition contains 20 phr to 30 phr of oil. 105. An emulsion styrene-butadiene rubber composition as defined in paragraph 104, wherein said emulsion styrene-butadiene rubber composition contains 10 phr to 15 phr of resin. 106. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the emulsion styrene-butadiene rubber composition contains 22 phr to 28 phr of oil. 107. An emulsion styrene-butadiene rubber composition as defined in paragraph 106, wherein said emulsion styrene-butadiene rubber composition contains 10 phr to 14 hr of resin. 108. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the oil is a petroleum extender oil selected from the group consisting of highly aromatic petroleum, aromatic petroleum, naphthenic petroleum, and paraffinic petroleum. 109. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the oil is a triglyceride oil. 110. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the oil is a vegetable oil. 111. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the oil is a triglyceride oil selected from the group consisting of soybean oil, sunflower oil, canola (rapeseed) oil, corn oil, coconut oil, cottonseed oil, olive oil, palm oil, peanut oil, and safflower oil. 112. An emulsion styrene-butadiene rubber composition as defined in 109, wherein the triglyceride oil is soybean oil. 113. An emulsion styrene-butadiene rubber composition as defined in 109, wherein the triglyceride oil is corn oil. 114. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the emulsion styrene-butadiene rubber has a polydispersity of at least 40. 115. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the emulsion styrene-butadiene rubber has a polydispersity of at least 45. 116. An emulsion styrene-butadiene rubber composition as defined in 80, wherein the emulsion styrene-butadiene rubber has a polydispersity of at least 50. 117. A rubber composition comprising (1) a rubbery polymer, (2) a hydrocarbon resin, and (3) an oil, said rubber composition having only one glass transition temperature, and said rubber composition being free of compounding additives. 118. A rubber composition as defined in paragraph 117, wherein the oil is present at a level of at least 5 phr. 119. A rubber composition as defined in paragraph 117, wherein the resin is present at a level of at least 5 phr. 120. A rubber composition as defined in paragraph 117, wherein the rubbery polymer is a polydiene rubber. 121. The rubber composition as defined in paragraph 117, wherein the rubbery polymer is selected from the group consisting of polyisoprene rubber, polybutadiene rubber, styrene butadiene rubber, and styrene-isoprene-butadiene rubber. 122. A rubber composition as defined in paragraph 117, wherein the oil is a triglyceride oil. 123. A rubber composition as defined in paragraph 122, wherein the triglyceride oil is a vegetable oil. 124. A rubber composition as defined in paragraph 122, wherein the triglyceride oil is soybean oil. 125. A rubber composition as defined in 117, wherein the compounding additives include fillers, curatives, plasticizers, and cure accelerators. 126. A rubber composition comprising (1) a rubbery polymer, (2) a hydrocarbon resin, and (3) a triglyceride oil, the rubber composition having only one glass transition temperature. 127. A rubber composition as defined in paragraph 126, wherein the oil is present at a level of at least 5 phr. 128. A rubber composition as defined in paragraph 127, wherein the resin is present at a level of at least 5 phr. 129. A rubber composition as defined in paragraph 126, wherein the rubbery polymer is a polydiene rubber. 130. A rubber composition as defined in paragraph 127, further comprising a reinforcing filler. 130. A rubber composition as defined in paragraph 127, wherein the rubber composition is cured. 131. A rubber composition as defined in 130, wherein the rubber composition is cured with sulfur. 132. A rubber composition as defined in paragraph 126, wherein the oil is a triglyceride oil. 133. A rubber composition as defined in paragraph 132, wherein the triglyceride oil is a vegetable oil. 134. A rubber composition as defined in paragraph 133, wherein the vegetable oil is soybean oil. 135. A tire comprising a generally toroidal carcass having a circumferential tread, two sidewalls, two spaced apart beads, at least one ply extending from bead to bead, and sidewalls extending radially from and connecting said tread to said beads, said tread adapted for ground contact, and at least one component of said tire comprising a rubber composition as defined in any of the foregoing. 136. A tire comprising a generally toroidal carcass having a circumferential tread, two sidewalls, two spaced apart beads, at least one ply extending from bead to bead, and sidewalls extending radially from and connecting said tread to said beads, said tread adapted for ground contact, said tread comprising a rubber composition as defined in any of 1 to 134. 137. A tire comprising a generally toroidal carcass having a circumferential tread, two sidewalls, two spaced apart beads, at least one ply extending from bead to bead, and sidewalls extending radially from and connecting said tread to said beads, said tread adapted for ground contact, and said sidewalls comprising a rubber composition as defined in any of 1 to 134. 