US6908972B2
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Method for making polyolefins
Assignee: Equistar Chemicals LP
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Filing: 2002-04-16
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Granted: 2005-06-21
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Expires: 2022-04-16
Abstract
Abstract A method for making ethylene polymers and copolymers is disclosed. The method uses a catalyst system comprising a low level of an aluminum-containing activator, a bridged indenoindolyl transition metal complex, and a treated silica support. The method enables economical preparation of ethylene copolymers having very low density. The silica-supported, bridged complexes incorporate comonomers efficiently and are valuable for a commercial slurry loop process. Use of a bridged indeno[2,1-b]indolyl complex provides exceptionally efficient comonomer incorporation, and gives polymers with a substantial and controlled level of long-chain branching. The method facilitates the production of a wide variety of polyolefins, from HDPE to plastomers.
Inventors
- 👤 Barbara M. Tsuie
- 👤 Karen L. Neal-Hawkins
- 👤 Sandor Nagy
- 👤 Michael W. Lynch
- 👤 Mark P. Mack
- 👤 Shaotian Wang
- 👤 Jean A Merrick-Mack
- 👤 Clifford C. Lee
- 👤 Joel A. Mutchler
- 👤 Kenneth W. Johnson
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 06:06
CPC Classifications
C; C08; C08F; C08F210/00; C08F210/02; C08F110/00; C08F110/02; C08F210/16; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F4/659; C08F4/65908; C08F4/65912; C08F4/65916
Claims Analysis
Total Claims: 31
Claim 1
Independent Claim
69 words
A method which comprises copolymerizing ethylene and a 1-olefin in the presence of a catalyst system comprising (a) an aluminum-containing activator; (b) a bridged, indenoindolyl Group 3-10 transition metal complex; and (c) an alumoxane-treated silica support, to produce a linear low density or plastomeric ethylene copolymer having a density less than 0.930 g/cm 3 , wherein the catalyst system has an aluminum:transition metal [Al:M] mole ratio less than 500.
Claim 2
Independent Claim
69 words
A method which comprises copolymerizing ethylene and a 1-olefin in the presence of a catalyst system comprising (a) an aluminum-containing activator; (b) a bridged, indenoindolyl Group 3-10 transition metal complex; and (c) an alumoxane-treated silica support, to produce a linear low density or plastomeric ethylene copolymer having a density less than 0.930 g/cm 3 , wherein the catalyst system has an aluminum:transition metal [Al:M] mole ratio less than 500.
Claim 3
Dependent Claim
14 words
The method of claim 1 wherein the complex includes a Group 4-6 transition metal.
Claim 4
Dependent Claim
12 words
The method of claim 1 wherein the complex includes an indeno[2,1-b]indolyl ligand.
Claim 5
Dependent Claim
13 words
The method of claim 1 wherein the complex includes an indeno[1 2-b]indolyl ligand.
Claim 6
Dependent Claim
23 words
The method of claim 1 wherein the complex incorporates a bridging group selected from the group consisting of methylene, dimethylene, isopropylidene, and dimethylsilyl.
Claim 7
Dependent Claim
29 words
The method of claim 1 wherein an indenoindolyl ligand of the complex is covalently bridged to a polymerization-stable ligand selected from the group consisting of cyclopentadienyl, indenyl, and fluorenyl.
Claim 8
Dependent Claim
18 words
The method of claim 1 wherein the activator is methylalumoxane or a mixture of methylalumoxane and an organoborane.
Claim 9
Dependent Claim
10 words
The method of claim 7 wherein the organoborane is tris-(pentafluorophenyl)borane.
Claim 10
Dependent Claim
15 words
The method of claim 1 wherein the [Al:M] mole ratio is less than about 250.
Claim 11
Dependent Claim
22 words
The method of claim 1 wherein the 1-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene, 1-octene, and mixtures thereof.
Claim 12
Dependent Claim
18 words
The method of claim 1 wherein the ethylene copolymer has a density less than 0.920 g/cm 3 .
