EP0643066A2
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Monocyclopentadienyl transition metal olefin polymerization catalysts
Assignee: ExxonMobil Chemical Patents Inc
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Filing: 1990-09-13
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Granted: —
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Expires: 2010-09-13
Abstract
Abstract This invention relates to a compound of the general formula: wherein M is Zr, Hf or Ti; (C 5 H 4-x R x ) is a cyclopentadienyl ring which is substituted with up to five groups R, "x" is 1, 2, 3 or 4 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C,-C 2o hydrocarbyl radicals, substituted C 1 -C 20 hydrocarbyl radicals wherein one or more hydrogen atoms are replaced by a halogen atom, an amido radical, a phosphido radical, an alkoxy radical or any other radical containing a Lewis acidic or basic functionality; C 1 -C 20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements; halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkyl borido radicals or any other radical containing Lewis acidic or basic functionality or (C 5 H 4-x R x ) is a cyclopentadienyl ring in which two adjacent R-groups are joined from C 4 -C 2 o ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; (JR' z - 2 ) is a heteroatom ligand with a coordination number of three from Group V A of the Periodic Table of Elements, each R' is, independently a radical selected from a group consisting of C 1 -C 20 hydrocarbyl radicals, substituted C 1 -C 20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, an amido radical, a phosphido radical, an alkoxy radical or any other radical containing Lewis acidic or basic functionality, and "z" is the coordination number of the element J; each Q or Q' is, independently any univalent anionic ligand or Q and Q' are a divalent anionic chelating agent, M' has the same meaning as M; B is covalent bridging group containing a Group IV A or V A element; and L is a Lewis base where "w" denotes a number from 0 to 3.
Inventors
- 👤 Jo Ann Marie Canich
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-01 22:46
CPC Classifications
C; C08; C08F; C08F10/00; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C07; C07F; C07F17/00; C07F7/00; C07F7/02; C07F7/08; C07F7/10; C08F10/04; C08F10/06; C08F210/00; C08F210/16; C08F110/00; C08F110/02; C08F110/04; C08F110/06; C08F210/04; C08F210/06; C08F210/18; C08F4/659; C08F4/65908; C08F4/65912; C08F4/65916; C08F4/6592; Y; Y10; Y10S; Y10S526/00; Y10S526/943
Claims Analysis
Total Claims: 22
Claim 1
Independent Claim
328 words
A compound of the general formula: wherein M is Zr, Hf or Ti; (C 5 H 4-x R x ) is a cyclopentadienyl ring which is substituted with up to five groups R, "x" is 1, 2, 3 or 4 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C,-C 2o hydrocarbyl radicals, substituted C 1 -C 20 hydrocarbyl radicals wherein one or more hydrogen atoms are replaced by a halogen atom, an amido radical, a phosphido radical, an alkoxy radical or any other radical containing a Lewis acidic or basic functionality; C,-C 2 o hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements; halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkyl borido radicals or any other radical containing Lewis acidic or basic functionality or (C 5 H 4-x R x ) is a cyclopentadienyl ring in which two adjacent R-groups are joined from C 4 -C 2 o ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; (JR' z - 2 ) is a heteroatom ligand with a coordination number of three from Group V A of the Periodic Table of Elements, each R' is, independently a radical selected from a group consisting of C 1 -C 20 hydrocarbyl radicals, substituted C 1 -C 20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, an amido radical, a phosphido radical, an alkoxy radical or any other radical containing Lewis acidic or basic functionality, and "z" is the coordination number of the element J; each Q or Q' is, independently any univalent anionic ligand or Q and Q' are a divalent anionic chelating agent, M' has the same meaning as M; B is covalent bridging group containing a Group IV A or V A element; and L is a Lewis base where "w" denotes a number from 0 to 3.
