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US4732882A Expired / Lapsed US ⏱️ 0.0 years remaining

Catalyst composition for polymerizing alpha-olefins

Assignee: Univation Technologies LLC
•
Filing: 1986-01-24
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Granted: 1988-03-22
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Expires: 2006-01-24
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Abstract

Abstract A catalyst composition for polymerizing alpha-olefins is prepared by reacting a transition metal compound, e.g., titanium, with trimethylaluminum catalyst activator. In a preferred embodiment, the catalyst is supported on a porous refractory support and is prepared by additionally reacting a magnesium compound or an organomagnesium composition with the support. Also disclosed is a process for polymerizing alpha-olefins in the presence of the catalyst of the invention. The polymer products have higher bulk density and produce films of greater strength than polymers prepared with similar catalysts utilizing different alkyl-aluminum activators, e.g., triethylaluminum and tri-isobutylaluminum.

Inventors

  • 👤 Luanne M. Allen
  • 👤 Robert O. Hagerty
  • 👤 Richard O. Mohring

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-02 20:09
CPC Classifications
C; C08; C08F; C08F10/00

Claims Analysis

Total Claims: 58
Claim 1
Independent Claim 31 words
In a process for preparing an alpha-olefin polymerization catalyst composition comprising a transition metal compound, a magnesium compound and a metal alkyl, the improvement comprising using trimethylaluminum as the metal alkyl.
Claim 2
Dependent Claim 31 words
In a process for preparing an alpha-olefin polymerization catalyst composition comprising a transition metal compound, a magnesium compound and a metal alkyl, the improvement comprising using trimethylaluminum as the metal alkyl.
Claim 3
Dependent Claim 13 words
A process of claim 1 wherein the magnesium compound is an organomagnesium composition.
Claim 4
Dependent Claim 45 words
A process of claim 2 wherein the catalyst composition is prepared by: (A) contacting a solid, porous carrier with the organomagnesium composition; (B) contacting the product of step (A) with the transition metal compound; and (C) contacting the product of step (B) with the trimethylaluminum.
Claim 5
Dependent Claim 199 words
A process of claim 3 wherein the catalyst composition is prepared in a process comprising the steps of: (i) contacting a solid, porous carrier having reactive OH groups with a liquid containing at least one organomagnesium composition having the empirical formula: R.sub.n MgR'.sub.(2-n) where R and R' are the same or different and they are C 1 -C 12 hydrocarbyl groups, provided that R' may also be 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 produce a supported magnesium composition in the form of a dry, free-flowing powder; and (iii) reacting said powder of step (ii) with at least one transition metal compound in a liquid medium, the number of moles of said transition metal compound being in excess of the number of moles of the OH groups on said carrier prior to the reaction of the carrier with said organomagnesium composition in step (i), said transition metal compound being soluble in said liquid medium, and said supported magnesium composition being substantially insoluble in said liquid medium.
Claim 6
Dependent Claim 14 words
A process of claim 4 wherein the transition metal compound is a titanium compound.
Claim 7
Dependent Claim 14 words
A process of claim 5 wherein the titanium compound is a tetravalent titanium compound.
Claim 8
Dependent Claim 36 words
A process of claim 6 wherein the catalyst composition comprises such an amount of the trimethylaluminum that the polymer prepared with the catalyst composition comprises about 15 to about 300 parts per million of the trimethylaluminum.
Claim 9
Dependent Claim 9 words
A process of claim 7 wherein n is 1.
Claim 10
Dependent Claim 40 words
A process of claim 8 wherein said step (i) comprises: (a) slurrying the carrier in a non-Lewis base liquid; and (b) adding to the slurry resulting from step (a) the organomagnesium composition in the form of an ether solution thereof.
Claim 11
Dependent Claim 10 words
A process of claim 9 wherein the ether is tetrahydrofuran.
Claim 12
Dependent Claim 16 words
A process of claim 10 wherein the porous, solid carrier is silica, alumina or combinations thereof.
Claim 13
Dependent Claim 12 words
A process of claim 11 wherein the porous, solid carrier is silica.
