Metallocene catalysts and associated methods of preparation and use

A metallocene catalyst containing more than one active site, having the structure B(Z).sub.q of structural formula (I) ##STR34## wherein:

• B is a covalent bridging group comprising carbyl, silyl, disilyl, germanyl, ammonium, phosphonium, ##STR35## or a C.sub.1 -C.sub.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.sub.max substituents through single covalent bonds, where n.sub.max is at least 4;
• R and R.sup.1 are independently selected from the group consisting of halogen, C.sub.1 -C.sub.24 hydrocarbyl, C.sub.1 -C.sub.24 hydrocarbyl substituted with one or more halogen atoms, and C.sub.1 -C.sub.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.sup.1 are ortho to each other and x and y are each 1 or greater, R and R.sup.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.sub.1 -C.sub.24 hydrocarbyl, C.sub.1 -C.sub.24 hydrocarbyl substituted with one or more halogen atoms, and C.sub.1 -C.sub.24 hydrocarbyl-substituted Group IVB elements;
• Q is cyclopentadienyl, indenyl, fluorenyl, indolyl or aminoboratobenzyl, optionally substituted with one or more R and R.sup.1 substituents as above, or Q is J(R.sup.2).sub.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.sup.2 is selected from the group consisting of hydrogen, C.sub.1 -C.sub.24 hydrocarbyl, C.sub.1 -C.sub.24 hydrocarbyl substituted with one or more halogen atoms, and C.sub.1 -C.sub.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.sub.1 -C.sub.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.sub.1 -C.sub.24 hydrocarbyl, C.sub.1 -C.sub.24 hydrocarbyl radicals substituted with one or more electron-withdrawing groups, and C.sub.1 -C.sub.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.sub.max is 4 or 5, then q is 2, and if n.sub.max is greater than 5, then q is an integer in the range of 2 to q.sub.max, wherein q.sub.max is equal to 1/2n.sub.max when n.sub.max is an even number, and 1/2(n.sub.max -1) when n.sub.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.sup.2).sub.z-2 ;
• and
• the Z substituents bound to B may be the same or different.

A metallocene catalyst containing more than one active site, having the structure B(Z).sub.q of structural formula (I) ##STR36## wherein:

• B is a covalent bridging group comprising carbyl, silyl, disilyl, germanyl, ammonium, phosphonium, ##STR37## or a C.sub.1 -C.sub.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.sub.max substituents through single covalent bonds, where n.sub.max is at least 4;
• R and R.sup.1 are independently selected from the group consisting of halogen, C.sub.1 -C.sub.24 hydrocarbyl, C.sub.1 -C.sub.24 hydrocarbyl substituted with one or more halogen atoms, and C.sub.1 -C.sub.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.sup.1 are ortho to each other and x and y are each 1 or greater, R and R.sup.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.sub.1 -C.sub.24 hydrocarbyl, C.sub.1 -C.sub.24 hydrocarbyl substituted with one or more halogen atoms, and C.sub.1 -C.sub.24 hydrocarbyl-substituted Group IVB elements;
• Q is cyclopentadienyl, indenyl, fluorenyl, indolyl or aminoboratobenzyl, optionally substituted with one or more R and R.sup.1 substituents as above, or Q is J(R.sup.2).sub.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.sup.2 is selected from the group consisting of hydrogen, C.sub.1 -C.sub.24 hydrocarbyl, C.sub.1 -C.sub.24 hydrocarbyl substituted with one or more halogen atoms, and C.sub.1 -C.sub.24 alkoxy, and z is the coordination number of J, and further wherein Q substituents on different Z groups are linked through a C.sub.1 -C.sub.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.sub.1 -C.sub.24 hydrocarbyl, C.sub.1 -C.sub.24 hydrocarbyl radicals substituted with one or more electron-withdrawing groups, and C.sub.1 -C.sub.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.sub.max is 4 or 5, then q is 2, and if n.sub.max is greater than 5, then q is an integer in the range of 2 to q.sub.max, wherein q.sub.max is equal to 1/2n.sub.max when n.sub.max is an even number, and 1/2(n.sub.max -1) when n.sub.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.sup.2).sub.z-2 ;
• and
• the Z substituents bound to B may be the same or different.

