Metallocene catalysts and associated methods of preparation and use

Claim 2

A metallocene catalyst containing more than one active site, having the structure B(Z) q of structural formula (I) ##STR32## wherein: B is a covalent bridging group comprising carbyl, silyl, disilyl, germanyl, ammonium, phosphonium, ##STR33## or a C 1 -C 24 hydrocarbyl radical optionally containing a Group IVB element, a Group VB element, or both a Group IVB element and a Group VB element, and is capable of binding up to n max substituents through single covalent bonds, where n max is at least 4; R and R 1 are independently selected from the group consisting of halogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements, x is 0, 1, 2, 3 or 4, and y is 1, 0, 2, 3 or 4, with the proviso that the sum of x and y cannot exceed 4, or, when R and R 1 are ortho to each other and x and y are each 1 or greater, R and R 1 can together form a five- or six-membered cyclic structure optionally substituted with one to four substituents selected from the group consisting of halogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements; Q is J(R 2 ) z-2 J is an element with a coordination number of three from Group VB or an element with a coordination number of two from Group VIB, R 2 is selected from the group consisting of hydrogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 alkoxy, and z is the coordination number of J, and further wherein Q substituents on different Z groups may be linked through a C 1 -C 24 hydrocarbylene bridge; M is a Group IIIA element, a Group IVA element, a Group VA element, a lanthanide, or an actinide; X is selected from the group consisting of hydride, halide, alkoxy, amido, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl radicals substituted with one or more electron-withdrawing groups, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements, or, when two or more X substituents are present, they may together form an alkylidene olefin, acetylene, or a five- or six-membered cyclic hydrocarbyl group; Y is a neutral Lewis base; m is 1, 2, 3 or 4, and n is 0, 1, 2 or 3, with the proviso that if M is a Group IIIA element, m is 1 and n is 0, and with the further proviso that if M is a Group IVA element, the sum of m and n does not exceed 2; if n max is 4 or 5, then q is 2, and if n max is greater than 5, then q is an integer in the range of 2 to q max , wherein q max is equal to 1/2n max when n max is an even number, and 1/2(n max -1) when n max is an odd number, with the proviso that when q is 2 and the M elements in the two Z groups are the same, Q is necessarily J(R 2 ) z-2 , and at least two of the Z substituents bound to B are different.

Claim 3

The metallocene catalyst of claim 1, wherein q is 2.

Claim 4

The metallocene catalyst of claim 1, wherein q is 3.

Claim 5

The metallocene catalyst of claim 3, wherein all three of the Z substituents bound to B are different.

Claim 6

The metallocene catalyst of claim 1, wherein, in Formula (I): B is a covalent bridging group comprising carbyl, silyl, disilyl or a C 1 -C 12 hydrocarbyl radical optionally containing a Group IVB element, a Group VB element, or both; x is 0, 1 or 2; y is 0, 1 or 2; R and R 1 are independently selected from the group consisting of halogen and C 1 -C 12 alkyl, or are ortho to each other and linked to form a cyclopentadienyl or indenyl group; J is nitrogen, phosphorus, oxygen or sulfur, and R 2 is C 1 -C 12 alkyl, C 1 -C 12 alkyl substituted with a halogen atom, or monocyclic aryl; M is a Group IVA element; m is 1 or 2, n is 0 or 1, and the sum of m and n is 2; X is selected from the group consisting of hydride, halide, amido, C 1 -C 12 alkyl, C 1 -C 12 alkyl substituted with one or more halogen and/or alkoxy groups, and C 1 -C 12 hydrocarbyl-substituted Group IVB elements; Y is a selected from the group consisting of diethylether, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, and n-butylamine; and q is 2 or 3.

Claim 7

The metallocene catalyst of claim 2, wherein the Z substituents bound to B contain different M moieties.

Claim 8

The metallocene catalyst of claim 4, wherein two of the Z substituents bound to B contain different M moieties.

Claim 9

The metallocene catalyst of claim 5, wherein: B is carbyl, a C 1 -C 6 hydrocarbyl radical or silyl; x and y are independently 0 or 1; R and R 1 are independently selected from the group consisting of halogen and lower alkyl, or are ortho to each other and linked to form a cyclopentadienyl ring; J is nitrogen, R 2 is lower alkyl or phenyl, and z is 3; M is Zr, Hf or Ti; m is 2; n is 0; x is hydride, halide or lower alkyl; and q is 2.

