Multi-catalyst system for olefin polymerization

• US 20040259722A1
• Filed: 06/20/2003
• Published: 12/23/2004
• Est. Priority Date: 06/20/2003
• Status: Active Grant

• Current Assignee: Equistar Chemicals LP (Lyondellbasell Industries NV)
• Original Assignee: Equistar Chemicals LP (Lyondellbasell Industries NV)
• Inventors: Wang, Shaotian
• Granted Patent: US 6,861,485 B2
• Time in Patent Office: Days
• US Class Current: 502/103
• CPC Class Codes: C08F 110/02 Ethene
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2420/02 Cp or analog bridged to a non-Cp X anionic donor
• CPC Class Codes: C08F 2420/05 Cp or analog where at least one of the carbon atoms of the coordinating ring is replaced by a heteroatom
• CPC Class Codes: C08F 2420/06 Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom
• CPC Class Codes: C08F 2500/05 Bimodal or multimodal molecular weight distribution
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 4/65904 in combination with another component of C08F4/64
• 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

A multi-catalyst system is disclosed. The catalyst system comprises catalyst A and catalyst B. Catalyst A comprises a supported bridged indenoindolyl transition metal complex. Catalyst B comprises a supported non-bridged indenoindolyl transition metal complex. The catalyst system of the invention produces polyolefins which have bi- or multi-modal molecular weight distribution.

Claims

1. A multi-catalyst system that comprises

(a) catalyst A, a supported bridged indenoindolyl transition metal complex;

and

(b) catalyst B, a supported non-bridged indenoindolyl transition metal complex;

wherein A and B are separately supported.

2. The catalyst system of claim 1 wherein the complex of catalyst A has the general structure of I, II, III or IV:

3. The catalyst system of claim 2 wherein L is selected from the group consisting of cyclopentadienyls, indenyls, fluorenyls, boraarys, pyrrolyls, azaborolinyls, quinolinyls, indenoindolyls, phosphinimines, and alkylaminos.

4. The catalyst system of claim 2 wherein G is selected from the group consisting of dialkylsilyl, diarylsilyl, methylene, ethylene, isopropylidene, and diphenylmethylene.

5. The catalyst system of claim 2 wherein the bridged complex has the general structure of I or II and wherein M is a Group 4 transition metal, L is alkylamido, and G is dialkylsilyl.

6. The catalyst system of claim 5 wherein M is Ti or Zr, L is t-butylamino, G is dimethylsilyl, and X is halide or alkyl.

7. The catalyst system of claim 2 wherein the bridged complex has the general structure of III or IV and wherein M is a Group 4 transition metal, L is alkylamido, and G is dialkylsilyl.

8. The catalyst system of claim 7 wherein M is Ti or Zr, L is t-butylamino, G is dimethylsilyl, and X is halide or alkyl.

9. The catalyst system of claim 1 wherein the non-bridged complex of catalyst B has the general structure of

10. The catalyst system of claim 9 wherein R is methyl, L is cyclopentadienyl;

M is Zr;

X is chloride, and n is 2.

11. The catalyst system of claim 1 wherein catalyst A further comprises an activator selected from the group consisting of alumoxanes, alkyl aluminums, alkyl aluminum halides, anionic compounds of boron or aluminum, trialkylboron and triarylboron compounds, and mixtures thereof.

12. The catalyst system of claim 11 wherein the activator is an alumoxane.

13. The catalyst system of claim 1 wherein catalyst B further comprises an activator selected from the group consisting of alumoxanes, alkyl aluminums, alkyl aluminum halides, anionic compounds of boron or aluminum, trialkylboron and triarylboron compounds, and mixtures thereof.

14. The catalyst system of claim 13 wherein the activator is an alumoxane.

15. The catalyst system of claim 1 wherein the support in catalyst A and catalyst B is silica.

16. A process comprising polymerizing an o-olefin in the presence of the catalyst system of claim 1.

17. The process of claim 16 which produces a polyolefin having bi- or multi-modal molecular weight distribution.

18. The process of claim 16 wherein the a-olefin is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and mixtures thereof.

19. A process comprising polymerizing an α

-olefin in the presence of a multi-catalyst system that comprises

(a) catalyst A, a supported bridged indenoindolyl transition metal complex; and

(b) catalyst B, a supported non-bridged indenoindolyl transition metal complex;

wherein A and B are separately supported, said process produces an polyolefin having bi- or multi-modal molecular weight distribution.