A metallocene catalyst having the structure ##STR38## wherein:

• B is carbyl, lower alkylene, lower alkenylene or silyl;
• Ar.sup.1 and Ar.sup.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.sup.1 and M.sup.2 are independently selected from the group consisting of Zr, Hf and Ti;
• the X.sup.1 and X.sup.2 may be the same of different and are selected from the group consisting of halide, lower alkyl and lower alkoxy;
• and
• R.sup.2a and R.sup.2b are selected from the group consisting of C.sub.1 to C.sub.12 alkyl and phenyl, with the proviso that R.sup.2a and R.sup.2b are different.

A metallocene catalyst having the structure ##STR43## wherein:

• B is carbyl, lower alkylene, lower alkenylene or silyl;
• Ar.sup.1 and Ar.sup.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.sup.1 and M.sup.2 are independently selected from the group consisting of Zr, Hf and Ti;
• the X.sup.1 and X.sup.2 may be the same of different and are selected from the group consisting of halide, lower alkyl and lower alkoxy;
• and
• Q.sup.1 and Q.sup.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.sup.1 and Q.sup.2 are different, and with the further provisos that (a) when M.sup.1 (X.sup.1).sub.2 is the same as M.sup.2 (X.sup.2).sub.2 and Q.sup.1 is the same Ar.sup.2, then Q.sup.2 and Ar.sup.1 must be different, and (b) when M.sup.1 (X.sup.2).sub.2 is the same as M.sup.2 (X.sup.1).sub.2 and Q.sup.2 is the same as Ar.sup.1, the Q.sup.1 and Ar.sup.2 must be different.

A metallocene catalyst having the structure ##STR48## wherein:

• B is carbyl, lower alkylene, lower alkenylene or silyl;
• Ar.sup.1 and Ar.sup.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.sup.1 and M.sup.2 are independently selected from the group consisting of Zr, Hf and Ti;
• the X.sup.1 and X.sup.2 may be the same of different and are selected from the group consisting of halide, lower alkyl and lower alkoxy;
• R.sup.2a and R.sup.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.

A metallocene catalyst containing more than one active site, having the structure B(Z).sub.q wherein:

• B is a covalent bridging group comprising carbyl, silyl, disilyl, germanyl, ammonium, phosphonium, ##STR70## or a C.sub.1 -C.sub.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.sub.max substituents through single covalent bonds, where n.sub.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.sub.1 -C.sub.24 hydrocarbyl, C.sub.1 -C.sub.24 hydrocarbyl radicals substituted with one or more electron-withdrawing groups, and C.sub.1 -C.sub.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.sup.1 are independently selected from the group consisting of halogen, C.sub.1 -C.sub.24 hydrocarbyl, C.sub.1 -C.sub.24 hydrocarbyl substituted with one or more halogen atoms, and C.sub.1 -C.sub.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.sup.1 are ortho to each other and x and y are each 1 or greater, R and R.sup.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.sub.1 -C.sub.24 hydrocarbyl, C.sub.1 -C.sub.24 hydrocarbyl substituted with one or more halogen atoms, and C.sub.1 -C.sub.24 hydrocarbyl-substituted Group IVB elements;
• Q is cyclopentadienyl, indenyl, fluorenyl, indolyl or aminoboratobenzyl, optionally substituted with one or more R and R.sup.1 substituents as above,
• if n.sub.max is 4 or 5, then q is 2, and if n.sub.max is greater than 5, then q is an integer in the range of 2 to q.sub.max, wherein q.sub.max is equal to 1/2n.sub.max when n.sub.max is an even number, and 1/2(n.sub.max -1) when n.sub.max is an odd number;
• and
• at least two of the Z substituents bound to B are different.