US6127484A
Expired / Lapsed
US
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Olefin polymerization process
Assignee: Equistar Chemicals LP
•
Filing: 1999-04-29
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Granted: 2000-10-03
•
Expires: 2019-04-29
Abstract
Abstract A multiple stage or multiple zone process for making olefin polymers is disclosed. A single-site catalyst, preferably one that contains a heteroatomic ligand, is used in the first stage or zone, and a Ziegler-Natta catalyst is used at a higher temperature in later stages or zones. A parallel multiple zone process is also described. The processes, which can be performed adiabatically, give polymers with improved thermal processing ability.
Inventors
- 👤 Leonard V. Cribbs
- 👤 Bradley P. Etherton
- 👤 Mark P. Mack
- 👤 James H. Meas, Jr.
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 20:20
CPC Classifications
C; C08; C08L; C08L23/00; C08L23/02; C08L23/04; C08F; C08F10/00; C08F10/02; C08F110/00; C08F110/04; C08F110/06; C08F110/02; C08F210/00; C08F210/16; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F4/659; C08F4/65908; C08L2205/00; C08L2205/02; C08L2314/00; C08L2314/02; C08L2314/06
Claims Analysis
Total Claims: 30
Claim 1
Independent Claim
124 words
A multiple zone process which comprises: (a) polymerizing an olefin in a first reaction zone with a single-site catalyst in the presence of a non-alumoxane activator at a temperature within the range of about 130° C. to about 200° C. to produce a first polymer having a weight average molecular weight (Mw) within the range of about 5,000 to about 500,000; and (b) transferring the first polymer to a second reaction zone at a higher temperature within the range of about 140° C. to about 280° C. with additional olefin in the presence of a Ziegler-Natta catalyst to produce a final polymer composition having a density less than about 0.98 g/mL and Ml 2 within the range of about 0.5 to about 300 dg/min.
Claim 2
Dependent Claim
124 words
A multiple zone process which comprises: (a) polymerizing an olefin in a first reaction zone with a single-site catalyst in the presence of a non-alumoxane activator at a temperature within the range of about 130° C. to about 200° C. to produce a first polymer having a weight average molecular weight (Mw) within the range of about 5,000 to about 500,000; and (b) transferring the first polymer to a second reaction zone at a higher temperature within the range of about 140° C. to about 280° C. with additional olefin in the presence of a Ziegler-Natta catalyst to produce a final polymer composition having a density less than about 0.98 g/mL and Ml 2 within the range of about 0.5 to about 300 dg/min.
Claim 3
Dependent Claim
25 words
The process of claim 1 wherein the temperature of the first reaction zone is within the range of about 130° C. to about 150° C.
Claim 4
Dependent Claim
6 words
An adiabatic process of claim 1.
Claim 5
Dependent Claim
7 words
A solution polymerization process of claim 1.
Claim 6
Dependent Claim
24 words
The process of claim 1 wherein the olefin is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and mixtures thereof.
Claim 7
Dependent Claim
10 words
The process of claim 1 wherein the olefin is ethylene.
Claim 8
Dependent Claim
24 words
The process of claim 1 wherein the single-site catalyst contains a heteroatomic ligand selected the group consisting of boraaryl, azaborolinyl, pyridinyl, pyrrolyl, and quinolinyl.
Claim 9
Dependent Claim
32 words
The process of claim 1 wherein the non-alumoxane activator is selected from the group consisting of alkyl aluminums, alkyl aluminum halides, anionic compounds of boron or aluminum, trialkylboron compounds, and triarylboron compounds.
Claim 10
Dependent Claim
25 words
The process of claim 1 wherein the Ziegler-Natta catalyst is selected from the group consisting of titanium halides, titanium alkoxides, vanadium halides, and mixtures thereof.
Claim 11
Dependent Claim
24 words
The process of claim 1 wherein the process is performed at a pressure within the range of about 500 psi to about 5,000 psi.
Claim 12
Dependent Claim
143 words
A multiple zone process which comprises: (a) polymerizing an olefin in a first reaction zone with a single-site catalyst that contains at least one heteroatomic ligand selected from the group consisting of boraaryl, azaborolinyl, pyridinyl, pyrrolyl, and quinolinyl, in the presence of a non-alumoxane activator at a temperature within the range of about 130° C. to about 200° C. to produce a first polymer having a weight average molecular weight (Mw) within the range of about 5,000 to about 500,000; and (b) transferring the first polymer to a second reaction zone at a higher temperature within the range of about 140° C. to about 280° C. with additional olefin in the presence of a Ziegler-Natta catalyst to produce a final polymer composition having a density less than about 0.98 g/mL and Ml 2 within the range of about 0.5 to about 300 dg/min.
