Mono-Cp heteroatom containing group IVB transition metal complexes with MAO: supported catalyst for olefin polymerization

Claim 2

A catalyst system comprising: (A) an inert support; (B) a transition metal compound of the formula: ##STR7## wherein M is Zr, Hf, or Ti in its highest formal oxidation state: (C 5 H 5 -y- x R x ) is a cyclopentadienyl ring which is substituted with from zero to five substituent groups R, "x" is 0, 2, 3, 4 or 5 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 is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or a 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; and halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals, or a radical containing Lewis acidic or basic functionality; or (C 5 H 5-Y-x R x ) is a cyclopentadienyl ring in which two adjacent R-groups are joined forming C 4 -C 2 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; (JR' z-1-y ) 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, 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 atom is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or a radical containing a Lewis acidic or basic functionality; and "z" is the coordination number of the element J; each Q is, independently, a univalent anionic ligand provided that where Q is a hydrocarbyl ligand such Q is different from (C 5 H 5-y-x R x ) or both Q together are an alkylidene, a cyclometallated hydrocarbyl or a divalent anionic chelating ligand; "y" is 0 or 1 when "w" is greater than 0; "y" is 1 when "w" is 0; when "y" is 1, T is a covalent bridging group containing a Group IV A or V A element; L is a neutral Lewis base where "w" denotes a number from 0 to 3; and (C) an alumoxane.

Claim 3

The catalyst system of claim 1 wherein the heteroatom ligand group J element is nitrogen, phosphorous, oxygen or sulfur.

Claim 4

The catalyst system of claim 1 wherein Q is a halogen or hydrocarbyl radical.

Claim 5

The catalyst system of claim 2 wherein the heteroatom ligand group J element is nitrogen.

Claim 6

The catalyst system of claim 1 wherein M is titanium or zirconium.

Claim 7

The catalyst system of claim 1 wherein the aluminum atom to transition metal atom mole ratio is from about 10:1 to about 1,000:1.

Claim 8

The catalyst system of claim 1 wherein the support is an inorganic support selected from the group consisting of talc, silica, alumina, silica-alumina, magnesia, titania, zirconia, or mixtures thereof.

Claim 9

The catalyst system of claim 7, wherein said support is dehydrated.

Claim 10

The catalyst system of claim 8, wherein said support is treated with an alumoxane or a trialkylaluminum.

Claim 11

The catalyst system of claim 9, wherein said support is dehydrated silica treated with methylalumoxane or triethylaluminum.

Claim 12

The catalyst system of claim 1 further comprising a modifier compound containing a Lewis acidic or basic functionality.

Claim 13

The catalyst system of claim 2, further comprising a modifier compound containing a Lewis acidic or basic functionality.

Claim 14

The catalyst system of claim 12, wherein the aluminum atom to transition metal atom mole ratio is about 10:1 to about 20,000:1.

Claim 15

The catalyst system of claim 13, wherein the aluminum atoms to molecules of modifier compound ratio is from about 1:1 to about 20,000:1.

Claim 16

The catalyst system of claim 14, wherein the modifier compound is tetraethoxysilane.

Claim 17

The catalyst system of claim 1, wherein the alumoxane is formed on the support by reaction of a hydrated support with a trialkylaluminum.

Claim 18

The catalyst system of claim 16, wherein the hydrated support is an inorganic oxide selected from the group consisting of talc, silica, alumina, silica-alumina, magnesia, titania, zirconia, or mixtures thereof.

Claim 19

The catalyst system of claim 17, wherein the hydrated support is silica containing from about 6 to about 20 weight percent water and is reacted with trimethylaluminum.

Claim 20

A process for producing a supported catalyst system comprising the steps of: dissolving in a hydrocarbon solvent a Group IV B transition metal component of the formula: ##STR8## wherein M is Zr, Hf, or Ti in its highest formal oxidation state: (C 5 H 5-Y-x R x ) is a cyclopentadienyl ring which is substituted with from zero to five substituent groups R, "x" is 0, 1, 2, 3, 4 or 5 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 is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or a radical containing 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; and halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals, or a radical containing Lewis acidic or basic functionality; or (C 5 H 5-y-x R x ) is a cyclopentadienyl ring in which two adjacent R-groups are joined forming C 4 -C 20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; (JR' z-1-y ) 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, 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 atom is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or a radical containing Lewis acidic or basic functionality; and "z" is the coordination number of the element J; each Q is, independently, a univalent anionic ligand provided that where Q is a hydrocarbyl ligand such Q is different from (C 5 H 5-y-x R x ) or both Q together are an alkylidene, a cyclometallated hydrocarbyl or a divalent anionic chelating ligand; "y" is 0 or 1 when "w" is greater than 0; "y" is 1 when "w" is when "y" is 1, T is a covalent bridging group containing a Group IV A or V A element; L is a neutral Lewis base where "w" denotes a number from 0 to 3; and mixing with the dissolved transition metal component an alumoxane and an inert support material; and recovering from the mixture a supported catalyst.

