Amine-terminated telechelic polymers and precursors thereto and methods for their preparation

Patent metadata

Field	Value
Publication number	US-9315595-B2
Application number	US-201314040256-A
Country	US
Kind code	B2
Filing date	Sep 27, 2013
Priority date	Mar 31, 2009
Publication date	Apr 19, 2016
Grant date	Apr 19, 2016

Abstract

Disclosed is a method of preparing terminally functionalized telechelic polymers using a cationic living polymer product or a terminal tert-chloride chain end of a carbocationic quasiliving polymer product, which comprises quenching the polymer product with a functionalized N-substituted pyrrole to thereby introduce the functionalized N-substituted pyrrole at the terminal reactive polymer chain end(s). A method is also disclosed whereby the N-substituent may be derivatized to a basic amine containing functional group. Also disclosed are the terminal functionalized polyisobuyl N-substituted pyrrole compounds where the polyisobutyl group is substituted at the 2 and 3 position of the N-substituted pyrrole.

First claim

What is claimed is:

1. A method for preparing a telechelic polymer of formula I:

wherein:
R 1 and R 2 are independently in each —(CR 1 R 2 )— unit, hydrogen or alkyl from 1 to 6 carbon atoms;
m is an integer from 2 to 20;
Z 1 is —F, —Cl, —Br, —I, —At, —CN, —NC, —N 3 , —NCO, —OCN, —NCS, or —SCN; and
R′ is a monovalent polyolefin group;

comprising:
a) ionizing a polyolefin in the presence of a Lewis acid or mixture of Lewis acids to form a carbocation-terminated polyolefin; and
b) reacting the carbocation-terminated polyolefin from step (a) with an N-substituted pyrrole of formula II:

2. The method of claim 1 , wherein R 1 and R 2 are both hydrogen.

3. The method of claim 1 , wherein m is an integer from 2-6.

4. The method of claim 1 , wherein m is 2 or 3.

5. The method of claim 1 , wherein Z 1 is —Cl, —Br, —CN, or —N 3 .

6. The method of claim 1 , wherein the N-substituted pyrrole of formula II is

7. The method of claim 1 , wherein the telechelic polymer of formula I is

8. The method of claim 1 , wherein the telechelic polymer of formula I is

9. The method of claim 1 , wherein R′ is a polyisobutyl group.

10. A method for preparing a telechelic polymer of the formula:

wherein:
R 1 and R 2 are independently in each —(CR 1 R 2 )— unit, hydrogen or alkyl from 1 to 6 carbon atoms;
m is an integer from 2 to 20;
Z 1 is —F, —Cl, —Br, —I, —At, —CN, —NC, —N 3 , —NCO, —OCN, —NCS, or —SCN;
R″ is a divalent polyolefin group: and
R 3 is a monofunctional or polyfunctional carbocationic initiator residue of functionality r, wherein r is an integer from 1 to 8;

comprising:
a) ionizing a polyolefin in the presence of a Lewis acid or mixture of Lewis acids to form a carbocation-terminated polyolefin; and
b) reacting the carbocation-terminated polyolefin from step (a) with an N-substituted pyrrole of formula II:

11. The method of claim 10 , wherein R″ is a polyisobutylene group.

12. The method of claim 10 , wherein r is 2.

13. The method of claim 10 , wherein the ionized polyolefin is a quasiliving carbocationic polyolefin and the method is performed under quasiliving carbocationic polymerization conditions.

14. The method of claim 13 , wherein the quasiliving carbocationic polyolefin is prepared by adding a Lewis acid and a monomer to an initiator in the presence of an electron donor, common ion salt, or common ion salt precursor.

15. The method of claim 14 , wherein the Lewis acid is a titanium tetrahalide or boron trihalide.

16. The method of claim 14 , wherein the monomer is isobutylene.

17. The method of claim 1 , further comprising:
reacting the telechelic polymer formed in claim 1 with a reagent or reagents to form a compound of formula III;

wherein:
R 1 and R 2 are, independently in each —(CR 1 R 2 )— unit, hydrogen or alkyl from 1 to 6 carbon atoms;
R′ is a monovalent polyolefin group;
m is an integer from 2 to 20; and
Z 2 is —NR 4 R 5 , —N[(R 4 )(COR 5 )], —N[(COR 4 )(COR 5 )], polyamino, polyamidoamino, polyaminoamido, —OR 6 , a polyether group, polyetheramino, or —COOR 6 ;
wherein:
R 4 and R 5 are each, independently, hydrogen, alkyl, or aryl; and
R 6 is hydrogen, alkyl, aryl, alkaryl, or aralkyl.

18. The method of claim 17 , wherein Z 2 is —NR 4 R 5 .

19. The method of claim 18 , wherein R 4 is hydrogen and R 5 is aryl.

20. The method of claim 18 , wherein —NR 4 R 5 is NH 2 .

21. The method of claim 17 , wherein the reagent is a nucleophile or reducing agent.

22. The method of claim 10 , further comprising:
reacting the telechelic polymer formed in claim 10 with a reagent or reagents to form a compound of the formula:

wherein:
R 1 and R 2 are, independently in each —CR 1 R 2 )— unit, hydrogen or alkyl from 1 to 6 carbon atoms;
R″ is a divalent polyolefin group;
R 3 is a monofunctional or polyfunctional carbocationic initiator residue of functionality r, wherein r is an integer from 1 to 8;
m is an integer from 2 to 20; and
Z 2 is —NR 4 R 5 , —N[(R 4 )(COR 5 )], —N[(COR 4 )(COR 5 )], polyamino, polyamidoamino, polyaminoamido, —OR 6 , a polyether group, polyetheramino, or —COOR 6 ;
wherein:
R 4 and R 5 are each, independently, hydrogen, alkyl, or aryl; and
R 6 is hydrogen, alkyl, aryl, alkaryl, or aralkyl.

23. The method of claim 22 , wherein R″ is a polyisobutylene group.

24. The method of claim 22 , wherein r is 2.

25. The product prepared by the method of claim 1 .

26. The product prepared by the method of claim 17 .

27. The method of claim 1 , wherein the ionized polyolefin is a quasiliving carbocationic polyolefin and the method is performed under quasiliving carbocationic polymerization conditions.

28. The method of claim 10 , wherein R 1 and R 2 are both hydrogen.

29. The method of claim 10 , wherein m is an integer between 2-6.

30. The method of claim 10 , wherein m is 2 or 3.

31. The method of claim 10 , wherein Z 1 is —Cl, —Br, —CN, or —N 3 .

32. The method of claim 10 , wherein the N-substituted pyrrole of formula II is

33. The method of claim 22 , wherein Z 2 is —NR 4 R 5 .

34. The method of claim 33 , wherein R 4 is hydrogen and R 5 is aryl.

35. The method of claim 22 , wherein Z 2 is NH 2 .

36. The method of claim 22 , wherein the reagent is a nucleophile or reducing agent.

Assignees

• Chevron Oronite Co
• Univ Southern Mississippi

Inventors

• Storey Robson F
• Stokes Casey D
• Harrison James J
• Martinez-Castro Nemesio

Classifications

• C08F2810/40

  taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains · CPC title

• C10M2215/30

  Heterocyclic compounds · CPC title

• C10L10/06

  for facilitating soot removal · CPC title

• C10N2070/00

  Specific manufacturing methods for lubricant compositions · CPC title

• C10L1/238

  obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds {(C10L1/221 takes precedence)} · CPC title