Claim 14
Dependent Claim 14 words
A process of claim 12 wherein the tetravalent titanium compound is TiCl 4 .
Claim 15
Dependent Claim 39 words
A process of claim 13 wherein, in step (i), the ratio of the number of moles of said organomagnesium composition to the number of moles of the OH groups on said silica is from about 1.1 to about 3.5.
Claim 16
Dependent Claim 37 words
A process of claim 14 wherein in step (i), the ratio of the number of moles of said organomagnesium composition to the number of moles of the OH groups on said silica is about 1.5 to 3.5.
Claim 17
Dependent Claim 17 words
A process of claim 15 wherein said liquid medium is an alkane, cycloalkane, aromatics or halogenated aromatics.
Claim 18
Dependent Claim 11 words
A process of claim 16 wherein said liquid medium is hexane.
Claim 19
Dependent Claim 29 words
A process of claim 17 wherein, prior to contacting the silica in step (i), it is heated at a temperature of about 750° C. for at least four hours.
Claim 20
Dependent Claim 12 words
A process of claim 18 wherein the organomagnesium composition is ethylmagnesium chloride.
Claim 21
Dependent Claim 27 words
In an alpha-olefin polymerization catalyst composition comprising a transition metal compound, a magnesium compound and a metal alkyl, the improvement comprising using trimethylaluminum as the metal alkyl.
Claim 22
Dependent Claim 27 words
In an alpha-olefin polymerization catalyst composition comprising a transition metal compound, a magnesium compound and a metal alkyl, the improvement comprising using trimethylaluminum as the metal alkyl.
Claim 23
Dependent Claim 14 words
A catalyst composition of claim 20 wherein the magnesium compound is an organomagnesium composition.
Claim 24
Dependent Claim 44 words
A catalyst composition of claim 21 wherein it is prepared by: (A) contacting a solid, porous carrier with the organomagnesium composition; (B) contacting the product of step (A) with the transition metal compound; and (C) contacting the product of step (B) with the trimethylaluminum.
Claim 25
Dependent Claim 198 words
A catalyst composition of claim 22 wherein it is prepared in a process comprising the steps of (i) contacting a solid, porous carrier having reactive OH groups with a liquid containing at least one organomagnesium composition having the empirical formula: R.sub.n MgR'.sub.(2-n) where R and R' are the same or different and they are C 1 -C 12 hydrocarbyl groups, provided that R' may also be 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 produce a supported magnesium composition in the form of a dry, free-flowing powder; and (iii) reacting said powder of step (ii) with at least one transition metal compound in a liquid medium, the number of moles of said transition metal compound being in excess of the number of moles of the OH groups on said carrier prior to the reaction of the carrier with said organomagnesium composition in step (i), said transition metal compound being soluble in said liquid medium, and said supported magnesium composition being substantially insoluble in said liquid medium.
Claim 26
Dependent Claim 15 words
A catalyst composition of claim 23 wherein the transition metal compound is a titanium compound.
Claim 27
Dependent Claim 15 words
A catalyst composition of claim 24 wherein the titanium compound is a tetravalent titanium compound.
Claim 28
Dependent Claim 34 words
A catalyst composition of claim 25 which comprises such an amount of the trimethylaluminum that the polymer prepared with the catalyst composition comprises about 15 to about 300 parts per million of the trimethylaluminum.
Claim 29
Dependent Claim 10 words
A catalyst composition of claim 26 wherein n is 1.
Claim 30
Dependent Claim 41 words
A catalyst composition of claim 27 wherein said step (i) comprises: (a) slurrying the carrier in a non-Lewis base liquid; and (b) adding to the slurry resulting from step (a) the organomagnesium composition in the form of an ether solution thereof.
Claim 31
Dependent Claim 11 words
A catalyst composition of claim 28 wherein the ether is tetrahydrofuran.
Claim 32
Dependent Claim 17 words
A catalyst composition of claim 29 wherein the porous, solid carrier is silica, alumina or combinations thereof.
Claim 33
Dependent Claim 13 words
A catalyst composition of claim 30 wherein the porous, solid carrier is silica.
Claim 34
Dependent Claim 15 words
A catalyst composition of claim 31 wherein the tetravalent titanium compound is TiCl 4 .
Claim 35
Dependent Claim 40 words
