Method for preparing polyolefins containing a high percentage of exo-olefin chain ends

• US 8,530,586 B2
• Filed: 04/26/2010
• Issued: 09/10/2013
• Est. Priority Date: 08/20/2004
• Status: Expired due to Fees

• Current Assignee: Chevron Oronite Company LLC (Chevron Corp.), University of Southern Mississippi
• Original Assignee: Chevron Oronite Company LLC (Chevron Corp.), University of Southern Mississippi
• Inventors: Stokes, Casey D., Simison, Kelby, Storey, Robson F., Harrison, James J.
• Primary Examiner(s): Choi, Ling
• Assistant Examiner(s): REUTHER, ARRIE L
• Application Number:
  US12/767,672
• Publication Number:
  US 20100311913A1
• Time in Patent Office: 1,233 Days
• Field of Search: 525/375
• US Class Current: 525/331.4
• CPC Class Codes: C08F 110/10 Isobutene
• CPC Class Codes: C08F 2/38 Polymerisation using regulators, e.g. chain terminating agents , e.g. telomerisation
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2810/30 leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
• CPC Class Codes: C08F 2810/40 taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
• CPC Class Codes: C08F 8/00 Chemical modification by after-treatment graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C
• CPC Class Codes: C08F 8/26 Removing halogen atoms or halogen-containing groups from the molecule

Abstract

The present invention is directed to a method for preparing polyolefins containing a high percentage of exo-olefin chain ends. The method involves ionizing a polyolefin containing tert-chloride chain ends and reacting the ionized polyolefin with one or more nitrogen-containing five-membered aromatic ring or one or more hindered secondary or tertiary amines, or mixtures thereof.

Claims

1. A method for preparing a polyolefin product containing exo-olefinic end groups on the polymer chain, comprising:

(a) ionizing a polyolefin containing terminal tert-chloride chain ends on the polymer chain in the presence of a Lewis acid to form an ionized polyolefin; and

(b) reacting the ionized polyolefin with;

(i) one or more pyrroles of formula I;

7. The method of claim 1, wherein the ionized polyolefin of step (b) is reacted with one or more hindered secondary or tertiary amines of:

formula II;

8. The method of claim 7, wherein the one or more hindered secondary or tertiary amines are a compound of formula II:

9. The method of claim 7, wherein the one or more hindered secondary or tertiary amines are a compound of formula III:

10. The method of claim 7, wherein the one or more hindered secondary or tertiary amines are a compound of formula IV:

11. The method of claim 7, wherein the one or more hindered secondary or tertiary amines are a compound of formula V:

12. The method of claim 7, wherein the one or more hindered secondary or tertiary amines are a compound of formula VI:

13. The method of claim 7, wherein the one or more hindered secondary or tertiary amines are a compound of formula VII:

14. The method of claim 13, wherein the one or more hindered secondary or tertiary amines have the following formula:

15. The method of claim 13, wherein the one or more hindered secondary or tertiary amines have the following formula:

16. The method of claim 7, wherein the one or more hindered secondary or tertiary amines are a compound of formula VIII:

17. The method of claim 16, wherein one of R₅ and R₆ is hydrogen.

18. The method of claim 7, wherein the one or more hindered secondary or tertiary amines are a compound of:

formula IX;

19. The method of claim 18, wherein the one or more hindered secondary or tertiary amines have the following formula:

20. The method of claim 18, wherein the one or more hindered secondary or tertiary amines have the following formula:

21. The method of claim 1, wherein steps (a) and (b) are independently carried out at a temperature in the range of about -130°

C. to about 10°

C.

22. The method of claim 1, wherein steps (a) and (b) are independently carried out at a temperature in the range of about -80°

C. to about 0°

C.

23. The method of claim 1, wherein steps (a) and (b) are independently carried out at a temperature in the range of about -70°

C. to about -10°

C.

24. The method of claim 1, wherein steps (a) and (b) are independently carried out at a temperature in the range of about -60°

C. to about -20°

C.

25. The method of claim 1, wherein in step (a) the Lewis acid is a halide of titanium or boron.

26. The method of claim 1, wherein in step (a) the Lewis acid is a titanium halide.

27. The method of claim 1, wherein in step (a) the Lewis acid is titanium tetrachloride.

28. The method of claim 1, wherein the polyolefin is polyisobutylene.

29. The method of claim 1, wherein the exo-olefinic end group on the polyolefin product is present in the range of one percent to about 100 percent of the total end groups.

30. The method of claim 1, wherein the polyolefin product has at least 3 percent exo-olefin end groups.

31. The method of claim 1, wherein the polyolefin product has at least 20 percent exo-olefin end groups.

32. The method of claim 1, wherein the polyolefin product has at least 50 percent exo-olefin end groups.

33. The method of claim 1, wherein the polyolefin product has at least 70 percent exo-olefin end groups.

2. The method of claim I, wherein the ionized polyolefin of step (b) is reacted with one or more pyrroles of formula I:

3. The method of claim 2, wherein the one or more pyrroles have the following formula:

4. The method of claim 2, wherein the ionized polyolefin of step (b) is reacted with one or more imidazoles having at least two hydrocarbyl substituents.

5. The method of claim 4, wherein the one or imidazoles have the following formula:

6. The method of claim 5, wherein R₁ is methyl, R₂ is hydrogen, and R₃ is tert-butyl.

34. A method for preparing a polyolefin product containing exo-olefinic end groups on the polymer chain, comprising:

(a) ionizing a polyolefin containing terminal tert-chloride chain ends on the polymer chain in the presence of a Lewis acid to form an ionized polyolefin; and

(b) reacting the ionized polyolefin with;

(i) one or more pyrroles of formula I

35. The method of claim 34, wherein the Lewis acid is titanium tetrachloride and the substituted pyrrole is 2,3-dimethyl indole.

36. The method of claim 34, wherein the Lewis acid is titanium tetrachloride and the hindered amine is 1,2,2,6,6-pentamethylpiperidine.

37. The method of claim 34, wherein the Lewis acid is titanium tetrachloride.