Phillips Petroleum Company

Bernd Peifer

Helmut G Alt

M Bruce Welch

Syriac J Palackal

Rolf L Geerts

Darryl R Fahey

Peter Schertl

Konstantinos Patsidis

Harold R Deck

Gil R Hawley

Ted M Pettijohn

Gary L Glass

Polymeric ligands, polymeric metallocenes, and processes for preparing same are provided. The process for preparing polymeric metallocenes comprises reacting a polymeric ligand, a transition metal compound, and an alkali metal compound. In one embodiment, a process for preparing polymeric ligands comprises reacting at least one bridged cyclopentadienyl-type monomer and an initiator under polymerization conditions. In another embodiment, a polymeric ligand is represented by the formula &lsqb;Q&prime;&rsqb; , wherein Q&prime; is a unit containing at least one bridged cyclopentadienyl-type group and wherein n is 1-5000. In another embodiment, a polymeric metallocene is represented by the formula &lsqb;Q&Prime;MX &rsqb; , wherein Q&Prime; is a unit containing at least one fluorenyl-type group, M is a transition metal, each X is individually a hydrocarbyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 12 carbon atoms, an aryloxy group containing 6 to 20 carbon atoms, a halide, or hydride, m is 2 or 3, and wherein n is 1-5000. Other aspects of the present invention include a catalyst system comprising the polymeric metallocene and an organoaluminoxane, a method for preparing same, and a polymerization process employing the catalyst system.

Polymeric ligands, polymeric metallocenes, catalyst systems, preparation, and use

The present invention provides polymers of ethylene having ethyl branches, a narrow molecular weight distribution, no substantial amount of branches longer than any comonomer employed in the polymerization, and an unusually low branching to density ratio. In one embodiment the polyethylenes are substantially free of any branches having more than 2 carbon atoms, i.e. ethyl branches, and the molar percent of ethyl branches is substantially the same for molecular fractions across the molecular weight distribution. In another embodiment the polyethylenes have other branches having 3 or more carbons and the molar percent of the ethyl branches is substantially the same for molecular fractions across the molecular weight distribution.

Polyethylenes containing a unique distribution of short chain branching

A catalyst system comprising an organoaluminoxane cocatalyst and a polymeric fluorenyl-containing metallocene prepared from a polymer resulting from the polymerization of a 2-vinylfluorene compound or the alkylation of a fluorene compound.

Fluorenyl-containing polymeric metallocene catalyst systems

Polymeric ligands, polymeric metallocenes, and processes for preparing same are provided. The process for preparing polymeric metallocenes comprises reacting a polymeric ligand, a transition metal compound, and an alkali metal compound. In one embodiment, a process for preparing polymeric ligands comprises reacting at least one bridged cyclopentadienyl-type monomer and an initiator under polymerization conditions. In another embodiment, a polymeric ligand is represented by the formula [Q'].sub.n, wherein Q' is a unit containing at least one bridged cyclopentadienyl-type group and wherein n is 1-5000. In another embodiment, a polymeric metallocene is represented by the formula [Q'MX.sub.m ].sub.n, wherein Q' is a unit containing at least one fluorenyl-type group, M is a transition metal, each X is individually a hydrocarbyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 12 carbon atoms, an aryloxy group containing 6 to 20 carbon atoms, a halide, or hydride, m is 2 or 3, and wherein n is 1-5000. Other aspects of the present invention include a catalyst system comprising the polymeric metallocene and an organoaluminoxane, a method for preparing same, and a polymerization process employing the catalyst system.

Polymeric ligands, polymeric metallocenes, catalyst systems,

A polymerization process comprising contacting at least one olefin under polymerization conditions with a catalyst composition produced by combining an organoaluminoxane cocatalyst and a polymeric metallocene catalyst prepared by (1) forming a fluorine-containing polymer by (a) polymerizing a 2-vinyl fluorenyl compound or (b) polymerizing a fluorenyl compound by reacting it with chloro methyl methyl ether in the presence of zinc dichloride or aluminum trichloride; (2) reacting the fluorenyl-containing polymer with an alkali metal compound; and (3) reacting the product of step (2) with a transition metal-containing compound.

