US5384299A
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Ionic metallocene catalyst compositions
Assignee: Exxon Mobil Corp
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Filing: 1993-02-19
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Granted: 1995-01-24
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Expires: 2013-02-19
Abstract
Abstract Ionic catalyst compositions can be prepared by combining two components. The first component is a bis(cyclopentadienyl) Group IV-B metal complex containing at least one ligand which will combine irreversibly with the second component or at least a portion thereof such as a cation portion thereof. The second component comprises a cation which will irrevesibly react with at least one ligand on the Group IV-B metal complex and a non-coordinating anion. The combination of the two components produces an ionic catalyst composition comprising a cationic bis(cyclopentadienyl) Group IV-B metal complex which has a formal coordination number of 3 and a 4+ valence charge and the aforementioned non-coordinating anion. The anion is (i) labile and can be displaced by an olefin, diolefin or acetylenically unsaturated monomer; (ii) has a molecular diameter about or greater than 4 angstroms; (iii) forms stable salts with reducible Lewis acids and protonated Lewis bases; (iv) has a negative charge delocalized over the framework on the anion or within the core thereof; (v) is not a reducing or oxidizing agent; and (vi) is a relatively poor nucleophile. These ionic catalyst compositions can be used to polymerize α-olefins, diolefins and/or acetylenically unsaturated monomers, either alone or in combination, to polymers and copolymers.
Inventors
- 👤 Howard W. Turner
- 👤 Gregory G. Hlatky
- 👤 Richard R. Eckman
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 21:40
CPC Classifications
C; C08; C08F; C08F10/00; C07; C07F; C07F17/00; C08F110/00; C08F110/02; C08F110/04; C08F110/06; C08F210/00; C08F210/04; C08F210/06; C08F210/16; C08F210/18; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F4/659; C08F4/6592; C08F4/65922; C08F4/65925; C08F4/65927; Y; Y10; Y10S; Y10S526/00; Y10S526/943
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
50 words
An ionic polymerization catalyst comprising (1) a cation derived from a bis(cyclopentadienyl) Group IV-B metal compound by abstracting a ligand to create a positively charged species and (2) a stabilizing non-coordinating anion, said anion being sufficiently labile to permit displacement by an olefin, diolefin and/or acetylenically unsaturated monomer during polymerization.
Claim 2
Dependent Claim
50 words
An ionic polymerization catalyst comprising (1) a cation derived from a bis(cyclopentadienyl) Group IV-B metal compound by abstracting a ligand to create a positively charged species and (2) a stabilizing non-coordinating anion, said anion being sufficiently labile to permit displacement by an olefin, diolefin and/or acetylenically unsaturated monomer during polymerization.
Claim 3
Dependent Claim
205 words
A composition of matter comprising a Group IV-B metal cation and a non-coordination anion, which composition is represented by one of the following general formulae: {[(A--Cp)MX.sub.1 ].sup.+ }.sub.d [B'].sup.d- ( 1) {[(A--Cp)MX.sub.5 L'].sup.+ }.sub.d [B'}.sup.d- ( 2) wherein: (A--Cp) is either (Cp)Cp') or Cp--A'--Cp'; Cp and Cp' are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbylosubstituted organometalloid or halogen radical, or Cp and Cp' are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C 4 to C 20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; and A' is a bridging group restricting rotation of the Cp and Cp' rings; M is titanium, zirconium or hafnium; L' is a neutral Lewis base; X 1 is a hydride radical, hydrocarbyl radicals, substituted-hydrocarbyl radicals, hydrocarbyl-substituted organometalloid radicals or halocarbyl-substituted organometalloid radical; X 5 is a hydride radical, hydrocarbyl radical or substituted-hydrocarbyl radical or substituted organometalloid radicals, which radical may optionally be covalently bonded to both M and L'; B' is a compatible non-coordinating anionic complex; and d is an integer representing the charge of B'.