138. A method for preparing a resin-modified, oil-extended rubber composition, comprising: (1) blending an oil composition into rubber cement, the resin-modified, oil-extended rubber composition comprising oil and a hydrocarbon resin; and (2) recovering the resin-modified, oil-extended rubber from the rubber cement. 139. 138. A method for recovering resin-modified oil-extended rubber from rubber cement by removing the organic solvent. 140. A method of recovering resin-modified oil-extended rubber from rubber cement by settling, 139. 141. A method of recovering resin-modified oil-extended rubber from rubber cement by steam distillation, 139. 142. A method of recovering resin-modified oil-extended rubber from rubber cement by filtration, 139. 143. A method of recovering resin-modified oil-extended rubber from rubber cement by centrifugation, 139. 144. The method of claim 139, wherein the resin-modified oil-extended rubber is recovered from rubber cement by drying. 145. The method of claim 138, wherein the oil is a triglyceride oil. 146. Blend about 5 phr to about 60 phr of triglyceride oil into rubber cement. 138 ways to do this. 147. The method of 138, wherein the rubber is emulsion styrene-butadiene rubber. 148. The method of 138, wherein the rubber is a high cis-1,4-polybutadiene rubber. 149. The method of 138, wherein the rubber is high cis-1,4-polyisoprene rubber. 150. The method of 149, wherein the high cis-1,4-polyisoprene rubber is neodymium polyisoprene rubber. 151. The method of 149, wherein the high cis-1,4-polyisoprene rubber is titanium polyisoprene rubber. 152. The method of 149, wherein the high cis-1,4-polyisoprene rubber is lithium polyisoprene rubber. 153. The method of 147, wherein about 10 phr to about 40 phr of triglyceride oil is blended into an emulsion styrene-butadiene rubber cement. 154. 138 ways to make oil free of petroleum. 155. The method of 145, wherein the triglyceride oil is selected from the group consisting of soybean oil, sunflower oil, canola (rapeseed) oil, corn oil, coconut oil, cottonseed oil, olive oil, palm oil, peanut oil, and safflower oil. 156. The method of 145, wherein the triglyceride oil is soybean oil. 157. The method of 145, wherein the triglyceride oil is corn oil. 158. A resin-modified rubber composition prepared by the method specified in any of paragraphs 138 to 157. 159. A tire having a component including the rubber composition of 158. 160. A method for preparing a resin-modified emulsion rubber composition, comprising: (1) blending an oil composition into a rubber emulsion, the oil composition comprising an oil and a hydrocarbon resin; and (2) recovering the resin-modified rubber from the rubber emulsion. 161. The method of 160, wherein the resin-modified rubber is recovered from the rubber emulsion by coagulation. 162. The method of 160, wherein the oil is a triglyceride oil. 163. 160 ways in which the oil is vegetable oil. 164. The method of 162, wherein about 5 phr to about 60 phr of triglyceride oil is blended into the rubber emulsion. 165. The method of 160, wherein the rubber is emulsion styrene-butadiene rubber. 166. The method of 165, wherein the emulsion styrene-butadiene rubber has a bound styrene content in the range of 22% to 60% by weight and a bound butadiene content in the range of 40% to 78% by weight. 167. A method of 166, wherein 60% to 70% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are trans 1,4-microstructure, 13% to 23% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are cis-microstructure, and 12% to 22% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are vinyl-microstructure. 168. The method of 167, wherein the emulsion styrene-butadiene rubber has a bound styrene content in the range of 24% to 32% by weight and a bound butadiene content in the range of 68% to 76% by weight. 169. A method according to claim 168, wherein 62% to 68% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in a trans 1,4-microstructure, 15% to 21% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in a cis-microstructure, and 14% to 20% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in a vinyl-microstructure. 170. The method of 169, wherein the emulsion styrene-butadiene rubber has a bound styrene content in the range of 22% to 30% by weight and a bound butadiene content in the range of 70% to 78% by weight. 171. The method of 170, wherein 63% to 67% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in the trans 1,4-microstructure, 16% to 20% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in the cis-microstructure, and 15% to 19% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in the vinyl-microstructure. 172. The method of 170, wherein 64% to 66% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in the trans 1,4-microstructure, 17% to 19% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in the cis-microstructure, and 16% to 18% of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are in the vinyl-microstructure. 173. The method of 162, wherein about 10 phr to about 40 phr of triglyceride oil is blended into a styrene-butadiene rubber emulsion. 