Coupled radial anionic polymers
View Patent ↗The present invention is a coupled radial anionic polymer comprising a polyhedral oligosilsesquioxane [POSS] of the formula [R—SiO 3/2 ] n . POSS compounds having R=vinyl, glycidyldimethyl silyl, and isobutyl have been found effective in coupling anionic living polymers to yield radial polymers having 2 to 10 arms. Radial polymers of the present invention have been formed using POSS octamers and mixtures of POSS octamers, decamers and dodecamers. The present invention also relates to a process for coupling living anionic polymers with POSS compounds.
1. A radial polymer having at least two arms wherein each arm is comprised of at least one anioncially polymerizable monomer chosen from the group consisting of monovinyl arenes and conjugated dienes and the arms are joined at a polyhedral oligosilsesquioxane coupling agent of the formula [R—SiO 3/2 ] n wherein n ranges from 6 to 12, and R is an organo substituent.
2. The radial polymer of claim 1 wherein R is selected from the group consisting of olefinic hydrocarbons, aliphatic hydrocarbons, aromatic hydrocarbons, organo halides and organo silyl glycidyl epoxies.
3. The radial polymer of claim 2 wherein R is a vinyl group of the formula [—CH═CH 2 ] and the coupling agent is a mixture of species having n=8, 10 and 12.
4. The radial polymer of claim 2 wherein R is an organo silyl glycidyl epoxy of the formula [—O—Si(CH 3 ) 2 —(CH 2 ) 2 —O—CH 2 —CH(O)CH 2 ] and n=8.
5. The radial polymer of claim 2 wherein the number of coupled arms is 2 to 10.
6. The radial polymer of claim 2 wherein R is an isobutyl group and n=8.
7. The radial polymer of claim 1 wherein the polymerizable monomer is predominantly butadiene or isoprene.
8. The radial polymer of claim 1 wherein the polymerizable monomer is predominantly styrene.
9. The radial polymer of claim 1 having at least one polymeric block predominantly composed of styrene and at least one polymeric block predominantly composed of a conjugated diene.
10. The radial polymer of claim 7 wherein the polymer is hydrogenated.
11. The radial polymer of claim 9 wherein the polymeric blocks predominantly composed of a conjugated diene are selectively hydrogenated.
12. A process for making a radial polymer having at least two arms, wherein each arm comprises at least one anionically polymerizable monomer, and a polyhedral oligosilsesquioxane coupling agent of the formula [R—SiO 3/2 ] n wherein n ranges from 6 to 12, and R is an organo substituent comprising:
a) initiating polymerization of a first anionically polymerizable monomer in an inert hydrocarbon solvent using an alkali metal initiator;
b) optionally adding a polar polymerization modifier;
c) optionally adding a second anionically polymerizable monomer;
d) adding a sufficient amount of coupling agent to produce a coupled polymer;
e) optionally hydrogenating the coupled polymer using a Group VIII transition metal based catalyst; and
f) recovering the coupled polymer.
13. The process of claim 12 wherein the polar modifier is selected from the group consisting of diethyl ether, ortho dimethoxy benzene, and 1,2-diethoxy propane.
14. The process of claim 12 wherein the organo lithium initiator is selected from the group consisting of nBuLi, sBuLi and tBuLi.
15. The process of claim 12 wherein the Group VIII transition metal is selected from the group consisting of nickel or cobalt.
16. The process of claim 12 wherein the first anionically polymerizable monomer is selected from the group consisting of styrene, butadiene and isoprene.
17. The process of claim 12 wherein the first anionically polymerizable monomer is styrene and the second anionically polymerizable monomer is a conjugated diene.
18. The process of claim 12 wherein the entire amount of coupling agent is added at the beginning of the coupling reaction of step d).
19. The process of claim 12 wherein the coupling agent is continuously added over a 30 minute period beginning at the onset of the coupling reaction of step d).
20. The process of claim 12 wherein the amount of coupling agent is such that the molar ratio of Li to coupling agent is in the range of from about 1 to about 14.
21. The process of claim 12 wherein the amount of coupling agent is such that the molar ratio of Li to coupling agent is in the range of from about 1 to about 8.