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EP0427697B1 Expired / Lapsed EP ⏱️ 0.0 years remaining

Metallocene catalysts with Lewis acids and aluminum alkyls

Assignee: Fina Technology Inc
•
Filing: 1990-10-09
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Granted: 1996-05-08
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Expires: 2010-10-09
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Abstract

Abstract This invention is for a catalyst system comprising a neutral metallocene compound, an aluminum alkyl and a Lewis acid. The Lewis acid must be of sufficient acidity to ionize a neutral metallocene compound to form a cationic metallocene catalyst. The ligands of the Lewis acid should not be reactive with the metallocene cation. Any metallocene catalyst compound having two cyclopentadienyl rings attached to a transition metal would be useful in this invention. The invention is also for the process of using the catalyst system in polymerization of olefins. The metallocene is contacted with the Lewis acid. The aluminum alkyl is contacted with the olefin. The two mixtures are contacted with each other under polymerization conditions.

Inventors

  • 👤 John A. Ewen
  • 👤 Michael J. Elder

Bibliographic Details

Application Number —
Jurisdiction EP
Data Source google_patents
Last Synchronized 2026-10-24 18:48
CPC Classifications
C; C08; C08F; C08F4/00; C08F10/00; C08F10/04; C08F10/06; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/639; C08F4/63908; C08F4/63912; C08F4/6392; C08F4/63922; C08F4/64; C08F4/659; C08F4/65908; C08F4/6592; C08F4/65922; C08F4/65927; Y; Y10; Y10S; Y10S526/00; Y10S526/901; Y10S526/943

