US5442018A
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US
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Ethylene polymerization using a titanium and vanadium catalyst system in staged reactors
Assignee: Union Carbide Chemicals and Plastics Technology LLC
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Filing: 1994-04-01
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Granted: 1995-08-15
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Expires: 2014-04-01
Abstract
Abstract A process for producing polyethylene having a broad molecular weight distribution is provided, in which ethylene and optionally a comonomer are contacted in two reactors connected in series, one reactor containing a titanium-based catalyst and the other reactor containing a vanadium-based catalyst and a halohydrocarbon promoter, or alternatively, both reactors containing a mixed metal catalyst comprising both titanium and vanadium. In the latter case, the halohydrocarbon promoter is present in only one of the reactors to activate the vanadium sites of the catalyst and deactivate the titanium sites of the catalyst simultaneously.
Inventors
- 👤 Kevin J. Cann
- 👤 James W. Nicoletti
- 👤 Frederick J. Karol
- 👤 Arthur E. Marcinkowsky
- 👤 Thomas E. Spriggs
- 👤 Mark C. Hwu
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 21:26
CPC Classifications
C; C08; C08F; C08F10/00; C08F10/02; C08L; C08L23/00; C08L23/02; C08L23/04; C08F210/00; C08F210/16; C08F2410/00; C08F2410/05
Claims Analysis
Total Claims: 22
Claim 1
Independent Claim
210 words
A process for preparing polyethylene, comprising 1) contacting in a first reactor under polymerization conditions ethylene and optionally a comonomer in the presence of: a titanium-based catalyst containing: a titanium complex that is the reaction product of a titanium-containing compound in which the titanium is in the +3 or +4 oxidation state, a magnesium halide and a first electron donor; and optionally, a first modifier compound having the formula AlX a R.sub.(3-a), wherein X is a halide, each R is independently an alkyl having 1 to about 14 carbon atoms, and a is 0, 1, 2, or 3; and a first cocatalyst having the formula AlR 3 , to form a mixture; 2) transferring the mixture to a second reactor connected in series to the first reactor; and 3) contacting the mixture with further ethylene and optionally further comonomer in the second reactor under polymerization conditions in the presence of: a vanadium-based catalyst comprising: a vanadium complex that is a vanadium-containing compound in which the vanadium is in the +2, +3, +4, or +5 oxidation state optionally reacted with a second electron donor; and optionally, a second modifier compound having the formula AlX a R.sub.(3-a) ; and a second cocatalyst having the formula AlR 3 ; and a halohydrocarbon promoter.
Claim 2
Dependent Claim
210 words
A process for preparing polyethylene, comprising 1) contacting in a first reactor under polymerization conditions ethylene and optionally a comonomer in the presence of: a titanium-based catalyst containing: a titanium complex that is the reaction product of a titanium-containing compound in which the titanium is in the +3 or +4 oxidation state, a magnesium halide and a first electron donor; and optionally, a first modifier compound having the formula AlX a R.sub.(3-a), wherein X is a halide, each R is independently an alkyl having 1 to about 14 carbon atoms, and a is 0, 1, 2, or 3; and a first cocatalyst having the formula AlR 3 , to form a mixture; 2) transferring the mixture to a second reactor connected in series to the first reactor; and 3) contacting the mixture with further ethylene and optionally further comonomer in the second reactor under polymerization conditions in the presence of: a vanadium-based catalyst comprising: a vanadium complex that is a vanadium-containing compound in which the vanadium is in the +2, +3, +4, or +5 oxidation state optionally reacted with a second electron donor; and optionally, a second modifier compound having the formula AlX a R.sub.(3-a) ; and a second cocatalyst having the formula AlR 3 ; and a halohydrocarbon promoter.
Claim 3
Dependent Claim
30 words
The process of claim 1, wherein the titanium-containing compound is TiCl 3 or TiCl 4 , the vanadium-containing compound is VCl 3 and the magnesium halide is MgCl 2 .
Claim 4
Dependent Claim
33 words
The process of claim 1, wherein the halohydrocarbon promoter is selected from CHCl 3 , CCl 4 , C 3 HCl 7 , CFCl 3 , CClF 2 CCl 3 and mixtures thereof.
Claim 5
Dependent Claim
30 words
The process of claim 1, wherein the first reactor and the second reactor are each fluidized bed reactors and contacting in each reactor takes place continuously in the gas phase.
Claim 6
Dependent Claim
221 words
A process for preparing polyethylene, comprising 1) contacting in a first reactor under polymerization conditions ethylene and optionally a comonomer in the presence of: a vanadium-based catalyst comprising: a vanadium complex that is a vanadium-containing compound in which the vanadium is in the +2, +3, +4, or +5 oxidation state optionally reacted with a first electron donor; and optionally, a first modifier compound having the formula AlX a R.sub.(3-a), wherein X is a halide, each R is independently an alkyl having 1 to about 14 carbon atoms, and a is 0, 1, 2, or 3; and a first cocatalyst having the formula AlR 3 ; and a halohydrocarbon promoter to form a mixture; 2) removing substantially all of the halohydrocarbon promoter from the mixture; 3) transferring the mixture to a second reactor connected in series to the first reactor; and 4) contacting the mixture with further ethylene and optionally further comonomer in the second reactor under polymerization conditions in the presence of: a titanium-based catalyst comprising: a titanium complex that is the reaction product of a titanium-containing compound in which the titanium is in the +3 or +4 oxidation state, a magnesium halide and a second electron donor; and optionally, a second modifier compound having the formula AlX a R.sub.(3-a) ; and a second cocatalyst having the formula AlR 3 .
