Highly active supported catalyst compositions

• US 6,846,770 B2
• Filed: 02/11/2002
• Issued: 01/25/2005
• Est. Priority Date: 08/26/1998
• Status: Expired due to Fees

• Current Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: ExxonMobil Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Speca, Anthony N.
• Primary Examiner(s): Harlan, Robert D.
• Application Number:
  US10/073,839
• Publication Number:
  US 20020160914A1
• Time in Patent Office: 1,079 Days
• Field of Search: 502/402, 502/405, 502/407, 502/415, 502/104, 502/117, 502/152, 526/133, 526/134, 526/160, 526/943, 526/128, 526/129
• US Class Current: 502/104
• 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 110/06 Propene
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 4/025 Metal oxides
• CPC Class Codes: C08F 4/65908 in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

This invention relates to metallocene catalyst compositions which are highly active for the polymerization of olefins, particularly prochiral α-olefins. The catalyst compositions contain at least one metallocene, and least one activator and a support that has been fluorided using a fluoride containing compound.

Claims

1. An olefin polymerization method comprising the steps of contacting a polymerizable olefin with a supported catalyst composition, said supported catalyst composition comprising one or more fluorided supports, one or more metallocenes, and one or more activators selected from highly fluorinated tris-arylboranes, characterized in that the degree of fluoridation of the support allows association between the fluorided support and one or more activators such that when contacted with one or more metallocenes and α

-olefin monomers, the supported catalyst composition exhibits a productivity of from 919 to 6012 g polymer/g metallocene·

hr.

2. The method of claim 1, wherein the activity of the composition is from 38.8 to 207.3 kg polymer/mM metallocene·

hr.

3. The method of claim 1, the support having a fluorine concentration is in the range of from 0.01 to 10.0 millimoles of fluorine per gram of support.

4. The method of claim 1, the support having a fluorine concentration is in the range of from 0.6 to 3.5 wt % of the support.

5. The method of claim 1, wherein the one or more activators are selected from alkylalumoxanes (MAO), non-coordinating anions, and activator anion neutral precursors, and combinations thereof.

6. The method of claim 1, wherein the one or more activators is selected from highly fluorinated tris-arylborane compounds and mixtures thereof.

7. The method of claim 1, wherein the activator is selected from the group consisting of tris-perfluorophenyl borane, trisperfluoronaphthyl borane, trisperfluorobiphenyl borane, tris(3,5-di(trifluoromethyl)phenyl)borane, tris(di-t-butylmethylsilyl)perfluorophenylborane, and mixtures thereof.

8. The method of claim 1, wherein the one or more metallocenes is represented by the following:

wherein M is a metal of Group 4, 5, or 6 of the Periodic Table;

R¹ and R² are identical or different, and are one of a hydrogen atom, a C₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀ aryl group, a C₆-C₁₀ aryloxy group, a C₂-C₁₀ alkenyl group, a C₇-C₄₀ arylalkyl group, a C₇-C₄₀ alkylaryl group, a C₈-C₄₀ arylalkenyl group, or a halogen atom;

R⁵ and R⁶ are identical or different, are one of a halogen atom, a C₁-C₁₀ alkyl group, which may be halogenated, a C₆-C₁₀ aryl group, which may be halogenated, a C₂-C₁₀ alkenyl group, a C₇-C₄₀-arylalkyl group, a C₇-C₄₀ alkylaryl group, a C₈-C₄₀ arylalkenyl group, a —

NR₂¹⁵, —

SR¹⁵, —

OR¹⁵, —

OSiR₃¹⁵ or —

PR₂¹⁵ radical, wherein R¹⁵ is one of a halogen atom, a C₁-C₁₀ alkyl group, or a C₆-C₁₀ aryl group;

R⁷ is

wherein R¹¹, R¹² and R¹³ are identical or different and are a hydrogen atom, a halogen atom, a C₁-C₂₀ alkyl group, a C₁-C₂₀ fluoroalkyl group, a C₆-C₃₀ aryl group, a C₆-C₃₀ fluoroaryl group, a C₁-C₂₀ alkoxy group, a C₂-C₂₀ alkenyl group, a C₇-C₄₀ arylalkyl group, a C₈-C₄₀ arylalkenyl group, or a C₇-C₄₀ alkylaryl group; and

wherein R¹¹ and R¹², or R¹¹ and R¹³, together with the atoms binding them, can form ring systems;

M² is silicon, germanium or tin;

R⁸ and R⁹ are identical or different and have the meanings stated for R¹¹;

m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2; and

the radicals R³, R⁴, and R¹⁰ are identical or different and have the meanings stated for R¹¹, R¹² and R¹³.

