Halogen substituted heteroatom-containing metallocene compounds for olefin polymerization

• US 8,546,595 B2
• Filed: 03/20/2012
• Issued: 10/01/2013
• Est. Priority Date: 12/14/2005
• Status: Active Grant

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Voskoboynikov, Alexander Z., Ryabov, Alexey N., Nikulin, Mikhail V., Lygin, Alexander V., Uborsky, Dmitry V., Coker, Catalina L., Canich, Jo Ann M.
• Primary Examiner(s): LU, C CAIXIA
• Application Number:
  US13/424,782
• Publication Number:
  US 20120202956A1
• Time in Patent Office: 560 Days
• Field of Search: 556/1, 556/32, 556/53, 502/152, 526/160, 526/943
• US Class Current: 556/53
• 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 110/06 Propene
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2420/02 Cp or analog bridged to a non-Cp X anionic donor
• CPC Class Codes: C08F 2420/06 Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom
• CPC Class Codes: C08F 2500/02 Low molecular weight, e.g. <100,000 Da.
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/6592 containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• CPC Class Codes: C08F 4/65925 two cyclopentadienyl rings being mutually non-bridged
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

Halogen substituted metallocene compounds are described and comprise one or more monocyclic or polycyclic ligands that are pi-bonded to the metal atom and include at least one halogen substituent directly bonded to an sp² carbon atom at a bondable ring position of the ligand, wherein the or at least one ligand has one or more ring heteroatoms in its cyclic structure. When combined with a suitable activator, these compounds show activity in the polymerization of olefins, such as ethylene and propylene.

Claims

1. A metallocene compound represented by the formula (1):

AMX_n-1

M is a transition metal atom having a coordination number of n selected from Group 3, 4, 5 or 6 of the Periodic Table of Elements, or a lanthanide metal atom, or actinide metal atom;

A is a substituted monocyclic or polycyclic ligand that is pi-bonded to M and is substituted with at least one halogen substituent directly bonded to any sp² carbon atom at a bondable ring position of the ligand, wherein said ligand also includes one or more ring heteroatoms selected from boron, a Group 14 atom that is not carbon, a Group 15 atom, or a Group 16 atom; and

each X is a univalent anionic ligand, or two X are joined and bound to the metal atom to form a metallocycle ring, or two X are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand.

2. The compound of claim 1 wherein A is a substituted heterocyclopentadienyl ligand, a substituted heteroindenyl ligand, a substituted heterofluorenyl ligand, or a substituted heterocyclopentanaphthyl ligand.

3. The compound of claim 1 wherein each heteroatom is selected from boron, nitrogen, oxygen, phosphorus, and sulfur.

4. The compound of claim 1 wherein A is selected from substituted arsacyclopentadienyl ligands, substituted azaboratabenzene ligands, substituted azaborindenyl ligands, substituted azaborollide ligands, substituted azacyclopentadienyl ligands, substituted benzothiaborollide ligands, substituted boratabenzene ligands, substituted boracyclopentadienyl ligands, substituted cyclopentathienyl ligands, substituted cyclopentabenzothienyl ligands, substituted cyclopentafuryl ligands, substituted cyclopentapyrrolyl ligands, substituted cyclopentapyridyl ligands, substituted cyclopentaphospholyl ligands, substituted cyclopentaphosphinyl ligands, substituted cyclopentaindolyl ligands, substituted cyclopentaquinolyl ligands, substituted indenodioxolyl ligands, substituted indenothienyl ligands, substituted indenopyridyl ligands, substituted indenophosphinyl ligands, substituted indenofuryl ligands, substituted indenobenzothienyl ligands, substituted indenoindolyl ligands, substituted oxaborollide ligands, substituted phosphaboratabenzene ligands, substituted stibacyclopentadienyl ligands and substituted thiaborollide ligands.

5. The compound of claim 1 wherein M is a Group 4 transition metal atom selected from titanium, zirconium or hafnium.

6. The compound of claim 1 wherein said at least one halogen substituent is a chloro, bromo or iodo substituent.

7. The compound of claim 1 wherein said at least one halogen substituent is a chloro or bromo substituent.

32. A catalyst system comprising the metallocene compound of claim 1 and an activator.

33. A process for polymerizing olefins comprising contacting the catalyst system of claim 32 with at least one olefin.

34. The process of claim 33 wherein said at least one olefin comprises ethylene and/or propylene.

8. A metallocene compound represented by the formula (1)(a):

9. The compound of claim 8 wherein M is a Group 4 transition metal atom selected from titanium, zirconium or hafnium.

10. The compound of claim 8 wherein Z is boron, nitrogen, or phosphorus.

11. The compound of claim 8 wherein said at least one ring heteroatom in G is selected from boron, nitrogen, oxygen, phosphorus, and sulfur.

12. The compound of claim 8 wherein each R is independently selected from hydrogen and a C₁ to C₃₀ hydrocarbyl.

13. The compound of claim 8 wherein each R is independently selected from hydrogen and methyl.

14. The compound of claim 8 wherein R includes a heteroatom substituent and the heteroatom is selected from boron, nitrogen, oxygen, phosphorus, and sulfur.