174. 160 methods for making resin-modified styrene-butadiene rubber petroleum-free. 175. The method of 162, wherein the triglyceride oil is selected from the group consisting of soybean oil, sunflower oil, canola (rapeseed) oil, corn oil, coconut oil, cottonseed oil, olive oil, palm oil, peanut oil, and safflower oil. 176. The method of 162, wherein the triglyceride oil is soybean oil. 177. The method of 162, wherein the triglyceride oil is corn oil. 178. Any of the methods 138-177, wherein the resin is a hydrocarbon resin. 179. Any of the methods 138 to 177, wherein the resin is a phenolic / acetylene resin. 180. Any of the methods 138 to 177, wherein the resin is a terpene phenolic resin. 181. Any of the methods 138 to 177, wherein the resin is a rosin-derived resin. 182. Any of the methods 138 to 177, wherein the resin is a coumarone-indene resin. 183. Any of the methods 138 to 177, wherein the resin is a petroleum resin. 184. The method of any of 138 to 177, wherein the resin is a terpene polymer resin. 185. The method of any of 138 to 177, wherein the resin is a styrene / α-methylstyrene resin. 186. A resin-modified rubber composition prepared by a method specified in any of paragraphs 160 to 185. 187. A tire having a component containing a resin-modified rubber composition as specified in any of 160 to 185. 188. A rubber composition as defined in any of paragraphs 1 to 134, wherein the resin is a hydrocarbon resin. 189. A rubber composition as defined in any of paragraphs 1 to 134, wherein the resin is a phenolic / acetylene resin. 190. A rubber composition as defined in any of paragraphs 1 to 134, wherein the resin is a terpene phenolic resin. 191. A rubber composition as defined in any of paragraphs 1 to 134, wherein the resin is a rosin-derived resin. 192. A rubber composition as defined in any of paragraphs 1 to 134, wherein the resin is a coumarone-indene resin. 193. A rubber composition as defined in any of paragraphs 1 to 134, in which the resin is a petroleum resin. 194. A rubber composition as defined in any of paragraphs 1 to 134, wherein the resin is a terpene polymer resin. 195. A rubber composition as defined in any of paragraphs 1 to 134, wherein the resin is a styrene / α-methylstyrene resin. 196. A solution styrene-butadiene rubber composition comprising a solution styrene-butadiene rubber, at least 5 phr of oil, and at least 5 phr of resin, wherein the solution styrene-butadiene rubber has a bound styrene content in the range of 10% to 60% by weight and a bound styrene content of 4. and a solution styrene-butadiene rubber having bound butadiene in the range of 0% to 90% by weight, wherein 25% to 55% of the bound butadiene repeat units in the solution styrene-butadiene rubber are in the trans 1,4-microstructure, 25% to 50% of the bound butadiene repeat units in the solution styrene-butadiene rubber are in the cis-microstructure, and 5% to 45% of the bound butadiene repeat units in the solution styrene-butadiene rubber are in the vinyl microstructure, and the solution styrene-butadiene rubber has an M of at least 800 kDa. z The molecular weight of the solution styrene-butadiene rubber is z A solution styrene-butadiene rubber composition having a ratio of molecular weight to number average molecular weight of at least 1.58. 197. A solution styrene-butadiene rubber composition as defined in paragraph 196, wherein the solution styrene-butadiene rubber has a bound styrene content within the range of 24% to 32% by weight and a bound butadiene content within the range of 68% to 76% by weight. 198. A solution styrene-butadiene rubber composition as defined in paragraph 196, wherein the solution styrene-butadiene rubber has a bound styrene content in the range of 27% to 30% by weight and a bound butadiene content in the range of 70% to 73% by weight. 199. A solution styrene-butadiene rubber composition as defined in paragraph 196, wherein 30% to 52% of the bound butadiene repeat units in the solution styrene-butadiene rubber are in the trans 1,4-microstructure, 25% to 48% of the bound butadiene repeat units in the solution styrene-butadiene rubber are in the cis-microstructure, and 6% to 45% of the bound butadiene repeat units in the solution styrene-butadiene rubber are in the vinyl-microstructure. 200. A solution styrene-butadiene rubber composition as defined in paragraph 196, wherein 40% to 50% of the bound butadiene repeat units in the solution styrene-butadiene rubber are in the trans 1,4-microstructure, 30% to 46% of the bound butadiene repeat units in the solution styrene-butadiene rubber are in the cis-microstructure, and 8% to 28% of the bound butadiene repeat units in the solution styrene-butadiene rubber are in the vinyl-microstructure. 