Functionalized polymer
A method for providing a polymer having terminal functionality involves reacting a terminally active polymer with an α,β-ethylenically unsaturated compound that includes a group 2-13 element so as to provide a functionalized polymer. The resulting polymer exhibits enhanced interactivity with particulate fillers and can be used in the manufacture of vulcanizates.
1. A method of providing terminal functionality to a polymer, said method comprising reacting a terminally active polymer that comprises polyene mer with an α,β-ethylenically unsaturated compound having the general formula
where each R independently is a hydrogen atom or C 1 -C 10 alkyl group, M is a group 2-13 element, y and z are integers with the provisos that z is not zero and y+z is equal to a valence of M, and each X independently is R 1 , OR 1 , OC(O)R 1 , C(O)OR 1 or NR 1 2 in which each R 1 independently is a C 1 -C 30 alkyl group, thereby providing said terminal functionality to said polymer.
2. The method of claim 1 wherein said terminally active polymer comprises polydiene mer.
3. The method of claim 2 wherein said terminally active polymer is provided in the presence of a lanthanide-based catalyst.
4. The method of claim 1 wherein said terminally active polymer further comprises vinyl aromatic mer.
5. The method of claim 4 wherein said terminally active polymer is provided in the presence of an anionic initiator.
6. The method of claim 1 wherein z is 1 and wherein M is B and y is 2, M is Al and y is 2, or M is Zn and y is 1.
7. The method of claim 1 wherein said α,β-ethylenically unsaturated compound has the general formula
where R″ is a hydrogen atom or C 1 -C 3 alkyl group, M is a group 2-13 element, y and z are integers with the provisos that z is not zero and y+z is equal to a valence of M, and each X independently is R 1 , OR 1 , OC(O)R 1 , C(O)OR 1 or NR 1 2 in which each R 1 independently is a C 1 -C 30 alkyl group.
8. The method of claim 1 wherein said α,β-ethylenically unsaturated compound has the general formula
where R′ is a C 1 -C 10 alkyl group, M is a group 2-13 element, y and z are integers with the provisos that z is not zero and y+z is equal to a valence of M, and each X independently is R 1 , OR 1 , OC(O)R 1 , C(O)OR 1 or NR 1 2 in which each R 1 independently is a C 1 -C 30 alkyl group.
9. The method of claim 1 wherein said α,β-ethylenically unsaturated compound has the general formula
where each R′ independently is a C l -C 10 alkyl group, M is a group 2-13 element, y and z are integers with the provisos that z is not zero and y+z, is equal to a valence of M, and each X independently is R 1 , OR 1 , OC(O)R 1 , C(O)OR 1 or NR 1 2 in which each R 1 independently is a C 1 -C 30 alkyl group.
10. The method of claim 7 wherein z is 1 and wherein M is B and y is 2, M is Al and y is 2, or M is Zn and y is 1.
11. A terminally functional polymer defined by the general formula
wherein
π is a polymer chain that comprises ethylenic unsaturation,
n is an integer of from 1 to 10 inclusive,
each R is a hydrogen atom or C 1 -C 10 alkyl group,
M is a group 2-13 element,
y and z are integers with the provisos that z is not zero and y+z is equal to a valence of M, and
each X independently is R 1 , OR 1 , OC(O)R 1 , C(O)OR 1 or NR 1 2 in which each R 1 independently is a C 1 -C 30 alkyl group.
12. The polymer of claim 11 wherein said polymer chain comprises polydiene mer.
13. The polymer of claim 12 wherein said polymer chain further comprises vinyl aromatic mer.
14. The polymer of claim 11 wherein z is 1 and wherein M is B and y is 2, M is Al and y is 2, or M is Zn and y is 1.
15. The polymer of claim 11 wherein n is an integer of from 1 to 5 inclusive.
16. The polymer of claim 11 wherein each R is a hydrogen atom.
17. The polymer of claim 11 wherein one R is a C 1 -C 10 alkyl group and the other two are hydrogen atoms.
18. The polymer of claim 11 wherein one R is a hydrogen atom and the other two are C 1 -C 10 alkyl groups.
19. The polymer of claim 11 wherein each X is R 1 .
20. The polymer of claim 19 wherein each R 1 is a C 1 -C 6 alkyl group.