US4988783A
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Ethylene polymerization using supported vanadium catalyst
Assignee: Union Carbide Chemicals and Plastics Technology LLC
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Filing: 1990-02-02
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Granted: 1991-01-29
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Expires: 2010-02-02
Abstract
Abstract An ethylene polymerization catalyst comprising a supported precursor of vanadium trihalide/electron donor complex and alkylaluminum or boron halides, when combined with alkylaluminum cocatalyst and alkyl halide promoter, provides enhanced polymerization and productivity plus superior polyethylene.
Inventors
- 👤 Debra L. Beran
- 👤 Kevin J. Cann
- 👤 Robert J. Jorgensen
- 👤 Frederick J. Karol
- 👤 Norma J. Maraschin
- 👤 Arthur E. Marcinkowsky
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 22:24
CPC Classifications
C; C08; C08F; C08F10/00; C08F10/02; C08F210/00; C08F210/16; Y; Y10; Y10S; Y10S526/00; Y10S526/901
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
293 words
A process for producing ethylene polymers which comprises polymerizing ethylene with or without at least one C 3 to C 10 alpha-olefin monomer in the gas phase at a temperature between about 10° C. to about 115° C., by contacting the monomers with a catalyst composition comprising: (A) a supported precursor consisting essentially of a vanadium compound and modifier impregnated on a solid, inert carrier, said carrier consisting essentially of silica or alumina and being free of preparative chemical treatment with an alkylaluminum compound prior to formation of the supported precursor, said supported precursor composition being prepared by impregnating said carrier first with the vanadium compound and subsequently with the modifier, (1) said vanadium compound being the reaction product of: (a) a vanadium trihalide of chlorine, bromine or iodine; and (b) an electron donor which is a liquid, organic Lewis base in which said vanadium trihalide is soluble, said electron donor being selected from the group consisting of alkyl esters of aliphatic and a romatic carboxylic acids, aliphatic ketones, aliphatic amines, alkyl and cycloalkyl ethers, and mixtures thereof; and (2) said modifier having the formula: MX.sub.a wherein: M is AlR.sub.(3-a) and wherein each R is independently alkyl, provided that the total number of aliphatic carbon atoms in any one R group may not exceed 14; X is chlorine, bromine or iodine; and a is 1 or 2; and said modifier being employed in an amount of from 0.2 to 2.5 moles per mole of electron donor present in said vanadium compound; (B) a cocatalyst having the formula: AlR.sub.3 wherein R is as previously defined; and (C) a promoter having the formula: R'.sub.b CX'.sub.(4-b) wherein: R' is hydrogen or unsubstituted or halosubstituted lower alkyl; X' is halogen; and b is 0, 1 or 2.
Claim 2
Dependent Claim
293 words
A process for producing ethylene polymers which comprises polymerizing ethylene with or without at least one C 3 to C 10 alpha-olefin monomer in the gas phase at a temperature between about 10° C. to about 115° C., by contacting the monomers with a catalyst composition comprising: (A) a supported precursor consisting essentially of a vanadium compound and modifier impregnated on a solid, inert carrier, said carrier consisting essentially of silica or alumina and being free of preparative chemical treatment with an alkylaluminum compound prior to formation of the supported precursor, said supported precursor composition being prepared by impregnating said carrier first with the vanadium compound and subsequently with the modifier, (1) said vanadium compound being the reaction product of: (a) a vanadium trihalide of chlorine, bromine or iodine; and (b) an electron donor which is a liquid, organic Lewis base in which said vanadium trihalide is soluble, said electron donor being selected from the group consisting of alkyl esters of aliphatic and a romatic carboxylic acids, aliphatic ketones, aliphatic amines, alkyl and cycloalkyl ethers, and mixtures thereof; and (2) said modifier having the formula: MX.sub.a wherein: M is AlR.sub.(3-a) and wherein each R is independently alkyl, provided that the total number of aliphatic carbon atoms in any one R group may not exceed 14; X is chlorine, bromine or iodine; and a is 1 or 2; and said modifier being employed in an amount of from 0.2 to 2.5 moles per mole of electron donor present in said vanadium compound; (B) a cocatalyst having the formula: AlR.sub.3 wherein R is as previously defined; and (C) a promoter having the formula: R'.sub.b CX'.sub.(4-b) wherein: R' is hydrogen or unsubstituted or halosubstituted lower alkyl; X' is halogen; and b is 0, 1 or 2.