Claim 10

A method for making the metallocene catalyst of claim 1, comprising the steps of: (a) contacting a starting material B(Hal) 2q , wherein Hal is halogen, with an alkali metal salt of an aromatic compound Ar containing one, two or three cyclopentadiene rings each optionally substituted with x R substituents and y R 1 substituents, to give an intermediate having the formula Ar q B(Hal) q ; (b) reacting the intermediate with an alkali metal salt of J(R 2 ) z-2 H 2 , to provide a ligand Ar q B J(R 2 ) z-2 H 2 ! q ; (c) treating the ligand with a deprotonating agent; and (d) reacting the deprotonated ligand with a mixture of halogenated metal compounds M(Hal) y , wherein y represents the number of Hal atoms corresponding to the oxidation state of M, to provide the metallocene catalyst having the structure of formula (I).

Claim 11

The method of claim 9, wherein q is 2.

Claim 12

A method for making the metallocene catalyst of claim 1, comprising the steps of: (a) contacting a starting material B(Hal) 2q wherein Hal is halogen, with an alkali metal salt of an aromatic compound Ar containing one, two or three cyclopentadiene rings each optionally substituted with x R substituents and y R 1 substituents, to give an intermediate having the formula Ar q B(Hal) q ; (b) reacting the intermediate with an alkali metal salt of J(R 2 ) z-2 H 2 , to provide a ligand Ar q B J(R 2 ) z-2 H 2 ! q ; (c) treating the ligand with a deprotonating agent; and (d) successively reacting the deprotonated ligand with a first, a second, and, when q is 3, a third halogenated metal compound, to provide a metallocene catalyst having the structure of formula (I), wherein the metal atoms in each Z substituent are different.

Claim 13

A method for making the metallocene catalyst of claim 1 wherein, comprising the steps of: (a) contacting a starting material B(Hal) 2q with an alkali metal salt of an aromatic compound Ar containing one, two or three cyclopentadiene rings each optionally substituted with x "R" substituents and y "R 1 " substituents, to give an intermediate having the formula Ar q B(Hal) q ; (b) reacting the intermediate with an alkali metal salt of J(R 2 ) z-2 H 2 , to provide a ligand Ar q B J(R 2 ) z-1 H 2 ! q ; (c) treating the ligand with a deprotonating agent; and (d) reacting the deprotonated ligand with a compound having the structure M(X) m .

Claim 14

A method for making the metallocene catalyst of claim 1, comprising the steps of: (a) contacting a starting material B(Hal) 4 with an alkali metal salt of an aromatic compound Ar containing one, two or three cyclopentadiene rings each optionally substituted with x "R" substituents and y "R 1 " substituents, to give an intermediate having the formula Ar 2 B(Hal) 2 ; (b) reacting the intermediate with a bridging compound comprising a C 1 -C 12 linear or branched alkylene linker L substituted with two primary amine substituents, to provide a ligand Ar 2 BL 2 ; (c) treating the ligand with a deprotonating agent; and (d) successively reacting the deprotonated ligand with first and second halogenated metal compounds M(Hal) y , wherein y represents the number of Hal atoms corresponding to the oxidation state of M, wherein the metal atoms in each of said metal compounds are different, to provide a metallocene catalyst having the structure of formula (I), wherein the metal atoms in each Z substituent are different.

