IP Library Granted Patent US 7,399,809
Granted Patent B1
US 7,399,809 · App. 11/652,236 · Granted Jul 15, 2008

Modifying polyethylene made by Ziegler or single-site catalyst with free radical initiator

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Quick Facts
Patent No.
US 7,399,809
App. No.
11/652,236
Granted
Jul 15, 2008
Kind
B1
Abstract

A method of modifying a polyethylene is disclosed. In the method ethylene or a mixture of ethylene and a C3-C10 α-olefin is polymerized in an organic solvent with a Ziegler or single-site catalyst to form an initial polyethylene solution. The initial polyethylene solution is then reacted with a free radical initiator to produce a modified polyethylene. The modified polymer has an enhanced melt elasticity and increased long chain branching index, and is essentially free of gel.

Claims (12)

1. A process of producing a polyethylene comprising (a) polymerizing ethylene or a mixture of ethylene and a C3-C10 α-olefin with a Ziegler or single-site catalyst in an organic solvent to produce an initial polyethylene solution; (b) reacting the polyethylene solution with a free radical initiator at a temperature within the range of about 150° C. to about 250° C. to produce a modified polyethylene; and (c) isolating the modified polyethylene from the solution, wherein the modified polyethylene has an increase in melt elasticity (ER), and an increase in long chain branching index (LCBI) compared to the initial polyethylene, and wherein the modified polyethylene is essentially free of gel.

2. The process of claim 1 wherein the polyethylene is a high density polyethylene (HDPE).

3. The process of claim 1 wherein the organic solvent is a C 6 to C 16 hydrocarbon.

4. The process of claim 1 wherein the organic solvent is selected from the group consisting of hexadecane, toluene, xylene, hexane, cyclohexane, and mixtures thereof.

5. The process of claim 1 wherein the free radical initiator is selected from the group consisting of dicumyl peroxide, di-t-butyl peroxide, cumyl hydroperoxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di-t-butylperoxy hexyne, and mixtures thereof.

6. The process of claim 1 wherein the free radical initiator is used in an amount within the range of about 50 to about 5000 ppm of the initial polyethylene.

7. The process of claim 1 wherein the free radical initiator amount is used in an amount within the range of about 500 to about 4000 ppm of the initial polyethylene.

8. The method process of claim 1 wherein the LCBI of the modified polyethylene is about 100 to about 1000% higher than the LCBI of the initial polyethylene.

9. The process of claim 1 wherein the LCBI of the modified polyethylene is about 200 to about 800% higher than the LCBI of the initial polyethylene.

10. The process of claim 1 wherein the ER of the modified polyethylene is about 50% to about 250% higher than the ER of the initial polyethylene.

11. The process of claim 1 wherein the ER of the modified polyethylene is about 100% to about 150% higher than the ER of the initial polyethylene.

12. The process of claim 1 wherein the modified polyethylene has, compared to the initial polyethylene, an increase in the ER of about 100% to about 150% and an increase in the LCBI of about 200% to about 800%.

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 Jan 11, 2007
From: SCHEIE, ANDREW J.; REINKING, MARK K.
To: EQUISTAR CHEMICALS, LP
Reel/Frame 018804/0859 →