Claim 3
Dependent Claim
18 words
The process of claim 1 wherein said ethylene polymer is an ethylene homopolymer, propylene/ethylene, butene-l/ethylene or hexene-l/ethylene copolymer.
Claim 4
Dependent Claim
61 words
The process of claim 1 wherein said vanadium trihalide contains chlorine; said electron donor is an alkyl or cycloalkyl ether; said modifier is a C 1 to C 6 alkylaluminum mono- or di- chloride; said carrier is silica; said cocatalyst is a C 2 to C 8 trialkylaluminum; and said promoter is a fluoro, chloro or bromo substituted ethane or methane.
Claim 5
Dependent Claim
37 words
The process of claim 1 wherein said vanadium trihalide is vanadium trichloride; said electron donor is tetrahydrofuran; said modifier is diethylaluminum chloride; said carrier is silica; said cocatalyst is triisobutylaluminum or triethylaluminum; and said promoter is chloroform.
Claim 6
Dependent Claim
32 words
The process of claim 1 wherein an ethylene polymer having a density of greater than about 0.94 g/cc is produced at a temperature of between about 85° C. to about 115° C.
Claim 7
Dependent Claim
18 words
The process of claim 5 wherein said ethylene polymer is an ethylene homopolymer, propylene/ethylene, butene-l/ethylene or hexene-l/ethylene copolymer.
Claim 8
Dependent Claim
61 words
The process of claim 5 wherein said vanadium trihalide contains chlorine; said electron donor is an alkyl or cycloalkyl ether; said modifier is a C 1 to C 6 alkylaluminum mono- or di- chloride; said carrier is silica; said cocatalyst is a C 2 to C 8 trialkylaluminum; and said promoter is a fluoro, chloro or bromo substituted ethane or methane.
Claim 9
Dependent Claim
37 words
The process of claim 5 wherein said vanadium trihalide is vanadium trichloride; said electron donor is tetrahydrofuran; said modifier is diethylaluminum chloride; said carrier is silica; said cocatalyst is triisobutylaluminum or triethylaluminum; and said promoter is chloroform.
Claim 10
Dependent Claim
35 words
The process of claim 1 wherein an ethylene polymer having a density of from about 0.91 g/cc to about 0.94 g/cc is produced at a temperature of between about 75° C. to about 90° C.
Claim 11
Dependent Claim
15 words
The process of claim 9 wherein said ethylene polymer is propylene/ethylene butene-l/ethylene or hexene-l/ethylene copolymer.
Claim 12
Dependent Claim
61 words
The process of claim 9 wherein said vanadium trihalide contains chlorine; said electron donor is an alkyl or cycloalkyl ether; said modifier is a C 1 to C 6 alkylaluminum mono- or di- chloride; said carrier is silica; said cocatalyst is a C 2 to C 8 trialkylaluminum; and said promoter is a fluoro, chloro or bromo substituted ethane or methane.
Claim 13
Dependent Claim
37 words
The process of claim 9 wherein said vanadium trihalide is vanadium trichloride; said electron donor is tetrahydrofuran; said modifier is diethylaluminum chloride; said carrier is silica; said cocatalyst is triisobutylaluminum or triethylaluminum; and said promoter is chloroform.
Claim 14
Dependent Claim
32 words
The process of claim 1 wherein an ethylene polymer having a density of less than about 0.91 g/cc is produced at a temperature of between about 10° C. to about 80° C.
Claim 15
Dependent Claim
16 words
The process of claim 13 wherein said ethylene polymer is an propylene/ethylene butene-l/ethylene or hexene-l/ethylene copolymer.
Claim 16
Dependent Claim
61 words
The process of claim 13 wherein said vanadium trihalide contains chlorine; said electron donor is an alkyl or cycloalkyl ether; said modifier is a C 1 to C 6 alkylaluminum mono- or di- chloride; said carrier is silica; said cocatalyst is a C 2 to C 8 trialkylaluminum; and said promoter is a fluoro, chloro or bromo substituted ethane or methane.
Claim 17
Dependent Claim
37 words
The process of claim 13 wherein said vanadium trihalide is vanadium trichloride; said electron donor is tetrahydrofuran; said modifier is diethylaluminum chloride; said carrier is silica; said cocatalyst is triisobutylaluminum or triethylaluminum; and said promoter is chloroform.
References Cited (Backward Citations)
US4508842A
Cited
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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) | 1994-01-28 | 1994-07-30 | 1995-01-29 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1998-01-28 | 1998-07-30 | 1999-01-29 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2002-01-28 | 2002-07-30 | 2003-01-29 | $7700.00 | Window Closed / Lapsed |