9. The method of claim 1, wherein the one or more metallocenes is selected from the group consisting of Dimethylsilandiylbis (2-methyl-4-phenyl-1-indenyl) zirconium dimethyl;

Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl) zirconium dimethyl;

Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) zirconium dimethyl;

Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl) zirconium dimethyl;

Dimethylsilandiylbis(2-ethyl-4-naphthyl-1-indenyl) zirconium dimethyl;

Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl) zirconium dimethyl;

Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) zirconium dimethyl;

Dimethylsilandiylbis(2-methyl-indenyl) zirconium dimethyl;

Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl) zirconium dimethyl;

Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl) zirconium dimethyl;

Dimethylsilandiylbis(2-methyl-1-indenyl) zirconium dimethyl;

Dimethylsilandiylbis(2-ethyl-1-indenyl) zirconium dimethyl;

Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl) zirconium dimethyl;

Dimethylsilandiylbis(2-methyl-4-phenyl-1-indenyl) zirconium dichloride;

Dimethylsilandiylbis(2-methyl-4,5benzoindenyl) zirconium dichloride;

Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl) zirconium dichloride;

Dimethylsilandiylbis(2-ethyl-4-naphthyl-1-indenyl) zirconium dichloride;

Dimethylsilandiylbis(2-ethyl-4-naphthyl-1-indenyl) zirconium dichloride, Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl) zirconium dichloride;

Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl) zirconium dichloride;

Dimethylsilandiylbis(2-methyl-indenyl) zirconium dichloride;

Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl) zirconium dichloride;

Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl) zirconium dichloride;

Dimethylsilandiylbis(2-methyl-1-indenyl) zirconium dichloride;

Dimethylsilandiylbis(2-ethyl-1-indenyl) zirconium dichloride, and Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl) zirconium dichloride, and mixtures thereof.

10. The method of claim 1, wherein the fluorided support is selected from the group consisting of talc, clay, silica, alumina, magnesia zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium oxide thoria, aluminum phosphate gel, polyvinylchloride or substituted polystyrene, and mixtures thereof.

11. The method of claim 1, wherein the supported catalyst composition exhibits a productivity of from 919 to 5180 g polymer/g metallocene·

hr.

12. The method of claim 1, wherein the supported catalyst composition exhibits a productivity of from 1125 to 6012 g polymer/g metallocene·

hr.

13. The method of claim 1, wherein the supported catalyst composition exhibits a productivity of from 1125 to 5180 g polymer/g metallocene·

hr.

14. The method of claim 1, wherein the α

-olefin monomers are propylene.

15. The method of claim 1, wherein a support and a fluoriding agent are contacted with one another at from 200°

C. to 600°

C. to produce the fluorided support.

16. A polyolefin produced by the method of claim 1.

17. An olefin polymerization method comprising the steps of contacting a polymerizable olefin with a supported catalyst composition comprising a fluorided support end at least one highly fluorinated tris-arylborane bound to the fluorided support.

18. The method of claim 17, wherein the at least one highly fluorinated tris-arylborane is selected from the group consisting of tris-perfluorophenyl borane, trisperfluoronaphthyl borane, trisperfluorobiphenyl borane, tris(3,5-di(trifluoromethyl)phenyl)borane, tris(di-t-butylmethylsilyl)perfluorophenylborane, and mixtures thereof.

19. The method of claim 17, wherein the support comprises at least one metallocene represented by the following:

wherein M is titanium, zirconium, or hafnium;

R¹ and R² are identical or different, and are one of a hydrogen atom, a C₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀ aryl group, a C₆-C₁₀ aryloxy group, a C₂-C₁₀ alkenyl group, a C₇-C₄₀ arylalkyl group, a C₇-C₄₀ alkylaryl group, a C₈-C₄₀ arylalkenyl group, or a halogen atom;

R⁵ and R⁶ are identical or different, are one of a halogen atom, a C₁-C₁₀ alkyl group, which may be halogenated, a C₆-C₁₀ aryl group, which may be halogenated, a C₂-C₁₀ alkenyl group, a C₇-C₄₀ -arylalkyl group, a C₇-C₄₀ alkylaryl group, a C₈-C₄₀ arylalkenyl group, a -NR₂¹⁵, —

SR¹⁵, —

OR¹⁵, —

OSiR₃¹⁵ or —

PR₂¹⁵ radical, wherein R¹⁵ is one of a halogen atom, a C₁-C₁₀ alkyl group, or a C₆-C₁₀ aryl group;

wherein R¹¹, R¹² and R¹³ are identical or different and are a hydrogen atom, a halogen atom, a C₁-C₂₀ alkyl group, a C₁-C₂₀ fluoroalkyl group, a C₆-C₃₀ aryl group, a C₆-C₃₀ fluoroaryl group, a C₁-C₂₀ alkoxy group, a C₂-C₂₀ alkenyl group, a C₇-C₄₀ arylalkyl group, a C₈-C₄₀ arylalkenyl group, or a C₇-C₄₀ alkylaryl group; and

wherein R¹¹ and R¹², or R¹¹ and R¹³, together with the atoms binding them, can form ring systems;

M² is silicon, germanium or tin;

R⁸ and R⁹ are identical or different and have the meanings stated for R¹¹;

m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2; and

the radicals R³, R⁴, and R¹⁰ are identical or different and have the meanings stated for R¹¹, R¹² and R¹³.

