WO1996011961B1

WO1996011961B1 - Polymerization catalyst systems, their production and use

Info

Publication number: WO1996011961B1
Application number: PCT/US1995/012789
Authority: WO
Filing date: 1995-10-12
Publication date: 1996-06-27

Abstract

This invention is generally directed toward a supported catalyst system useful for polymerizing olefins. The method for supporting the catalyst of the invention provides for a supported bulky ligand transition metal catalyst which when utilized in a polymerization process substantially reduces the reactor fouling and sheeting in a gas, slurry or liquid pool polymerization process.

Claims

AMENDED CLAIMS [received by the International Bureau on 13 May 1996 (13.05.96); original claims 1-16 replaced by amended claims 1-15 (6 pages)]

1. A method for producing a supported catalyst system, said method comprising the steps of combining an alumoxane, a surface modifier, a porous carrier, and a metallocene catalyst component in a solvent to form a solution wherein the metallocene catalyst component is represented by the following formula:

wherein M¹ is a metal of group 4, 5, or 6 of the Periodic Table,

R¹ and R² are identical or different, are one of a hydrogen atom, a C₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₅-C₁₀ aryl group, a C₅-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;

R³ and R⁴ are hydrogen atoms;

R⁵ and R⁶ are identical or different, preferably identical, are one of a halogen atom, a C₁-C₁₀ alkyl group, which may be halogensted, 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 arylalkanyl group, a -NR₂ ¹⁵, -SR¹⁵, OR¹⁵, -OSiR₃ ¹⁵ or -PR₂ ¹⁵ radical, wherein R¹⁵ is one of a halogen atom, a C₁-C₁₀ alkyl group, or a C₆-C₁₀ aryl group; R⁵ and R⁶ are identical or different, preferably identical, 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 -NR₂ ¹⁵, SR¹⁵, - OR¹⁵, -OSiR₃ ¹⁵ or -PR₂ ¹⁵ radical, wherein R¹⁵ is one of a halogen atom, a C₁-C₁₀ alkyl group, or a C₆-C₁₀ aryl group;

.

-BR^{1 1}, =AlR¹¹, -Ge-, -Sn-, -O-, -S-, - SO, -SO₂, -NR¹¹, =CO, PR¹¹, or -P(O)R¹¹;

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 alkeayl group, a C₇-C₄₀ arylalkyl group, a C₈-C₄₀ arylalkonyl group, C₇-C₄₀ alkylaryl group, or R¹¹ and R¹², or R^{1 1} 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 as stated for R¹¹;

m and n are identical or different and are zero, 1 or 2, m plus n being aero, 1 or 2; and the radicals R¹⁰ are Identical or different and have the meanings stated for R^{1 1}, R¹² and R¹³ wherein further two adjacent R¹⁰ radicals can be joined together to form a ring system.

2. The method of claim 1 wherein the total volume of the solution is from 0.8 to 3.0 times the total pore volume of the porous support.

3. The method of claims 1 or 2 wherein the metallocene catalyst component comprises two or more metallocene catalyst components.

4. The method of any of the preceding claims further comprising the step of prepolymerizing the supported catalyst system with an olefinlc monomer.

5. The method of any of the preceding claims wherein m=n=0 and

M²-silicon.

6. The method of any of the preceding claims wherein R⁵ = R⁶ = C_1-10 alkyl.

7. The method of any of the preceding claims wherein three of the R¹⁰ radicals = hydrogen and one ia a C_6-30 aryl group.

8. The method of any of the preceding claims wherein at least one of the R¹⁰ radicals is C_1-10 alkyl.

9. The method of any of the preceding claims wherein the metailocene component is selected from the group consisting of:

rac-dimethylsilandiylbis(2-methyl-4,5-benzoindenyl)- zirconium dichloride, rac-dimethylsilandiylbis(2-methylindenyl)-zirconium dichloride,

rac-dimethylsilandiyl-bis(2-methyl-4,6-diianpropylindenyl)-zirconium dichloride, rac-dimethylsilandiylbis(2-methyl-4-phenylindenyl)zirconium dichloride, and rac-dimethylsilandiylbis(2-methyl-4-phenylindenyl)zirconium dichloride.

10. The method of any of the preceding claims wherein the surface modifier is present in an amount in the range of 0.2 weight percent to lets than 5 weight percent of the total weight of the supported catalyst system.

11. The method of any of the preceding claims wherein the surface modifier is selected from at least one of the group of compounds represented by the following chemical formulas. C₁₈H₃₇N(CH₂CH₂OH)₂, C₁₂H₂₅N(CH₂CH₂OH)₂ and (CH₃(CH₂)₇(CH)₂(CH₂)₇OCOCH₂(CHOH)₄CH₂OH.

12. A method for producing a supported catalyst system, said catalyst system comprising a first component comprising a chiral, Group 4 transition metal, bridged, substituted bisindenyl metailocene catalyst and a first solvent, a second component comprising an akumoxane and a second solvent, and a porous support, said method comprising the step of

a) combining the first component and the second component to form a reaction product solution;

b) combining the reaction product and the porous support, such that at any point during the formation of the supported catalyst system the total volume of the reaction product added to the porous support is leas than four times the total pore volume of the porous support; and

e) introducing a surface modifier.

13. The method of claim 13 wherein the metailocene catalyst component is represented by the general formula:

wherein: M¹ is a metal of group 4, 5, or 6 of the Periodic Table,

R¹ and R² are identical or different, 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.

R³ and R⁴ am hydrogen atoms;

R⁵ and R⁶ are identical or different, preferably identical, are one of a halogen nom, 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 -NR₂ ¹⁵, -SR¹⁵, - OR¹⁵, -OSiR₃ ¹⁵ or -PR₂ ¹⁵ radical, wherein R^{1 5} is one of a halogen atom, a C₁-C₁₀ alky, group, or a C₆-C₄₀ aryl group,

R⁷ is

=_BR^{1 1,}=AlR^{1 1}, -Ge-, -Sn-, -O-, -S-, - SO, -SO₂, =NR^{1 1}, -CO, PR^{1 1}, or

=P(O)R^{1 1};

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-G₄₀ arylalkaryl group, C₇-C₄₀ alkylaryl group, or R^{1 1} 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 as stated for

R^{1 1};

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

the radicals R¹⁰ are identical or different and have the meanings stated for R¹¹, R¹² and R¹³ wherein further two adjacent R¹⁰ radicals can be joined together to form a ring system.

14. A supported catalyst system produced by the method of any of the preceding claims.

15. A process for polymerizing propylene alone or in combination with one or more other olefins, said process comprising polymerizing in the presence of the supported catalyst system of claim 14.