201. A solution styrene-butadiene rubber composition as defined in 196, wherein the solution styrene-butadiene rubber has an Mz molecular weight of at least 810 kDa. 202. A solution styrene-butadiene rubber composition as defined in 196, wherein the solution styrene-butadiene rubber has an Mz molecular weight of at least 820 kDa. 203. A solution styrene-butadiene rubber composition as defined in 196, wherein the solution styrene-butadiene rubber has an Mz molecular weight of at least 830 kDa. 204. A solution styrene-butadiene rubber composition as defined in 196, wherein the solution styrene-butadiene rubber has an Mz molecular weight of at least 835 kDa. 206. A solution styrene-butadiene rubber composition as defined in 196, wherein the solution styrene-butadiene rubber has an Mz molecular weight of at least 840 kDa. 207. A solution styrene-butadiene rubber composition as defined in 196, wherein the ratio of the Mz molecular weight to the number average molecular weight of the solution styrene-butadiene rubber is at least 1.60. 208. A solution styrene-butadiene rubber composition as defined in 196, wherein the ratio of the Mz molecular weight to the number average molecular weight of the solution styrene-butadiene rubber is at least 1.62. 209. The solution styrene-butadiene rubber composition according to item 196, wherein the solution styrene-butadiene rubber composition contains 5 phr to 100 phr of oil. 210. The solution styrene-butadiene rubber composition according to item 209, wherein the solution styrene-butadiene rubber composition contains 5 phr to 100 phr of resin. 211. The solution styrene-butadiene rubber composition according to item 196, wherein the solution styrene-butadiene rubber composition contains 10 phr to 80 phr of oil. 212. The solution styrene-butadiene rubber composition according to item 211, wherein the solution styrene-butadiene rubber composition contains 6 phr to 80 phr of resin. 213. The solution styrene-butadiene rubber composition according to item 196, wherein the solution styrene-butadiene rubber composition contains 15 phr to 60 phr of oil. 214. The solution styrene-butadiene rubber composition according to item 213, wherein the solution styrene-butadiene rubber composition contains 8 phr to 60 phr of resin. 215. The solution styrene-butadiene rubber composition according to item 196, wherein the solution styrene-butadiene rubber composition contains 20 phr to 40 phr of oil and is the solution styrene-butadiene rubber composition according to item 196. 216. The solution styrene-butadiene rubber composition according to item 215, wherein the solution styrene-butadiene rubber composition contains 10 phr to 35 phr of resin. 217. The solution styrene-butadiene rubber composition according to item 196, wherein the solution styrene-butadiene rubber composition contains 20 phr to 30 phr of oil. [[ID=二十]]219. The solution styrene-butadiene rubber composition according to item 217, wherein the solution styrene-butadiene rubber composition contains 10 phr to 15 phr of resin. 220. The solution styrene-butadiene rubber composition according to item 196, wherein the solution styrene-butadiene rubber composition contains 22 phr to 28 phr of oil. 221. A solution styrene-butadiene rubber composition as defined in 220, wherein the emulsion styrene-butadiene rubber composition contains 10 phr to 14 phr of resin. 222. A solution styrene-butadiene rubber composition as defined in 196, wherein the oil is a petroleum extender oil selected from the group consisting of highly aromatic petroleum, aromatic petroleum, naphthenic petroleum, and paraffinic petroleum. 223. A solution styrene-butadiene rubber composition as defined in 196, wherein the oil is a triglyceride oil. 224. A solution styrene-butadiene rubber composition as defined in 196, wherein the oil is a vegetable oil. 225. A solution styrene-butadiene rubber composition as defined in paragraph 196, wherein the oil is a triglyceride oil selected from the group consisting of soybean oil, sunflower oil, canola (rapeseed) oil, corn oil, coconut oil, cottonseed oil, olive oil, palm oil, peanut oil, and safflower oil. 226. A solution styrene-butadiene rubber composition as defined in 223, wherein the triglyceride oil is soybean oil. 227. A solution styrene-butadiene rubber composition as defined in 223, wherein the triglyceride oil is corn oil. 228. A solution styrene-butadiene rubber composition as defined in 196, wherein the solution styrene-butadiene rubber has a polydispersity of at least 1.30. 229. A solution styrene-butadiene rubber composition as defined in 196, wherein the solution styrene-butadiene rubber has a polydispersity of at least 1.31. 230. A solution styrene-butadiene rubber composition as defined in 196, wherein the solution styrene-butadiene rubber has a polydispersity of at least 1.32. 231. A tire comprising a generally toroidal carcass having a circumferential tread, two sidewalls, two spaced apart beads, at least one ply extending from bead to bead, and sidewalls extending radially from and connecting said tread to said beads, said tread adapted for ground contact, and at least one component of said tire comprising a rubber composition as defined in any of 196 to 230. 232. A tire comprising a generally toroidal carcass having a circumferential tread, two sidewalls, two spaced apart beads, at least one ply extending from bead to bead, and sidewalls extending radially from and connecting said tread to said beads, said tread adapted for ground contact, said tread comprising a rubber composition as specified in any of 196 to 230. 