Claim 15

A metallocene catalyst containing more than one active site, having the structure B(Z) q of structural formula (I) ##STR34## wherein: B is a covalent bridging group comprising carbyl, silyl, disilyl, germanyl, ammonium, phosphonium, ##STR35## or a C 1 -C 24 hydrocarbyl radical optionally containing a Group IVB element, a Group VB element, or both a Group IVB element and a Group VB element, and is capable of binding up to n max substituents through single covalent bonds, where n max is at least 4; R and R 1 are independently selected from the group consisting of halogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements, x is 0, 1, 2, 3 or 4, and y is 0, 1, 2, 3 or 4, with the proviso that the sum of x and y cannot exceed 4, or, when R and R 1 are ortho to each other and x and y are each 1 or greater, R and R 1 can together form a five- or six-membered cyclic structure optionally substituted with one to four substituents selected from the group consisting of halogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements; Q is cyclopentadienyl, indenyl, fluorenyl, indolyl or aminoboratobenzyl, optionally substituted with one or more R and R 1 substituents as above, or Q is J(R 2 ) z-2 wherein J is an element with a coordination number of three from Group VB or an element with a coordination number of two from Group VIB, R 2 is selected from the group consisting of hydrogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 alkoxy, and z is the coordination number of J, and further wherein Q substituents on different Z groups may be linked through a C 1 -C 24 hydrocarbylene bridge; M is a Group IVA element, a Group VA element, a lanthanide, or an actinide; two X substituents together form an alkylidene olefin, acetylene, or a five- or six-membered cyclic hydrocarbyl group, and if additional X substituents are present, they are selected from the group consisting of hydride, halide, alkoxy, amido, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl radicals substituted with one or more electron-withdrawing groups, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements; Y is a neutral Lewis base; m is 2, 3 or 4, and n is 0, 1, 2 or 3, with the proviso that if M is a Group IVA element, m is 2 and n is 0; if n max is 4 or 5, then q is 2, and if n max is greater than 5, then q is an integer in the range of 2 to q max , wherein q max is equal to 1/2n max when n max is an even number, and 1/2(n max -1) when n max is an odd number, with the proviso that when q is 2 and the M elements in the two Z groups are the same, Q is necessarily J(R 2 ) z-2 ; and the Z substituents bound to B may be the same or different.

Claim 16

A metallocene catalyst containing more than one active site, having the structure B(Z) q of structural formula (I) ##STR34## wherein: B is a covalent bridging group comprising carbyl, silyl, disilyl, germanyl, ammonium, phosphonium, ##STR35## or a C 1 -C 24 hydrocarbyl radical optionally containing a Group IVB element, a Group VB element, or both a Group IVB element and a Group VB element, and is capable of binding up to n max substituents through single covalent bonds, where n max is at least 4; R and R 1 are independently selected from the group consisting of halogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements, x is 0, 1, 2, 3 or 4, and y is 0, 1, 2, 3 or 4, with the proviso that the sum of x and y cannot exceed 4, or, when R and R 1 are ortho to each other and x and y are each 1 or greater, R and R 1 can together form a five- or six-membered cyclic structure optionally substituted with one to four substituents selected from the group consisting of halogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements; Q is cyclopentadienyl, indenyl, fluorenyl, indolyl or aminoboratobenzyl, optionally substituted with one or more R and R 1 substituents as above, or Q is J(R 2 ) z-2 wherein J is an element with a coordination number of three from Group VB or an element with a coordination number of two from Group VIB, R 2 is selected from the group consisting of hydrogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 alkoxy, and z is the coordination number of J, and further wherein Q substituents on different Z groups may be linked through a C 1 -C 24 hydrocarbylene bridge; M is a Group IVA element, a Group VA element, a lanthanide, or an actinide; two X substituents together form an alkylidene olefin, acetylene, or a five- or six-membered cyclic hydrocarbyl group, and if additional X substituents are present, they are selected from the group consisting of hydride, halide, alkoxy, amido, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl radicals substituted with one or more electron-withdrawing groups, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements; Y is a neutral Lewis base; m is 2, 3 or 4, and n is 0, 1, 2 or 3, with the proviso that if M is a Group IVA element, m is 2 and n is 0; if n max is 4 or 5, then q is 2, and if n max is greater than 5, then q is an integer in the range of 2 to q max , wherein q max is equal to 1/2n max when n max is an even number, and 1/2(n max -1) when n max is an odd number, with the proviso that when q is 2 and the M elements in the two Z groups are the same, Q is necessarily J(R 2 ) z-2 ; and the Z substituents bound to B may be the same or different.

