Bridged fluorenyl/indenyl metallocenes and the use thereof

• US 5,886,202 A
• Filed: 09/12/1997
• Issued: 03/23/1999
• Est. Priority Date: 01/08/1997
• Status: Expired due to Term

• Current Assignee: Chevron Phillips Chemical Company LP (Chevron Corp.)
• Original Assignee: Phillips Petroleum Company (ConocoPhillips)
• Inventors: Alt, Helmut G., Jung, Michael, Welch, M. Bruce
• Primary Examiner(s): Shaver, Paul F.
• Application Number:
  US08/928,820
• Time in Patent Office: 557 Days
• Field of Search: 556/11, 556/12, 556/52, 556/53, 556/43, 556/466, 556/489, 585/426, 526/92, 526/121, 526/122, 526/126, 526/127, 526/128
• US Class Current: 556/11
• CPC Class Codes: C07F 17/00 Metallocenes
• CPC Class Codes: C07F 7/0805 comprising only Si, C or H atoms
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 110/02 Ethene
• CPC Class Codes: C08F 4/63912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/63927 two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged

Abstract

Bridged fluorenyl/indenyl metallocenes having substituents at the 3 position of the indenyl and the use thereof in the polymerization of olefins are disclosed. Also a new method for preparing bridged fluorenyl/indenyl ligands wherein the indenyl has a substituent in the 3 position and the preparation of metallocenes with such ligands.

Claims

1. A bridged fluorenyl/indenyl containing metallocenes of the formula ##STR3## wherein R is a divalent organo radical connecting Fl and In, Fl is a 9-fluorenyl radical, In is an indenyl radical connected to R at the 1 position and to R¹ at the 3 position, wherein R and R¹ are the only substituents on In, wherein R¹ is selected from the group consisting of alkyl, aralkyl, alkenyl, alkylsilyl, alkenylsilyl, and alkoxyalkyl radicals having 1 to 20 carbon atoms, M is a metal selected from the group consisting of titanium, zirconium, hafnium, niobium, and tantalum, and each R² can be the same or different and is selected from hydrogen, halides, alkyl radicals containing 1 to 10 carbon atoms, aryl radicals having 6 to 12 carbon atoms, alkenyl radicals having 2 to 10 carbon atoms, arylalkyl radicals having 7 to 40 carbon atoms, arylalkenyl radicals having 8 to 40 carbon atoms, and alkylaryl radicals having 7 to 40 carbon atoms, n is a number to fill the remaining valences of M, further characterized by the fact that R¹ is not allyl or propenyl if R is dimethylsilyl.

2. A metallocene according to claim 1 wherein R is a divalent radical selected from the group consisting of dimethyl silyl, diphenyl silyl, phenyl methyl silyl, dimethyl methylene, 1-methyl-1-phenyl methylene, diphenyl methylene, alkenyl substituted ethylenes having 4 to 12 carbons, alkyl substituted ethylenes having 4 to 12 carbons, and 1,2-ethylene.

3. A metallocene according to claim 1 wherein R¹ is a radical selected from the group consisting of trialkyl silyls having 3 to 12 carbon atoms, 1-omega-alkenyl-1,1-dimethyl silyls in which the alkenyl group contains 2 to 10 carbon atoms, 1-omega-alkenyls having 2 to 10 carbon atoms, and alkyls having 1 to 10 carbon atoms.

4. A metallocene according to claim 3 wherein M is zirconium, n is 2, and R² is Cl.

5. A metallocene according to claim 4 wherein R is selected from the group consisting of dimethyl silyl and diphenyl silyl.

6. A metallocene according to claim 5 wherein R¹ is an omega-alkenyl radical having 4 to 6 carbon atoms.

7. A metallocene according to claim 6 wherein R¹ is 1-pentenyl.

8. A metallocene according to claim 7 wherein R is diphenyl silyl.

9. A metallocene according to claim 4 wherein R is selected from the group consisting of dimethyl methylene and phenyl methyl methylene.

10. A metallocene according to claim 9 wherein R¹ is selected from the group consisting of trimethyl silyl, omega- alkyenyls having 3 to 6 carbon atoms, and omega-alkenyl dimethyl silyls wherein the alkenyl group has 3 to 6 carbon atoms.

13. A metallocene according to claim 10 wherein R is dimethyl methylene.

15. A metallocene according to claim 10 wherein R is phenyl methyl methylene.

16. A metallocene according to claim 4 wherein R is ethylidene.

18. A metallocene according to claim 1 wherein R is methyl omega-alkenyl methylene wherein the omega-alkenyl has 4 to 6 carbon atoms.

19. A metallocene according to claim 18 wherein R is methyl omega butenyl methylene.

20. A metallocene according to claim 19 wherein R¹ is an omega alkenyl.

21. A metallocene according to claim 20 wherein R¹ is 3-but-3-enyl.

22. A process for producing a polymer comprising contacting at least one olefin with a metallocene according to claim 1 under suitable polymerization conditions.

23. A process according to claim 22 wherein ethylene is polymerized and methylaluminoxane is used as a cocatalyst.

24. A process according to claim 23 wherein R is ethylidene.

25. A process according to claim 24 wherein R¹ is selected from the group consisting of omega alkenyl radicals having 4 to 6 carbon atoms.

26. A process according to claim 23 wherein R is methyl (omega alkenyl) methylene.

27. A process according to claim 23 wherein R is dimethyl methylene.

28. A process according to claim 27 wherein R¹ is 3-hex-5-enyldimethyl silyl.

29. A process according to claim 27 wherein R¹ is 3-pent-4-enyl.

30. A process according to claim 27 wherein R¹ is an omega alkenyl having 4 to 6 carbon atoms.

31. A process according to claim 30 wherein R is diphenyl silyl.

32. A process according to claim 30 wherein R is dimethyl silyl.

33. A process according to claim 23 wherein said polymerization is conducted using a catalyst system prepared by prepolymerizing said metallocene in the presence of aluminoxane and a particulate solid to obtain a particulate solid active as a polymerization catalyst.

11. A metallocene according to claim wherein R¹ is 1-pentenyl.

12. A metallocene according to claim 11 wherein R is phenyl methyl methylene.

14. A metallocene according to claim wherein R¹ is 5-hexenyl dimethyl silyl.

17. A metallocene according to claim 17 wherein R¹ is an omega alkenyl having 4 to 6 carbon atoms.

34. A process for producing a bridged fluorenyl/indenyl ligand having a substituent a the 3-position of the indenyl comprising reacting lithium fluorenyl with a Benzofulyenes in diethylether to produce a bridged fluorenyl/indenyl ligand lithium salt and then reacting said ligand lithium salt with an organic halide selected from the group consisting of alkyl halides, alkenyl halides, and organosilyl halides.

35. A process according to claim 34 wherein the organic halide is selected from the group consisting of alkyl halides having 1 to 10 carbon atoms, 1-omega-alkenyl-1,1-dimethyl silyl halides in which the alkenyl group contains 2 to 10 carbon atoms, and 1-omega-alkenyl halides having 2 to 10 carbon atoms.

36. A process for preparing a bridged flourenyl/indenyl metallocene comprising carrying out the process of claim 34 and then reacting the resulting bridged fluorenyl/indenyl ligand with an alkyl lithium to produce the lithium salt and then reacting the lithium salt with a transition metal halide wherein the metal is selected from the group consisting of titanium, zirconium, hafnium, niobium, and tantalum.