Claims Analysis

Total Claims: 25
Claim 1
Independent Claim 162 words
A catalyst system comprising: a) a neutral metallocene compound; b) an aluminum alkyl; and c) a Lewis acid; wherein the aluminum alkyl is of the general formula AlR'₃ where R' is a halogen, oxygen, hydride, alkyl, alkoxy or aryl, each R' being the same or different and at least one R' is an alkyl, wherein the neutral metallocene compound is of the general formula: Cp₂MR p wherein Cp is cyclopentadienyl or substituted cyclopentadienyl, each Cp being the same or different, M is a Group III, IV, V or VI metal, R is a hydride, a halogen, an amide or a hydrocarbyl radical, each R being the same or different, except when R is a hydride only one R is a hydride and p is from 1 to 4, wherein the Lewis acid is chosen from the group consisting of all Lewis acids containing boron and magnesium chloride, and wherein the ligands of the Lewis acid are not reactive with the metallocene cation.
Claim 2
Dependent Claim 36 words
A catalyst as recited in Claim 1 wherein R is a hydrocarbyl radical selected from the group consisting of an alkyl, an aryl, an alkenyl, an alkylaryl and an arylalkyl having up to 20 carbon atoms.
Claim 3
Dependent Claim 27 words
A catalyst as recited in Claim 2 wherein R is an alkyl or alkoxy of up to six carbons or an aryl of up to 10 carbons.
Claim 4
Dependent Claim 25 words
A catalyst as recited in Claim 1 wherein the M is a Group IV metal selected from the group consisting of titanium, zirconium and hafnium.
Claim 5
Dependent Claim 28 words
A catalyst as recited in Claim 4 wherein the neutral methyl derivative of a metallocene is chosen from the group consisting of ethylenebis(indenyl)zirconium dimethyl and isopropylidene(cyclopentadienyl-1-fluorenyl) zirconium dimethyl.
Claim 6
Dependent Claim 21 words
A catalyst as recited in Claim 1 wherein the aluminum alkyl is selected from the group consisting of triethylaluminum and trimethylaluminum.
Claim 7
Dependent Claim 13 words
A catalyst as recited in Claim 6 wherein the aluminum alkyl is triethylaluminum.
Claim 8
Dependent Claim 13 words
A catalyst as recited in Claim 1 wherein the Lewis acid is tris(pentafluorophenyl)boron.
Claim 9
Dependent Claim 190 words
A process for preparing a catalyst comprising: a) mixing a Lewis acid with a neutral metallocene compound; and b) allowing contact between the Lewis acid and the neutral metallocene compound to form a metallocene compound; and c) adding an aluminum alkyl; wherein the neutral metallocene is of the general formula : Cp₂MR p wherein Cp is a cyclopentadienyl or a substituted cyclopentadienyl group, each Cp being the same or different, M is a Group III, IV, V or VI metal, R is a hydride, a halogen, an amide or a hydrocarbyl radical, each R being the same or different, except when R is a hydride only one R is a hydride and p is from 1 to 4; wherein the Lewis acid is chosen from the group consisting of all Lewis acids containing boron and magnesium chloride; wherein the ligands of the Lewis acid are not reactive with the metallocene cation; and wherein the aluminum alkyl is of the general formula AIR'₃ where R' is a halogen , oxygen , hydride, alkyl, alkoxy or aryl, each R' being the same or different and at least one R' is an alkyl.
Claim 10
Dependent Claim 36 words
A process as recited in Claim 9 wherein R is a hydrocarbyl radical selected from the group consisting of an alkyl, an aryl, an alkenyl, an alkylaryl and an arylalkyl having up to 20 carbon atoms.
Claim 11
Dependent Claim 25 words
A process as recited in Claim 9 wherein the M is A Group IV metal selected from the group consisting of titanium, zirconium and hafnium.
Claim 12
Dependent Claim 12 words
A process as recited in Claim 11 wherein the M is zirconium.
Claim 13
Dependent Claim 27 words
A process as recited in Claim 12 wherein the neutral derivative of a metallocene is chosen from the group consisting of ethylenebis(indenyl)zirconium dimethyl and isopropylidene (cyclopentadienyl-1-fluorenyl)zirconium dimethyl.
Claim 14
Dependent Claim 26 words
A process as recited in Claim 9 wherein the Lewis acid is chosen from the group consisting of all Lewis acids containing boron and magnesium chloride.
Claim 15
Dependent Claim 13 words
A process as recited in Claim 14 wherein the Lewis acid is tris(pentafluorophenyl)boron.
Claim 16
Dependent Claim 166 words
A process for polymerization of olefins comprising: a) mixing an aluminum alkyl with an olefin; b) mixing a neutral metallocene compound with a Lewis acid; c) mixing the metallocene-Lewis acid mixture with the aluminum alkyl-olefin mixture. wherein the aluminum alkyl is of the general formula AlR'₃ where R' is a halogen, oxygen, hydride, alkyl, alkoxy or aryl, each R' being the same or different and at least one R' is an alkyl; wherein the neutral metallocene compound is of the general formula: Cp₂MR p wherein Cp is cyclopentadienyl or substituted cyclopentadienyl, each Cp being the same or different, M is a Group III, IV, V or VI metal, R is a hydride, a halogen, an amide or a hydrocarbyl radical, each R being the same or different, except when R is a hydride only one R is a hydride and p is from 1 to 4; and wherein the Lewis acid is chosen from the group consisting of all Lewis acids containing boron and magnesium chloride.
Claim 17
Dependent Claim 27 words
A process as recited in Claim 16 wherein R' is an alkyl or alkoxy of up to six carbons or an aryl of up to 10 carbons.
Claim 18
Dependent Claim 20 words
A process as recited in Claim 17 wherein the molar ratio for metallocene:Lewis acid:aluminum alkyl ranges from 0.01:1:0.1 to 5:1:350.
Claim 19
Dependent Claim 20 words
A process as recited in claim 18 wherein the molar ratio for metallocene:Lewis acid:aluminum alkyl ranges from 0.5:1:0.5 to 4:1:25.
Claim 20
Dependent Claim 17 words
A process as recited in Claim 19 wherein the molar ratio for metallocene:Lewis acid:aluminum alkyl is 0.02:1:1.
Claim 21
Dependent Claim 17 words
A process as recited in Claim 19 wherein the molar ratio for metallocene:Lewis acid:aluminum alkyl is 0.01:1:1.
Claim 22
Dependent Claim 21 words
A process as recited in Claim 14 wherein the aluminum alkyl is selected from the group consisting of triethylaluminum and trimethylaluminum.
Claim 23
Dependent Claim 13 words
A process as recited in Claim 19 wherein the aluminum alkyl is triethylaluminum.
Claim 24
Dependent Claim 26 words
A process as recited in Claim 16 wherein the Lewis acid is chosen from the group consisting of all Lewis acids containing boron and magnesium chloride.
Claim 25
Dependent Claim 13 words
A process as recited in Claim 24 wherein the Lewis acid is tris(pentafluorophenyl)boron.

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