Metallocenes and processes therefor and therewith

A process for preparing a bridged metallocene comprising:

• (1) contacting a hydrocarbon having at least two acidic, replaceable hydrogens and having the formula of ZH.sub.2 with an organolithium and an organohalocompound to prepare a ligand precursor having the formula of HZ-EX.sub.n+1 wherein at least two X's are halogens;
• (2) contacting said ligand precursor with an organo alkali metal compound having the formula of HZMa to form a bridged ligand having the formula of ZH-EX.sub.n -ZH wherein at least one X is a halogen;
• (3) contacting said bridged ligand with an inorganic material QOH to form a bridged ligand chemically bonded to inorganic moiety Q;
• (4) contacting said bridged ligand chemically bonded to inorganic moiety with an organolithium and a metal halide having the formula of MY.sub.m to prepare said bridged metallocene;
• wherein each Z is the same or different hydrocarbyl radical selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and mixtures thereof;
• each X is the same or different and is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, R, OR, NR.sub.2, PR.sub.2, OQ, and mixtures thereof wherein the R is a C.sub.1 -C.sub.20 hydrocarbyl radical and Q is an inorganic moiety selected from the group consisting of silica, alumina, clay, phosphated alumina, and mixtures thereof;
• each Y is the same or different and is selected from the group consisting of an alkyl group, hydrogen, fluorine, chlorine, bromine, iodine, and mixtures thereof;
• each E is selected from the group consisting of C, Sn, Si, Ge, B, Al, N, P, and mixtures thereof;
• M is a metal selected from the group consisting of Ti, Zr, Hf, Sc, Y, V, La, and mixtures thereof;
• m is a number sufficient to fill out the remaining valences of metal M;
• Ma is an alkali metal;
• and n is 1 or 2.

A process for preparing a bridged metallocene having the formula of ##STR8## comprising:

• (1) contacting a hydrocarbon having at least two acidic, replaceable hydrogens and having the formula of ZH.sub.2 with an organolithium and an organohalocompound to prepare a ligand precursor having the formula of HZ-EX.sub.n+1 wherein at least two X's are halogens;
• (2) contacting said ligand precursor with an organo alkali metal compound having the formula of HZMa to form a bridged ligand having the formula of ZH-EX.sub.n -ZH wherein at least one X is a halogen;
• (3) contacting said bridged ligand with an organolithium and a metal halide having the formula of MY.sub.m to prepare said bridged metallocene;
• and (4) contacting said bridged metallocene with an organic material QOH to form a metallocene chemically bonded to Q;
• wherein each Z is the same or different hydrocarbyl radical selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and mixtures thereof;
• each X is the same or different and is selected from the group consisting of hydrogen, fluorine, chlorine, bromine iodine, R, OR, NR, PR, OQ, and mixtures thereof wherein the R is a C.sub.1 -C.sub.20 hydrocarbyl radical and Q is an inorganic moiety selected from the group consisting of silica, alumina, clay phosphated alumina, and mixtures thereof;
• each Y is the same or different and is selected from the group consisting of an alkyl group, hydrogen, fluorine, chlorine, bromine, iodine, and mixtures thereof;
• each E is selected from the group consisting of Sn, Si, Ge, B, Al, N, P, and mixtures thereof;
• M is a metal selected from the group consisting of Ti, Zr, Hf, Sc, Y, V, La, and mixtures thereof;
• m is a number sufficient to fill out the valence of the metal M;
• Ma is an alkali metal;
• and n is 1 or 2.

A process comprising:

• (1) contacting a hydrocarbon selected from the group consisting of cyclopentadiene, fluorene, and mixtures thereof with butyllithium and an organosilane selected from the group consisting of methyltrichlorosilane, phenyltrichlorosilane, and mixtures thereof to prepare a ligand precursor;
• (2) contacting said ligand precursor with an organo alkali metal compound selected from the group consisting of cyclopentadienyllithium, cyclopentadienylsodium, fluorenyllithium, fluorenylsodium, and mixtures thereof to prepare a bridged ligand;
• (3) contacting said bridged ligand with silica to form a bridged ligand chemically bonded to silica;
• (4) contacting the bridged ligand chemically bonded to silica with zirconium chloride to form a metallocene.

A process for olefin polymerization comprising contacting an olefin under olefin polymerization conditions with a composition comprising a bridged metallocene having the formula of:

• ##STR9## wherein each Z is the same or different hydrocarbyl radical selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and mixtures thereof;
• each X is the same or different and is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, R, OR, NR.sub.2, PR.sub.2, OQ, and mixtures thereof wherein one X is OQ, R is a C.sub.1 -C.sub.20 hydrocarbyl radical and Q is an inorganic moiety selected from the group consisting of silica, alumina, clay, phosphated alumina, and mixtures thereof;
• each Y is the same or different and is selected from the group consisting of an alkyl group, hydrogen, fluorine, chlorine, bromine, iodine, and mixtures thereof;
• each E is selected from the group consisting of Sn, Si, Ge, B, Al, N, P, and mixtures thereof;
• M is a metal selected from the group consisting of Ti, Zr, Hf, Sc, Y, V, and La;
• n is 1 or 2;
• and m is a number sufficient to fill out the remaining valences of the metal M.

A composition produced by the process comprising contacting an olefin under olefin polymerization conditions with a composition comprising a bridged metallocene having the formula of:

• ##STR10## wherein each Z is the same or different hydrocarbyl radical selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and mixtures thereof;
• each X is the same or different and is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, R, OR, NR.sub.2, PR.sub.2, OQ, and mixtures thereof wherein one X is OQ, R is a C.sub.1 -C.sub.20 hydrocarbyl radical and Q is an inorganic moiety selected from the group consisting of silica, alumina, clay, phosphated alumina, and mixtures thereof;
• each Y is the same or different and is selected from the group consisting of an alkyl group, hydrogen, fluorine, chlorine, bromine, iodine, and mixtures thereof;
• each E is selected from the group consisting of Sn, Si, Ge, B, Al, N, P, and mixtures thereof;
• M is a metal selected from the group consisting of Ti, Zr, Hf, Sc, Y, V, and La;
• n is 1 or 2;
• and m is a number sufficient to fill out the remaining valences of metal M.