EP0662979B1
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EP
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Supported homogeneous catalyst complexes for olefin polymerization
Assignee: Dow Chemical Co
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Filing: 1993-09-30
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Granted: 1997-07-16
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Expires: 2013-09-30
Abstract
Abstract A supported catalyst complex having a Group 4 metal cyclopentadienyl derivative and an aluminoxane reacted with silica which show improved resistance to catalyst poisoning. The supported catalyst composition is particularly suitable for producing homogeneous ethylene polymers and copolymers having a narrow molecular weight distribution. The invention further includes the process of preparing the supported catalyst compositions and their use as olefin polymerization catalysts. The catalyst support is prepared by contacting silica with an aluminoxane, preferably either methylaluminoxane or modified methylaluminoxane.
Inventors
- 👤 Brian Kolthammer
- 👤 John C. Tracy
- 👤 Robert S. Cardwell
- 👤 Robert K. Rosen
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-10-30 05:32
CPC Classifications
C; C08; C08F; C08F10/00; C08F110/00; C08F110/02; C08F210/00; C08F210/16; C08F2420/00; C08F2420/02; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F4/659; C08F4/65908; C08F4/65912; C08F4/65916; C08F4/6592
Claims Analysis
Total Claims: 26
Claim 1
Independent Claim
288 words
An activated, supported homogeneous catalyst complex suitable for homopolymerizing ethylene or copolymerizing ethylene with at least one C 3 to C 18 α-olefin monomer to form an ethylene polymer having a narrow molecular weight distribution, said catalyst complex comprising: (a) an organometallic complex of the formula I: wherein: M is a metal of Group 4 of the Periodic Table of the Elements, Cp* is a cyclopentadienyl group bound in an η 5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amine, and mixtures thereof, said substituent having up to 20 non-hydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure; Z' is a divalent moiety other than a cyclopentadienyl group or substituted cyclopentadienyl groups, said moiety having up to 20 non-hydrogen atoms; X independently each occurrence is an anionic ligand group having up to 50 non-hydrogen atoms and X is not a cyclopentadienyl or substituted cyclopentadienyl group; and n is 1 or 2 depending on the valence of M; (b) a compound or complex capable of converting organometallic complex (a) into a cationic complex of the formula II: wherein: Cp*, Z', M, X, and n are as defined above, and A - is a monovalent, noncoordinating, compatible anion, and (c) a catalyst support in contact with (a) and (b), said catalyst support comprising silica reacted with an aluminoxane of the formula (R 4 x (CH 3 ) y AlO) n , wherein R 4 is a C 3 -C 10 hydrocarbyl, x is from 0 to 1, y is from 1 to greater than 0, and n is an integer from 3 to 25 or a mixture thereof.
Claim 2
Dependent Claim
30 words
A catalyst according to Claim 1, wherein Z' comprises boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally nitrogen, phosphorus, sulfur or oxygen.
Claim 3
Dependent Claim
22 words
A catalyst according to Claim 1 or Claim 2, wherein X is a monovalent ligand group of up to 30 nonhydrogen atoms.
Claim 4
Dependent Claim
14 words
A catalyst according to Claim 3, wherein X is a C 1-20 hydrocarbyl group.
Claim 5
Dependent Claim
14 words
A catalyst according to any one of the preceding claims, wherein M is titanium.
Claim 6
Dependent Claim
195 words
A catalyst according to Claim 1, wherein the organometallic complex comprises: a) a coordination complex corresponds to formula III: wherein: R' each occurrence is independently selected from hydrogen, alkyl, aryl, silyl, germyl, halo and combinations thereof having up to 20 non-hydrogen atoms or two R' groups together form a fused ring with the cyclopentadienyl ring; X each occurrence independently is an ionic ligand selected from hydride, halo, alkyl, aryl, silyl, germyl, aryloxy, alkoxy, amide, siloxy, and combinations thereof having up to 20 non-hydrogen atoms; Y is a divalent ligand group comprising nitrogen, phosphorus, oxygen or sulfur and having up to 20 non-hydrogen atoms, said Y being bonded to Z and M through said nitrogen, phosphorus, oxygen or sulfur, and optionally Y and Z together form a fused ring system; M is a Group 4 metal, Z is SiR* 2 , CR* 2 , SiR* 2 SiR* 2 , CR* 2 CR* 2 , CR*=CR*, CR* 2 SiR* 2 , GeR* 2 , or BR*; R* each occurrence is independently selected from hydrogen, alkyl, aryl, silyl, halogenated alkyl, halogenated aryl groups having up to 20 non-hydrogen atoms, and mixtures thereof; and n is 1 or 2.
