Patent US4461882A successfully refreshed from Google Patents.
US4461882A
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Olefin polymerization
Assignee: Phillips Petroleum Co
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Filing: 1982-09-30
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Granted: 1984-07-24
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Expires: 2002-09-30
Abstract
Abstract Catalysts effective for the polymerization of olefins at high productivity formed upon mixing (1) a solution of a titanium tetrahydrocarbyloxide or a zirconium tetrahydrocarbyloxide and an organoaluminum halide with (2) a dihydrocarbylmagnesium compound alone or admixed with a minor amount of a trialkylaluminum and (3) combining the product obtained in (2) with a metal halide selected from a silicon tetrahalide and a titanium tetrahalide. The catalyst component thus produced can be combined with an organoaluminum compound as a cocatalyst component.
Inventors
- 👤 M. Bruce Welch
- 👤 Richard E. Dietz
- 👤 Charles E. Capshew
- 👤 Joel L. Martin
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 14:19
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 18
Claim 1
Independent Claim
119 words
A process for the polymerization of olefins which comprises contacting at least one aliphatic 1-olefin under polymerization conditions with a catalyst consisting essentially of the catalytic reaction product which is formed by (1) preparing a hydrocarbon solution of a titanium tetrahydrocarbyloxide compound and an organoaluminum halide compound; (2) contacting the solution formed in step (1) with an organomagnesium compound alone or admixed with a minor amount of a trialkylaluminum to form a complex; (3) reacting the product obtained in step (2) with a metal halide which is a silicon tetrahalide or a titanium tetrahalide to form a precipitate; and (4) combining the precipitate product obtained in step (3) with an organoaluminum cocatalyst compound to form an active polymerization catalyst.
Claim 2
Dependent Claim
119 words
A process for the polymerization of olefins which comprises contacting at least one aliphatic 1-olefin under polymerization conditions with a catalyst consisting essentially of the catalytic reaction product which is formed by (1) preparing a hydrocarbon solution of a titanium tetrahydrocarbyloxide compound and an organoaluminum halide compound; (2) contacting the solution formed in step (1) with an organomagnesium compound alone or admixed with a minor amount of a trialkylaluminum to form a complex; (3) reacting the product obtained in step (2) with a metal halide which is a silicon tetrahalide or a titanium tetrahalide to form a precipitate; and (4) combining the precipitate product obtained in step (3) with an organoaluminum cocatalyst compound to form an active polymerization catalyst.
Claim 3
Dependent Claim
11 words
A process according to claim 1 wherein the olefin is ethylene.
Claim 4
Dependent Claim
25 words
A process according to claim 2 wherein said polymerization is carried out in the presence of hydrogen to adjust the molecular weight of the product.
Claim 5
Dependent Claim
148 words
A process for the polymerization of olefins according to claim 1 wherein the titanium tetrahydrocarbyloxide is a titanium alkoxide in which the alkyl group of the alkoxide contains from 1 to 20 carbon atoms, the organoaluminum halide compound can be expressed as monohalides of the formula R 2 AlX, dihalides of the formula RAlX 2 , and sesquihalides of the formula R 2 Al 2 X 3 in which R is a hydrocarbyl group having from 1 to 20 carbon atoms, and each X is a halogen atom and can be the same or different, and the organomagnesium compound can be expressed as MgR" 2 in which R" is a hydrcarbyl group containing from 1 to 12 carbon atoms and trialkylaluminum, if present can be expressed as AIR' in which R' is an alkyl group having 1 to 12 carbon atoms and the metal halide is titanium tetrahalide.
Claim 6
Dependent Claim
12 words
A process according to the claim 4 wherein the olefin is ethylene.
Claim 7
Dependent Claim
25 words
A process according to claim 5 wherein said polymerization is carried out in the presence of hydrogen to adjust the molecular weight of the product.
Claim 8
Dependent Claim
27 words
A process according to claim 5 for the production of broader molecular weight distribution polymer, based on higher HLMI/MI values, wherein said titanium compound is titanium isopropoxide.
Claim 9
Dependent Claim
23 words
A process according to claim 5 for the increased production of narrow molecular weight distribution polymer wherein said titanium compound is titanium tetraethoxide.