Claim 4
Dependent Claim
205 words
A composition of matter comprising a Group IV-B metal cation and a non-coordination anion, which composition is represented by one of the following general formulae: {[(A--Cp)MX.sub.1 ].sup.+ }.sub.d [B'].sup.d- ( 1) {[(A--Cp)MX.sub.5 L'].sup.+ }.sub.d [B'}.sup.d- ( 2) wherein: (A--Cp) is either (Cp)Cp') or Cp--A'--Cp'; Cp and Cp' are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbylosubstituted organometalloid or halogen radical, or Cp and Cp' are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C 4 to C 20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; and A' is a bridging group restricting rotation of the Cp and Cp' rings; M is titanium, zirconium or hafnium; L' is a neutral Lewis base; X 1 is a hydride radical, hydrocarbyl radicals, substituted-hydrocarbyl radicals, hydrocarbyl-substituted organometalloid radicals or halocarbyl-substituted organometalloid radical; X 5 is a hydride radical, hydrocarbyl radical or substituted-hydrocarbyl radical or substituted organometalloid radicals, which radical may optionally be covalently bonded to both M and L'; B' is a compatible non-coordinating anionic complex; and d is an integer representing the charge of B'.
Claim 5
Dependent Claim
36 words
The composition of claim 2, wherein B' is a single anionic complex comprising a plurality of lipophilic radicals covalently bonded to and shielding a central charge-bearing metal or metalloid atom, or a plurality of boron atoms.
Claim 6
Dependent Claim
75 words
The composition of claim 3 wherein B' is represented by the general formula: [(M').sup.m+ Q.sub.1 Q.sub.2 . . . Q.sub.n ].sup.d- wherein: M' is a metal or metalloid; Q 1 to Q n are, independently, hydride radicals, bridged or unbridged dialkylamido radicals, alkoxide and aryloxide radicals, substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals, and hydrocarbyl- and halocarbyl-substituted organometalloid radicals and any one, but not more than one, of Q1 to Qn may be a halide radical.
Claim 7
Dependent Claim
33 words
The composition of matter according to claim 2 wherein the substitutent group S on any of Cp, Cp', X 1 , or X 5 is independently a C 1 to C 20 radical.
Claim 8
Dependent Claim
17 words
The composition of claim 4, wherein at least one of Q 1 to Q n is pentafluorophenyl.
Claim 9
Dependent Claim
98 words
The composition of claim 4, wherein B' is represented by the formula: [BAr.sub.1 Ar.sub.2 X.sub.3 X.sub.4 ]-- wherein: B is boron in a valence state of 3 + ; Ar 1 Ar 2 are the same or different aromatic or substituted-aromatic hydrocarbon radicals and may be linked to each other through a stable bridging group; and X 3 X 4 are, independently, hydride radicals, halide radicals, with the proviso that only one of X 3 or X 4 will be halide, hydrocarbyl radicals, substituted-hydrocarbyl radicals, halocarbyl radicals, substituted-halocarbyl radicals, hydrocarbyl- and dialkylamido radicals, and alkoxide and aryloxide radicals.
Claim 10
Dependent Claim
15 words
The composition of claim 2, which composition has the following general formula: {[(A--Cp)MX.sub.1 }.sub.d [B'].sup.3-.
Claim 11
Dependent Claim
13 words
The composition of claim 3, wherein B' is a non-coordinating aryl boron anion.
Claim 12
Dependent Claim
44 words
The composition of claim 9, wherein the aryl boron anion is [B(C 6 F 5 ) 4 ]-- or [B(C 6 F 5 ) 3 Q]-- where Q is a monoanionic, non-bridging hydride, hydrocarbyl, substituted-hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, dialkylamido, alkoxy, aryloxy, or halide radical.
Claim 13
Dependent Claim
18 words
The composition of claim 10, wherein the aryl boron anion is [B(C 6 F 5 ) 4 ]--.
Claim 14
Dependent Claim
38 words
The composition of claim 5, wherein (A--Cp) is (Cp)(Cp') and Cp and Cp' are the same or different substituted or unsubstituted cyclopentadienyl radicals wherein the substituted cyclopentadienyl radicals are substituted with from 1 to 5 substituent groups S.
Claim 15
Dependent Claim
34 words
The composition of claim 12, wherein (A--Cp) is (C 5 (CH 3 ) 5 ) 2 or (C 5 H 5 ) 2 , M is Zr or Hf, and X 1 is methyl.
Claim 16
Dependent Claim
16 words
The composition of claim 12, wherein (A--Cp) is Cp--A'--Cp' and Cp--A'--Cp, forms a chiral ligand set.
Claim 17
Dependent Claim
41 words
The composition of claim 8, wherein (A--Cp) is Cp--A'--Cp' wherein Cp and Cp' are independently, substituted cyclopentadienyl radicals such that Cp and Cp' have different steric characteristics, or Cp is an unsubstituted cyclopentadienyl radical and Cp' is a substituted cyclopentadienyl radical.
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