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US5407884A Expired / Lapsed US ⏱️ 0.0 years remaining

Catalysts, method of preparing these catalysts, and polymerization processes wherein these catalysts are used

Assignee: ExxonMobil Chemical Patents Inc
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Filing: 1993-08-09
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Granted: 1995-04-18
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Expires: 2013-08-09
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Abstract

Abstract An ionic catalyst useful for the polymerization of olefins, diolefins and/or acetylenically unsaturated monomers is described. The catalyst comprises cyclopentadienyl derivatives of Group IV-B metals as cation and a compatible non-coordinating anion containing a plurality of boron atoms. Borate, carborate, borane, carborane, metallaborane and metallacarborane compounds exemplify anion sources and dihydrocarbyl-substituted bis(cyclopentadienyl) zirconium compounds exemplify the Group IV-B metal cation sources. Utility is illustrated for olefin polymerization.

Inventors

  • 👤 Howard W. Turner
  • 👤 Gregory G. Hlatky

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-31 00:55
CPC Classifications
C; C08; C08F; C08F10/00; C07; C07F; C07F17/00; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F4/659; C08F4/65908; C08F4/6592; C08F4/65922; Y; Y10; Y10S; Y10S526/00; Y10S526/943

Claims Analysis

Total Claims: 21
Claim 1
Independent Claim 30 words
An ionic polymerization catalyst comprising a bis(cyclopentadienyl)-substituted Group IV-B metal cation and a compatible non-coordinating anion comprising a plurality of boron atoms, said non-coordinating anion being stable, bulky and labile.
Claim 2
Dependent Claim 30 words
An ionic polymerization catalyst comprising a bis(cyclopentadienyl)-substituted Group IV-B metal cation and a compatible non-coordinating anion comprising a plurality of boron atoms, said non-coordinating anion being stable, bulky and labile.
Claim 3
Dependent Claim 343 words
The catalyst according to claim 1, represented by the following general formula: (A-Cp)MX.sub.1 B' Wherein: M is a metal selected from the Group consisting of titanium (TI), zirconium (Zr) and hafnium (Hf); (A-Cp) is either (Cp) (Cp * ) or CP-A'-Cp * and Cp and Cp * are the same or different substituted or unsubstituted cyclopentadienyl radicals; A' is a covalent bridging group containing a Group IV-A element; X 1 is selected from the Group consisting of hydride radicals, hydrocarbyl radicals, organo-metalloid radicals; and B' is a compatible non coordinating anion which may be represented by one of the following general formulae: [(CX).sub.a (BX').sub.m X".sub.b ].sup.c- Wherein: B and C are, respectively, boron and carbon; X, X' and X" are radicals selected, independently, from the Group consisting of hydride radicals, halide radicals, hydrocarbyl radicals containing 1 to about 20 carbon atoms, substituted-hydrocarbyl radicals having 1 to about 20 carbon atoms wherein one or more hydrogen atoms is replaced by a halogen, organo-metalloid radicals containing 1 to about 20 carbon atoms wherein the metal is a Grp-IVA metal; a and b are integers ≧0; c is an integer =1; a+b+c=an even-numbered integer from 2 to about 8; and m is an integer ranging from 5 to about 22; and 34; and [[[(CX.sub.3).sub.a' (BX.sub.4).sub.m' (X.sub.5 .sub.b' ].sup.c'- ].sub.2 M.sup.n+ ].sup.d- Wherein: B, C and M are, respectively, boron, carbon and a transition metal; X 3 , X 4 and X 5 are radicals selected, independently, from the Group consisting of hydride radicals, halide radicals, hydrocarbyl radicals containing 1 to about 20 carbon atoms, substituted-hydrocarbyl radicals having 1 to about 20 carbon atoms wherein one or more hydrogen atoms is replaced by a halogen, organo-metalloid radicals containing 1 to about 20 carbon atoms wherein the metal is a Grp-IVA metal; A' and b' are the same or a different integer ≧0; C' is an integer ≧2; a'+b'+c'=an even-numbered integer from 4 to about 8; m' is an integer from 6 to about 12; n is an integer such that 2c'-n=d; and d is an integer =1.