A process for preparing polynuclear metallocenes by reacting a metallocene in which one of the cyclopentadienyl-containing radicals has a substituent having olefinic or acetylenic unsaturation with a second metallocene having a metal which comes from groups IVb to VIb of the periodic table and a metal-hydride bond. The use of the resulting metallocenes in the polymerization of olefins is disclosed, including techniques for using such metallocenes to produce solid prepolymerized metallocene-containing catalyst systems suitable for use in the polymerization of olefins.

Polynuclear metallocene preparation and use

Double bound metallocenes, i.e. metallocenes having a cyclopentadienyl-containing radical that is bound to a transition metal both by a pi bond and by a sigma carbon bond of a substituent of that same cyclopentadienyl-containing radical can be prepared by reducing metallocenes having a cyclopentadienyl-containing radical having at least one an unsaturated substituent. Also a process for producing polymers comprising contacting at least one olefinic monomer under suitable polymerization conditions with such double bound metallocenes.

Metallocene preparation and use

Processes to prepare polymeric metallocene are provided. Said processes comprise reacting a polymeric ligand, an alkali metal compound, and a transition metal-containing compound to produce said polymeric metallocene. therefor.

Process to prepare polymeric metallocenes

A process for preparing an alkynyl fulvene group containing compound and said compound is provided. Said process comprises reacting an alkynyl ketone compound with a cyclopentadienyl-type compound.

Process for preparing an alkynyl fulvene group containing compound and

A process for preparing a bridged ligand, where said bridged ligand has an alkynyl group, and said bridged ligand is provided. Said process comprises reacting an alkynyl fulvene containing compound with an alkali metal salt of a cyclopentadienyl-type compound.

Process for preparing a bridged ligand and said bridged ligand

In accordance with the present invention there is provided a process for preparing a cyclopentadienyl-type ligand comprising reacting an alkali metal compound and a fulvene-type compound to form a dianion, and then reacting the dianion with water. In accordance with another embodiment of the present invention a process for preparing a metallocene compound is provided comprising reacting an alkali metal compound, a fulvene-type compound, and a transition metal-containing compound. In another embodiment, the metallocene compound and a cocatalyst are combined to form a catalyst system. Other aspects of the invention include the cyclopentadienyl-type ligands, metallocene compounds, and catalyst systems thus produced and polymerization processes employing the catalyst systems.

Cyclopentadienyl-type ligands, metallocene compounds catalyst systems,

Methods are disclosed for preparing a highly active solid metallocene-containing catalyst system and its use in the polymerization of olefins. The solid catalyst system is prepared by combining an aluminoxane with a metallocene having a substituent which has internal alkynyl unsaturation in a suitable liquid to form a liquid catalyst system, conducting prepolymerization of an olefin in the liquid catalyst system, and separating the resulting solid metallocene-containing catalyst system from the last reaction product mixture. Also polymerization of olefins using the inventive solid catalyst system is disclosed.

Method for making and using a supported metallocene catalyst system

In accordance with the present invention, there is provided an organoaluminoxy product prepared by the process comprising reacting an organoaluminoxane with an ene-ol compound. In another embodiment, the organoaluminoxane can be prepared in situ by the process comprising reacting a hydrocarbylaluminum compound, water, and the ene-ol compound. Further there is provided olefin polymerization catalyst systems comprising the organoaluminoxy product and at least one transition metal-containing catalyst. Optionally, the catalyst system is prepolymerized in the presence of at least one olefin to form a prepolymerized catalyst system. Still further there is provided processes for the polymerization of olefins using the catalyst systems.

Organoaluminoxy product, catalyst systems, preparation, and use

Metallocene compounds and processes for preparing such metallocene compounds are provided. Such processes for preparing such metallocene compounds comprise reacting an alkynyl ligand, an alkali metal compound, and a transition metal-containing compound.

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Bayreuth, Germany

Bernd Peifer