High-temperature solution process for polyolefin manufacture

• US 20030229188A1
• Filed: 05/31/2002
• Published: 12/11/2003
• Est. Priority Date: 05/31/2002
• Status: Active Grant

• Current Assignee: Equistar Chemicals LP (Lyondellbasell Industries NV)
• Original Assignee: Equistar Chemicals LP (Lyondellbasell Industries NV)
• Inventors: Nagy, Sandor, Holland, Charles S., Todd, William G., Tsuie, Barbara M.
• Granted Patent: US 6,756,455 B2
• Time in Patent Office: Days
• US Class Current: 526/134
• CPC Class Codes: C08F 10/02 Ethene
• CPC Class Codes: C08F 110/02 Ethene
• CPC Class Codes: C08F 2/06 Organic solvent
• CPC Class Codes: C08F 210/02 Ethene
• 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 2500/04 Broad molecular weight distribution, i.e. Mw/Mn > 6
• CPC Class Codes: C08F 2500/07 High density, i.e. > 0.95 g/cm3
• 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

Abstract

A high-temperature solution process for making polyolefins is disclosed. Olefins polymerize at greater than about 130° C. in the presence of an activator and an organometallic complex. The complex includes a bridged indenoindolyl ligand. One part of the ligand is a second indenoindolyl group or a polymerization-stable, cyclopentadienyl-like group having an extended pi-electron system. Because the catalysts activate quickly and thoroughly, even with low levels of an alumoxane, the invention provides an efficient way to make high-molecular-weight (Mw>100K) polyolefins.

Claims

1. A process which comprises polymerizing one or more olefins in solution in a reaction zone at a temperature greater than about 130°

C. and a pressure greater than about 200 psig in the presence of a catalyst system comprising;

(a) an activator; and

(b) an organometallic complex which comprises a Group 3-10 transition metal and a bridged indenoindolyl ligand of the general structure;

A-G-L

in which A is an indenoindolyl group, G is a bridging group, and L is another indenoindolyl group or a polymerization-stable, cyclopentadienyl-like group having an extended pi-electron system, wherein both A and L are pi-bonded to the metal; and

wherein the average residence time of the olefin in the reaction zone is less than 10 minutes.

2. The process of claim 1 wherein the temperature is greater than about 160°

C.

3. The process of claim 1 wherein the pressure is greater than about 500 psig.

4. The process of claim 1 wherein the activator is selected from the group consisting of alumoxanes, ionic borates, ionic aluminates, alkylaluminum compounds, organoboranes, and aluminoboronates.

5. The process of claim 1 wherein the activator is methyl-alumoxane, and the catalyst system has an aluminum:

transition metal [Al;

M] mole ratio less than 200.

6. The process of claim 1 wherein L is selected from the group consisting of boranaphthalenyl, boraanthracenyl, fluorenyl, indenyl, indolyl, and indenoindolyl.

7. The process of claim 1 wherein G is selected from the group consisting of methylene, dimethylene, dimethylsilyl, diphenylmethyl, alkylboranyl, arylboranyl, and isopropylidene.

8. The process of claim 1 wherein the organometallic complex has the general structure:

9. The process of claim 8 wherein the complex incorporates a Group 4 transition metal.

10. The process of claim 1 wherein the average residence time is less than 5 minutes.

11. The process of claim 1 performed in a multi-stage reactor under adiabatic conditions.

12. The process of claim 11 in which a Ziegler-Natta catalyst is also used.

19. The process of claim 1 wherein the average residence time is less than 5 minutes.

13. A process which comprises polymerizing ethylene, and optionally one or more 1-olefins, in solution in a reaction zone at a temperature greater than about 160°

C. and a pressure greater than about 500 psig in the presence of a catalyst system comprising;

(a) an alumoxane activator; and

(b) an organometallic complex which comprises a Group 4 transition metal and a bridged indenoindolyl ligand of the general structure;

A-G-L

in which A is an indenoindolyl group, G is a bridging group, and L is another indenoindolyl group or a polymerization-stable, cyclopentadienyl-like group having an extended pi-electron system, wherein both A and L are pi-bonded to the metal; and

wherein the average residence time of the olefin in the reaction zone is less than 10 minutes.

14. The process of claim 13 wherein the activator is methyl-alumoxane, and the catalyst system has an aluminum:

transition metal [Al;

M] mole ratio less than 200.

15. The process of claim 13 wherein L is fluorenyl.

16. The process of claim 13 wherein G is dimethylsilyl.

17. The process of claim 13 wherein the organometallic complex has the general structure:

18. The process of claim 17 wherein the complex has the structure:

20. The process of claim 13 performed in a multi-stage reactor under adiabatic conditions.