Claim 2
Dependent Claim
328 words
A compound of the general formula: wherein M is Zr, Hf or Ti; (C 5 H 4-x R x ) is a cyclopentadienyl ring which is substituted with up to five groups R, "x" is 1, 2, 3 or 4 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C,-C 2o hydrocarbyl radicals, substituted C 1 -C 20 hydrocarbyl radicals wherein one or more hydrogen atoms are replaced by a halogen atom, an amido radical, a phosphido radical, an alkoxy radical or any other radical containing a Lewis acidic or basic functionality; C,-C 2 o hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements; halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkyl borido radicals or any other radical containing Lewis acidic or basic functionality or (C 5 H 4-x R x ) is a cyclopentadienyl ring in which two adjacent R-groups are joined from C 4 -C 2 o ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; (JR' z - 2 ) is a heteroatom ligand with a coordination number of three from Group V A of the Periodic Table of Elements, each R' is, independently a radical selected from a group consisting of C 1 -C 20 hydrocarbyl radicals, substituted C 1 -C 20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, an amido radical, a phosphido radical, an alkoxy radical or any other radical containing Lewis acidic or basic functionality, and "z" is the coordination number of the element J; each Q or Q' is, independently any univalent anionic ligand or Q and Q' are a divalent anionic chelating agent, M' has the same meaning as M; B is covalent bridging group containing a Group IV A or V A element; and L is a Lewis base where "w" denotes a number from 0 to 3.
Claim 3
Dependent Claim
16 words
A compound according to claim 1 in which the transition metal atom is zirconium or hafnium.
Claim 4
Dependent Claim
25 words
A compound according to claim 1 or claim 2, wherein Q or Q' is a hydride, halogen or hydrocarbyl radical other than a cyclopentadienyl group.
Claim 5
Dependent Claim
62 words
A compound according to claim 3 in which Q or Q' is a substituted or unsubstituted C 1 -C 20 hydrocarbyl, alkoxide, aryloxide, amide, arylamide, phosphide or arylphosphide, provided that where any Q or Q' is a hydrocarbyl such Q or Q' is different from (C 5 H 4-x R x ) or both together are an alkylidene or a cyclometallated hydrocarbyl.
Claim 6
Dependent Claim
61 words
A catalyst system for olefin polymerization comprising (A) a compound according to any of claim 1 to 4 cyclopentadienyl mono -or polycyclic ligand and a Group V A or VI A element heteroatom ligand joined to a Group IV B transition metal atom and (B) an alumoxane or (C) a reaction producqt of such a compound, an aluminum alkyl and water.
Claim 7
Dependent Claim
19 words
The catalyst system according to claim 5 wherein the mole ration of AI:M is from 10:1 to 20 000:1.
Claim 8
Dependent Claim
18 words
A process for preparing an olefin polymer using a catalyst system according to claim 5 or claim 6.
Claim 9
Dependent Claim
28 words
A process according to claim 7 in which the metallocene compound, the alumoxane or the aluminum alkyl and water are reacted partly or wholly prior to the polymerization.
Claim 10
Dependent Claim
75 words
A process for producing a compound according to any of the claims 1 to 5 which comprises reacting of d O group IV B transition metal halide with a salt containing an anion of the formula [(C 5 H 4-x R x )-B-(JR' z-2 )] 2- and either two cations from the group I A of the Periodic Table of Elements or one cation from the Group II A of the Periodic Table of Elements.
Claim 11
Dependent Claim
36 words
A process according to claim 9 wherein the Group IV B metal is zirconium (IV) chloride or hafnium (IV) chloride. Claims for the following Contracting States : AT, BE, DE, ES, FR, GB, IT, NL, SE
Claim 12
Dependent Claim
325 words
A compound of the general formula: wherein M is Zr, Hf or Ti; (C 5 H 4-x R x ) is a cyclopentadienyl ring which is substituted with up to five groups R, "x" is 1, 2, 3 or 4 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C 1 -C 20 hydrocarbyl radicals, substituted C 1 -C 20 hydrocarbyl radicals, substituted C 1 -C 20 hydrocarbyl radicals wherein one or more hydrogen atoms are replaced by a halogen atom, C 1 -C 20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements and halogen radicals or (C 5 H 4-x R x ) is a cyclopentadienyl ring in which two adjacent R-groups are joined from C 4 -C 2 o ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; Elements, each R' is, independently a radical selected from a group consisting of C,-C 2 o hydrocarbyl radicals, substituted C 1 -C 20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, and "z" is the coordination number of the element J; each Q or Q' is, independently any univalent anionic ligand or Q and Q' are a divalent anionic chelating agent, M' has the same meaning as M; B is a covalent bridging group containing a Group IV A or V A element; and L is a Lewis base where "w" denotes a number from 0 to 3 but excluding compounds of the general formula: wherein M has the same meaning as above; R" is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl and combinations thereof having up to 10 carbon atoms, X is independently selected from halo, alkyl, aryl, aryloxy or alkoxy of up to 10 carbons, n being 1 or 2 depending on the valence of M and Y is nitrogen.