Claim 21

A process for producing a supported catalyst system comprising the steps of: dissolving in a hydrocarbon solvent a Group IV B transition metal component of the formula: ##STR8## wherein M is Zr, Hf, or Ti in its highest formal oxidation state: (C 5 H 5-Y-x R x ) is a cyclopentadienyl ring which is substituted with from zero to five substituent groups R, "x" is 0, 1, 2, 3, 4 or 5 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 is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or a radical containing 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; and halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals, or a radical containing Lewis acidic or basic functionality; or (C 5 H 5-y-x R x ) is a cyclopentadienyl ring in which two adjacent R-groups are joined forming C 4 -C 20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; (JR' z-1-y ) 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, 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 atom is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or a radical containing Lewis acidic or basic functionality; and "z" is the coordination number of the element J; each Q is, independently, a univalent anionic ligand provided that where Q is a hydrocarbyl ligand such Q is different from (C 5 H 5-y-x R x ) or both Q together are an alkylidene, a cyclometallated hydrocarbyl or a divalent anionic chelating ligand; "y" is 0 or 1 when "w" is greater than 0; "y" is 1 when "w" is when "y" is 1, T is a covalent bridging group containing a Group IV A or V A element; L is a neutral Lewis base where "w" denotes a number from 0 to 3; and mixing with the dissolved transition metal component an alumoxane and an inert support material; and recovering from the mixture a supported catalyst.

Claim 22

The process of claim 19, further comprising adding a modifier compound containing a Lewis acidic or basic functionality during the mixing of the dissolved transition metal component with the alumoxane and inert support.

Claim 23

A process for producing a supported catalyst system comprising the steps of: dissolving an alumoxane in a hydrocarbon solvent; mixing the alumoxane with an inert support material; adding to the mixture of alumoxane and support material, a Group IV B transition metal component of the formula: ##STR9## wherein M is Zr, Hf, or Ti in its highest formal oxidation state: (C 5 H 5-y-x R x ) is a cyclopentadienyl ring which is substituted with from zero to five substitutent groups R, "x" is 0, 1, 2, 3, 4 or 5 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 radials; substituted C 1 -C 20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or a radical containing Lewis acidic or basic functionality; C 1 -C 20 hydrocarbyl-substituted metalloid radicals wherein metalloid is selected from the Group IV A of the Periodic Table of Elements; and halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals, or a radical containing Lewis acidic or basic functionality, or (C 5 H 5-Y-x R x ) is a cyclopentadienyl ring in which two adjacent R-groups are joined forming C 4 -C 20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; (JR' z-1-y ) 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, 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 atom is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or a radical containing Lewis acidic or basic functionality, and "z" is the coordination number of the element J; each Q is, independently, a univalent anionic ligand, provided that where Q is a hydrocarbyl ligand such Q is different from (C 5 H 5-y-x R x ) or both Q together are an alkylidene, a cyclometallated hydrocarbyl or a divalent anionic chelating ligand; "y" is 0 or 1 when "w" is greater than 0; "y" is 1 when "w" is 0; when "y" is 1, T is a covalent bridging group containing a Group IV A or V A element; L is a neutral Lewis base where "w" denotes a number from 0 to 3; and recovering from the mixture a supported catalyst.

Claim 24

A process for producing a supported catalyst system comprising the steps of: dissolving an alumoxane in a hydrocarbon solvent; mixing the alumoxane with an inert support material; adding to the mixture of alumoxane and support material, a Group IV B transition metal component of the formula: ##STR9## wherein M is Zr, Hf, or Ti in its highest formal oxidation state: (C 5 H 5-y-x R x ) is a cyclopentadienyl ring which is substituted with from zero to five substitutent groups R, "x" is 0, 1, 2, 3, 4 or 5 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 radials; substituted C 1 -C 20 hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or a radical containing Lewis acidic or basic functionality; C 1 -C 20 hydrocarbyl-substituted metalloid radicals wherein metalloid is selected from the Group IV A of the Periodic Table of Elements; and halogen radicals, amido radicals, phosphido radicals, alkoxy radicals, alkylborido radicals, or a radical containing Lewis acidic or basic functionality, or (C 5 H 5-Y-x R x ) is a cyclopentadienyl ring in which two adjacent R-groups are joined forming C 4 -C 20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; (JR' z-1-y ) 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, 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 atom is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an alkylborido radical, or a radical containing Lewis acidic or basic functionality, and "z" is the coordination number of the element J; each Q is, independently, a univalent anionic ligand, provided that where Q is a hydrocarbyl ligand such Q is different from (C 5 H 5-y-x R x ) or both Q together are an alkylidene, a cyclometallated hydrocarbyl or a divalent anionic chelating ligand; "y" is 0 or 1 when "w" is greater than 0; "y" is 1 when "w" is 0; when "y" is 1, T is a covalent bridging group containing a Group IV A or V A element; L is a neutral Lewis base where "w" denotes a number from 0 to 3; and recovering from the mixture a supported catalyst.