Aluminoboronate activators for single-site olefin polymerization catalysts

• US 20040181017A1
• Filed: 03/23/2004
• Published: 09/16/2004
• Est. Priority Date: 06/04/2001
• Status: Active Grant

• Current Assignee: Equistar Chemicals LP (Lyondellbasell Industries NV)
• Original Assignee: Equistar Chemicals LP (Lyondellbasell Industries NV)
• Inventors: Neal-Hawkins, Karen L., Nagy, Sandor, Meverden, Craig C., Lynch, Michael W.
• Granted Patent: US 6,933,354 B2
• Time in Patent Office: Days
• US Class Current: 526/127
• 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 210/08 Butenes
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2500/02 Low molecular weight, e.g. <100,000 Da.
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• 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 4/6592 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

Abstract

Single-site catalyst systems useful for polymerizing olefins are disclosed. The catalyst systems comprise an organometallic complex and an activator. The complex includes a Group 3-10 transition metal, M, and at least one indenoindolyl ligand that is pi-bonded to M. The activator is a reaction product of an alkylaluminum compound and an organoboronic acid. Catalyst systems of the invention significantly outperform known catalyst-systems that employ a metallocene complex and similar aluminoboronate activators.

Claims

1. A catalyst system which comprises:

(a) an organometallic complex which comprises a Group 3-10 transition metal, M, and at least one indenoindolyl. ligand that is pi-bonded to M; and

(b) an activator which comprises the reaction product of an alkylaluminum compound and an organoboronic acid.

2. The catalyst system of claim 1 wherein the organometallic complex includes a Group 4-6 transition metal.

3. The catalyst system of claim 1 wherein the organometallic complex includes a Group 4 transition metal.

4. The catalyst system of claim 1 wherein the indenoindolyl ligand has a structure selected from the group consisting of:

5. The catalyst system of claim 1 wherein the organometallic complex further incorporates a polymerization-stable ligand selected from the group consisting of cyclopentadienyl, indenyl, fluorenyl, boraaryl, azaborolinyl, carbazolyl, pyrrolyl, indolyl, 8-quinolinoxy, and 2-pyridinoxy.

6. The catalyst system of claim 1 wherein the organometallic complex incorporates a labile ligand selected from the group consisting of halide, alkyl, aryl, aralkyl, alkoxy, aryloxy, dialkylamino, and siloxy.

7. The catalyst system of claim 1 wherein the indenoindolyl ligand is bridged to another ligand.

8. The catalyst system of claim 1 wherein the alkylaluminum compound is selected from the group consisting of trimethylaluminum and triethylaluminum.

9. The catalyst system of claim 1 wherein the organoboronic acid is a polyfluoroaryl boronic acid.

10. The catalyst system of claim 9 wherein the polyfluoroaryl boronic acid is pentafluorophenylboronic acid.

11. The catalyst system of claim 1 further comprising an alkyl alumoxane.

12. A supported catalyst system of claim 1.

13. The catalyst system of claim 12 wherein the support is selected from the group consisting of silicas and aluminum phosphates.

16. A process which comprises polymerizing an olefin in the presence of the catalyst system of claim 1.

17. A process which comprises polymerizing an olefin in the presence of the supported catalyst system of claim 12.

14. A catalyst system which comprises:

(a) an organometallic complex which comprises a Group 4 transition metal, M, and at least one indenoindolyl ligand that is pi-bonded to M; and

(b) an activator which comprises the reaction product of (1) an alkylaluminum compound selected from the group consisting of trimethylaluminum and triethylaluminum and (2) a polyfluoroaryl boronic acid.

15. A supported catalyst system of claim 14.

18. A process which comprises polymerizing an olefin in the presence of the catalyst system of claim 14.

19. A process which comprises polymerizing an olefin in the presence of the supported catalyst system of claim 15.