IP Library Granted Patent US 7,781,549
Granted Patent B2
US 7,781,549 · App. 11/899,090 · Granted Aug 24, 2010

Olefin polymerization process

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Quick Facts
Patent No.
US 7,781,549
App. No.
11/899,090
Granted
Aug 24, 2010
Kind
B2
Abstract

A slurry process for polymerizing ethylene is disclosed. The process comprises polymerizing ethylene in the presence of an α-olefin and a catalyst comprising an activator and a supported bridged indeno[1,2-b]indolyl zirconium complex. The process produces polyethylene characterized by good incorporation of the α-olefin and low long-chain branching. The process is capable of forming high-molecular-weight polyethylene and has good hydrogen sensitivity.

Claims (22)

1. A slurry process which comprises polymerizing ethylene at a temperature within the range of 40° C. to 90° C. in the presence of a C 3 -C 10 α-olefin and a catalyst comprising an activator and a supported complex to produce polyethylene with good incorporation of the α-olefin and low long-chain branching as indicated by a viscosity enhancement factor of less than 2.0, wherein the process forms polyethylene having weight-average molecular weight greater than 250,000, wherein the process has good hydrogen sensitivity such that introduction of 0.82 mmoles of hydrogen per mole of ethylene into the liquid phase reduces the weight-average molecular weight by at least 60%, and wherein the complex has the structure:

wherein each R 1 is independently selected from the group consisting of C 1 -C 6 n-alkyl; each R 2 is independently selected from the group consisting of H and C 1 -C 10 hydrocarbyl; and each L is independently selected from the group consisting of halide, alkoxy, aryloxy, siloxy, alkylamino, and C 1 -C 30 hydrocarbyl.

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

3. The process of claim 2 wherein the activator is methylalumoxane.

4. The process of claim 1 wherein R 1 is methyl.

5. The process of claim 1 wherein each L is Cl.

6. The process of claim 1 wherein the C 3 -C 10 α-olefin is selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

7. The process of claim 1 wherein the activity ratio as defined herein is greater than 2.

8. The process of claim 1 that forms polyethylene having a weight-average molecular weight greater than 400,000.

9. The process of claim 1 wherein 63 mmoles of 1-butene per mole of ethylene in the liquid phase forms polyethylene with greater than 5 tertiary carbons per 1000 carbons.

10. The process of claim 1 wherein the supported complex is supported on silica.

11. The process of claim 1 wherein the complex has the structure:

wherein each L is independently selected from the group consisting of halide, alkoxy, aryloxy, siloxy, alkylamino, and C 1 -C 30 hydrocarbyl.

12. A slurry process which comprises polymerizing ethylene at a temperature within the range of 40° C. to 90° C. in the presence of a C 3 -C 10 α-olefin and a catalyst comprising an activator and a supported complex to produce polyethylene with good incorporation of the α-olefin and low long-chain branching as indicated by a viscosity enhancement factor of less than 2.0, wherein the process forms polyethylene having a weight-average molecular weight greater than 250,000, wherein the process has good hydrogen sensitivity such that introduction of 0.82 mmole of hydrogen per mole of ethylene into the liquid phase reduces the weight-average molecular weight by greater than 60%, and wherein the complex has the structure selected from the group consisting of:

wherein R 1 is C 1 -C 6 n-alkyl; R 3 is C 1 -C 6 alkyl; and each L is independently selected from the group consisting of halide, alkoxy, aryloxy, siloxy, alkylamino, and C 1 -C 30 hydrocarbyl.

13. The process of claim 12 wherein 63 mmoles of 1-butene per mole of ethylene in the liquid phase forms polyethylene with greater than 5 tertiary carbons per 1000 carbons.

14. The process of claim 12 wherein the complex has the structure:

wherein each L is independently selected from the group consisting of halide, alkoxy, aryloxy, siloxy, alkylamino, and C 1 -C 30 hydrocarbyl.

15. The process of claim 12 wherein the supported complex is supported on silica.

16. The process of claim 14 wherein the activity ratio as defined herein is greater than 2.

17. The process of claim 12 wherein the activator is selected from the group consisting of alumoxanes, alkylaluminum compounds, organoboranes, ionic borates, ionic aluminates, aluminoboronates, and combinations thereof.