Claim 7
Dependent Claim
13 words
A catalyst according to Claim 6, wherein Y is -O-, -S-, -NR*-, -PR*-.
Claim 8
Dependent Claim
18 words
A catalyst according to Claim 7, wherein Y is -NR'- and R' is a C 1-10 hydrocarbyl group.
Claim 9
Dependent Claim
104 words
A catalyst according to Claim 6, wherein the organometallic complex corresponds to the formula IV: wherein: M is titanium bound in an η 5 bonding mode to the cyclopentadienyl group; R' at each occurrence is independently selected from hydrogen, silyl, alkyl, aryl and combinations thereof, said substituent having up to 10 carbon or silicon atoms, or two R' groups together with the cyclopentadienyl ring form a fused ring; E is silicon or carbon; X independently each occurrence is selected from hydride, halo, alkyl, aryl, aralkyl, aryloxy and alkoxy of up to 10 carbons; m is 1 or 2; and n is 1 or 2.
Claim 10
Dependent Claim
10 words
A catalyst according to Claim 9, wherein E is silicon.
Claim 11
Dependent Claim
96 words
A catalyst according to Claim 10, wherein the organometallic complex is selected from: (tert-butylamido) (tetramethyl-η 5 -cyclopentadienyl)-1,2-ethanediyltitanium dimethyl, (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)-1,2-ethanediyltitanium dibenzyl, (tert-butylamido)(tetramethyl-η 5 cyclopentadienyl)-dimethylsilanetitanium dimethyl, (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dibenzyl, (methylamido) (tetramethyl-η 5 -cyclopentadienyl) dimethylsilanetitanium dimethyl, (methylamido) (tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dibenzyl, (phenylamido) (tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dimethyl, (phenylamido) (tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dibenzyl, (benzylamido) (tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dimethyl, (benzylamido) (tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dibenzyl, (tert-butylamido)(η 5 -cyclopentadienyl)-1,2-ethanediyl-titanium dimethyl, (tert-butylamido) (η 5 -cyclopentadienyl)-1,2-ethanediyltitanium dibenzyl, (tert-butylamido) (η 5 -cyclopentadienyl)dimethylsilanetitanium dimethyl, (tert-butylamido)(η 5 -cyclopentadienyl)dimethylsilanetitanium dibenzyl, (methylamido) (η 5 -cyclopentadienyl)dimethylsilanetitanium dimethyl, (tert-butylamido) (η 5 -cyclopentadienyl)dimethylsilanetitanium dibenzyl, (tert-butylamido)indenyldimethylsilanetitanium dimethyl, (tert-butylamido)indenyldimethylsilanetitanium dibenzyl, and (benzylamido)indenyldimethylsilanetitanium dibenzyl.
Claim 12
Dependent Claim
29 words
A catalyst according to any one of Claims 1 to 10, wherein component (b) is a salt of a Bronsted acid and the non-coordinating, compatible anion A - .
Claim 13
Dependent Claim
18 words
A catalyst according to Claim 12, wherein the anion comprises a coordination complex containing a single boron atom.
Claim 14
Dependent Claim
52 words
A catalyst according to Claim 13, wherein component (b) corresponds to the formula VII: [L-H] + [BQ 4 ] - (VII) wherein: L is a neutral Lewis base; [L-H] + is a Bronsted acid; B is boron in a valence state of 3; and Q is a C 1-20 fluorinated hydrocarbyl group.
Claim 15
Dependent Claim
28 words
A catalyst according to any one of Claims 1 to 10, wherein component (b) is a salt of a carbenium and the non-coordinating, compatible anion A - .
