Claims
- 1. A method for preparing an activated olefin polymerization catalyst composition, which comprises reacting an olefin polymerization pre-catalyst having the formula:
- 2. The method of claim 1, wherein M is Zr or Hf.
- 3. The method of claim 2, wherein M is Zr.
- 4. The method of claim 1, wherein each R1 is the same and is hydrogen or alkyl.
- 5. The method of claim 4, wherein each R1 is hydrogen.
- 6. The method of claim 4, wherein each R1 is methyl.
- 7. The method of claim 1, wherein each R2, R3 and R4 is independently alkyl, cycloalkyl, phenyl, optionally substituted phenyl, alkphenyl or optionally substituted alkphenyl.
- 8. The method of claim 1 or 7, with the proviso that R2 and R3 are not the same.
- 9. The method of claim 1, wherein said alkyl, aryl, arylalkyl or alkylarylalkyl bridge is an alkyl bridge.
- 10. The method of claim 9, wherein said alkyl, aryl, arylalkyl or alkylarylalkyl bridge is a trimethylene bridge.
- 11. The method of claim 1, wherein each R5 is methyl.
- 12. The method of claim 1, wherein the activating co-catalyst is [A+][−BR64].
- 13. The method of claim 12, wherein the activating co-catalyst is [PhNMe2H][B(C6F5)4].
- 14. The method of claim 1, wherein the activating co-catalyst is BR63.
- 15. The method of claim 1 wherein the olefin polymerization pre-catalyst is (1,2,3,4,5-pentamethyl)cyclopentadienyl dimethyl zirconium (N-t-butyl-N-ethyl)amidinate.
- 16. An activated olefin polymerization catalyst composition obtained according to the method of claim 1.
- 17. The composition of claim 16, wherein said composition contains an enantiomeric excess of one enantiomer.
- 18. A method for preparing a polyolefin, comprising reacting an α-olefin with the activated olefin polymerization catalyst composition of claim 16 under conditions whereby said polyolefin is produced.
- 19. A method for preparing a polyolefin, comprising reacting a diene with the activated olefin polymerization catalyst composition of claim 16 under conditions whereby said polyolefin is produced.
- 20. A method for preparing a polyolefin, comprising reacting an aromatic compound having vinyl unsaturation with the activated olefin polymerization catalyst composition of claim 16 under conditions whereby said polyolefin is produced.
- 21. The method of claim 18, 19 or 20, wherein said polyolefin is produced in a living manner.
- 22. The polyolefin produced by the method of claim 18, 19 or 20.
- 23. The polyolefin of claim 22, wherein said polyolefin is highly isotactic.
- 24. The polyolefin of claim 22, wherein said polyolefin has a low polydispersity.
- 25. A method for preparing a block co-polymer, comprising reacting a combination of two or more different α-olefins, two or more different dienes or two or more different aromatic compounds having vinyl unsaturation or any combination thereof, with the activated olefin polymerization catalyst composition of claim 16 under conditions whereby said block co-polymer is produced.
- 26. The method of claim 25, wherein said block co-polymer is produced in a living fashion.
- 27. The block co-polymer obtained by the method of claim 25.
- 28. The block co-polymer of claim 27, wherein said block co-polymer is highly isotactic.
- 29. The block co-polymer of claim 27, wherein said block co-polymer has a low polydispersity.
- 30. A method for the preparation of a block co-polymer, comprising reacting an a-olefin and a non-conjugated diene with the activated olefin polymerization catalyst of claim 16 under conditions whereby said block co-polymer is produced.
- 31. The method of claim 30, wherein said a-olefin is propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 3,5,5-trimethyl-1-hexene, vinylcyclohexane, 3-methylbutene, 3-methyl-1-pentene, vinylcyclobutane, vinylcyclopentane, vinylcyclooctane, 1-decene or enantiomerically pure β-citronellene.
- 32. The method of claim 30, wherein said non-conjugated diene is a linear, branched or cyclic hydrocarbon having from 4 to 20 carbon atoms.
- 33. The method of claim 32, wherein said non-conjugated diene is 1,4-pentadiene, 1,5-hexadiene, 5-vinyl-2-norbornene, 1,7-octadiene, vinylcyclohexene, dicyclopentadiene, butadiene, isoprene or ethylidene norbornene.
- 34. The block co-polymer obtained by the method of claim 30.
- 35. The block co-polymer of claim 34, wherein said block co-polymer is highly isotactic.
- 36. The block co-polymer of claim 34, wherein said block co-polymer has a low polydispersity.
- 37. The block co-polymer of claim 34, wherein said block co-polymer is an iso-poly(1-hexene)/poly(methylene-1,3-cyclopentane) block co-polymer.
