Phillips Petroleum Company

Melvin B Welch

Max P McDaniel

Richard E Dietz

Charles E Capshew

Elizabeth Ann Benham

John D Hottovy

Lawrence M Fodor

Kent E Mitchell

Alonzo G Kitchen

Raymond G Rohlfing

Charles W Moberly

Grover W Cone

Max P Mcdaniel

Olefins such as ethylene can be polymerized in high productivities using a catalyst system wherein one catalyst component comprises a precipitated complex of zirconium tetrahydrocarbyloxide and/or titanium tetrahydrocarbyloxide and dihydrocarbylmagnesium. The productivity of the preferred catalyst containing both zirconium and titanium has been found to be substantially higher than the productivity of those catalysts obtained from either only Zr(OR').sub.4 or only Ti(OR').sub.4 and second catalyst component comprises at least one organometallic compound of a metal selected from the Groups I-III of the Mendeleev Periodic Table.

Zirconium-titanium catalyzed olefin polymerization

A high surface area catalyst component or support is produced by swelling a magnesium halide, e.g., MgCl.sub.2, with a secondary or tertiary alcohol, adding a hydrocarbon diluent, and removing some or substantially all of the free or unreacted alcohol. In one preferred embodiment, the alcoholate product is contacted with a halogenated tetravalent titanium compound, e.g., TiCl.sub.4, to form a first catalyst component (A) which can be combined with a cocatalyst component (B) comprising a metallic hydride or an organometallic compound, e.g., an organoaluminum compound to form a catalyst system active for olefin polymerization.

Catalyst and process

A transition metal compound and a metal halide compound are chemically combined to form a composition of matter. The composition of matter is mixed with a precipitating agent to form an active olefin polymerization catalyst. The catalyst can be further treated with a halide ion exchanging source to form an active olefin polymerization catalyst. Prepolymer is deposited on the catalyst(s) in an amount effective to reduce polymer fines when the catalyst(s) are used in polymerization processes.

Catalyst, method of producing the catalyst, and polymerization process

Alpha-olefins are polymerized employing a catalyst which forms on mixing a catalyst component A formed by milling together a magnesium halide or manganous halide with selected catalyst adjuvants comprising aryl carbonic acid esters followed by treatment of the resulting milled product with a halogenated tetravalent titanium compound and combining the product thus formed with a cocatalyst component B comprising at least one of an organoaluminum compound and an organoaluminum monohalide with or without an aromatic ester as a part of the cocatalyst system.

Polymerization catalyst and process

Active polymerization catalyst is deactivated using a high molecular weight epoxide.

Polymerization process using high molecular weight epoxides

An active olefin polymerization catalyst is produced by halogenating magnesium oxide, contacting the halogenated magnesium oxide product with an alcohol, and treating the product thus produced with a titanium tetrahalide to obtain the catalyst. The catalyst can be combined with a cocatalyst component comprising a metallic hydride or an organometallic compound, e.g., an organoaluminum compound, in the polymerization process.

A method for producing activated catalysts in which a catalyst containing chromium on a silica-containing support is (1) contacted with a gaseous environment consisting essentially of sulfur dioxide and oxygen at a temperature in a range of about 450.degree. C. to about 1100.degree. C. for a time ranging from about one to about five hours and (2) subsequently maintaining a temperature within the contact temperature range while contacting the catalyst with a gaseous environment consisting essentially of oxygen and gases inert to reaction with the catalyst. In another embodiment of the invention the temperature for a succeeding step is not raised above that attained in the previous step. In an embodiment of the invention the catalyst is contacted with a gaseous environment consisting essentially of oxygen and gases inert to reaction with the catalyst while the temperature is being increased prior to contact with sulfur dioxide.

SC.sub.2 activation of supported chromium oxide catalysts

A silica-containing composition suitable for supporting chromium to produce a catalyst capable of giving high melt flow olefin polymers for such applications as injection molding and the like requiring a narrow molecular weight distribution, is produced by treating a silica-containing material at an elevated temperature with either (1), CO, (2) a bromine or iodine component, or (3) an oxygen-containing sulfur component, more specifically a carbon, oxygen and sulfur-containing component. Thereafter, anhydrous chromium can be added, for instance, by means of a hydrocarbon solution of a soluble chromium compound, and the resulting composition activated in air to produce a catalyst. The bromine or iodine treated silica contains bound bromine or iodine if the treating agent is HBr, HI, an organic halide of Br or I or elemental Br or I used in conjunction with a reducing agent. This material is a novel composition of matter and is suitable for use as a reinforcing agent in rubber or plastics and as a support for a chromatographic column in addition to be suitable for supporting a chromium compound to produce a catalyst.

Treatment of silica

A method for producing activated catalysts in which a catalyst containing chromium on a silica-containing support is (1) contacted with a gaseous environment consisting essentially of sulfur dioxde and oxygen at a temperature in a range of about 450.degree. C. to about 1100.degree. C. for a time ranging from about one to about five hours and (2) subsequently maintaining a temperature within the contact temperature range while contacting the catalyst with a gaseous environment consisting essentially of oxygen and gases inert to reaction with the catalyst. In another embodiment of the invention the temperature for a succeeding step is not raised above that attained in the previous step. In an embodiment of the invention the catalyst is contacted with a gaseous environment consisting essentially of oxygen and gases inert to reaction with the catalyst while the temperature is being increased prior to contact with sulfur dioxide.

SO.sub.2 Activation of supported chromium oxide catalysts

Polymerization of olefins in the presence of a catalyst system comprising a titanium-containing composition associated with silica and a cocatalyst comprising a metal hydride or organic metal compound derived from an element of Groups I-III of the Periodic Table.

Olefin polymerization

High melt flow olefin polymers suitable for such applications as injection molding, and the like requiring a narrow molecular weight distribution are produced using a catalyst made by treating a chromium catalyst on a silica-containing base with a sulfur-containing material, and thereafter reoxidizing.

Sulfiding and reoxidation of chromium catalyst

A silica-containing composition suitable for supporting chromium to produce a catalyst capable of giving high melt flow olefin polymers for such applications as injection molding and the like requiring a narrow molecular weight distribution, is produced by treating a silica-containing material at an elevated temperature with either (1) CO, (2) a bromine or iodine component, or (3) an oxygen-containing sulfur component, more specifically a carbon, oxygen and sulfur-containing component. Thereafter, anhydrous chromium can be added, for instance, by means of a hydrocarbon solution of a soluble chromium compound, and the resulting composition activated in air to produce a catalyst. The bromine or iodine treated silica contains bound bromine or iodine if the treating agent is HBr, HI, an organic halide of Br or I or elemental Br or I used in conjunction with a reducing agent. This material is a novel composition of matter and is suitable for use as a reinforcing agent in rubber or plastics and as a support for a chromatographic column in addition to being suitable for supporting a chromium compound to produce a catalyst.

A method for activating supported chromium oxide catalysts in which a dry catalyst of inorganic or organic chromium compound dispersed on a silica-containing substrate (1) is contacted with a normally liquid organic aliphatic hydroxy compound, preferably at or above the boiling point of the hydroxy compound and (2) is reduced in a carbon monoxide containing environment and the reduced composition is reoxidized in an oxygen-containing environment to produce an activated catalyst. Steps (1) and (2) may take place in the opposite order, but both are necessary. A method for producing polymers of ethylene in which ethylene monomer, and suitable comonomer when used, are contacted at polymerization conditions in the presence of a catalyst activated by the method described above.

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Bartlesville, OK, United States of America

Melvin B Welch