Resin modified oil extended rubber
This invention is based upon the unexpected finding that a hydrocarbon traction resin can be dispersed into the oil used in making an oil extended emulsion and solution rubbers to attain improved performance characteristics. For instance, this technique allows for the hydrocarbon traction resin to be incorporated into the rubber at a higher level than would ordinarily be possible using conventional mixing techniques. In tire tread compounds this provides improved wet traction characteristics without compromising cured stiffness (dry traction) and ultimate properties (chip/chunk resistance). This technique can be used to incorporate a resin into virtually any synthetic rubber that can benefit from being oil extended. It is of particular value in making 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.
1. A method for preparing a resin modified oil extended rubber composition which comprises: (1) blending an oil composition into a rubber cement, wherein the resin modified oil extended rubber composition is comprised of an oil and a hydrocarbon resin, and (2) recovering the resin modified oil extended rubber from the rubber cement, wherein the oil is present at a level of at least 5 phr, wherein the resin is present at a level of at least 5 phr, wherein the resin modified oil extended rubber composition is comprised of a solution styrene-butadiene rubber compositions having a bound styrene content which is within the range of 10 percent to 60 weight percent and a bound butadiene content which is within the range of 40 weight percent to 90 weight percent, wherein 25 percent to 55 percent of the bound butadiene repeat units in the solution styrene-butadiene rubber are of trans 1,4-microstructure, wherein 25 percent to 50 percent of the bound butadiene repeat units in the solution styrene-butadiene rubber are of cis-microstructure, and wherein 5 percent to 45 percent of the bound butadiene repeat units in the solution styrene-butadiene rubber are of vinyl-microstructure, wherein the solution styrene-butadiene rubber has a M z molecular weight of at least 800 kDa, and wherein the solution styrene-butadiene rubber has a ratio of Mz molecular weight to number average molecular weight of at least 1.58.
2. The method of claim 1 wherein the oil is a triglyceride oil.
3. The method of claim 2 wherein the oil is void of petroleum oils.
4. The method of claim 2 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.
5. The method of claim 4 wherein the triglyceride oil is soybean oil.
6. The method of claim 1 wherein the resin modified oil extended rubber is recovered from the rubber cement by removal of an organic solvent.
7. The method of claim 1 wherein the hydrocarbon resin is selected from the group consisting of phenol/acetylene resin, terpene phenol resins, rosin derived resins, coumarone-indene resins, terpene polymer resins, and styrene/a-methylstyrene resins.
8. The method of claim 1 wherein the oil is present at a level which is within the range of 10 phr to 40 phr.
9. The method of claim 1 wherein the resin is a polyterpene resin.
10. The method of claim 1 wherein the solution styrene-butadiene rubber has a bound styrene content which with is within the range of 24 percent to 32 weight percent and a bound butadiene content which is within the range of 68 weight percent to 76 weight percent.
11. The method of claim 10 wherein from 38 percent to 52 percent of the bound butadiene repeat units in the solution styrene-butadiene rubber are of trans 1,4-microstructure, 28 percent to 48 percent of the bound butadiene repeat units in the solution styrene-butadiene rubber are of cis-microstructure, and 6 percent to 30 percent of the bound butadiene repeat units in the solution styrene-butadiene rubber are of vinyl-microstructure.
12. The method of claim 1 wherein the solution styrene-butadiene rubber has a bound styrene content which with is within the range of 27 percent to 30 weight percent and a bound butadiene content which is within the range of 70 weight percent to 73 weight percent.
13. The method of claim 12 wherein from 40 percent to 50 percent of the bound butadiene repeat units in the solution styrene-butadiene rubber are be of trans 1,4-microstructure, 30 percent to 46 percent of the bound butadiene repeat units in the solution styrene-butadiene rubber are of cis-microstructure, and 8 percent to 28 percent of the bound butadiene repeat units in the solution styrene-butadiene rubber are of vinyl-microstructure.
14. The method of claim 1 wherein the solution styrene-butadiene rubber has a M z molecular weight of at least 820 kDa.
15. The method of claim 1 wherein the solution styrene-butadiene rubber has a M z molecular weight of at least 830 kDa.
16. The method of claim 1 wherein the solution styrene-butadiene rubber has a M z molecular weight of at least 835 kDa.
17. The method of claim 1 wherein the solution styrene-butadiene rubber has a M z molecular weight of at least 840 kDa.
18. The method of claim 1 wherein the solution styrene-butadiene rubber has a ratio of Mz molecular weight to number average molecular weight of at least 1.60.
19. The method of claim 1 wherein the solution styrene-butadiene rubber has a ratio of Mz molecular weight to number average molecular weight of at least 1.62.
20. A method for preparing a resin modified oil extended rubber composition which comprises: (1) blending an oil composition into a rubber cement or a rubber emulsion, wherein the resin modified oil extended rubber composition is comprised of an oil and a hydrocarbon resin, and (2) recovering the resin modified oil extended rubber from the rubber cement or the rubber emulsion, wherein the oil is present at a level of at least 5 phr, wherein the resin is present at a level of at least 5 phr, wherein the resin modified oil extended rubber composition is comprised of a high cis-polyisoprene rubber having a cis-microstructure content of at least 90 percent, wherein the high cis-polyisoprene rubber has a M2 molecular weight of at least 750,000 Da, and wherein the high cis-1,4-polyisoprene rubber has a ratio of Mz molecular weight to number average molecular weight of at least 2.5.
21. A method for preparing a resin modified oil extended rubber composition which comprises: (1) blending an oil composition into a rubber emulsion, wherein the resin modified oil extended rubber composition is comprised of an oil and a hydrocarbon resin, and (2) recovering the resin modified oil extended rubber from the rubber emulsion, wherein the oil is present at a level of at least 5 phr, wherein the resin is present at a level of at least 5 phr, wherein the resin modified oil extended rubber composition is comprised of an emulsion styrene-butadiene rubber composition having a bound styrene content which is within the range of 22 percent to 60 weight percent and a bound butadiene content which is within the range of 40 weight percent to 78 weight percent, wherein 60 percent to 70 percent of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are of trans 1,4-microstructure, wherein 13 percent to 23 percent of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are of cis-microstructure, and wherein 12 percent to 22 percent of the bound butadiene repeat units in the emulsion styrene-butadiene rubber are of vinyl-microstructure, wherein the emulsion styrene-butadiene rubber has a M z molecular weight of at least 15,000 kDa, and wherein the emulsion styrene-butadiene rubber has a ratio of Mz molecular weight to number average molecular weight of at least 50.
22. The method of claim 21 wherein the rubber cement or the rubber emulsion is a rubber emulsion, and wherein the resin modified oil extended rubber is recovered from the rubber emulsion by removal of water.