Organometallic fluorenyl compounds, preparation, and use
AssigneePhillips Petroleum Company
InventorsHelmut G. Alt, Syriac J. Palackal, Konstantinos Patsidis, M. Bruce Welch, Rolf L. Geerts, Eric T. Hsieh, Max P. McDaniel, Gil R. Hawley, Paul D. Smith
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Abstract
Fluorenyl-containing metallocenes are disclosed along with methods for making the metallocenes. Also disclosed are methods for using the metallocenes as polymerization catalysts. In addition, polymers resulting from such polymerizations are disclosed.
Claims67
A process for preparing a fluorenyl-containing metallocene comprising (1) reacting an alkali metal alkyl with a suitable fluorenyl precursor in the presence of a non-halogenated liquid diluent consisting of at least one liquid selected from hydrocarbons and non-cyclic ethers to produce a fluorenyl-containing alkali metal salt which is substantially free of THF and (2) then reacting the thus produced fluorenyl-containing salt with a transition metal compound of the formula MeO.sub.k in the presence of a non-halogenated liquid diluent consisting essentially of a solvent for the fluorenyl salt which is non-coordinating with the transition metal compound, wherein Me is a metal selected from the group consisting of IVB, VB, and VIB of the Periodic Table, each Q is the same or different and is selected from hydrocarbyl or hydrocarbyloxy radicals having 1 to 20 carbon atoms or halogens, and k is a number sufficient to fill out the valences of Me.
A process for preparing a fluorenyl-containing metallocene comprising (1) reacting an alkali metal alkyl with a suitable fluorenyl precursor in the presence of a non-halogenated liquid diluent consisting of at least one liquid selected from hydrocarbons and non-cyclic ethers to produce a fluorenyl-containing alkali metal salt which is substantially free of THF and (2) then reacting the thus produced fluorenyl-containing salt with a transition metal compound of the formula MeQ.sub.k in the presence of a non-halogenated liquid diluent consisting essentially of at least one liquid selected from hydrocarbons and diethyl ether, wherein Me is a metal selected from the group consisting of IVB, VB, and VIB of the Periodic Table, each Q is the same or different and is selected from hydrocarbyl or hydrocarbyloxy radicals having 1 to 20 carbon atoms or halogens, and k is a number sufficient to fill out the valences of Me.
A process for polymerizing an olefin comprising contacting said olefin under suitable polymerization conditions with a catalyst system comprising a fluorenyl-containing metallocene and a suitable cocatalyst, wherein said fluorenyl-containing metallocene is selected from the group consisting of metallocenes of the formula R".sub.x (FlR.sub.n)(CpR.sub.m)MeQ.sub.k wherein Fl is a fluorenyl radical, Cp is a cyclopentadienyl, indenyl, tetrahydroindenyl, or fluorenyl radical, each R is the same or different and is an organo radical having 1 to 20 carbon atoms, R" is a structural bridge linking (FlR.sub.n) and (CpR.sub.m), Me is a metal selected from the group consisting of IVB and VB metals of the Periodic Table, each Q is the same or different and is selected from the group consisting of hydrocarbyl or hydrocarbyloxy radicals having 1 to 20 carbon atoms and halogen, x is 1 or 0, k is a number sufficient to fill out the remaining valances of Me, n is a number in the range of 0 to 7, m is a number in the range of 0 to 7, further characterized by the fact that if Cp is cyclopentadienyl and R" is a alkylene radical then R" is selected from the group consisting of --CH.sub.2 -- and alkylene radicals having at least two carbon atoms in the main alkylene chain and if (CpR.sub.m) is unsubstituted fluorenyl and x is 0, then n is 1 to 7.
A process comprising reacting fluorenyl methyl chloride with an alkali metal salt of cyclopentadiene to produce 1-fluorenyl-1-cyclopentadienyl methane;
- forming a divalent alkali metal salt of 1-fluorenyl-1-cyclopentadienyl methane;
- reacting the said divalent alkali metal salt with a transition metal compound of the formula MeQ.sub.k wherein Me is selected from Zr, Hf, and Ti;
- each Q is individually selected from the group consisting of hydrocarbyl or hydrocarbyloxy radicals having 1 to 20 carbon atoms and halogens;
- at least one Q is a halogen;
- and k is a number corresponding to the valence of Me;
- to produce the corresponding bridged metallocene;
- and using said metallocene with a cocatalyst to polymerize an alpha olefin containing at least three carbons per molecule.
Dependencies are inferred from the claim text.