Claim 13
Dependent Claim
18 words
The method of claim 1 wherein the ethylene copolymer has a density less than 0.910 g/cm 3 .
Claim 14
Dependent Claim
18 words
The method of claim 1 wherein the ethylene copolymer has a density less than 0.900 g/cm 3 .
Claim 15
Dependent Claim
12 words
The method of claim 1 wherein the ethylene copolymer has a Mw/Mn<4.0.
Claim 16
Dependent Claim
31 words
The method of claim 1 performed in the presence of a chain-transfer agent selected from the group consisting of hydrogen, organozinc compounds, and organoaluminum compounds, to produce a copolymer having Mw<150,000.
Claim 17
Dependent Claim
21 words
The method of claim 15 wherein the chain-transfer agent is triethylaluminum in combination with hydrogen, and the copolymer has a Mw/Mn<3.5.
Claim 18
Dependent Claim
19 words
The method of claim 1 performed in the absence of a chain-transfer agent to produce a copolymer having Mw>400,000.
Claim 19
Dependent Claim
19 words
The method of claim 1 wherein the complex incorporates a fluorenyl ligand, and the resulting copolymer has a Mw>200,000.
Claim 20
Independent Claim
62 words
A method which comprises polymerizing ethylene and optionally a 1-olefin in the presence of a catalyst system comprising (a) an aluminum-containing activator; (b) a bridged, indeno[2,1-b]indolyl Group 3-10 transition metal complex; and (c) an alumoxane-treated silica support, to produce an ethylene polymer or copolymer having a long-chain-branching index>0.2, wherein the catalyst system has an aluminum:transition metal [Al:M] mole ratio less than 500.
Claim 21
Independent Claim
62 words
A method which comprises polymerizing ethylene and optionally a 1-olefin in the presence of a catalyst system comprising (a) an aluminum-containing activator; (b) a bridged, indeno[2,1-b]indolyl Group 3-10 transition metal complex; and (c) an alumoxane-treated silica support, to produce an ethylene polymer or copolymer having a long-chain-branching index>0.2, wherein the catalyst system has an aluminum:transition metal [Al:M] mole ratio less than 500.
Claim 22
Dependent Claim
23 words
The method of claim 19 wherein the complex incorporates a bridging group selected from the group consisting of methylene, dimethylene, isopropylidene, and dimethylsilyl.
Claim 23
Dependent Claim
29 words
The method of claim 19 wherein an indeno[2,1-b]indolyl ligand of the complex is covalently bridged to a polymerization-stable ligand selected from the group consisting of cyclopentadienyl, indenyl, and fluorenyl.
Claim 24
Dependent Claim
15 words
The method of claim 19 wherein the [Al:M] mole ratio is less than about 250.
Claim 25
Dependent Claim
14 words
The method of claim 19 wherein the polymer or copolymer has a long-chain-branching index>0.5.
Claim 26
Dependent Claim
14 words
The method of claim 19 wherein the polymer or copolymer has a long-chain-branching index>1.0.
Claim 27
Dependent Claim
13 words
The method of claim 19 wherein the polymer or copolymer has a Mw/Mn<4.0.
Claim 28
Dependent Claim
22 words
The method of claim 19 wherein the 1-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene, 1-octene, and mixtures thereof.
Claim 29
Dependent Claim
20 words
The method of claim 26 wherein the copolymer is plastomeric and has a density less than 0.915 g/cm 3 .
Claim 30
Dependent Claim
17 words
The method of claim 27 wherein the copolymer has a density less than 0.900 g/cm 3 .
Claim 31
Dependent Claim
39 words
The method of claim 19 wherein the transition metal complex incorporates a dimethylsilyl bridging group, the 1-olefin is 1-hexene, the mole ratio of 1-hexene to ethylene is at least about 0.3, and the resulting copolymer has a long-chain-branching index>1.0.
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 2008-06-20 | 2008-12-20 | 2009-06-21 | $2000.00 | Window Closed / Lapsed |
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| 11.5 Years (Year 12) | 2016-06-20 | 2016-12-20 | 2017-06-21 | $7700.00 | Window Closed / Lapsed |