Claim 17

A metallocene catalyst containing more than one active site, having the structure B(Z) q of structural formula (I) ##STR36## wherein: B is a covalent bridging group comprising carbyl, silyl, disilyl, germanyl, ammonium, phosphonium, ##STR37## or a C 1 -C 24 hydrocarbyl radical optionally containing a Group IVB element, a Group VB element, or both a Group IVB element and a Group VB element, and is capable of binding up to n max substituents through single covalent bonds, where n max is at least 4; R and R 1 are independently selected from the group consisting of halogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements, x is 0, 1, 2, 3 or 4, and y is 0, 1, 2, 3 or 4, with the proviso that the sum of x and y cannot exceed 4, or, when R and R 1 are ortho to each other and x and y are each 1 or greater, R and R 1 they can together form a five- or six-membered cyclic structure optionally substituted with one to four substituents selected from the group consisting of halogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements; Q is cyclopentadienyl, indenyl, fluorenyl, indolyl or aminoboratobenzyl, optionally substituted with one or more R and R 1 substituents as above, or Q is J(R 2 ) z-2 wherein J is an element with a coordination number of three from Group VB or an element with a coordination number of two from Group VIB, R 2 is selected from the group consisting of hydrogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 alkoxy, and z is the coordination number of J, and further wherein Q substituents on different Z groups are linked through a C 1 -C 24 hydrocarbylene bridge; M is a Group IIIA element, a Group IVA element, a Group VA element, a lanthanide, or an actinide; X is selected from the group consisting of hydride, halide, alkoxy, amido, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl radicals substituted with one or more electron-withdrawing groups, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements, or, when two or more X substituents are present, they may together form an alkylidene olefin, acetylene, or a five- or six- membered cyclic hydrocarbyl group; Y is a neutral Lewis base; m is 1, 2, 3 or 4, and n is 0, 1, 2 or 3, with the proviso that if M is a Group IIIA element, m is 1 and n is 0, and with the further provoso that, if M is a Group IVA element, the sum of m and n does not exceed 2; if n max is 4 or 5, then q is 2, and if n max is greater than 5, then q is an integer in the range of 2 to q max , wherein q max is equal to 1/2n max when n max is an even number, and 1/2(n max -1) when n max is an odd number, with the proviso that when q is 2 and the M elements in the two Z groups are the same, Q is necessarily J(R 2 ) z-2 ; and the Z substituents bound to B may be the same or different.

Claim 18

A metallocene catalyst containing more than one active site, having the structure B(Z) q of structural formula (I) ##STR36## wherein: B is a covalent bridging group comprising carbyl, silyl, disilyl, germanyl, ammonium, phosphonium, ##STR37## or a C 1 -C 24 hydrocarbyl radical optionally containing a Group IVB element, a Group VB element, or both a Group IVB element and a Group VB element, and is capable of binding up to n max substituents through single covalent bonds, where n max is at least 4; R and R 1 are independently selected from the group consisting of halogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements, x is 0, 1, 2, 3 or 4, and y is 0, 1, 2, 3 or 4, with the proviso that the sum of x and y cannot exceed 4, or, when R and R 1 are ortho to each other and x and y are each 1 or greater, R and R 1 they can together form a five- or six-membered cyclic structure optionally substituted with one to four substituents selected from the group consisting of halogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements; Q is cyclopentadienyl, indenyl, fluorenyl, indolyl or aminoboratobenzyl, optionally substituted with one or more R and R 1 substituents as above, or Q is J(R 2 ) z-2 wherein J is an element with a coordination number of three from Group VB or an element with a coordination number of two from Group VIB, R 2 is selected from the group consisting of hydrogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 alkoxy, and z is the coordination number of J, and further wherein Q substituents on different Z groups are linked through a C 1 -C 24 hydrocarbylene bridge; M is a Group IIIA element, a Group IVA element, a Group VA element, a lanthanide, or an actinide; X is selected from the group consisting of hydride, halide, alkoxy, amido, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl radicals substituted with one or more electron-withdrawing groups, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements, or, when two or more X substituents are present, they may together form an alkylidene olefin, acetylene, or a five- or six- membered cyclic hydrocarbyl group; Y is a neutral Lewis base; m is 1, 2, 3 or 4, and n is 0, 1, 2 or 3, with the proviso that if M is a Group IIIA element, m is 1 and n is 0, and with the further provoso that, if M is a Group IVA element, the sum of m and n does not exceed 2; if n max is 4 or 5, then q is 2, and if n max is greater than 5, then q is an integer in the range of 2 to q max , wherein q max is equal to 1/2n max when n max is an even number, and 1/2(n max -1) when n max is an odd number, with the proviso that when q is 2 and the M elements in the two Z groups are the same, Q is necessarily J(R 2 ) z-2 ; and the Z substituents bound to B may be the same or different.