Claim 10
Dependent Claim
54 words
A process according to claim 1 wherein (1) is a solution of titanium tetraethoxide and ethylaluminum dichloride; (2) is a solution of (1) which is contacted with n-butyl-sec-butylmagnesium; (3) the product of step (2) is reacted with titanium tetrachloride, and the product of (3) is combined in (4) with diethylaluminum chloride, triisobutylaluminum or triethylaluminum.
Claim 11
Dependent Claim
74 words
A process according to claim 1 wherein the molar ratio of titanium tetrahydrocarbyloxide compound to organoaluminum halide compound in step (1) ranges from 5:1 to 1:5; the molar ratio of tetravalent titanium compound in step (1) to organomagnesium compound in step (2) ranges from 5:1 to 1:2; and the molar ratio of titanium tetrahalide added in step (3) to the combined moles of components of step (2) ranges from about 10:1 to about 0.5:1.
Claim 12
Dependent Claim
65 words
A process according to claim 1 wherein the catalyst is formed by (1) preparing a hydrocarbon solution of titanium tetraethoxide or titanium tetraisopropoxide, and ethylaluminum sesquichloride or diethylaluminum chloride, (2) contacting the solution of (1) with dibutylmagnesium or dibutylmagnesium and a minor amount of triethylaluminum, (3) reacting the product obtained in step (2) with titanium tetrachloride, and (4) combining the product of (3) with triethylaluminum.
Claim 13
Dependent Claim
26 words
A process according to claim 11 wherein (2) is formed by contacting (1) with a mixture of dibutylmagnesium and triethylaluminum containing about 1-25 mole percent triethylaluminum.
Claim 14
Dependent Claim
111 words
A process for the polymerization of ethylene under polymerization conditions in the presence of a catalyst consisting essentially of the reaction product which is formed by (1) admixing together a titanium tetrahydrocarbyloxide compound, an organoaluminum halide compound and a hydrocarbon to produce a first catalyst component solution, (2) contacting the first catalyst component solution in (1) with an organomagnesium compound alone or in admixture with a minor amount of a trialkylaluminum compound to form a complex, (3) reacting the complex of step (2) with a titanium tetrahalide to form a precipitate, and (4) combining the precipitated product formed in step (3) with a co-catalyst component B which is an organoaluminum compound.
Claim 15
Dependent Claim
111 words
A process for the polymerization of ethylene under polymerization conditions in the presence of a catalyst consisting essentially of the reaction product which is formed by (1) admixing together a titanium tetrahydrocarbyloxide compound, an organoaluminum halide compound and a hydrocarbon to produce a first catalyst component solution, (2) contacting the first catalyst component solution in (1) with an organomagnesium compound alone or in admixture with a minor amount of a trialkylaluminum compound to form a complex, (3) reacting the complex of step (2) with a titanium tetrahalide to form a precipitate, and (4) combining the precipitated product formed in step (3) with a co-catalyst component B which is an organoaluminum compound.
Claim 16
Dependent Claim
73 words
A process according to claim 13 wherein the catalyst is prepared by (1) forming a paraffinic or aromatic hydrocarbon solution of an alkylaluminum dichloride and a titanium alkoxide, (2) combining (1) with a dialkylmagnesium compound alone or in admixture with a minor amount of trialkylaluminum compound, (3) reacting (2) with titanium tetrachloride, (4) removing unreacted titanium tetrachloride from the product formed in (3), and (5) combining the product of (4) with a trialkylaluminum.
Claim 17
Dependent Claim
71 words
A process according to claim 14 comprising (1) preparing a n-hexane or mixed xylenes solution of titanium tetraethoxide or titanium tetraisopropoxide and ethylaluminum dichloride, ethylaluminum sesquichloride or diethylaluminum chloride, (2) containing the solution of (1) with dibutylmagnesium or dibutylmagnesium and a minor amount of triethylaluminum, (3) reacting (2) with titanium tetrachloride, (4) removing unreacted titanium tetrachloride from the product formed in (3), and (5) combining the product of (3) with triethylaluminum.
Claim 18
Dependent Claim
45 words
A process according to claim 13 wherein the final product in (3) is washed with an inert solvent to remove unreacted metal halide compound prior to combining with component B and the reactants are contacted at a temperature in the range of about 0°-100° C.
References Cited (Backward Citations)
DE2543219A1
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-07-24 | 1988-01-23 | 1988-07-24 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-07-24 | 1992-01-23 | 1992-07-24 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-07-24 | 1996-01-23 | 1996-07-24 | $7700.00 | Window Closed / Lapsed |