Claim 13
Dependent Claim
325 words
A compound of the general formula: wherein M is Zr, Hf or Ti; (C 5 H 4-x R x ) is a cyclopentadienyl ring which is substituted with up to five groups R, "x" is 1, 2, 3 or 4 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from a group consisting of C 1 -C 20 hydrocarbyl radicals, substituted C 1 -C 20 hydrocarbyl radicals, substituted C 1 -C 20 hydrocarbyl radicals wherein one or more hydrogen atoms are replaced by a halogen atom, C 1 -C 20 hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements and halogen radicals or (C 5 H 4-x R x ) is a cyclopentadienyl ring in which two adjacent R-groups are joined from C 4 -C 2 o ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; Elements, each R' is, independently a radical selected from a group consisting of C,-C 2 o hydrocarbyl radicals, substituted C 1 -C 20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, and "z" is the coordination number of the element J; each Q or Q' is, independently any univalent anionic ligand or Q and Q' are a divalent anionic chelating agent, M' has the same meaning as M; B is a covalent bridging group containing a Group IV A or V A element; and L is a Lewis base where "w" denotes a number from 0 to 3 but excluding compounds of the general formula: wherein M has the same meaning as above; R" is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl and combinations thereof having up to 10 carbon atoms, X is independently selected from halo, alkyl, aryl, aryloxy or alkoxy of up to 10 carbons, n being 1 or 2 depending on the valence of M and Y is nitrogen.
Claim 14
Dependent Claim
16 words
A compound according to claim 1 in which the transition metal atom is zirconium or hafnium.
Claim 15
Dependent Claim
26 words
A compound according to claim 1 or claim 2, wherein Q or Q' is a hydride, halogen or hydrocarbyl radical other than a cyclopentadienyl cyclic group.
Claim 16
Dependent Claim
61 words
A compound according to claim 3 in which Q or Q' is a substituted or unsubstituted C,-C 2 o hydrocarbyl, alkoxide, aryloxide, amide, arylamide, phosphide or arylphosphide, provided that where any Q or Q' is a hydrocarbyl such Q or Q' is different from (C 5 H 4-x R x ) or both together are an alkylidene or a cyclometallated hydrocarbyl.
Claim 17
Dependent Claim
18 words
A catalyst system for olefin polymerization comprising (A) a compound according to any of claims 1 to 4.
Claim 18
Dependent Claim
19 words
The catalyst system according to claim 5, wherein the mole ration of AI:M is from 10:1 to 20 000:1.
Claim 19
Dependent Claim
18 words
A process for preparing an olefin polymer using a catalyst system according to claim 5 or claim 6.
Claim 20
Dependent Claim
27 words
A process according to claim 7 in which the compound, the alumoxane or the aluminum alkyl and water are reacted partly or wholly prior to the polymerization.
Claim 21
Dependent Claim
72 words
A process for producing a compound according to any of claims 1 to 5 which comprises reacting of d O group IV B transition metal halide with a salt containing an anion of the formula [(C 5 H 4-x R x )-B-(JR' z-2 )]-2-and either two cations from the group I A of the Periodic Table of Elements or one cation from the Group II A of the Periodic Table of Elements.
Claim 22
Dependent Claim
21 words
A process according to claim 9 wherein the Group IV B metal halide is zirconium (IV) chloride or hafnium (IV) chloride.
References Cited (Backward Citations)
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