15. The compound of claim 8 wherein each X* is a chloro, bromo or iodo substituent.

16. The compound of claim 8 wherein each X* is a chloro or bromo substituent.

35. A catalyst system comprising the metallocene compound of claim 8 and an activator.

36. A process for polymerizing olefins comprising contacting the catalyst system of claim 35 with at least one olefin.

37. The process of claim 36 wherein said at least one olefin comprises ethylene and/or propylene.

17. A metallocene compound represented by the formula (3):

18. The compound of claim 17 wherein A contains an aromatic five-membered ring pi-bonded to M.

19. The compound of claim 17 wherein A is a substituted or unsubstituted heterocyclopentadienyl ligand, a substituted or unsubstituted heteroindenyl ligand, a substituted or unsubstituted heterofluorenyl ligand, or a substituted or unsubstituted heterocyclopentanaphthyl ligand.

20. The compound of claim 17 wherein said one or more ring heteroatoms of A is selected from boron, nitrogen, oxygen, phosphorus, and sulfur.

21. The compound of claim 17 wherein A is selected from substituted and unsubstituted arsacyclopentadienyl ligands, substituted and unsubstituted azaboratabenzene ligands, substituted and unsubstituted azaborindenyl ligands, substituted and unsubstituted azaborollide ligands, substituted and unsubstituted azacyclopentadienyl ligands, substituted and unsubstituted benzothiaborollide ligands, substituted and unsubstituted boratabenzene ligands, substituted and unsubstituted boracyclopentadienyl ligands, substituted and unsubstituted cyclopentathienyl ligands, substituted and unsubstituted cyclopentabenzothienyl ligands, substituted and unsubstituted cyclopentafuryl ligands, substituted and unsubstituted cyclopentapyrrolyl ligands, substituted and unsubstituted cyclopentapyridyl ligands, substituted and unsubstituted cyclopentaphospholyl ligands, substituted and unsubstituted cyclopentaphosphinyl ligands, substituted and unsubstituted cyclopentaindolyl ligands, substituted and unsubstituted cyclopentaquinolyl ligands, substituted and unsubstituted indenodioxolyl ligands, substituted and unsubstituted indenothienyl ligands, substituted and unsubstituted indenopyridyl ligands, substituted and unsubstituted indenophosphinyl ligands, substituted and unsubstituted indenofuryl ligands, substituted and unsubstituted indenobenzothienyl ligands, substituted and unsubstituted indenoindolyl ligands, substituted and unsubstituted oxaborollide ligands, substituted and unsubstituted phosphaboratabenzene ligands, substituted and unsubstituted stibacyclopentadienyl ligands and substituted and unsubstituted thiaborollide ligands.

22. The compound of claim 17 wherein A includes at least one halogen substituent directly bonded to any sp² carbon atom at a bondable ring position.

23. The compound of claim 17 wherein E is a substituted or unsubstituted cyclopentadienyl ligand, a substituted or unsubstituted indenyl ligand, a substituted or unsubstituted fluorenyl ligand, or a substituted or unsubstituted cyclopentanaphthyl ligand.

24. The compound of claim 17 wherein E includes at least one halogen substituent directly bonded to any sp² carbon atom at a bondable ring position.

25. The compound of claim 17 wherein Y is present and is a bridging group containing boron or a Group 14, 15 or 16 element.