A catalyst composition of claim 32 wherein, in step (i), the ratio of the number of moles of said organomagnesium composition to the number of moles of the OH groups on said silica is from about 1.1 to about 3.5.
Claim 36
Dependent Claim 38 words
A catalyst composition of claim 33 wherein, in step (i), the ratio of the number of moles of said organomagnesium composition to the number of moles of the OH groups on said silica is about 1.5 to 3.5.
Claim 37
Dependent Claim 18 words
A catalyst composition of claim 34 wherein said liquid medium is an alkane, cycloalkane, aromatics or halogenated aromatics.
Claim 38
Dependent Claim 12 words
A catalyst composition of claim 35 wherein said liquid medium is hexane.
Claim 39
Dependent Claim 30 words
A catalyst composition of claim 36 wherein, prior to contacting the silica in step (i), it is heated at a temperature of about 750° C. for at least four hours.
Claim 40
Dependent Claim 13 words
A catalyst composition of claim 37 wherein the organomagnesium composition is ethylmagnesium chloride.
Claim 41
Dependent Claim 54 words
A process of claim 1 wherein the catalyst composition is prepared by (A) contacting a solution of a magnesium compound in a liquid with a titanium compound; (B) contacting the resulting solution of step (A) with a solid, inert porous carrier to form a catalyst precursor; and (C) contacting the precursor with the trimethylaluminum.
Claim 42
Dependent Claim 23 words
A process of claim 39 wherein the magnesium compound has the empirical formula MgX.sub.2 wherein X is Cl, Br, I or mixtures thereof.
Claim 43
Dependent Claim 13 words
A process of claim 40 wherein the magnesium compound is MgCl 2 .
Claim 44
Dependent Claim 14 words
A process of claim 41 wherein said liquid is at least one Lewis base.
Claim 45
Dependent Claim 29 words
A process of claim 42 wherein the Lewis base is selected from the group consisting of aliphatic carboxylic acids, aromatic carboxylic acids, aliphatic ethers, cyclic ethers and aliphatic ketones.
Claim 46
Dependent Claim 21 words
A process of claim 43 wherein the Lewis base is selected from the group consisting of aliphatic ethers and cyclic ethers.
Claim 47
Dependent Claim 11 words
A process of claim 44 wherein the Lewis base is tetrahydrofuran.
Claim 48
Dependent Claim 40 words
A process of claim 45 wherein the titanium compound is TiCl 3 , TiCl 4 , Ti(OCH 3 )Cl 3 , Ti(OC 6 H 5 )Cl 3 , Ti(OCOCH 3 )Cl 3 or Ti(OCOC 6 H 5 )Cl 3 .
Claim 49
Dependent Claim 13 words
A process of claim 46 wherein the titanium compound is TiCl 3 .
Claim 50
Dependent Claim 53 words
A catalyst composition of claim 20 wherein it is prepared by (A) contacting a solution of a magnesium compound in a liquid with a titanium compound; (B) contacting the resulting solution of step (A) with a solid, inert porous carrier to form a catalyst precursor; and, (C) contacting the precursor with the trimethylaluminum.
Claim 51
Dependent Claim 24 words
A catalyst composition of claim 48 wherein the magnesium compound has the empirical formula MgX.sub.2 wherein X is Cl, Br, I or mixtures thereof.
Claim 52
Dependent Claim 14 words
A catalyst composition of claim 49 wherein the magnesium compound is MgCl 2 .
Claim 53
Dependent Claim 15 words
A catalyst composition of claim 50 wherein the liquid is at least one Lewis base.
Claim 54
Dependent Claim 30 words
A catalyst composition of claim 51 wherein the Lewis base is selected from the group consisting of aliphatic carboxylic acids, aromatic carboxylic acids, aliphatic ethers, cyclic ethers and aliphatic ketones.
Claim 55
Dependent Claim 22 words
A catalyst composition of claim 52 wherein the Lewis base is selected from the group consisting of aliphatic ethers and cyclic ethers.
Claim 56
Dependent Claim 12 words
A catalyst composition of claim 53 wherein the Lewis base is tetrahydrofuran.
Claim 57
Dependent Claim 41 words
A catalyst composition of claim 54 wherein the titanium compound is TiCl 3 , TiCl 4 , Ti(OCH 3 )Cl 3 , Ti(OC 6 H 5 )Cl 3 , Ti(OCOCH 3 )Cl 3 or Ti(OCOC 6 H 5 )Cl 3 .
Claim 58
Dependent Claim 14 words
A catalyst composition of claim 55 wherein the titanium compound is TiCl 3 .

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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) 1991-03-22 1991-09-21 1992-03-22 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1995-03-22 1995-09-21 1996-03-22 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1999-03-22 1999-09-21 2000-03-22 $7700.00 Window Closed / Lapsed

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