EP0671404A2
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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 The 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 zero 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 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 radicals 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 in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, and each R' is, independently a radical selected from a group consisting of C 1 -C 20 hydrocarbyl radicals, substituted C,-C 2 o hydrocarbyl radicals, wherein one or more hydrogen atoms is replaced by a halogen atom, an amido radical, a phosphido radical and 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, and M' has the same meaning as M; B is a covalent bridging group containing a Group IV A or V A element selected from dialkyl, alkylaryl or diaryl silicon or germanium radical alkyl or aryl phosphine or amine radical or a hydrocarbyl radical 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 20:23
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: 25
Claim 1
Independent Claim
375 words
A compound of the general formula: or wherein M is Zr, Hf or Ti; (C 5 H 4-x R x ) is a cyclopentadienyl ring which is substituted with up zero 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 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 radicals 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 in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, and each R' is, independently a radical selected from a group consisting of C l -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 and 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, and M' has the same meaning as M; B is a covalent bridging group containing a Group IV A or V A element selected from dialkyl, alkylaryl or diaryl silicon or germanium radical alkyl or aryl phosphine or amine radical or a hydrocarbyl radical and L is a Lewis base where "w" denotes a number from 0 to 3.
Claim 2
Dependent Claim
375 words
A compound of the general formula: or wherein M is Zr, Hf or Ti; (C 5 H 4-x R x ) is a cyclopentadienyl ring which is substituted with up zero 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 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 radicals 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 in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, and each R' is, independently a radical selected from a group consisting of C l -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 and 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, and M' has the same meaning as M; B is a covalent bridging group containing a Group IV A or V A element selected from dialkyl, alkylaryl or diaryl silicon or germanium radical alkyl or aryl phosphine or amine radical or a hydrocarbyl radical 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 heteroatom is nitrogen, phosphorus, oxygen or sulfur.
Claim 4
Dependent Claim
19 words
A compound according to claim 1 or claim 2 in which the transition metal atom is zirconium or hafnium.
Claim 5
Dependent Claim
27 words
A compound according to any of claims 1 to 3, wherein Q or Q' is a hydride, halogen or hydrocarbyl radical other than a cyclopentadienyl cyclic group.
Claim 6
Dependent Claim
62 words
A compound according to claim 4 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 7
Dependent Claim
36 words
A catalyst system for olefin polymerization comprising (A) a compound according to any of claims 1 to 5 and (B) an alumoxane or (C) a reaction product of such a compound, an aluminum alkyl and water.
Claim 8
Dependent Claim
20 words
The catalyst system according to claim 6 wherein the mole ration of Al: M is from 10:1 to 20 000:1.
Claim 9
Dependent Claim
16 words
A process for preparing an olefin polymer using a catalyst system according to 6 and 7.
Claim 10
Dependent Claim
16 words
A process for preparing an olefin polymer using a catalyst system according to 6 and 7.
Claim 11
Dependent Claim
27 words
A process according to claim 8 in which the compound, the alumoxane or the aluminum alkyl and water are reacted partly or wholly prior to the polymerization.
Claim 12
Dependent Claim
76 words
A process for producing a compound according to any of claims 1 to 5 in which comprises reacting of a 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 13
Dependent Claim
21 words
A process according to claim 10 wherein the Group IV B metal halide is zirconium (IV) chloride or hafnium (IV) chloride.
Claim 14
Dependent Claim
379 words
A compound of the general formula: or 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 A, "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 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 (Cs H 4-x R x ) is a cyclopentadienyl ring in which two adjacent R-groups are joined from C 4 -C 20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; (JR' z - 2 ) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, and each R' is, independently a radical selected from a group consisting of C 1 -C 20 hydrocarbyl radicals, substituted C,-C 2o 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 or V A element selected from dialkyl, alkylaryl or diaryl silicon or germanium radical alkyl or aryl phosphine or amine radical or hydrocarbyl radical; 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 15
Dependent Claim
379 words
A compound of the general formula: or 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 A, "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 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 (Cs H 4-x R x ) is a cyclopentadienyl ring in which two adjacent R-groups are joined from C 4 -C 20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; (JR' z - 2 ) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, and each R' is, independently a radical selected from a group consisting of C 1 -C 20 hydrocarbyl radicals, substituted C,-C 2o 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 or V A element selected from dialkyl, alkylaryl or diaryl silicon or germanium radical alkyl or aryl phosphine or amine radical or hydrocarbyl radical; 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 16
Dependent Claim
16 words
A compound according to claim 12 in which the heteroatom is nitrogen, phosphorus, oxygen or sulfur.
Claim 17
Dependent Claim
19 words
A compound according to claim 12 or claim 13 in which the transition metal atom is zirconium or hafnium.
Claim 18
Dependent Claim
27 words
A compound according to any of claims 12 to 14, wherein Q or Q' is a hydride, halogen or hydrocarbyl radical other than a cyclopentadienyl cyclic group.
Claim 19
Dependent Claim
62 words
A compound according to claim 15 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 20
Dependent Claim
16 words
A catalyst system for olefin polymerization comprising (A) a compound according to any of claims 16.
Claim 21
Dependent Claim
20 words
The catlyst system of claim 21 to 22, wherein the mole ration of AI:M is from 10:1 to 20 000:1.
Claim 22
Dependent Claim
20 words
A process for preparing an olefin polymer using a catalyst system according to any of claim 17 or claim 18.
Claim 23
Dependent Claim
27 words
A process according to claim 19 in which the compound, the alumoxane or the aluminum alkyl and water are reacted partly or wholly prior to the polymerization.
Claim 24
Dependent Claim
75 words
A process for producing a compound according to any of the claims 12 to 16 in which y = 1 or 4 to 9 which comprises reacting of a d O group IV B transition metal halide with a salt containing an anion of the formula 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 25
Dependent Claim
21 words
A process according to claim 21 wherein the Group IV B metal halide is zirconium (IV) chloride or hafnium (IV) chloride.
References Cited (Backward Citations)
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