26. The compound of claim 17 wherein Y is present and is selected from R′

₂C, R′

₂Si, R′

₂Ge, R′

₂CCR′

₂, R′

₂CCR′

₂CR′

₂, R′

₂CCR′

₂CR′

₂CR′

₂, R′

C═

CR′

, R′

C═

CR′

CR′

₂, R′

₂CCR′

═

CR′

CR′

₂, R′

C═

CR′

CR′

═

CR′

, R′

C═

CR′

CR′

₂CR′

₂, R′

₂CSiR′

₂, R′

₂SiSiR′

₂, R′

₂CSiR′

₂CR′

₂, R′

₂SiCR′

₂SiR′

₂, R′

C═

CR′

SiR′

₂, R′

₂CGeR′

₂, R′

₂GeGeR′

₂, R′

₂CGeR′

₂CR′

₂, R′

₂GeCR′

₂GeR′

₂, R′

₂SiGeR′

₂, R′

C═

CR′

GeR′

₂, R′

B, R′

₂C—

BR′

, R′

₂C—

BR′

—

CR′

₂, R′

N, R′

P, O, S, Se, AsR′

, SbR′

, O—

O, S—

S, R′

N—

NR′

, R′

P—

PR′

, O—

S, O—

NR′

, O—

PR′

, S—

NR′

, S—

PR′

, R′

N—

PR′

, R′

₂C—

O—

CR′

₂, R′

₂CR′

₂C—

O—

CR′

₂CR′

₂, R′

₂C—

O—

CR′

₂CR′

₂, R′

₂C—

O—

CR′

═

CR′

, R′

₂C—

S—

CR′

₂, R′

₂CR′

₂C—

S—

CR′

₂CR′

₂, R′

₂C—

S—

CR′

₂CR′

₂, R′

₂C—

S—

CR′

═

CR′

, R′

₂C—

Se—

CR′

₂, R′

₂CR′

₂C—

Se—

CR′

₂CR′

₂, R′

₂C—

Se—

CR′

₂CR′

₂, R′

₂C—

Se—

CR′

═

CR′

, R′

₂C—

N═

CR′

, R′

₂C—

NR′

—

CR′

₂, R′

₂C—

NR′

—

CR′

₂CR′

₂, R′

₂C—

NR′

—

CR′

═

CR′

, R′

₂CR′

₂C—

NR′

—

CR′

₂CR′

₂, R′

₂C—

P═

CR′

, and R′

₂C—

PR′

—

CR′

₂ where R′

is hydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl substituent and optionally two or more adjacent R′

may join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent.

27. The compound of claim 17 wherein Y is present and is selected from CH₂, CH₂CH₂, C(CH₃)₂, O, S, NPh, PPh, NMe, PMe, SiMe₂, SiPh₂, SiMePh, Si(CH₂)₃ and Si(CH₂)₄, where Me is methyl and Ph is phenyl.

28. The compound of claim 17 wherein M is a Group 4 transition metal atom selected from titanium, zirconium or hafnium.

29. The compound of claim 17 wherein the or each halogen substituent is a chloro, bromo or iodo substituent.

30. The compound of claim 17 wherein the or each halogen substituent is a chloro or bromo substituent.

38. A catalyst system comprising the metallocene compound of claim 17 and an activator.

39. A process for polymerizing olefins comprising contacting the catalyst system of claim 38 with at least one olefin.

40. The process of claim 39 wherein said at least one olefin comprises ethylene and/or propylene.

44. The compound of claim 17, wherein y=0.

45. The process of claim 39, wherein the activator is an alumoxane, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetra(perfluorophenyl)borate, or trispentafluorophenylborane.

46. The catalyst system of claim 38, wherein the activator is an alumoxane, N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetra(perfluorophenyl)borate, or trispentafluorophenylborane.

31. A metallocene compound selected from:

(η

⁵-3-bromo-5-methylcyclopenta[b]thienyl)(η

⁵-pentamethylcyclopentadienyl) zirconium dichloride,

rac-bis(η

⁵-3-bromo-5-methylcyclopenta[b]thienyl)zirconium dichloride,

meso-bis(η

⁵-3-bromo-5-methylcyclopenta[b]thienyl)zirconium dichloride,

rac-[dimethylsilanediyl-bis(η

⁵-3-bromo-5-methylcyclopenta[b]thien-6-yl)](N¹,N³-diphenyl-1,3-propanediamido)zirconium,

rac-dimethylsilanediyl-bis(η

⁵-3-bromo-5-methylcyclopenta[b]thien-6-yl) zirconium dichloride,

rac-[dimethylsilanediyl-bis(η

⁵-3-bromo-2,5-dimethylcyclopenta[b]thien-6-yl)](N¹,N³-diphenyl-1,3-propanediamido)zirconium,

rac-dimethylsilanediylbis(η

⁵-3-bromo-2,5-dimethylcyclopenta[b]thien-6-yl) zirconium dichloride,

dimethylsilanediyl(η

⁵-4,5-dimethylcyclopenta[b]thien-6-yl)(N-(2,4-dimethyl-6-bromophenylamido))titanium dichloride,

dimethylsilanediyl(η

⁵-4,5-dimethylcyclopenta[b]thien-6-yl)(N-(2,6-dimethyl-4-bromophenylamido))titanium dichloride,

dimethylsilanediyl(η

⁵-4,5-dimethylcyclopenta[b]thien-6-yl)(N-(2,6-dimethyl-4-bromophenylamido))zirconium dichloride,

dimethylsilanediyl(η

⁵-4,5-dimethylcyclopenta[b]thien-6-yl)(N-(2,4-dimethyl-6-bromophenylamido))zirconium dichloride,

dimethylsilanediyl(η

⁵-4,5-dimethylcyclopenta[b]thien-6-yl)(N-(2,6-diisopropyl-4-bromophenylamido))titanium dichloride,

dimethylsilanediyl(η

⁵-4,5-dimethylcyclopenta[b]thien-6-yl)(N-(2,6-diisopropyl-4-bromophenylamido))zirconium dichloride, and

rac-dimethylsilanediylbis(η

⁵-3-bromo-4,5-dimethylcyclopenta[b]thien-6-yl)zirconium dichloride.

41. A catalyst system comprising the metallocene compound of claim 31 and an activator.

42. A process for polymerizing olefins comprising contacting the catalyst system of claim 41 with at least one olefin.

43. The process of claim 42 wherein said at least one olefin comprises ethylene and/or propylene.