Claim 4
Dependent Claim 56 words
The catalysts of claim 2 wherein (A-Cp) is a bis(peralkyl-substituted cyclopentadienyl); X 1 is an alkyl group; B' is (dodecahydrido-7,8-dicarbaundecaborato) and M is zirconium and wherein each of the alkyl groups in the peralkyl-substituted cyclopentadienyl radicals are, independently, C 1 -C 20 alkyl radicals and the alkyl group is a C 1 -C 20 alkyl radical.
Claim 5
Dependent Claim 19 words
The catalyst of claim 3 wherein the peralkyl substitution is pentamethyl and the alkyl radical is a methyl radical.
Claim 6
Dependent Claim 19 words
The catalyst of claim 3 wherein the peralkyl substitution is ethyltetramethyl and the alkyl group is a methyl radical.
Claim 7
Dependent Claim 15 words
The catalyst of claim 1 wherein said Group IV-B metal is titanium, zirconium or hafnium.
Claim 8
Dependent Claim 79 words
The catalyst of claim 2 wherein said bis(cyclopentadienyl)-substituted Group IV-B meal cation contains cyclopentadienyl radicals having carbon atoms that are unsubstituted or substituted with the same or different 1 to about 20 carbon atom radical selected from the group consisting of hydrocarbyl radicals and substituted-hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, a hydrocarbyl-substituted metalloid radical wherein the metalloid is selected from Group IV-A of the Periodic Table of Elements or halogen radical.
Claim 9
Dependent Claim 24 words
The catalyst of claim 7 wherein said cyclopentadienyl radicals are substituted with the same or different 1 to about 20 carbon atom hydrocarbyl radical.
Claim 10
Dependent Claim 27 words
The catalyst of claim 8 wherein said hydrocarbyl radical is a cyclic hydrocarbyl radical, an alkyl-substituted cyclic hydrocarbyl radical, an aromatic radical or an alkyl-substituted aromatic radical.
Claim 11
Dependent Claim 25 words
The catalyst of claim 9 wherein said Group IV-B metal cation is bis(indenyl) zirconium dimethyl, bis(indenyl) hafnium dimethyl, (indenyl) (cyclopentadienyl) zirconium dimethyl or (indenyl)(cyclopentadienyl)hafnium dimethyl.
Claim 12
Dependent Claim 12 words
The catalyst of claim 2 wherein said hydrocarbyl radicals are bridged-cyclopentadienyl compounds.
Claim 13
Dependent Claim 31 words
The catalyst of claim 1 wherein said non-coordinating anion is a borate, carborate, salt of borates or carbonates, borane, carborane, salt of boranes or carboranes, or salt of metalloborane or metallacarborane.
Claim 14
Dependent Claim 15 words
The catalyst of claim 12 wherein said non-coordinating anion is a salt of a borate.
Claim 15
Dependent Claim 12 words
The catalyst of claim 12 wherein said non-coordinating anion is a carborate.
Claim 16
Dependent Claim 14 words
The catalyst of claim 12 wherein said non-coordinating anion is a borane or carborane.
Claim 17
Dependent Claim 18 words
The catalyst of claim 14 wherein said non-coordinating anion is a salt of boranes, carboranes, metalloboranes or metallacarboranes.
Claim 18
Dependent Claim 11 words
The catalyst of claim 13 wherein said salt is bis(tri(n-butyl)ammonium dodecaborate.
Claim 19
Dependent Claim 17 words
The catalyst of claim 14 wherein said carborate is tri(n-butyl)ammonium 1-carbaundecaborate, tri(n-butyl)ammonium 7,8-dicarbaundecaborate, or tri(n-butyl) ammonium tridecahydrido-7-carbaundecaborate.
Claim 20
Dependent Claim 12 words
The catalyst of claim 15 wherein said borane is 7,8-dicarbaundecaborane or decaborane.
Claim 21
Dependent Claim 22 words
The catalyst of claim 16 wherein said salt is selected from the group consisting of N,N-dimethylanilinium bis(7,8-dicarbaundecaborato)nickelate(III), N,N-dimethylanilinium bis(7,8-dicarbaundecaborato)ferrate(III), and N,N-dimethylanilinium bis(undecahydrido-7,8-dicarbaundecaborato)cobaltate(III).

References Cited (Backward Citations)

EP0129368B1 Cited
US5198401A Cited
US5278119A Cited
US5064802A Cited
US5162466A Cited
US5214173A Cited

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