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US4568658A Expired / Lapsed US ⏱️ 0.0 years remaining

Catalyst composition for polymerizing alpha-olefins at low reactants partial pressures

Assignee: Mobil Oil AS
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Filing: 1984-09-05
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Granted: 1986-02-04
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Expires: 2004-09-05
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Abstract

Abstract A catalyst composition for polymerizing alpha-olefins in a gas phase continuous process is prepared by combining a catalyst precursor with a catalyst activator in such proportions that the polymer product comprises about 9x10-7 to about 18x10-7 gram-moles of the activator per gram of the polymer produced. The use of the activator in these proportions lowers the partial pressure of the monomers used in the process without sacrificing quality of the product. The catalyst precursor is prepared by reacting a carrier having OH groups with a stoichiometric excess, with respect to the OH groups, of an organomagnesium composition, and subsequently reacting the product with a transition metal compound.

Inventors

  • 👤 John E. Cook
  • 👤 Thomas J. Giacobbe
  • 👤 Robert O. Hagerty

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-30 09:03
CPC Classifications
C; C08; C08F; C08F10/00

Claims Analysis

Total Claims: 42
Claim 1
Independent Claim 237 words
In a process for preparing a catalyst composition for use in alpha-olefin polymerization reactions comprising the steps of: (i) contacting a solid, porous carrier having reactive OH groups with a liquid, said liquid containing at least one organomagnesium composition having the empirical formula R.sub.n MgR'.sub.(2-n) (I) where R is a C 1 -C 12 hydrocarbyl group, R' is a halogen, and n is 0, 1 or 2, the number of moles of said organomagnesium composition being in excess of the number of moles of said OH groups on said carrier; (ii) evaporating said liquid from step (i) to obtain a magnesium-containing carrer in the form of a dry, free-flowing powder; (iii) contacting said powder of step (ii) with a solution comprising a liquid medium at least one transition metal compound, said transition metal compound being soluble in said liquid medium, and said magnesium of said carrier being substantially insoluble in said liquid medium, whereby a compound of transition metal, which is insoluble in said liquid medium becomes incorporated onto said carrier, thereby forming a catalyst precursor; and (iv) contacting said catalyst precursor with a sufficient amount of a catalyst activator to provide a catalystically active catalyst composition, an improvement comprising using such an amount of the catalyst activator as to provide about 9×10 -7 to about 18×10 -7 gram-moles of the activator per gram of the polymer produced when the catalyst is used in alpha-olefin polymerization reactions.
Claim 2
Dependent Claim 237 words
In a process for preparing a catalyst composition for use in alpha-olefin polymerization reactions comprising the steps of: (i) contacting a solid, porous carrier having reactive OH groups with a liquid, said liquid containing at least one organomagnesium composition having the empirical formula R.sub.n MgR'.sub.(2-n) (I) where R is a C 1 -C 12 hydrocarbyl group, R' is a halogen, and n is 0, 1 or 2, the number of moles of said organomagnesium composition being in excess of the number of moles of said OH groups on said carrier; (ii) evaporating said liquid from step (i) to obtain a magnesium-containing carrer in the form of a dry, free-flowing powder; (iii) contacting said powder of step (ii) with a solution comprising a liquid medium at least one transition metal compound, said transition metal compound being soluble in said liquid medium, and said magnesium of said carrier being substantially insoluble in said liquid medium, whereby a compound of transition metal, which is insoluble in said liquid medium becomes incorporated onto said carrier, thereby forming a catalyst precursor; and (iv) contacting said catalyst precursor with a sufficient amount of a catalyst activator to provide a catalystically active catalyst composition, an improvement comprising using such an amount of the catalyst activator as to provide about 9×10 -7 to about 18×10 -7 gram-moles of the activator per gram of the polymer produced when the catalyst is used in alpha-olefin polymerization reactions.
Claim 3
Dependent Claim 15 words
A process of claim 1 wherein said transition metal compound is a tetravalent titanium compound.
Claim 4
Dependent Claim 29 words