Claim 19

A metallocene catalyst having the structure ##STR38## wherein: B is carbyl, lower alkylene, lower alkenylene or silyl; Ar 1 and Ar 2 are independently selected from the group consisting of cyclopentadienyl, indenyl and fluorenyl, optionally substituted with at least one substituent selected from the group consisting of halogen and lower alkyl; M 1 and M 2 are independently selected from the group consisting of Zr, Hf and Ti; the X 1 and X 2 may be the same of different and are selected from the group consisting of halide, lower alkyl and lower alkoxy; and R 2a and R 2b are selected from the group consisting of C 1 to C 12 alkyl and phenyl, with the proviso that R 2a and R 2b are different.

Claim 20

A metallocene catalyst having the structure ##STR38## wherein: B is carbyl, lower alkylene, lower alkenylene or silyl; Ar 1 and Ar 2 are independently selected from the group consisting of cyclopentadienyl, indenyl and fluorenyl, optionally substituted with at least one substituent selected from the group consisting of halogen and lower alkyl; M 1 and M 2 are independently selected from the group consisting of Zr, Hf and Ti; the X 1 and X 2 may be the same of different and are selected from the group consisting of halide, lower alkyl and lower alkoxy; and R 2a and R 2b are selected from the group consisting of C 1 to C 12 alkyl and phenyl, with the proviso that R 2a and R 2b are different.

Claim 21

The metallocene catalyst of claim 16, wherein B is selected from the group consisting of ##STR39##

Claim 22

The metallocene catalyst of claim 17, wherein B is selected from the group consisting of ##STR40##

Claim 23

The metallocene catalyst of claim 18, wherein B is ##STR41##

Claim 24

The metallocene catalyst of claim 18, wherein B is ##STR42##

Claim 25

The metallocene catalyst of claim 16, wherein B is silyl.

Claim 26

The metallocene catalyst of claim 16, wherein M 1 and M 2 are different.

Claim 27

The metallocene catalyst of claim 16, wherein M 1 and M 2 are the same.

Claim 28

The metallocene catalyst of claim 16, wherein the X 1 and X 2 are independently chloro or methyl.

Claim 29

The metallocene catalyst of claim 24, wherein the X 1 are chloro and the X 2 are methyl.

Claim 30

The metallocene catalyst of claim 24, wherein the X 1 and X 2 are all chloro.

Claim 31

The metallocene catalyst of claim 24, wherein the X 1 and X 2 are all methyl.

Claim 32

A metallocene catalyst having the structure ##STR43## wherein: B is carbyl, lower alkylene, lower alkenylene or silyl; Ar 1 and Ar 2 are independently selected from the group consisting of cyclopentadienyl, indenyl and fluorenyl, optionally substituted with at least one substituent selected from the group consisting of halogen and lower alkyl; M 1 and M 2 are independently selected from the group consisting of Zr, Hf and Ti; the X 1 and X 2 may be the same of different and are selected from the group consisting of halide, lower alkyl and lower alkoxy; and Q 1 and Q 2 are selected from the group consisting of cyclopentadienyl, indenyl, fluorenyl, indolyl and aminoboratobenzyl, optionally substituted with at least one substituent selected from the group consisting of halogen and lower alkyl, with the proviso that Q 1 and Q 2 are different, and with the further provisos that (a) when M 1 (X 1 ) 2 is the same as M 2 (X 2 ) 2 and Q 1 is the same Ar 2 , then Q 2 and Ar 1 must be different, and (b) when M 1 (X 2 ) 2 is the same as M 2 (X 1 ) 2 and Q 2 is the same as Ar 1 , the Q 1 and Ar 2 must be different.

Claim 33

A metallocene catalyst having the structure ##STR43## wherein: B is carbyl, lower alkylene, lower alkenylene or silyl; Ar 1 and Ar 2 are independently selected from the group consisting of cyclopentadienyl, indenyl and fluorenyl, optionally substituted with at least one substituent selected from the group consisting of halogen and lower alkyl; M 1 and M 2 are independently selected from the group consisting of Zr, Hf and Ti; the X 1 and X 2 may be the same of different and are selected from the group consisting of halide, lower alkyl and lower alkoxy; and Q 1 and Q 2 are selected from the group consisting of cyclopentadienyl, indenyl, fluorenyl, indolyl and aminoboratobenzyl, optionally substituted with at least one substituent selected from the group consisting of halogen and lower alkyl, with the proviso that Q 1 and Q 2 are different, and with the further provisos that (a) when M 1 (X 1 ) 2 is the same as M 2 (X 2 ) 2 and Q 1 is the same Ar 2 , then Q 2 and Ar 1 must be different, and (b) when M 1 (X 2 ) 2 is the same as M 2 (X 1 ) 2 and Q 2 is the same as Ar 1 , the Q 1 and Ar 2 must be different.

