Protected aminofunctionalized polymerization initiators and methods of making and using same
View Patent ↗Anionic polymerization initiators useful in the preparation of polymers having a protected amine functional group. The amine functionality is part of a heterocyclic radical and includes a protecting group.
1. A compound of the formula:
wherein:
M is an alkali metal selected from the group consisting of lithium, sodium and potassium;
Z is a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally substituted with aryl or substituted aryl;
Q is a saturated or unsaturated hydrocarbyl group;
n is from 0 to 5;
each R′ is independently selected from the group consisting of H, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, alkoxy, substituted alkoxy, aryl, substituted aryl, heteroaryl, or substituted heteroaryl; and
PG is a protecting group.
2. The compound of claim 1 , wherein the protecting group PG is aralkyl, allyl, tertiary alkyl, methyl, silyl, trimethylsilyl, or tert-butyl, dimethylsilyl.
3. The compound of claim 2 , wherein PG comprises a benzyl group.
4. The compound of claim 2 , wherein PG is allyl.
5. The compound of claim 2 , wherein PG is tertiary alkyl.
6. The compound of claim 5 , wherein PG is tertiary butyl.
7. The compound of claim 2 , wherein PG is methyl.
8. The compound of claim 2 , wherein PG is silyl.
9. The compound of claim 2 , wherein PG is trimethylsilyl.
10. The compound of claim 2 , wherein PG is tert-butyl, dimethylsilyl.
11. The compound of claim 1 , wherein said compound comprises a compound selected from the group consisting of 3-(4-benzylpiperazine)-1-propyllithium, 3-(4-tert-butylpiperazine)-1-propyllithium, 3-(4-allylpiperazine)-1-propyllithium, 3-(4-methylpiperazine)-1-propyllithium, 3-(4-trimethylsilylpiperazine)-1-propyllithium, and 3-(4-tert-butyl, dimethylsilylpiperazine)-1-propyllithium.
12. The compound of claim 13 , wherein said compound comprises 3-(4-benzylpiperazine)-1-propyllithium.
13. The compound of claim 1 , wherein M is lithium.
14. The compound of claim 1 , wherein n is zero.
15. The compound of claim 1 , wherein n is greater than zero and less than or equal to 5.
16. The compound of claim 15 , wherein Q is an extended hydrocarbon chain formed from one or more compounds selected from the group consisting of conjugated diene hydrocarbons, and alkenylsubstituted aromatic compounds.
17. The compound of claim 16 , wherein said conjugated diene is selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene (piperylene), myrcene, 2-methyl-3-ethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene, 1,3-heptadiene, 3-methyl-1,3-heptadiene, 1,3-octadiene, 3-butyl-1,3-octadiene, 3,4-dimethyl-1,3-hexadiene, 3-n-propyl-1,3-pentadiene, 4,5-diethyl-1,3-octadiene, 2,4-diethyl-1,3-butadiene, 2,3-di-n-propyl-1,3-butadiene, and 2-methyl-3-isopropyl-1,3-butadiene.
18. The compound of claim 16 , wherein said alkenylsubstituted aromatic compound is selected from the group consisting of styrene, alpha-methylstyrene, vinyltoluene, 2-vinylpyridine, 4-vinylpyridine, 1-vinylnaphthalene, 2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene, 2-alpha-methylvinylnaphathalene, and 1,2-diphenyl-4-methyl-1-hexene.
19. A process, comprising reacting one or more omega-tertiary-amino-1-haloalkanes of the formula
wherein:
X is halide;
Z is a branched or straight chain hydrocarbon connecting group which contains 3-25 carbon atoms, optionally substituted with aryl or substituted aryl;
each R′ is independently selected from the group consisting of H, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, alkoxy, substituted alkoxy, aryl, substituted aryl, heteroaryl, or substituted heteroaryl;
PG is a protecting group; and with an alkali metal in an alkane, cycloalkane, or aromatic reaction solvent or mixtures of such solvents to form one or more compounds of the formula
wherein M is an alkali metal and Z, PG and R′ are the same defined above; and
optionally reacting said compound with one or more unsaturated organic compounds to form a compound having a saturated or unsaturated hydrocarbyl group Q of the formula
wherein:
Q is a saturated or unsaturated hydrocarbyl group;
n is from 0 to 5; and Z, PG, and R′ are the same defined above.
20. The process of claim 19 , wherein the protecting group PG is aralkyl, allyl, tertiary alkyl, methyl, silyl, trimethylsilyl, or tert-butyl, dimethylsilyl.
21. The process of claim 20 , wherein PG comprises a benzyl group.
22. The process of claim 20 , wherein PG is allyl.
23. The process of claim 20 , wherein PG is tertiary alkyl.
24. The process of claim 23 , wherein PG is tertiary butyl.
25. The process of claim 20 , wherein PG is methyl.
26. The process of claim 20 , PG is silyl.
27. The process of claim 20 , wherein PG is trimethylsilyl.
28. The process of claim 20 , wherein PG is tert-butyl, dimethylsilyl.
29. The process of claim 19 , wherein said initiator comprises a compound selected from the group consisting of 3-(4-benzylpiperazine)-1-propyllithium, 3-(4-tert-butylpiperazine)-1-propyllithium, 3-(4-allylpiperazine)-1-propyllithium, 3-(4-methylpiperazine)-1-propyllithium, 3-(4-trimethylsilylpiperazine)-1-propyllithium, and 3-(4-tert-butyl, dimethylsilylpiperazine)-1-propyllithium.
30. The process of claim 29 , wherein said initiator comprises 3-(4-benzylpiperazine)-1-propyllithium.
31. The process of claim 19 , wherein M is lithium.