A process of claim 2 wherein the number of moles of said titanium compound present in said solution of step (iii) is in excess of the stoichiometric amount thereof.
Claim 5
Dependent Claim 34 words
A process of claim 3 wherein the solid, porous carrier, prior to the contact thereof with the liquid in step (i), is heated at a temperature of about 150° C. to about 850° C.
Claim 6
Dependent Claim 17 words
A process of claim 4 wherein the carrier is heated at a temperature of about 800° C.
Claim 7
Dependent Claim 29 words
A process of claim 5 wherein the heating is continued until the carrier contains about 0.3 to about 0.7 mmoles of the OH groups per gram of the carrier.
Claim 8
Dependent Claim 38 words
A process of claim 6 wherein the carrier is silica having a surface hydroxyl group concentration of about 0.5 mmoles/gr, a surface area of 300 m 2 /gram and a pore volume of 1.65 m 3 / gram.
Claim 9
Dependent Claim 15 words
A process of claim 7 wherein R is a C 1 -C 4 alkane group.
Claim 10
Dependent Claim 11 words
A process of claim 8 wherein R' is bromine or chlorine.
Claim 11
Dependent Claim 12 words
A process of claim 9 wherein the organomagnesium composition is ethylmagnesium chloride.
Claim 12
Dependent Claim 13 words
A process of claim 10 wherein the liquid containing ethylmagnesium chloride is tetrahydrofuran.
Claim 13
Dependent Claim 23 words
A process of claim 11 wherein said liquid is removed in step (ii) by evaporation at about the boiling point of the liquid.
Claim 14
Dependent Claim 31 words
A process of claim 12 wherein the molar ratio of the organomagnesium composition to the number of moles of the OH groups on the carrier is about 1.1 to about 3.5.
Claim 15
Dependent Claim 31 words
A process of claim 13 wherein the molar ratio of the organomagnesium composition to the number of moles of the OH groups on the carrier is about 2.0 to about 3.5.
Claim 16
Dependent Claim 25 words
A process of claim 14 wherein the molar ratio of the tetravalent titanium compound to the organomagnesium composition is from about 3 to about 6.
Claim 17
Dependent Claim 14 words
A process of claim 15 wherein the tetravalent titanium compound is a titanium halide.
Claim 18
Dependent Claim 13 words
A process of claim 16 wherein the tetravalent titanium compound is titanium tetrachloride.
Claim 19
Dependent Claim 35 words
A process of claim 17 wherein such an amount of the catalyst activator is used as to provide about 12×10 -7 to about 16×10 -7 gram-moles of the activator per gram of the polymer produced.
Claim 20
Dependent Claim 23 words
A process of claim 18 wherein the catalyst activator is selected from the group consisting of trimethylaluminum, triisobutylaluminum, aluminoxane, diethylaluminum chloride and triethylaluminum.
Claim 21
Dependent Claim 11 words
A process of claim 19 wherein the catalyst activator is triethylaluminum.
Claim 22
Dependent Claim 224 words
In an alpha-olefin polymerization catalyst composition prepared by: (i) contacting a solid, porous carrier having reactive OH groups with a liquid, said liquid containing at least one organomagnesium composition having the empirical formula RnMgR'(2-n) (I) wherein R is a Cl-C12 hydrocarbyl group, R' is a halogen, and n is 0, 1 or 2, the number of moles of said organomagnesium composition being in excess of the number of moles of said OH groups on said carrer; (ii) evaporating said liquid from step (i) to obtain a magnesium-containing carrier in the form of a dry, free-flowing powder; (iii) contacting said powder of step (ii) with a solution comprising a liquid medium and at least one transition metal compound, said transition metal compound being soluble in said liquid medium, and said magnesium of said carrier being substantially insoluble in said liquid medium, whereby a compound of transition metal, which is insoluble in said liquid medium, becomes incorporated onto said carrier, thereby forming a catalyst precursor; and, (iv) contacting said catalyst precursor with a sufficient amount of a catalyst activator to provide a catalytically active catalyst composition, an improvement comprising using such an amount of the catalyst activator as to provide about 9×10 -7 to about 18×10 -7 gram-moles of the activator per gram of the polymer produced when the catalyst is used in aplha-olefin polymerization recations.
Claim 23
Dependent Claim 224 words