- 38. A method for preparing a highly isotactic polyolefin, comprising:
(a) preparing an activated olefin polymerization catalyst, which comprises reacting an olefin polymerization pre-catalyst having the formula: 17wherein the dotted lines indicate a delocalized bond; M is Ti, Zr or Hf; each R1 is independently hydrogen or alkyl or two adjacent R1 form an aromatic ring; each R2, R3 and R4 is independently alkyl, cycloalkyl, Si(alkyl)3, Si(aryl)3, optionally substituted Si(aryl)3, phenyl, optionally substituted phenyl, alkphenyl or optionally substituted alkphenyl; or one R1 and one of R2, R3 and R4 together form an alkyl, aryl, arylalkyl or alkylarylalkyl bridge; and each R5 is independently alkyl, cycloalkyl, aryl, optionally substituted aryl, arylalkyl or optionally substituted arylalkyl; with an activating co-catalyst having the formula: [A+][−BR64] or BR63 wherein A+ is a cationic Lewis or Brønsted acid capable of abstracting a methyl from the metal, M, of the olefin polymerization pre-catalyst; B is the element boron; and R6 is phenyl or an optionally substituted phenyl; and (b) reacting an a-olefin or a combination of two or more unlike α-olefins with the activated olefin polymerization catalyst under conditions whereby said highly isotactic polyolefin is produced.
- 39. The method of claim 38, wherein M is Zr or Hf.
- 40. The method of claim 39, wherein M is Zr.
- 41. The method of claim 38, wherein said highly isotactic polyolefin is produced in a living fashion.
- 42. The method of claim 38, wherein each R1 is the same and is hydrogen or alkyl.
- 43. The method of claim 42, wherein each R1 is hydrogen.
- 44. The method of claim 42, wherein each R1 is methyl.
- 45. The method of claim 38, wherein each R2, R3 and R4 is independently alkyl, cycloalkyl, phenyl, optionally substituted phenyl, alkphenyl or optionally substituted alkphenyl.
- 46. The method of claim 38 or 45, with the proviso that R2 and R3 are not the same.
- 47. The method of claim 38, wherein said alkyl, aryl, arylalkyl or alkylarylalkyl bridge is an alkyl bridge.
- 48. The method of claim 47, wherein said alkyl, aryl, arylalkyl or alkylarylalkyl bridge is a trimethylene bridge.
- 49. The method of claim 38, wherein each R5 is methyl.
- 50. The method of claim 38, wherein the activating co-catalyst is [A+][−BR64]
- 51. The method of claim 50, wherein the activating co-catalyst is [PhNMe2H][B(C6F5)4].
- 52. The method of claim 38, wherein the activating co-catalyst is BR63.
- 53. The highly isotactic polyolefin obtained by the method of claim 38.
- 54. The polyolefin of claim 53, wherein said polyolefin is a homopolymer.
- 55. The polyolefin of claim 53, wherein said polyolefin is a co-polymer.
- 56. The polyolefin of claim 53, wherein said polyolefin is a block co-polymer.
- 57. An olefin polymerization pre-catalyst of the formula:
- 58. The pre-catalyst of claim 57, wherein M is Zr.
- 59. The pre-catalyst of claim 57, wherein each R1 is hydrogen.
- 60. The pre-catalyst of claim 57, wherein each R1 is methyl.
- 61. The pre-catalyst of claim 57, wherein each of R2 and R3 is independently selected from the group consisting of ethyl, t-butyl, cyclohexyl, 1-phenyl-ethyl and 2,6-di(i-propyl)phenyl.
- 62. The pre-catalyst of claim 61, wherein said pre-catalyst is selected from the list consisting of:
(η5-C5(CH3)5)Zr(CH3)2-N-(1-phenylethyl)-N′-(t-butyl)acetamidinate; (η5-C5(CH3)5)Zr(CH3)2-N-(t-butyl)-N′-(ethyl)acetamidinate; (η5-C5(CH3)5)Zr(CH3)2-N-(t-butyl)-N′-(cyclohexyl)acetamidinate; and (η5-C5(CH3)5)Zr(CH3)2-N-(t-butyl)-N′-(2,6-di(i-propyl)phenyl)-acetamidinate.
- 63. The pre-catalyst of claim 57, wherein each R5 is methyl.
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This is a continuation-in-part of PCT/US00/00328 filed Jan. 7, 2000, which claims the benefit of U.S. application No. 60/162,037, the contents of each of which are fully incorporated by reference herein.
Provisional Applications (1)
|
Number |
Date |
Country |
|
60162037 |
Oct 1999 |
US |
Continuation in Parts (1)
|
Number |
Date |
Country |
Parent |
PCT/US00/00328 |
Jan 2000 |
US |
Child |
09849244 |
May 2001 |
US |