Claim 34

The metallocene catalyst of claim 28, wherein B is selected from the group consisting of ##STR44##

Claim 35

The metallocene catalyst of claim 29, wherein B is selected from the group consisting of ##STR45##

Claim 36

The metallocene catalyst of claim 30, wherein B is ##STR46##

Claim 37

The metallocene catalyst of claim 30, wherein B is ##STR47##

Claim 38

The metallocene catalyst of claim 16, wherein B is silyl.

Claim 39

The metallocene catalyst of claim 28, wherein M 1 and M 2 are different.

Claim 40

The metallocene catalyst of claim 28, wherein M 1 and M 2 are the same.

Claim 41

The metallocene catalyst of claim 28, wherein the X 1 and X 2 are independently chloro or methyl.

Claim 42

The metallocene catalyst of claim 36, wherein the X 1 are chloro and the X 2 are methyl.

Claim 43

The metallocene catalyst of claim 36, wherein the X 1 and X 2 are all chloro.

Claim 44

The metallocene catalyst of claim 36, wherein the X 1 and X 2 are all methyl.

Claim 45

A metallocene catalyst having the structure ##STR48## wherein: B is carbyl, lower alkylene, lower alkenylene or silyl; Ar 1 and Ar 2 are independently selected from the group consisting of cyclopentadienyl, indenyl and fluorenyl, optionally substituted with at least one substituent selected from the group consisting of halogen and lower alkyl; M 1 and M 2 are independently selected from the group consisting of Zr, Hf and Ti; the X 1 and X 2 may be the same of different and are selected from the group consisting of halide, lower alkyl and lower alkoxy; R 2a and R 2b are independently selected from the group consisting of methylene, phenylmethylene, lower alkyl-substituted methylene, di(lower alkyl)-substituted methylene, and methylene substituted with one lower alkyl group and phenyl, L is methylene optionally substituted with 1 or 2 lower alkyl groups; and q is 0 or 1.

Claim 46

A metallocene catalyst having the structure ##STR48## wherein: B is carbyl, lower alkylene, lower alkenylene or silyl; Ar 1 and Ar 2 are independently selected from the group consisting of cyclopentadienyl, indenyl and fluorenyl, optionally substituted with at least one substituent selected from the group consisting of halogen and lower alkyl; M 1 and M 2 are independently selected from the group consisting of Zr, Hf and Ti; the X 1 and X 2 may be the same of different and are selected from the group consisting of halide, lower alkyl and lower alkoxy; R 2a and R 2b are independently selected from the group consisting of methylene, phenylmethylene, lower alkyl-substituted methylene, di(lower alkyl)-substituted methylene, and methylene substituted with one lower alkyl group and phenyl, L is methylene optionally substituted with 1 or 2 lower alkyl groups; and q is 0 or 1.

Claim 47

The metallocene catalyst of claim 40, wherein B is selected from the group consisting of ##STR49##

Claim 48

The metallocene catalyst of claim 41, wherein B is selected from the group consisting of ##STR50##

Claim 49

The metallocene catalyst of claim 42, wherein B is ##STR51##

Claim 50

The metallocene catalyst of claim 42, wherein B is ##STR52##

Claim 51

The metallocene catalyst of claim 40, wherein B is silyl.

Claim 52

The metallocene catalyst of claim 40, wherein M 1 and M 2 are different.

Claim 53

The metallocene catalyst of claim 40, wherein M 1 and M 2 are the same.

Claim 54

The metallocene catalyst of claim 40, wherein the X 1 and X 2 are independently chloro or methyl.

Claim 55

The metallocene catalyst of claim 48, wherein the X 1 are chloro and the X 2 are methyl.

Claim 56

The metallocene catalyst of claim 48, wherein the X 1 and X 2 are all chloro.

Claim 57

The metallocene catalyst of claim 48, wherein the X 1 and X 2 are all methyl.

Claim 58

The metallocene catalyst of claim 40, wherein q is 0.