233. A tire comprising a generally toroidal carcass having a circumferential tread, two sidewalls, two spaced apart beads, at least one ply extending from bead to bead, and sidewalls extending radially from and connecting said tread to said beads, said tread adapted for ground contact, and said sidewalls comprising a rubber composition as specified in any of 196 to 230. 234. A tire including a generally toroidal carcass having a peripheral tread, two sidewalls, two spaced apart beads, at least one ply extending from bead to bead, and sidewalls extending radially from and connecting said tread to said beads, said tread adapted for ground contact, and said innerliner being any of the following: 1 to 134 or 19 A tire comprising a rubber composition as defined in any one of paragraphs 6 to 230. 235. A tire comprising a generally toroidal carcass having a circumferential tread, two sidewalls, two spaced apart beads, at least one ply extending from bead to bead, and sidewalls extending radially from and connecting said tread to said beads, said tread adapted for ground contact, and said innerliner comprising a rubber composition as specified in any of 1 to 134 or 196 to 230. 236. A power transmission belt including a compression section, a tension section, and a load section, wherein the compression section, the tension section, and / or the load section comprises a rubber composition as specified in any of 1 to 134 or 196 to 230. 237. A conveyor belt comprising a carry cover layer, a reinforcing layer, and a pulley cover layer, wherein the carry cover layer and / or the pulley cover layer comprises a rubber composition specified in any of 1 to 134 or 196 to 230. 238. Trucks containing a rubber composition as specified in either 1 to 134 or 196 to 230. 239. Air springs containing a rubber composition as specified in either 1 to 134 or 196 to 230. 240. An asphalt composition comprising asphalt and a rubber composition as specified in either 1 to 134 or 196 to 230. 241. An adhesive composition containing a rubber composition as specified in any of paragraphs 1 to 134 or 196 to 230. 242. Shoe soles containing a rubber composition as specified in either 1 to 134 or 196 to 230. 243. A windshield wiper blade comprising a head, a body, a neck portion, a rotating portion, and an edge portion, wherein the head, body, neck portion, rotating portion, and / or edge portion comprise a rubber composition as specified in any of 1 to 134 or 196 to 230. 244. Bowling balls containing a rubber composition specified in either 1 to 134 or 196 to 230. 245. Energy-absorbing pads containing a rubber composition specified in either 1 to 134 or 196 to 230. 246. Anti-vibration pads containing a rubber composition specified in either 1 to 134 or 196 to 230. 247. Seals containing a rubber composition specified in either 1 to 134 or 196 to 230. 248. Gaskets containing a rubber composition as specified in either 1 to 134 or 196 to 230. 249. A golf ball comprising a core and a cover, wherein the core comprises a rubber composition specified in any of 1 to 134 or 196 to 230. 250. A tire comprising a generally toroidal carcass having a circumferential tread, two sidewalls, two spaced apart beads, at least one ply extending from bead to bead, and sidewalls extending radially from and connecting said tread to said bead, said tread adapted for contact with the ground, and at least one component of said tire being comprised of a solution styrene-butadiene rubber composition comprising solution styrene-butadiene rubber, at least 5 phr of oil, and at least 5 phr of resin, and wherein the solution styrene-butadiene rubber has a bound styrene content in the range of 10% to 60% by weight and a bound butadiene content in the range of 40% to 90% by weight, wherein 30% to 55% of the bound butadiene repeat units in the solution styrene-butadiene rubber are trans 1,4-microstructure, 25% to 50% of the bound butadiene repeat units in the solution styrene-butadiene rubber are cis-microstructure, and 5% to 45% of the bound butadiene repeat units in the solution styrene-butadiene rubber are vinyl-microstructure, and the solution styrene-butadiene rubber has an M z The molecular weight of the solution styrene-butadiene rubber is z A tire having a ratio of molecular weight to number average molecular weight of at least 1.58. 251. The method of 138, wherein the rubber is high cis-1,4-polybutadiene made utilizing a nickel-based catalyst system. 252. The method of 138, wherein the rubber is a high cis-1,4-polybutadiene made utilizing a rare earth metal-based catalyst system. 253. The method of 138, wherein the rubber is high cis-1,4-polybutadiene made utilizing a lanthanum-based catalyst system. 254. The method of 253, wherein the lanthanum is a metal selected from the group consisting of cerium, lanthanum, praseodymium, neodymium, and gadolinium. 255. The method of 138, wherein the rubber is polybutadiene made utilizing an anionic initiator. 256. The method of 138, wherein the rubber is polybutadiene made utilizing a lithium initiator. 257. The method of 256, wherein the lithium initiator is an alkyllithium compound. 258. A golf ball as defined in 249, in which the rubber composition is cured using a peroxide cure system.

