Amine-containing polyalkenyl coupling agents and polymers prepared therefrom
View Patent ↗A coupling agent having at least two alkenylbenzene groups each covalently bonded with a nitrogen of an amine compound. The coupling agent can have the structure I: wherein Z is an amine; R 1 -R 10 are each, independent of one another, H, an organic functional group or a terminal alkene, wherein at least one terminal alkene is on each benzene ring; m is an integer from 1 to 8.
1. A process for coupling a polymer comprising:
polymerizing a monomer or a mixture of monomers to form polymer segments; and
reacting the polymer segments with a coupling agent, the coupling agent having at least two alkenylbenzene groups each covalently bonded with a nitrogen of an amine compound.
2. The process of claim 1 , wherein the coupling agent has the structure I:
wherein
Z is an amine;
R 1 -R 10 are each, independent of one another, H, an organic functional group, or a terminal alkene, wherein at least one terminal alkene is on each benzene ring; and
m is an integer from 1 to 8,
wherein the process further comprises terminating the polymerization if any living polymer segments remain after reacting with the coupling agent.
3. The process of claim 2 , wherein Z is an acyclic amine.
4. The process of claim 3 , wherein the acyclic amine is one of alkylamine or an arylamine.
5. The process of claim 3 , wherein the acyclic amine is one of n-butyl amine or benzylamine.
6. The process of claim 2 , wherein Z is a cyclic amine.
7. The process of claim 2 , wherein one of the groups R 1 -R 5 and one of the groups R 6 -R 10 is a terminal alkene.
8. The process of claim 1 , wherein polymerizing the monomer or the mixture of monomers is initiated in the presence of an anionic initiator.
9. The process of claim 1 , wherein the monomers are selected from the group consisting of conjugated dienes, styrenes, and mixtures thereof.
10. The process of claim 1 , further comprising hydrogenating the coupled polymer.
11. A polymer comprising a residue of a coupling agent, the coupling agent, prior to coupling, having at least two alkenylbenzene groups each covalently bonded with a nitrogen of an amine compound.
12. The polymer of claim 11 , comprising the residue of a coupling agent having the structure II:
wherein
Z is an amine;
R 11 and R 12 are C 1 -C 7 alkyl;
the remaining positions of each benzene ring may be substituted with one or more of H or organic functional group; and
m is an integer from 1 to 8.
13. The polymer of claim 12 , comprising two polymer blocks:
(a) block A, wherein the block A has a number average molecular weight of from about 1,000 to about 160,000; and
(b) block A′, wherein the block A′ has a number average molecular weight of from about 1,000 to about 160,000,
wherein the coupling agent residue couples at least one of block A or block A′, or couples block A to block A′.
14. The polymer of claim 13 , having the general configuration A-X-A′, A-X-A′-X-A, A′-X-A-X-A′, (A-A′) n X, (A-A′-A) n X, (A′-A-A′) n X or mixtures thereof, wherein X is the coupling agent reside of formula II, n is an integer from 2 to 30, and wherein the blocks A and blocks A′ are the same or different.
15. The polymer of claim 13 , wherein each block A and each block A′ is polymerized from monomers selected, independently of one another, from the group consisting of conjugated dienes, monoalkenyl arenes, and mixtures thereof.
16. The polymer of claim 12 , wherein R 11 and R 12 are each C 1 .
17. The polymer of claim 12 , wherein m is 1.
18. The polymer of claim 12 , wherein Z is an acyclic amine.
19. The polymer of claim 12 , wherein the acyclic amine is one of alkylamine or an arylamine.
20. The polymer of claim 12 , wherein the acyclic amine is one of n-butyl amine or benzylamine.
21. The polymer of claim 12 , wherein Z is a cyclic amine.
22. The polymer of claim 12 , wherein the polymer is hydrogenated.
23. A process for forming a polymer comprising:
reacting a coupling agent, having at least two alkenylbenzene groups each covalently bonded with a nitrogen of an amine compound, with an initiator to form a living coupling agent with a reactive polymerization site;
reacting the reactive polymerization site with a monomer or mixtures of monomers; and
polymerizing the a monomer or mixtures of monomers to form polymer segments extending from the coupling agent.
24. The process of claim 23 , wherein the polymerizing of the monomer or mixture of monomers is conducted in the presence of an anionic initiator.
25. The process of claim 23 , wherein the coupling agent has the structure I:
wherein
Z is an amine;
R 1 -R 10 are each, independent of one another, H, an organic functional group, or a terminal alkene, wherein at least one terminal alkene is on each benzene ring; and
m is an integer from 1 to 8,
wherein the process further comprises terminating the polymerization if any living polymer segments remain after polymerization.
26. The process of claim 25 , wherein Z is an acyclic amine.
27. The process of claim 26 , wherein the acyclic amine is one of alkylamine or an arylamine.
28. The process of claim 26 , wherein the acyclic amine is one of n-butyl amine or benzylamine.
29. The process of claim 25 , wherein Z is a cyclic amine.
30. The process of claim 25 , wherein one of the groups R 1 -R 5 and one of the groups R 6 -R 10 is a terminal alkene.
31. The process of claim 23 , wherein the monomer or mixtures of monomers are selected from the group consisting of conjugated dienes, styrenes, and mixtures thereof.
32. The process of claim 23 , wherein the monomer or mixtures of monomers are selected from the group consisting of isoprene, butadiene, and mixtures thereof.
33. The process of claim 23 , further comprising hydrogenating the coupled polymer.
34. The process of claim 23 , wherein an excess amount of coupling agent is reacted with the initiator, to form a multifunctional core comprising a plurality of polymerized or cross-linked coupling agent molecules.