Metallocene ligands, metallocene compounds and metallocene catalysts, their synthesis and their use for the polymerization of olefins

A compound of the formula:

• or its double bond isomers, wherein
• R9 is a bridge having one of the structures:
• where R40 and R41, can be identical or different, with or without heteroatoms, and are each an alkyl group of from 2 to about 30 carbon atoms, a fluoroalkyl group of from 2 to about 10 carbon atoms, an alkoxy group of from 2 to about 10 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenyl group of from 3 to about 10 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl or arylsilyl group, or an arylalkenyl group of from 8 to about 40 carbon atoms, or R40 and R41 together with any atoms connecting them form one or more ring systems, and with the proviso that if R40 and R41 are different and R40 is a hydrocarbon group of from 4 to about 40 carbon atoms, R41 is a hydrocarbon group of from 1 to about 40 carbon atoms,
• M12 is silicon, germanium or tin, and
• R3, R4, R5, R6, R7, R8 and also R3′, R4′, R5′, R6′, R7′ and R8′ are identical or different and are each a hydrogen atom, or a linear, cyclic or branched hydrocarbon group, with or without heteroatoms, selected from the group consisting of an alkyl group of from 1 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an aryl group of from 6 to about 20 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms or an arylalkenyl group of from 8 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl or arylsilyl group, with the proviso that R3 and R3 are not hydrogen, or wherein two adjacent radicals R5, R6 or R5′, R6′, or R6, R7 or R6′, R7′ or R7, R8 or R7′, R8′ can form one or more hydrocarbon ring system(s).

A process for the production of a mixture of racemic and meso isomers of metallocene compounds comprising the steps of:

• a) providing a ligand system of the formula
• wherein
• R9 is a bridge having one of the structures:
• where R40 and R41, can be identical or different, with or without heteroatoms, and are each an alkyl group having from 2 to about 30 carbon atoms, a fluoroalkyl group of from 2 to about 10 carbon atoms, an alkoxy group of from 2 to about 10 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenyl group of from about 3 to about 10 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl or arylsilyl group, or an arylalkenyl group of from 8 to about 40 carbon atoms, or R40 and R41 together with the atoms connecting them can form one or more cyclic systems, and if R40 and R41 are different and R40 is a hydrocarbon group of from about 4 to about 40 carbon atoms, R41 is a hydrocarbon group of from 1 to about 40 carbon atoms,
• M12 is silicon, germanium or tin, and
• R3, R4, R5, R6, R7, R8 and also R3′, R4′, R5′, R6′, R7′ and R8′ are identical or different and are each a hydrogen atom, or a linear, cyclic or branched group, with or without heteroatoms, selected from the group consisting of an alkyl group of from 1 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an aryl group of from 6 to about 20 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms or an arylalkenyl group of from 8 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl or arylsilyl group, with the proviso that R3 and R3 are not hydrogen, or wherein two adjacent radicals R5, R6 or R5′, R6′, or R6, R7 or R6′, R7′, or R7, R8 or R7′, R8′ can form one or more hydrocarbon ring system(s),
• wherein said ligand system is produced by deprotonation of a compound of the formula
• with a base in an inert solvent at temperatures of −70° C. to 80° C.;
• and,
• b) combining said ligand system of formula LS with a compound having the formula M1X4 at a temperature of from about −70° C. to about 80° C., wherein M1 is zirconium, titanium or hafnium and X is a halogen, to provide a metallocene compound(s) having a weight ratio of racemic to meso isomers of greater than 5:1 as synthesized.

A catalyst composition comprising:

• a) mixed isomers of at least one metallocene compound having the formula 1a:
• R9L1 L2 M1R1R2 (formula 1a)
• where L1 and L2 are identical or different ligands and are each a substituted mononuclear or polynuclear hydrocarbon radical selected from the group consisting of substituted cyclopentadienyl, indenyl, tetrahydroindenyl, azurenyl, fluorenyl, azapentalenyl, thiapentalenyl or oxapentalenyl, which form a sandwich structure with atom M1, therebetween,
• R1 and R2 are identical or different and are each a hydrogen atom, an alkyl group of from 1 to about 10 carbon atoms, an alkoxy group of from 1 to about 10 carbon atoms, an aryl group of from 6 to about 20 carbon atoms, an aryloxy group of from about 6 to about 10 carbon atoms, an alkenyl group of from 2 to about 10 carbon atoms, an OH group, a halogen atom, or a NR232 group, where R32 is an alkyl group of from 1 to about 10 carbon atoms or an aryl group of from 6 to about 14 carbon atoms, or R1 and R2 form one or more ring system(s),
• M1 is a metal of group IVb of the Periodic Table of the Elements,
• R9 is a bridge between the ligands L1 and L2 having one of the structures:
• where R40 and R4′, can be identical or different, with or without heteroatoms, and are each an alkyl group having from 2 to about 30 carbon atoms, a fluoroalkyl group of from 2 to about 10 carbon atoms, an alkoxy group of from 2 to about 10 carbon atoms, an aryloxy group of from 6 to about 10 carbon atoms, an alkenyl group of from about 3 to about 10 carbon atoms, an arylalkyl group of from 7 to about 40 carbon atoms, an alkylaryl group of from 7 to about 40 carbon atoms, a substituted or unsubstituted alkylsilyl or arylsilyl group, or an arylalkenyl group of from 8 to about 40 carbon atoms, or R40 and R41 together with the atoms connecting them can form one or more cyclic systems, and if R40 and R41 are different and R40 is a hydrocarbon group of from about 4 to about 40 carbon atoms, R41 is a hydrocarbon group of from 1 to about 40 carbon atoms,
• M12 is silicon, germanium or tin, and
• wherein the compound as synthesized has a ratio of racemic or pseudoracemic isomers to meso or pseudomeso isomers of greater than 5:1;
• b) at least one cocatalyst;
• and
• c) at least one porous support.