Claim 59

The metallocene catalyst of claim 40, wherein R 2a and R 2b are independently selected from the group consisting of methylene, methylmethylene, dimethylmethylene and methylethylmethylene.

Claim 60

The metallocene catalyst of claim 53, wherein R 2a and R 2b are both dimethylmethylene.

Claim 61

A metallocene catalyst having the structure ##STR53##

Claim 62

A metallocene catalyst having the structure ##STR53##

Claim 63

A metallocene catalyst having the structure ##STR54##

Claim 64

A metallocene catalyst having the structure ##STR54##

Claim 65

A metallocene catalyst having the structure ##STR55##

Claim 66

A metallocene catalyst having the structure ##STR55##

Claim 67

A metallocene catalyst having the structure ##STR56##

Claim 68

A metallocene catalyst having the structure ##STR56##

Claim 69

A metallocene catalyst having the structure ##STR57##

Claim 70

A metallocene catalyst having the structure ##STR57##

Claim 71

A metallocene catalyst having the structure ##STR58##

Claim 72

A metallocene catalyst having the structure ##STR58##

Claim 73

A metallocene catalyst having the structure ##STR59##

Claim 74

A metallocene catalyst having the structure ##STR59##

Claim 75

A metallocene catalyst having the structure ##STR60##

Claim 76

A metallocene catalyst having the structure ##STR60##

Claim 77

A metallocene catalyst having the structure ##STR61##

Claim 78

A metallocene catalyst having the structure ##STR61##

Claim 79

A metallocene catalyst having the structure ##STR62##

Claim 80

A metallocene catalyst having the structure ##STR62##

Claim 81

A metallocene catalyst having the structure ##STR63##

Claim 82

A metallocene catalyst having the structure ##STR63##

Claim 83

A metallocene catalyst having the structure ##STR64##

Claim 84

A metallocene catalyst having the structure ##STR64##

Claim 85

A metallocene catalyst having the structure ##STR65##

Claim 86

A metallocene catalyst having the structure ##STR65##

Claim 87

A metallocene catalyst having the structure ##STR66##

Claim 88

A metallocene catalyst having the structure ##STR66##

Claim 89

A metallocene catalyst having the structure ##STR67##

Claim 90

A metallocene catalyst having the structure ##STR67##

Claim 91

A metallocene catalyst having the structure ##STR68##

Claim 92

A metallocene catalyst having the structure ##STR68##

Claim 93

A metallocene catalyst having the structure ##STR69##

Claim 94

A metallocene catalyst having the structure ##STR69##

Claim 95

A metallocene catalyst containing more than one active site, having the structure B(Z) q wherein: B is a covalent bridging group comprising carbyl, silyl, disilyl, germanyl, ammonium, phosphonium, ##STR70## or a C 1 -C 24 hydrocarbyl radical optionally containing a Group IVB element, a Group VB element, or both a Group IVB element and a Group VB element, and is capable of binding up to n max substituents through single covalent bonds, where n max is at least 4; Z is a ligand having the structure ##STR71## in which ** represents the point of binding to B, M is a Group IIIA element, a Group IVA element, a Group VA element, a lanthanide, or an actinide; X is selected from the group consisting of hydride, halide, alkoxy, amido, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl radicals substituted with one or more electron-withdrawing groups, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements, or, when two or more X substituents are present, they may together form an alkylidene olefin, acetylene, or a five- or six-membered cyclic hydrocarbyl group; Y is a neutral Lewis base; m is 1, 2, 3 or 4, and n is 0, 1, 2 or 3, with the proviso that if M is a Group IIIA element, m is 1 and n is 0, and with the further proviso that if M is a Group IVA element, the sum of m and n does not exceed 2; Ar* is ##STR72## in which R and R 1 are independently selected from the group consisting of halogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements, x is 0, 1, 2, 3 or 4, and y is 0, 1, 2, 3 or 4, with the proviso that the sum of x and y cannot exceed 4, or, when R and R 1 are ortho to each other and x and y are each 1 or greater, R and R 1 can together form a five- or six-membered cyclic structure optionally substituted with one to four substituents selected from the group consisting of halogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements; Q is cyclopentadienyl, indenyl, fluorenyl, indolyl or aminoboratobenzyl, optionally substituted with one or more R and R 1 substituents as above, if n max is 4 or 5, then q is 2, and if n max is greater than 5, then q is an integer in the range of 2 to q max , wherein q max is equal to 1/2n max when n max is an even number, and 1/2(n max -1) when n max is an odd number; and at least two of the Z substituents bound to B are different.