Claim 7
Dependent Claim
221 words
A process for preparing polyethylene, comprising 1) contacting in a first reactor under polymerization conditions ethylene and optionally a comonomer in the presence of: a vanadium-based catalyst comprising: a vanadium complex that is a vanadium-containing compound in which the vanadium is in the +2, +3, +4, or +5 oxidation state optionally reacted with a first electron donor; and optionally, a first modifier compound having the formula AlX a R.sub.(3-a), wherein X is a halide, each R is independently an alkyl having 1 to about 14 carbon atoms, and a is 0, 1, 2, or 3; and a first cocatalyst having the formula AlR 3 ; and a halohydrocarbon promoter to form a mixture; 2) removing substantially all of the halohydrocarbon promoter from the mixture; 3) transferring the mixture to a second reactor connected in series to the first reactor; and 4) contacting the mixture with further ethylene and optionally further comonomer in the second reactor under polymerization conditions in the presence of: a titanium-based catalyst comprising: a titanium complex that is the reaction product of a titanium-containing compound in which the titanium is in the +3 or +4 oxidation state, a magnesium halide and a second electron donor; and optionally, a second modifier compound having the formula AlX a R.sub.(3-a) ; and a second cocatalyst having the formula AlR 3 .
Claim 8
Dependent Claim
30 words
The process of claim 5, wherein the titanium-containing compound is TiCl 3 or TiCl 4 , the vanadium-containing compound is VCl 3 and the magnesium halide is MgCl 2 .
Claim 9
Dependent Claim
33 words
The process of claim 5, wherein the halohydrocarbon promoter is selected from CHCl 3 , CCl 4 , C 3 HCl 7 , CFCl 3 , CClF 2 CC 3 and mixtures thereof.
Claim 10
Dependent Claim
30 words
The process of claim 5, wherein the first reactor and the second reactor are each fluidized bed reactors and contacting in each reactor takes place continuously in the gas phase.
Claim 11
Dependent Claim
197 words
A process for preparing polyethylene, comprising 1) contacting in a first reactor under polymerization conditions ethylene and optionally a comonomer in the presence of: a mixed metal catalyst comprising: a titanium complex that is the reaction product of a titanium-containing compound in which the titanium is in the +3 or +4 oxidation state, a magnesium halide and a first electron donor; a vanadium complex that is a vanadium-containing compound in which the vanadium is in the +2, +3, +4, or +5 oxidation state optionally reacted with a second electron donor; and optionally, a modifier compound having the formula AlX a R.sub.(3-a), wherein X is a halide, each R is independently an alkyl having 1 to about 14 carbon atoms, and a is 0, 1, 2, or 3; and a first cocatalyst having the formula AlR 3 , to form a mixture; 2) transferring the mixture to a second reactor connected in series to the first reactor; and 3) contacting the mixture with further ethylene, optionally further comonomer, and a second cocatalyst having the formula AlR 3 in the second reactor under polymerization conditions; wherein a halohydrocarbon promoter is present in one but not both of the reactors.
Claim 12
Dependent Claim
197 words
A process for preparing polyethylene, comprising 1) contacting in a first reactor under polymerization conditions ethylene and optionally a comonomer in the presence of: a mixed metal catalyst comprising: a titanium complex that is the reaction product of a titanium-containing compound in which the titanium is in the +3 or +4 oxidation state, a magnesium halide and a first electron donor; a vanadium complex that is a vanadium-containing compound in which the vanadium is in the +2, +3, +4, or +5 oxidation state optionally reacted with a second electron donor; and optionally, a modifier compound having the formula AlX a R.sub.(3-a), wherein X is a halide, each R is independently an alkyl having 1 to about 14 carbon atoms, and a is 0, 1, 2, or 3; and a first cocatalyst having the formula AlR 3 , to form a mixture; 2) transferring the mixture to a second reactor connected in series to the first reactor; and 3) contacting the mixture with further ethylene, optionally further comonomer, and a second cocatalyst having the formula AlR 3 in the second reactor under polymerization conditions; wherein a halohydrocarbon promoter is present in one but not both of the reactors.
Claim 13
Dependent Claim
21 words
The process of claim 9, wherein the mixed metal catalyst comprises titanium complex and vanadium complex coimpregnated in a support material.
Claim 14
Dependent Claim
30 words
The process of claim 9, wherein the titanium-containing compound is TiCl 3 or TiCl 4 , the vanadium-containing compound is VCl 3 and the magnesium halide is MgCl 2 .
Claim 15
Dependent Claim
33 words
The process of claim 9, wherein the halohydrocarbon promoter is selected from CHCl 3 , CCl 14 , C 3 HCl 7 , CFCl 3 , CClF 2 CCl 3 and mixtures thereof.
Claim 16
Dependent Claim
30 words
The process of claim 9, wherein the first reactor and the second reactor are each fluidized bed reactors and contacting in each reactor takes place continuously in the gas phase.
Claim 17
Dependent Claim
8 words
Polyethylene made by the process of claim 1.
Claim 18
Dependent Claim
23 words
The polyethylene of claim 14 having a PDI of about 10 to about 30 and an MFR of about 100 to about 200.
Claim 19
Dependent Claim
8 words
Polyethylene made by the process of claim 5.
Claim 20
Dependent Claim
23 words
The polyethylene of claim 16 having a PDI of about 10 to about 30 and an MFR of about 100 to about 200.
Claim 21
Dependent Claim
8 words
Polyethylene made by the process of claim 10.
Claim 22
Dependent Claim
23 words
The polyethylene of claim 18 having a PDI of about 10 to about 30 and an MFR of about 100 to about 200.
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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) | 1998-08-14 | 1999-02-13 | 1999-08-15 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2002-08-14 | 2003-02-13 | 2003-08-15 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2006-08-14 | 2007-02-13 | 2007-08-15 | $7700.00 | Window Closed / Lapsed |