Claim 16
Dependent Claim
30 words
A catalyst according to any one of Claims 1 to 10, wherein component (b) is a salt of a cationic oxidizing agent and the non-coordinating, compatible anion A - .
Claim 17
Dependent Claim
61 words
A catalyst according to any one of Claims 1 to 10, wherein component (a) is a reduced metal derivative of the desired ionic complex (II) in which the metal is in an oxidation state one less than that of the metal in the ionic complex (II) and component (b) is a neutral oxidizing agent in combination a Lewis acid mitigating agent.
Claim 18
Dependent Claim
33 words
A catalyst according to any one of Claims 1 to 10, wherein component (b) is a Lewis acid having sufficient acidity to cause abstraction of an anionic ligand of the metal coordination complex.
Claim 19
Dependent Claim
18 words
A catalyst according to Claim 6, wherein the activating cocatalyst is an alkylcycloborane, tris(perfluorophenyl)borane or a mixture thereof.
Claim 20
Dependent Claim
15 words
A catalyst according to any one of the preceding claims, wherein said aluminoxane is methylaluminoxane.
Claim 21
Dependent Claim
63 words
A catalyst according to Claims 1 to 19, wherein said aluminoxane is a modified methylaluminoxane of the formula: (R 4 x (CH 3 ) y AlO) n wherein R 4 is a linear or branched C 3 to C 9 hydrocarbyl, x is from 0.15 to 0.50, y is from 0.85 to 0.5 and n is an integer of from 4 to 20.
Claim 22
Dependent Claim
39 words
A catalyst according to Claim 21, wherein R 4 is selected from isobutyl, tertiary butyl and n-octyl, x is from 0.2 to 0.4, y is from 0.8 to 0.6 and n is an integer of from 4 to 15.
Claim 23
Dependent Claim
21 words
A catalyst according to any one of the preceding claims, wherein the silica is dehydroxylated prior to reaction with the aluminoxane.
Claim 24
Dependent Claim
46 words
A process for polymerizing an olefin, diolefin, or mixture thereof comprising contacting an olefin, diolefin, or mixture thereof with a catalyst composition according to any of the preceding claims under polymerization reaction conditions to polymerize said olefin, diolefin, or mixture thereof, and recovering the resulting polymer.
Claim 25
Dependent Claim
268 words
A process for preparing a supported catalyst composition comprising the steps of: (i) reacting (a) an organometallic complex of the formula I: wherein: M is a metal of Group 4 of the Periodic Table of the Elements, Cp* is a cyclopentadienyl group bound in an η 5 bonding mode to M or such a cyclopentadienyl group substituted with from one to four substituents selected from hydrocarbyl, silyl, germyl, halo, hydrocarbyloxy, amine, and mixtures thereof, said substituent having up to 20 nonhydrogen atoms, or optionally, two substituents together cause Cp* to have a fused ring structure; Z' is a divalent moiety other than a cyclopentadienyl group or substituted cyclopentadienyl groups, said moiety having up to 20 non-hydrogen atoms; X independently each occurrence is an anionic ligand group having up to 50 non-hydrogen atoms and X is not a cyclopentadienyl or substituted cyclopentadienyl group; and n is 1 or 2 depending on the valence of M; with (b) a compound or complex capable of converting organometallic complex (a) into a cationic complex of the formula II: wherein: Cp*, Z', M, X, and n are as defined with respect to previous formula I, and A - is a monovalent, noncoordinating, compatible anion, and (ii) contacting the product of step (i) with (c) a catalyst support comprising silica reacted with an aluminoxane of the formula (R 4 x (CH 3 ) y AlO) n , wherein R 4 is a C 3 -C 10 hydrocarbyl, x is from 0 to 1, y is from 1 to greater than 0, and n is an integer from 3 to 25, or a mixture thereof.
Claim 26
Dependent Claim
22 words
A process according to Claim 25, wherein (a), (b) and/or (c) is as defined in any one of Claims 2 to 23.
References Cited (Backward Citations)
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