Texas Alkyls, Inc.

Akzo Nobel N.v.

Exxon Research and Engineering Company

Stauffer Chemical Company

Akzo Chemicals Inc.

Akzo Nobel Chemicals Inc.

Dennis B Malpass

Andrzej M Piotrowski

Loyd W Fannin

G Scott Yeargin

Gregory M Smith

Spencer C Watson

Clark C Crapo

Michael J Breen

Dennis L Deavenport

Nam H Tran

Stanley W Palmaka

Kelly B Triplett

Paul D Jones

Jonathan S Rogers

James T Hodges, Iii

Joseph H Merkley

Ramiro Sanchez

Elliot I Band

John J Eisch

Bor-Ping E Wang

Marek P Boleslawski

George Charles Heilig

Connie S Rabbit

Constance S Rabbitt

Barbara L Hudock

Thomas C Foley

William N Smith

Dale W Webb

John R Rohrer

A catalytically active aluminoxane can be synthesized from a precursor formed by the combination of at least one trialkylaluminum compound and at least one organoaluminum compound containing a carbon-oxygen bond therein, such as an alkoxy group-containing organoaluminum compound of the formula (CH.sub.3).sub.2 Al--O--R, where R is alkyl.

Aluminoxane synthesis employing reduced amount of trialkylaluminum

Hydrocarbon solutions of a dialkylmagnesium compound having reduced viscosity contain: (a) a hydrocarbon solvent; (b) a dialkylmagnesium compound normally soluble in hydrocarbon solvents; and (c) an effective viscosity reducing amount of a compound selected from the group consisting of a compound having silicon-oxygen bonding, a compound having silicon-nitrogen bonding, and mixtures thereof. Representative viscosity reducing agents include: tetraalkylorthosilicate compounds, such as those of the general formula Si(OR).sub.4, where R is an alkyl group containing from 1 to about 4 carbon atoms, as exemplified by tetraethylorthosilicate; alkylsilazane compounds, including a hexaalkyldisilazane compound containing from 1 to about 4 carbon atoms in the alkyl groups therein as exemplified by hexamethyldisilazane; and silicone oil.

Viscosity reduction of organomagnesium solutions

The present invention relates to a process which comprises the non-hydrolytic transformation of an aluminoxane precursor composition, comprising carbon-to-oxygen bonds which can be alkylated by an alkylaluminum moiety, into a catalytically useful aluminoxane composition. In one embodiment of this invention, the catalytically useful aluminoxane composition is a polymethylaluminoxane composition substantially free of trimethylaluminum. The intermediate precursor is formed by the reaction of a trialkylaluminum compound, or a mixture of trialkylaluminum compounds, and a compound containing a carbon-to-oxygen bond, such as an alcohol, ketone, carboxylic acid, or carbon dioxide. Either unsupported or supported polymethyl-aluminoxane compositions can be formed.

Polyalkylaluminoxane compositions formed by non-hydrolytic means

A hydrocarbon-soluble alkylaluminoxane composition, such as, methylaluminoxane or even a modified methylaluminoxane, can be prepared by preparing an alkylaluminoxane precursor via non-hydrolytic means, such as, by treating at least one trialkylaluminum compound with a compound containing an oxygen-carbon bond, adding to that precursor an effective amount of an organoaluminum compound which prevents formation of insoluble species, such as, a trialkylaluminum compound where each alkyl group contains two or more carbon atoms, and converting that modified precursor to an alkylaluminoxane, such as, by thermolysis. In a distinct embodiment of the invention, if an insoluble methylaluminoxane product is formed using the non-hydrolytic technique, it can be solubilized by treatment with a solubilizing amount of an alkylaluminoxane, prepared by either hydrolytic or non-hydrolytic means, wherein the alkyl moieties contain two or more carbon atoms. These aluminoxane products show high solubility in aliphatic hydrocarbons and improved thermal stability in aromatic hydrocarbons.

Hydrocarbon soluble alkylaluminoxane compositions formed by use of

A process is disclosed for forming an aluminoxane composition comprising methylaluminoxane by mixing trimethylaluminum, or a mixture of trimethylaluminum and one or more other trihydrocarbylaluminum compounds, with an organoaluminum compound containing a trialkylsiloxide moiety and then oxygenating the mixture to form the aluminoxane. Oxygenation can be carried out by controlled hydrolysis or by treatment with an organic compound containing carbon-oxygen bonds, such as carbon dioxide. A preferred trialkylsiloxide moiety is of the formula --OSi(CH.sub.3).sub.3, such as in a compound of the formula (CH.sub.3).sub.2 AlOSi(CH.sub.3).sub.3.

