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US4246384A Expired / Lapsed US ⏱️ 0.0 years remaining

Magnesium reducing agent for producing titanium trihalide catalyst component

Assignee: Phillips Petroleum Co
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Filing: 1978-11-08
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Granted: 1981-01-20
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Expires: 1998-11-08
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Abstract

Abstract Magnesium metal is contacted with an organic halide in the absence of an ether or other complexing diluent to produce a magnesium reducing agent for converting titanium tetrahalide to titanium trihalide. In a first embodiment, the magnesium metal, organic halide, and titanium tetrahalide are introduced into a mill and milled. In a second embodiment, the organic halide is metered dropwise onto the magnesium metal in the absence of any extraneous diluent, and the resulting magnesium reducing agent is thereafter added to a titanium tetrahalide and milled. In a third embodiment, an organic halide containing the titanium tetrahalide is metered dropwise onto magnesium metal in the absence of any extraneous diluent. In each instance the resulting titanium trihalide catalyst component is contacted with an organoaluminum compound activator and used for the polymerization of olefins, preferably the polymerization of propylene.

Inventors

  • 👤 Charles M. Selman

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-01 18:09
CPC Classifications
C; C08; C08F; C08F10/00; Y; Y10; Y10S; Y10S526/00; Y10S526/906

Claims Analysis

Total Claims: 14
Claim 1
Independent Claim 208 words
A process comprising contacting magnesium metal, a primary alkyl halide or alkyl dihalide, said halide or dihalide being selected from chloride and bromide, said alkyl radical containing from 1 to 12 carbon atoms in the case of the halide and 2 to 12 in the case of the dihalide, and titanium tetrachloride essentially simultaneously and subjecting same to intensive milling by means of ball milling, rod milling, pebble milling, or vibratory ball milling in the absence of any extraneous diluent; thereafter activating the thus produced titanium catalyst component by contacting same with an activator comprising a trialkylaluminum compound, a dialkylaluminum chloride, and a polar organic adjuvant which is an electron donor, said adjuvant further being characterized as a 1 to 4 carbon atom alkyl ester of a substituted or unsubstituted benzoic acid, a mole ratio of said aluminum compound to said adjuvant being within the range 1:1 to 350:1; an atom ratio of aluminum to titanium being within the range of 40:1 to 150:1, said magnesium metal and organic halide being introduced in a ratio within the range of 0.75:1 to 1:1 gram atoms of Mg:moles of organic halide, and wherein an atom ratio of the titanium to magnesium used is within the range of 0.75:1 to 1.25:1.
Claim 2
Dependent Claim 208 words
A process comprising contacting magnesium metal, a primary alkyl halide or alkyl dihalide, said halide or dihalide being selected from chloride and bromide, said alkyl radical containing from 1 to 12 carbon atoms in the case of the halide and 2 to 12 in the case of the dihalide, and titanium tetrachloride essentially simultaneously and subjecting same to intensive milling by means of ball milling, rod milling, pebble milling, or vibratory ball milling in the absence of any extraneous diluent; thereafter activating the thus produced titanium catalyst component by contacting same with an activator comprising a trialkylaluminum compound, a dialkylaluminum chloride, and a polar organic adjuvant which is an electron donor, said adjuvant further being characterized as a 1 to 4 carbon atom alkyl ester of a substituted or unsubstituted benzoic acid, a mole ratio of said aluminum compound to said adjuvant being within the range 1:1 to 350:1; an atom ratio of aluminum to titanium being within the range of 40:1 to 150:1, said magnesium metal and organic halide being introduced in a ratio within the range of 0.75:1 to 1:1 gram atoms of Mg:moles of organic halide, and wherein an atom ratio of the titanium to magnesium used is within the range of 0.75:1 to 1.25:1.
Claim 3
Dependent Claim 15 words
A method according to claim 1 wherein said intensive milling is done by ball milling.
Claim 4
Dependent Claim 25 words
A method according to claim 1 wherein said alkyl halide is a primary alkyl halide, said alkyl radical containing from 1 to 12 carbon atoms.
Claim 5
Dependent Claim 12 words
A method according to claim 1 wherein said trialkylaluminum compound is triethylaluminum.
Claim 6
Dependent Claim 12 words
A method according to claim 1 wherein said adjuvant is ethyl anisate.
Claim 7
Dependent Claim 13 words
A method according to claim 1 wherein said dialkylaluminum chloride is diethylaluminum chloride.
Claim 8
Dependent Claim 18 words
A method according to claim 6 wherein said trialkylaluminum compound is triethylaluminum and said adjuvant is ethyl anisate.
Claim 9
Dependent Claim 20 words
A method according to claim 1 wherein said magnesium metal and said organic halide are introduced in about stoichiometric amounts.
Claim 10
Dependent Claim 37 words
A method according to claim 1 wherein said milling is done by ball milling, said activator is triethylaluminum plus ethyl anisate and diethylaluminum chloride, and said magnesium metal and organic halide are introduced in about stoichiometric amounts.
Claim 11
Dependent Claim 6 words
A catalyst according to claim 9.
Claim 12
Dependent Claim 6 words
A catalyst according to claim 1.
Claim 13
Dependent Claim 25 words
A process comprising contacting at least one mono-1-olefin having 2 to 8 carbon atoms per molecule under polymerization conditions with the catalyst of claim 11.
Claim 14
Dependent Claim 14 words
A process comprising contacting propylene under polymerization conditions with the catalyst of claim 10.

References Cited (Backward Citations)

US3293232A Cited
GB1017977A Cited
US3451768A Cited
GB1299862A Cited
GB1359547A Cited
US3821186A Cited
GB1391322A Cited
DE2230672A1 Cited
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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) 1984-01-20 1984-07-21 1985-01-20 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1988-01-20 1988-07-21 1989-01-20 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1992-01-20 1992-07-21 1993-01-20 $7700.00 Window Closed / Lapsed

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