Highly active supported catalyst compositions

• US 6,664,348 B2
• Filed: 02/11/2002
• Issued: 12/16/2003
• 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:
  US10/073,840
• Publication Number:
  US 20020123582A1
• Time in Patent Office: 673 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: 526/133
• 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. A 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 allows association between the fluorided supports 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 supported catalyst composition of claim 1, wherein the productivity is from 38.8 to 207.3 kg polymer/mM metallocene·

hr.

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

4. The supported catalyst composition 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 supported catalyst composition of claim 1, wherein the one or more activators are selected front the group consisting of alkylalumoxanes (MAO), non-coordinating anions, and activator anion neutral precursors, and combinations thereof.

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

7. The support catalyst composition 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 supported catalyst composition 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 supported catalyst composition of claim 1, wherein the one or more metallocenes is selected from 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-4,5-benzoindenyl) zirconium dichloride;

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

Dimethylsilandiylbis(2-ethyl-4-phenyl-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-methylindenyl) 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 supported catalyst composition of claim 1, wherein the 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 supported catalyst composition of claim 1, wherein the supported catalyst composition exhibits a productivity of from 919 to 5180 g polymer/g metallocene·

hr.

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

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

14. The supported catalyst composition of claim 1, wherein the α

-olefin monomers are propylene.

15. A polymer made from the supported catalyst composition of claim 1.

16. A supported catalyst composition consisting essentially of one or more fluorided supports, one or more metallocenes, and one or more activators selected from highly fluorinated tris-arylboranes.