20. The method of claim 19, wherein R₁ and R₂ are methyl groups.

21. The method of claim 17, having a fluorine concentration is in the range of from 0.01 to 10.0 millimoles of fluorine per gram of support.

22. The method of claim 17, having a fluorine concentration is in the range of from 0.6 to 3.5 wt % of the support.

23. The method of claim 17, wherein the fluorided support is selected from the group consisting of fluorided talc, clay, silica, alumina, magnesia, zirconia, iron oxides, boria, calcium oxide, zinc oxide, barium oxide thoria, aluminum phosphate gel, polyvinylchloride or substituted polystyrene, and mixtures thereof.

24. The method claim 17, wherein the support and a fluoriding agent are contacted with one another at from 100°

C. to 1000°

C. to produce the fluorided support.

25. The method of claim 17, wherein a support and a fluoriding agent are contacted with one another at from 200°

C. to 600°

C. to produce the fluorided support.

26. The method of claim 25, wherein the fluoriding agent is selected from the group consisting of NH₄BF₄, (NH₄)₂SiF₆, NH₄PF₆, NH₄F, (NH₄)₂TaF₇, NH₄NbF₄, (NH₄)GeF₆, (NH₄)₂SmF₆, (NH₄)₂TiF₆, (NH₄)₂ZrF ₆, MoF₆, ReF₆, GaF₃, SO₂ClF, F₂, SiF₄, SF₆, ClF₃, ClF₅, BrF₅, lF₇, NF₃, HF, BF₃, NHF₂ and NH₄HF₂ and mixtures thereof.

27. The method of claim 17, wherein the supported catalyst composition exhibits a productivity of from 919 to 5180 g polymer/g metallocene·

hr.

28. The method of claim 17, wherein the supported catalyst composition exhibits a productivity of from 1125 to 6012 g polymer/g metallocene·

hr.

29. The method of claim 17, wherein the supported catalyst composition exhibits a productivity of from 1125 to 5180 g polymer/g metallocene·

hr.

30. A polyolefin produced by the method of claim 17.

31. An olefin polymerization method comprising the steps of contacting a polymerizable olefin with a supported catalyst composition, said supported catalyst composition consisting essentially of one or more fluorided supports, one or more metallocenes, and alkylalumoxanes (MAO) characterized in that the degree of fluoridation of the support allows association between the fluorided support and MAO such that when contacted with one or more metallocenes and α

-olefin monomers, the supported catalyst composition exhibits a productivity of from 919 to 6012 g polymer/g metallocene·

hr.

32. An olefin polymerization method comprising the stops of contacting a polymerizable olefin with a supported catalyst composition, said supported catalyst composition consisting essentially of one or more fluorided supports, one or more metallocenes, and one or more non-coordinating anions, characterized in that the degree of fluoridation of the support allows association between the fluorided support and non-coordinating anions such that when contacted with one or more metallocenes and α

-olefin monomers, the supported catalyst composition exhibits a productivity of from 919 to 6012 g polymer/g metallocene·

hr.

33. An olefin polymerization method comprising the steps or contacting a polymerizable olefin with a supported catalyst composition, said supported catalyst composition consisting essentially of one or more fluorided supports, one or more metallocenes, and activator anion neutral precursors, characterized in that the degree of fluoridation of the support allows association between the fluorided support and activator anion neutral precursors such that when contacted with one or more metallocenes and α

-olefin monomers, the supported catalyst composition exhibits a productivity of from 919 to 6012 g polymer/g metallocene.

34. An olefin polymerization method comprising the steps of contacting a polymerizable olefin with a supported catalyst composition, said supported catalyst composition consisting essentially of one or more fluorided supports, one or more metallocenes, and one or more highly fluorinated tris-arylboranes, characterized in that the degree of fluoridation of the support allows association between the fluorided support and non-coordinating anions such that when contacted with one or more metallocenes and α

-olefin monomers, the supported catalyst composition exhibits a productivity of from 919 to 6012 g polymer/g metallocene·

hr.