Claims

1. 1. An oil-extended solution-polymerization-produced styrene-butadiene rubber composition comprising 100 parts by weight of a solution-polymerization-produced styrene-butadiene rubber, at least 5 phr of a triglyceride oil, and at least 5 phr of a hydrocarbon resin, wherein the solution-polymerization-produced styrene-butadiene rubber has a bound styrene content in the range of 10% to 60% by weight and a bound butadiene content in the range of 40% to 90% by weight, and 25% to 55% of the bound butadiene repeat units in the solution-polymerization-produced styrene-butadiene rubber are in a trans 1,4-microstructure. wherein 25% to 50% of the bound butadiene repeat units in the solution polymerization prepared styrene-butadiene rubber are in cis-microstructure and 5% to 45% of the bound butadiene repeat units in the solution polymerization prepared styrene-butadiene rubber are in vinyl-microstructure, the solution polymerization prepared styrene-butadiene rubber has an Mz molecular weight of at least 800 kDa, and the ratio of Mz molecular weight to number average molecular weight of the solution polymerization prepared styrene-butadiene rubber is at least 1.

58.

2. The rubber composition of claim 1 , wherein the rubber composition has only one glass transition temperature.

3. 3. The rubber composition according to claim 1, wherein the triglyceride oil is selected from the group consisting of soybean oil, sunflower oil, canola (rapeseed) oil, corn oil, coconut oil, cottonseed oil, olive oil, palm oil, peanut oil, and safflower oil.

4. 4. The rubber composition according to claim 1, 2 or 3, wherein the hydrocarbon resin is selected from the group consisting of coumarone-indene resin, petroleum resin, terpene polymer resin, and styrene / α-methylstyrene resin.

5. 5. The rubber composition of claim 1, 2, 3 or 4, wherein the solution polymerization prepared styrene-butadiene rubber has a Mz molecular weight of at least 840 kDa, and the ratio of Mz molecular weight to number average molecular weight of the solution polymerization prepared styrene-butadiene rubber is at least 1.

62.

6. 6. A tire comprising a generally toroidal carcass having a circumferential tread, two sidewalls, two spaced apart beads, at least one ply extending from bead to bead, and sidewalls extending radially from and connecting the tread to the beads, the tread adapted for contact with the ground, and at least one of the tire components comprising the rubber composition of any one of claims 1 to 5.

7. 7. Tire according to claim 6, characterized in that the tread comprises the rubber composition according to any one of claims 1 to 5.

8. 10. A method for preparing the oil-extended solution polymerization-made styrene-butadiene rubber composition of claim 1, comprising the steps of: (1) blending an oil composition into a solution polymerization-made styrene-butadiene rubber cement, wherein the oil composition comprises a triglyceride oil and a hydrocarbon resin; and (2) recovering the oil-extended solution polymerization-made styrene-butadiene rubber composition from the cement.

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