Process for preparing block copolymer and resulting composition
View Patent ↗Lithium-terminated polymers of one or more conjugated dienes and of one or more mono alkenyl arenes are coupled by reaction with an alkoxy silane coupling agent having the formula R x —Si—(OR′) y , where x is 0 or 1, x+y=4, R and R′ are the same or different, R is selected from aryl hydrocarbon radicals, linear alkyl hydrocarbon radicals and branched alkyl hydrocarbon radicals, and R′ is selected from linear and branched alkyl hydrocarbon radicals, such that the resulting polymer composition contains less than about ten weight percent of uncoupled polymer diblock. The polymer compositions are subsequently selectively hydrogenated, and are useful in a variety of compounds and end use applications.
1. A process for making a hydrogenated block copolymer, comprising the steps of:
a. reacting a living lithium-terminated polymer having the formula P-Li where P is a copolymer chain of one or more conjugated dienes having from 4 to 12 carbon atoms and one or more mono alkenyl arenes having from 8 to 18 carbon atoms with an alkoxy silane coupling agent having the formula R x —Si—(OR′) y , where x is 0 or 1, x+y=4, R and R′ are the same or different, R is selected from aryl hydrocarbon radicals, linear alkyl hydrocarbon radicals and branched alkyl hydrocarbon radicals, and R′ is selected from linear and branched alkyl hydrocarbon radicals, and where the molar ratio of Si to Li is from about 0.35 to about 0.7, thereby forming a coupled polymer;
b. hydrogenating the coupled polymer under hydrogenation conditions to substantially saturate at least the olefinically derived double bonds of said coupled polymer without substantial degradation of the coupled polymer; and
c. recovering the resulting hydrogenated polymer;
wherein the resulting hydrogenated block copolymer comprises a mixture of from 0 to 5 weight percent tetra-branched block copolymer, from 0 to 60 weight percent tri-branched block copolymer, from 40 to 95 weight percent di-branched block copolymer and from 2 to 10 weight percent linear diblock copolymer.
2. The process according to claim 1 wherein said conjugated diene is selected from the group consisting of butadiene and isoprene and said mono alkenyl arene is styrene.
3. The process according to claim 2 wherein P is a block copolymer of styrene and butadiene with the butadiene block being adjacent to the lithium ion.
4. The process according to claim 3 wherein the styrene block has an average molecular weight of from about 3,000 to about 60,000 and said butadiene block has an average molecular weight of from about 20,000 to about 200,000.
5. The process according to claim 3 wherein said alkoxy silane coupling agent is a tetra alkoxy silane where x is zero and R′ is a linear or branched alkyl hydrocarbon radical having 1 to 12 carbon atoms.
6. The process according to claim 5 wherein said alkoxy silane coupling agent is tetramethoxy silane and wherein the coupled polymer is contacted with an alcohol prior to hydrogenation.
7. The process according to claim 6 wherein said alcohol is methanol and the molar ratio of methanol to Li is from 1 to 1.5 moles of methanol per mole of Li.
8. The process according to claim 5 wherein said alkoxy silane coupling agent is tetraethoxy silane.
9. The process according to claim 8 wherein the coupled polymer is contacted with an alcohol prior to hydrogenation.
10. The process according to claim 9 wherein said alcohol is methanol and the molar ratio of methanol to Li is from 0.05 to 0.5 moles of methanol per mole of Li.
11. The process according to claim 5 wherein said hydrogenation takes place at a temperature of between about 20° C. to about 60° C.
12. The process according to claim 11 wherein the catalyst used in the hydrogenation is selected from cobalt, nickel and titanium catalysts.
13. The process according to claim 12 wherein the coupled polymer is contacted with an alcohol prior to hydrogenation.
14. The process according to claim 3 wherein said alkoxy silane oupling agent is an alkyl trialkoxy silane.
15. The process according to claim 14 wherein said alkyl trialkoxy silane is methyl trimethoxy silane.
16. The process according to claim 15 wherein the coupled polymer is contacted with an alcohol prior to hydrogenation.
17. The process according to claim 16 wherein said alcohol is 2-ethyl hexanol and the molar ratio of alcohol to Li is from 0.05 to 0.5 moles of alcohol per mole of Li.
18. The process according to claim 3 wherein said alkoxy silane is an aryl trialkoxy silane.
19. The process according to claim 18 wherein said aryl trialkoxy silane is phenyl trimethoxy silane and the coupled polymer is contacted with an alcohol prior to hydrogenation.
20. The process according to claim 19 wherein said alcohol is 2-ethyl hexanol and the molar ratio of alcohol to Li is from 0.05 to 0.5 moles of alcohol per mole of Li.
21. The process according to claim 1 wherein the coupling efficiency is greater than 90%.
22. The process according to claim 1 wherein the molar ratio of Si to Li is from about 0.4 to about 0.55.
23. The polymer produced by the process of claim 7 .
24. The polymer produced by the process of claim 10 .
25. The polymer produced by the process of claim 17 .
26. The process according to claim 2 wherein P is a block copolymer of styrene and isoprene with the isoprene black being adjacent to the lithium ion.
27. The process according to claim 26 wherein the styrene block has an average molecular weight of from about 3,000 to about 60,000 and said isoprene block has an average molecular weight of from about 20,000 to about 200,000.
28. The process according to claim 26 wherein the alkoxy silane coupling agent is selected from tetramethoxy silane, tetraethoxy silane, tetrabutoxy silane, tetrakis(2-etylhexyloxy)silane, methyl trimnethoxy silane, methyl triethoxy silane, isobutyl trimethoxy silane and phenyl trimethoxy silane.
29. The process according to claim 4 wherein the alkoxy silane coupling agent is selected from tetramethoxy silane, tetraethoxy silane, tetrabutoxy silane, tetrakis(2-ethylhexyloxy)silane, methyl trimethoxy silane, methyl triethoxy silane, isobutyl trimethoxy silane and phenyl trimethoxy silane.