Modified polyalkylauminoxane composition formed using reagent containing

The present invention relates to a process for forming a composition comprising oligomeric alkylaluminoxane, e.g., preferably methylaluminoxane, and moieties having the structure--OC(R).sub.3, where R is, for example, methyl, which comprises initially treating a composition comprising trialkylaluminum with a reagent containing a carbon-oxygen double bond, such as, carbon dioxide, followed by hydrolysis of the resulting composition with water. Another embodiment of the invention a composition comprising oligomeric methylaluminoxane and greater than 10 mole % of moieties of the structure --OC(R).sub.3, where R is methyl, which, when such composition is hydrolyzed, there is an evolution of hydrolysis products of methane and at least one C.sub.2 or higher alkane, such as t-butane.

Modified polyalkylaluminoxane composition formed using reagent

Polymethylaluminoxane compositions having increased solution stability in organic solvent and, in some cases, increased polymerization activity, which comprise moieties derived from an organic compound containing an electron-rich heteroatom (e.g., from Group V and/or Group VI of the Periodic Table) and a hydrocarbyl moiety. These compositions can be formed by reaction of trimethylaluminum, the organic compound, and water. They can also be formed by reaction of pre-formed polymethylaluminoxane the organic compound, which can be a hydrocarbyl group-containing compound containing an electron-rich heteroatom (e.g., oxygen, nitrogen, or sulfur), either with or without an active hydrogen atom connected to the heteroatom. The organic compound, in some embodiments, has also been found to be effective in increasing the catalytic activity of modified polymethylaluminoxane which, in addition to methyl, contain C.sub.2 and higher alkyl groups for enhanced solution stability.

Polymethylaluminoxane of enhanced solution stability

The efficient production of alkylaluminoxane by the reaction of water, e.g., in the form of atomized water, and trialkylaluminum, e.g., trimethylaluminum, in an organic solvent medium can be achieved using a preformed alkylaluminoxane as a reaction moderator in the reaction mixture.

Method of making alkylaluminoxane

A catalyst system for the polymerization of olefins is disclosed which comprises a metallocene component, for example, organometallic coordination compounds of a Group IVB or Group VB hydrolysis products comprising methane and C.sub.2 or higher alkanes, such as isobutane, n-butane or n-hexane.

Catalyst system for polymerization of olefins

A catalyst component, adapted for use in the polymerization and copolymerization of ethylene, is formed by reaction of an organomagnesium compound and a tetraaalkyl silicate, contact of the resulting product with a chlorinating reagent, and treatment of the product from the previous step with liquid titanium halide.

Catalyst component for ethylene polyermization and copolymerization

Copper alkoxy alkoxides of the formula CuOR or Cu(OR).sub.2, where R is derived from an alkoxy alkanol of from 3 to 8 carbon atoms, are superconducting ceramic precursors. They can be formed by reacting an alkoxy alkanol with a copper alkoxide. Compositions containing theser alkoxides solubilized in an organic solvent, such as toluene, can be prepared by the additional use of a barium alkoxide solubilization agent.

Hydrocarbon soluble copper alkoxide compositions

Methylaluminoxane can be formed by the reaction of a tetraalkyldialuminoxane containing C.sub.2 or higher alkyl groups with trimethylaluminum with the trimethylaluminum being present in an amount which is not present in stoichiometric excess. Another embodiment of the present invention involves the synthesis of the methylaluminoxane by reaction of a trialkylaluminum compound or a tetraalkyldialuminoxane containing C.sub.2 or higher alkyl groups with water to form a polyalkylaluminoxane with is then reacted with trimethylaluminum. A third embodiment of the present invention involves the synthesis of the methylaluminoxane by reaction of the aforementioned polyalkylaluminoxane with trimethylaluminum and then with water.

Modified methylaluminoxane

Aluminoxanes can be produced by contacting an organic solvent containing a trialkylaluminum compound with an atomized spray of water. If desired, a pore-formed aluminoxane can be present as a reaction moderator.

Preparation of aluminoxanes

Methylaluminoxane can be formed by the reaction of a tetraalkyldialuminoxane containing C.sub.2 or higher alkyl groups with trimethylaluminum with the trimethylaluminum being present in an amount which is not present in stoichiometric excess. Another embodiment of the present invention involves the synthesis of the methylaluminoxane by reaction of a trialkylaluminum compound or a tetraalkyldialuminoxane containing C.sub.2 or higher alkyl groups with water to form a polyalkylaluminoxane which is then reacted with trimethylaluminum. A third embodiment of the present invention involves the synthesis of the methylaluminoxane by reaction of the aforementioned polyalkylaluminoxane with trimethylaluminum and then with water.

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LaPorte, TX, United States of America

Dennis B Malpass