Claim 96

A metallocene catalyst containing more than one active site, having the structure B(Z) q wherein: B is a covalent bridging group comprising carbyl, silyl, disilyl, germanyl, ammonium, phosphonium, ##STR70## or a C 1 -C 24 hydrocarbyl radical optionally containing a Group IVB element, a Group VB element, or both a Group IVB element and a Group VB element, and is capable of binding up to n max substituents through single covalent bonds, where n max is at least 4; Z is a ligand having the structure ##STR71## in which ** represents the point of binding to B, M is a Group IIIA element, a Group IVA element, a Group VA element, a lanthanide, or an actinide; X is selected from the group consisting of hydride, halide, alkoxy, amido, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl radicals substituted with one or more electron-withdrawing groups, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements, or, when two or more X substituents are present, they may together form an alkylidene olefin, acetylene, or a five- or six-membered cyclic hydrocarbyl group; Y is a neutral Lewis base; m is 1, 2, 3 or 4, and n is 0, 1, 2 or 3, with the proviso that if M is a Group IIIA element, m is 1 and n is 0, and with the further proviso that if M is a Group IVA element, the sum of m and n does not exceed 2; Ar* is ##STR72## in which R and R 1 are independently selected from the group consisting of halogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements, x is 0, 1, 2, 3 or 4, and y is 0, 1, 2, 3 or 4, with the proviso that the sum of x and y cannot exceed 4, or, when R and R 1 are ortho to each other and x and y are each 1 or greater, R and R 1 can together form a five- or six-membered cyclic structure optionally substituted with one to four substituents selected from the group consisting of halogen, C 1 -C 24 hydrocarbyl, C 1 -C 24 hydrocarbyl substituted with one or more halogen atoms, and C 1 -C 24 hydrocarbyl-substituted Group IVB elements; Q is cyclopentadienyl, indenyl, fluorenyl, indolyl or aminoboratobenzyl, optionally substituted with one or more R and R 1 substituents as above, if n max is 4 or 5, then q is 2, and if n max is greater than 5, then q is an integer in the range of 2 to q max , wherein q max is equal to 1/2n max when n max is an even number, and 1/2(n max -1) when n max is an odd number; and at least two of the Z substituents bound to B are different.

Claim 97

The metallocene catalyst of claim 72, wherein q is 2.

Claim 98

The metallocene catalyst of claim 72, wherein q is 3.

Claim 99

The metallocene catalyst of claim 72, wherein all three of the Z ligands bound to B are different.

Claim 100

The metallocene catalyst of claim 1, wherein, in each ligand Z: B is a covalent bridging group comprising carbyl, silyl, disilyl or a C 1 -C 12 hydrocarbyl radical optionally containing a Group IVB element, a Group VB element, or both; x is 0, 1 or 2; y is 0, 1 or 2; R and R 1 are independently selected from the group consisting of halogen and C 1 -C 12 alkyl, or are ortho to each other and linked to form a cyclopentadienyl or indenyl group; Q is cyclopentadienyl indenyl, fluorenyl, or aminoboratobenzyl; M is a Group IVA element; m is 1 or 2, n is 0 or 1, and the sum of m and n is 2; X is selected from the group consisting of hydride, halide, amido, C 1 -C 12 alkyl, C 1 -C 12 alkyl substituted with one or more halogen and/or alkoxy groups, and C 1 -C 12 hydrocarbyl-substituted Group IVB elements; Y is a selected from the group consisting of diethylether, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, and n-butylamine; and q is 2 or 3.

Claim 101

The metallocene catalyst of claim 76, wherein, in each ligand Z: B is carbyl, a C 1 -C 6 hydrocarbyl radical or silyl; x and y are independently 0 or 1; R and R 1 are independently selected from the group consisting of halogen and lower alkyl, or are ortho to each other and linked to form a cyclopentadienyl ring; Q is cyclopentadienyl or indenyl; M is Zr, Hf or Ti; m is 2; n is 0; x is hydride, halide or lower alkyl; and q is 2.

Claim 102

The metallocene catalyst of claim 72, wherein the Z substituents bound to B contain different M moieties.