18. The process of claim 12 wherein the activator is methylalumoxane.

Assignments (18)
RELEASE OF SECURITY INTEREST Recorded Jan 22, 2014
From: WELLS FARGO BANK, NATIONAL ASSOCIATION
To: EQUISTAR CHEMICALS, LP
Reel/Frame 032112/0786 →
APPOINTMENT OF SUCCESSOR ADMINISTRATIVE AGENT Recorded Jan 22, 2014
From: UBS AG, STAMFORD BRANCH
To: BANK OF AMERICA, N.A.
Reel/Frame 032112/0863 →
RELEASE OF SECURITY INTEREST Recorded Jan 22, 2014
From: CITIBANK, N.A.
To: EQUISTAR CHEMICALS, LP
Reel/Frame 032113/0644 →
RELEASE OF SECURITY INTEREST Recorded Jan 22, 2014
From: DEUTSCHE BANK TRUST COMPANY AMERICAS
To: EQUISTAR CHEMICALS, LP
Reel/Frame 032113/0684 →
RELEASE OF SECURITY INTEREST Recorded Jan 22, 2014
From: BANK OF AMERICA, N.A.
To: EQUISTAR CHEMICALS, LP
Reel/Frame 032113/0730 →
SECURITY AGREEMENT Recorded May 19, 2010
From: EQUISTAR CHEMICALS, LP
To: WELLS FARGO BANK, NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 024402/0655 →
SECURITY AGREEMENT Recorded May 18, 2010
From: EQUISTAR CHEMICALS, LP
To: CITIBANK, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 024397/0861 →
SECURITY AGREEMENT Recorded May 7, 2010
From: EQUISTAR CHEMICALS. LP
To: UBS AG, STAMFORD BRANCH, AS COLLATERAL AGENT
Reel/Frame 024351/0001 →
SECURITY AGREEMENT Recorded May 6, 2010
From: EQUISTAR CHEMICALS, LP
To: DEUTSCHE BANK TRUST COMPANY AMERICAS, AS COLLATERAL AGENT
Reel/Frame 024342/0443 →
RELEASE OF SECURITY INTEREST Recorded May 5, 2010
From: CITIBANK, N.A., AS COLLATERAL AGENT
To: LYONDELL CHEMICAL TECHNOLOGY, L.P.; EQUISTAR CHEMICALS, LP
Reel/Frame 024337/0705 →
RELEASE OF SECURITY INTEREST Recorded May 5, 2010
From: UBS AG, STAMFORD BRANCH, AS COLLATERAL AGENT
To: EQUISTAR CHEMICALS, LP
Reel/Frame 024337/0186 →
RELEASE OF SECURITY INTEREST Recorded May 5, 2010
From: CITIBANK, N.A., AS COLLATERAL AGENT
To: LYONDELL CHEMICAL TECHNOLOGY, L.P.; EQUISTAR CHEMICALS, LP
Reel/Frame 024337/0856 →
RELEASE OF SECURITY INTEREST Recorded May 4, 2010
From: CITIBANK, N.A., AS COLLATERAL AGENT
To: EQUISTAR CHEMICALS, LP
Reel/Frame 024329/0535 →
SECURITY AGREEMENT Recorded Oct 30, 2009
From: EQUISTAR CHEMICALS, LP
To: UBS AG, STAMFORD BRANCH, AS COLLATERAL AGENT
Reel/Frame 023449/0687 →
SECURITY AGREEMENT Recorded Apr 9, 2009
From: EQUISTAR CHEMICALS, LP
To: CITIBANK, N.A., AS ADMINISTRATIVE AGENT AND COLLATERAL AGENT
Reel/Frame 022678/0860 →
SECURITY AGREEMENT Recorded Aug 4, 2008
From: BASELL POLYOLEFINE GMBH; ARCO CHEMICAL TECHNOLOGY L.P.; ARCO CHEMICAL TECHNOLOGY, INC.; ATLANTIC RICHFIELD COMPANY; BASELL NORTH AMERICA, INC.; BASELL POLYOLEFIN GMBH; LYONDELL CHEMICAL COMPANY; EQUISTAR CHEMICALS, L.P.
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 021354/0708 →
GRANT OF SECURITY INTEREST IN UNITED STATES PATENTS AND PATENT APPLICATIONS Recorded Mar 26, 2008
From: BASELL POLYOLEFINE GMBH; ARCO CHEMICAL TECHNOLOGY L.P.; ARCO CHEMICAL TECHNOLOGY, INC.; ATLANTIC RICHFIELD COMPANY; BASELL NORTH AMERICA, INC.; EQUISTAR CHEMICALS. LP.; LYONDELL CHEMICAL COMPANY; LYONDELL CHEMICAL TECHNOLOGY, L.P.; LYONDELL PETROCHEMICAL COMPANY; NATIONAL DISTILLERS AND CHEMICAL CORPORATION; OCCIDENTAL CHEMICAL CORPORATION; OLIN CORPORATION; QUANTUM CHEMICAL CORPORATION; BASELL POLYOLEFIN GMBH
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 020704/0562 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 27, 2007
From: NAGY, SANDOR; TSUIE, BARBARA M.
To: EQUISTAR CHEMICALS, LP
Reel/Frame 019906/0887 →