In an alpha-olefin polymerization catalyst composition prepared by: (i) contacting a solid, porous carrier having reactive OH groups with a liquid, said liquid containing at least one organomagnesium composition having the empirical formula RnMgR'(2-n) (I) wherein R is a Cl-C12 hydrocarbyl group, R' is a halogen, and n is 0, 1 or 2, the number of moles of said organomagnesium composition being in excess of the number of moles of said OH groups on said carrer; (ii) evaporating said liquid from step (i) to obtain a magnesium-containing carrier in the form of a dry, free-flowing powder; (iii) contacting said powder of step (ii) with a solution comprising a liquid medium and at least one transition metal compound, said transition metal compound being soluble in said liquid medium, and said magnesium of said carrier being substantially insoluble in said liquid medium, whereby a compound of transition metal, which is insoluble in said liquid medium, becomes incorporated onto said carrier, thereby forming a catalyst precursor; and, (iv) contacting said catalyst precursor with a sufficient amount of a catalyst activator to provide a catalytically active catalyst composition, an improvement comprising using such an amount of the catalyst activator as to provide about 9×10 -7 to about 18×10 -7 gram-moles of the activator per gram of the polymer produced when the catalyst is used in aplha-olefin polymerization recations.
Claim 24
Dependent Claim 16 words
A catalyst composition of claim 21 wherein said transition metal compounds is a tetravalent titanium compound.
Claim 25
Dependent Claim 30 words
A catalyst composition of claim 22 wherein the number of moles of said titanium compound present in said solution of step (iii) is in excess of the stoichiometric amount thereof.
Claim 26
Dependent Claim 35 words
A catalyst composition of claim 23 wherein the solid, porous carrier, prior to the contact thereof with the liquid in step (i), is heated at a temperature of about 150° C. to about 850° C.
Claim 27
Dependent Claim 18 words
A catalyst composition of claim 24 wherein the carrier is heated at a temperature of about 800° C.
Claim 28
Dependent Claim 29 words
A catalyst composition of claim 25 wherein the heating is continued until the carrier contains about 0.3 to about 0.7 mmoles of the OH groups per gram of carrier.
Claim 29
Dependent Claim 38 words
A catalyst composition of claim 26 wherein the carrier is silica having a surface hydroxyl group concentration of about 0.5 mmoles/gr, a surface area of 300 m 2 /gram and a pore volume of 1.65 m 3 /gram.
Claim 30
Dependent Claim 13 words
A catalyst composition of claim 27 wherein R is a Cl-C-4 alkane group.
Claim 31
Dependent Claim 12 words
A catalyst composition of claim 28 wherein R' is bromine or chlorine.
Claim 32
Dependent Claim 13 words
A catalyst composition of claim 29 wherein the organomagnesium composition is ethylmagnesium chloride.
Claim 33
Dependent Claim 14 words
A catalyst composition of claim 30 wherein the liquid containing ethylmagnesium chloride is tetrahydrofuran.
Claim 34
Dependent Claim 24 words
A catalyst composition of claim 31 wherein said liquid is removed in step (ii) by evaporation at about the boiling point of the liquid.
Claim 35
Dependent Claim 32 words
A catalyst composition of claim 32 wherein the molar ratio of the organomagnesium composition to the number of moles of the OH groups on the carrier is about 1.1 to about 3.5.
Claim 36
Dependent Claim 32 words
A catalyst composition of claim 33 wherein the molar ratio of the organomagnesium composition of the number of moles of the OH groups on the carrier is about 2.0 to about 3.5.
Claim 37
Dependent Claim 26 words
A catalyst composition of claim 34 wherein the molar ratio of the tetravalent titanium compound to the organomagensium composition is from about 3 to about 6.
Claim 38
Dependent Claim 15 words
A catalyst composition of claim 35 wherein the tetravalent titanium compound is a titanium halide.
Claim 39
Dependent Claim 14 words
A catalyst composition of claim 36 wherein the tetravelent titanium compound is titanium tetrachloride.
Claim 40
Dependent Claim 36 words
A catalyst composition of claim 37 wherein such an amount of the catalyst activator is used as to provide about 12×10 -7 to about 16×10 -7 gram-moles of the activator per gram of the polymer produced.
Claim 41
Dependent Claim 24 words
A catalyst composition of claim 38 wherein the catalyst activator is selector from the group consisting of trimethylaluminum, triisobutylaluminum, aluminoxane, diethylaluminum chloride and triethylaluminum.
Claim 42
Dependent Claim 12 words
A catalyst composition of claim 39 wherein the catalyst activator is triethylaluminum.

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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) 1989-02-03 1989-08-05 1990-02-04 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1993-02-03 1993-08-05 1994-02-04 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1997-02-03 1997-08-05 1998-02-04 $7700.00 Window Closed / Lapsed

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