Claim 13
Dependent Claim
143 words
A multiple zone process which comprises: (a) polymerizing an olefin in a first reaction zone with a single-site catalyst that contains at least one heteroatomic ligand selected from the group consisting of boraaryl, azaborolinyl, pyridinyl, pyrrolyl, and quinolinyl, in the presence of a non-alumoxane activator at a temperature within the range of about 130° C. to about 200° C. to produce a first polymer having a weight average molecular weight (Mw) within the range of about 5,000 to about 500,000; and (b) transferring the first polymer to a second reaction zone at a higher temperature within the range of about 140° C. to about 280° C. with additional olefin in the presence of a Ziegler-Natta catalyst to produce a final polymer composition having a density less than about 0.98 g/mL and Ml 2 within the range of about 0.5 to about 300 dg/min.
Claim 14
Dependent Claim
119 words
A multiple stage process which comprises: (a) in a first stage, polymerizing an olefin with a single-site catalyst in a reactor in the presence of a non-alumoxane activator at a temperature within the range of about 130° C. to about 200° C. to produce a first polymer having Mw within the range of about 5,000 to about 500,000; and (b) continuing polymerization in a second stage by adding a Ziegler-Natta catalyst and additional olefin to the reactor at a higher temperature within the range of about 140° C. to about 280° C. to produce a final polymer composition having a density less than about 0.98 g/mL and Ml 2 within the range of about 0.5 to about 300 dg/min.
Claim 15
Dependent Claim
119 words
A multiple stage process which comprises: (a) in a first stage, polymerizing an olefin with a single-site catalyst in a reactor in the presence of a non-alumoxane activator at a temperature within the range of about 130° C. to about 200° C. to produce a first polymer having Mw within the range of about 5,000 to about 500,000; and (b) continuing polymerization in a second stage by adding a Ziegler-Natta catalyst and additional olefin to the reactor at a higher temperature within the range of about 140° C. to about 280° C. to produce a final polymer composition having a density less than about 0.98 g/mL and Ml 2 within the range of about 0.5 to about 300 dg/min.
Claim 16
Dependent Claim
24 words
The process of claim 12 wherein the temperature for the first stage is within the range of about 130° C. to about 150° C.
Claim 17
Dependent Claim
6 words
An adiabatic process of claim 12.
Claim 18
Dependent Claim
7 words
A solution polymerization process of claim 12.
Claim 19
Dependent Claim
24 words
The process of claim 12 wherein the olefin is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and mixtures thereof.
Claim 20
Dependent Claim
10 words
The process of claim 12 wherein the olefin is ethylene.
Claim 21
Dependent Claim
24 words
The process of claim 12 wherein the single-site catalyst contains a heteroatomic ligand selected the group consisting of boraaryl, azaborolinyl, pyridinyl, pyrrolyl, and quinolinyl.
Claim 22
Dependent Claim
32 words
The process of claim 12 wherein the non-alumoxane activator is selected from the group consisting of alkyl aluminums, alkyl aluminum halides, anionic compounds of boron or aluminum, trialkylboron compounds, and triarylboron compounds.
Claim 23
Dependent Claim
25 words
The process of claim 12 wherein the Ziegler-Natta catalyst is selected from the group consisting of titanium halides, titanium alkoxides, vanadium halides, and mixtures thereof.
Claim 24
Dependent Claim
20 words
The process of claim 12 wherein the process is performed under pressure of about 500 psi to about 5,000 psi.
Claim 25
Dependent Claim
138 words
A multiple stage process which comprises: (a) in a first stage, polymerizing an olefin with a single-site catalyst that contains at least one heteroatomic ligand selected from the group consisting of boraaryl, azaborolinyl, pyridinyl, pyrrolyl, and quinolinyl, in a reactor in the presence of a non-alumoxane activator at a temperature within the range of about 130° C. to about 200° C. to produce a first polymer having Mw within the range of about 5,000 to about 500,000; and (b) continuing polymerization in a second stage by adding a Ziegler-Natta catalyst and additional olefin to the reactor at a higher temperature within the range of about 140° C. to about 280° C. to produce a final polymer composition having a density less than about 0.98 g/mL and Ml 2 within the range of about 0.5 to about 300 dg/min.
Claim 26
Dependent Claim
138 words
A multiple stage process which comprises: (a) in a first stage, polymerizing an olefin with a single-site catalyst that contains at least one heteroatomic ligand selected from the group consisting of boraaryl, azaborolinyl, pyridinyl, pyrrolyl, and quinolinyl, in a reactor in the presence of a non-alumoxane activator at a temperature within the range of about 130° C. to about 200° C. to produce a first polymer having Mw within the range of about 5,000 to about 500,000; and (b) continuing polymerization in a second stage by adding a Ziegler-Natta catalyst and additional olefin to the reactor at a higher temperature within the range of about 140° C. to about 280° C. to produce a final polymer composition having a density less than about 0.98 g/mL and Ml 2 within the range of about 0.5 to about 300 dg/min.
Claim 27
Dependent Claim
180 words
A parallel multiple zone process which comprises: (a) polymerizing an olefin in a first reaction zone with a single-site catalyst in the presence of a non-alumoxane activator at a temperature within the range of about 130° C. to about 200° C. to produce a first polymer having Mw within the range of about 5,000 to about 500,000; (b) polymerizing an olefin in a second reaction zone that is parallel to the first reaction zone at a higher temperature within the range of about 140° C. to about 280° C. in the presence of a Ziegler-Natta catalyst to produce a second polymer having Mw within the range of about 20,000 to about 500,000; and (c) combining the first and second polymers in a third reaction zone to continue the polymerization at a temperature within the range of about 140° C. to about 280° C. with additional olefin in the presence of a Ziegler-Natta catalyst to produce a final polymer composition having a density less than about 0.98 g/mL and Ml 2 within the range of about 0.5 to about 300 dg/min.
Claim 28
Dependent Claim
180 words
A parallel multiple zone process which comprises: (a) polymerizing an olefin in a first reaction zone with a single-site catalyst in the presence of a non-alumoxane activator at a temperature within the range of about 130° C. to about 200° C. to produce a first polymer having Mw within the range of about 5,000 to about 500,000; (b) polymerizing an olefin in a second reaction zone that is parallel to the first reaction zone at a higher temperature within the range of about 140° C. to about 280° C. in the presence of a Ziegler-Natta catalyst to produce a second polymer having Mw within the range of about 20,000 to about 500,000; and (c) combining the first and second polymers in a third reaction zone to continue the polymerization at a temperature within the range of about 140° C. to about 280° C. with additional olefin in the presence of a Ziegler-Natta catalyst to produce a final polymer composition having a density less than about 0.98 g/mL and Ml 2 within the range of about 0.5 to about 300 dg/min.
Claim 29
Dependent Claim
199 words
A parallel multiple zone process which comprises: (a) polymerizing an olefin in a first reaction zone with a single-site catalyst that contains at least one heteroatomic ligand selected from the group consisting of boraaryl, azaborolinyl, pyridinyl, pyrrolyl, and quinolinyl, in the presence of a non-alumoxane activator at a temperature within the range of about 130° C. to about 200° C. to produce a first polymer having Mw within the range of about 5,000 to about 500,000; (b) polymerizing an olefin in a second reaction zone that is parallel to the first reaction zone at a higher temperature within the range of about 140° C. to about 280° C. in the presence of a Ziegler-Natta catalyst to produce a second polymer having Mw within the range of about 20,000 to about 500,000; and (c) combining the first and second polymers in a third reaction zone to continue the polymerization at a temperature within the range of about 140° C. to about 280° C. with additional olefin in the presence of a Ziegler-Natta catalyst to produce a final polymer composition having a density less than about 0.98 g/mL and Ml 2 within the range of about 0.5 to about 300 dg/min.
Claim 30
Dependent Claim
199 words
A parallel multiple zone process which comprises: (a) polymerizing an olefin in a first reaction zone with a single-site catalyst that contains at least one heteroatomic ligand selected from the group consisting of boraaryl, azaborolinyl, pyridinyl, pyrrolyl, and quinolinyl, in the presence of a non-alumoxane activator at a temperature within the range of about 130° C. to about 200° C. to produce a first polymer having Mw within the range of about 5,000 to about 500,000; (b) polymerizing an olefin in a second reaction zone that is parallel to the first reaction zone at a higher temperature within the range of about 140° C. to about 280° C. in the presence of a Ziegler-Natta catalyst to produce a second polymer having Mw within the range of about 20,000 to about 500,000; and (c) combining the first and second polymers in a third reaction zone to continue the polymerization at a temperature within the range of about 140° C. to about 280° C. with additional olefin in the presence of a Ziegler-Natta catalyst to produce a final polymer composition having a density less than about 0.98 g/mL and Ml 2 within the range of about 0.5 to about 300 dg/min.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 2003-10-03 | 2004-04-03 | 2004-10-03 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2007-10-03 | 2008-04-03 | 2008-10-03 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2011-10-03 | 2012-04-03 | 2012-10-03 | $7700.00 | Window Closed / Lapsed |