W. R. Grace Co.-conn.

Chevron Chemical Company LLC

Chevron Research & Technology Company

The Dow Chemical Company

Michael John Carney

David L Beach

Dean Alexander Denton

Keng-Yu Shih

Edmund M Carnahan

Peter N Nickias

Eduardo J Baralt

David R Neithamer

Lee Spencer

David George Ward

Javier M Mora

Jana B Cole

The present invention is directed to a coordinating catalyst system comprising at least one metallocene or constrained geometry pre-catalyst transition metal compound, (e.g., di-(n-butylcyclopentadienyl)zirconium dichloride), at least one support-activator (e.g., spray dried silica/clay agglomerate), and optionally at least one organometallic compound (e.g., triisobutyl aluminum), in controlled amounts, and methods for preparing the same. The resulting catalyst system exhibits enhanced activity for polymerizing olefins and yields polymer having very good morphology. The support-activator is a layered material having a negative charge on its interlaminar surfaces and is sufficiently Lewis acidic to activate the transition metal compound for olefin polymerization.

Metallocene and constrained geometry catalyst systems employing agglomerated metal oxide/clay support-activator and method of their preparation

In accordance with this invention are methods for making the novel compositions and methods of using the compositions for polymerization of olefins. In its broadest form, the method of producing the supported catalytic composition of the present invention comprises treating an inorganic or inorganic oxide support which has incorporated uniformly therein a Group 3-10 transition metal from the Periodic Table with a metal alkylating reagent wherein the reaction product is then treated with a halogenating reagent. The resultant reaction product can be recovered and is available for use in conjunction with the activating co-catalyst for the polymerization of polyolefins.

Supported catalyst composition for polymerization of olefins

The present invention is directed to a coordinating catalyst system comprising at least one bidentate or tridentate ligand containing pre-catalyst transition metal compound, (e.g., 2,6-bis (2,4,6-trimethylarylamino)pyridyl iron dichloride), at least one support-activator (e.g., spray dried silica/clay agglomerate), and optionally at least one organometallic compound (e.g., triisobutyl aluminum), in controlled amounts, and methods for preparing the same. The resulting catalyst system exhibits enhanced activity for polymerizing olefins and yields polymer having very good morphology.

Coordination catalyst systems employing agglomerated metal oxide/clay support-activator and method of their preparation

Frangible, spray dried agglomerate catalyst supports are provided, e.g. of silica gel, which possess a controlled morphology of microspheroidal shape, rough, scabrous appearance, and interstitial void spaces which penetrate the agglomerate surface and are of substantially uniform size and distribution. The agglomerates also possess a 1-250 micron particle size, 1-1000 m,/gm. surface area, and an Attrition Quality Index (AQI) of at least 10. The agglomerates are derived from a mixture of dry milled inorganic oxide particles, e.g. silica gel, and optionally but preferably wet milled inorganic oxide particles, e.g. silica gel particles, (which preferably contain a colloidal segment of <1 micron particles) slurried in water for spray drying. The high AQI assures that the agglomerates are frangible and that polymerization performance is improved. The controlled morphology is believed to permit the constituent particles of the agglomerates to be more uniformly impregnated or coated with conventional olefin polymerization catalysts.

Frangible, spray dried agglomerated supports, method of making such supports, and olefin polymerization catalysts supported thereon

A method of making frangible, spray dried agglomerate catalyst supports is provided, e.g. of silica gel, which possess a controlled morphology of microspheroidal shape, preferably a rough, scabrous appearance, and interstitial void spaces which penetrate the agglomerate. The agglomerates also possess a 4-250 micron particle size, 1-1000 m,/gm. surface area, and an Attrition Quality Index (AQI) of at least 10. The method comprises dry milling inorganic oxide particles, e.g. silica gel, wet milling the dry milled inorganic oxide particles (to preferably impart a colloidal segment of <1 micron particles), and spray drying the particles. The high AQI assures that the agglomerates are frangible and that polymerization performance is improved. The controlled morphology is believed to permit the constituent particles of the agglomerates to be more uniformly impregnated or coated with conventional olefin polymerization catalysts.

Method of making frangible spray dried agglomerated supports and olefin polymerization catalysts supported thereon

Supported Ziegler-Natta catalyst component adapted for the polymerization of ethylene is provided. More specifically, certain organomagnesium compounds (e.g., dibutylmagnesium) which do not contain an oxygen linkage between the organo moiety and the magnesium are impregnated into a porous inorganic oxide support (e.g., agglomerated silica particles) to form a first reaction product. The first reaction product is halogenated, e.g., with HCl, to convert the organomagnesium derived component to MgCl,thereby forming a second reaction product. The second reaction product is then treated with a transition metal compound (e.g., TiCl,), a particular type of electron donor (e.g., 2,6-dimethyl pyridine) and optionally at least one Group 2 or 13 organo metal compound (e.g., diethylaluminum chloride). The combination of the particular organomagnesium compounds and electron donor impart a low melt flow ratio and enhanced activity to resulting catalyst component.

Donor-modified olefin polymerization catalysts

Supported catalyst containing tethered cation forming activator

According to the present invention, a catalyst is provided which is represented by the formula �RC(YR').sub.2 !.sub.2 CrX, wherein R and R' are individually selected from the group consisting of carbyl and carbylsilyl groups; Y is N, C or P; and X is a halogen, halogen alkyl, Si, alkylsilyl or a carbyl group. Also provided is a process for preparing the catalyst and an oligomerization process employing the catalyst. The process produces linear alpha-olefins with low amounts of polymer, vinylidine and isomerized olefins.

Olefin oligomerization catalyst and process employing and preparing same

Disclosed is a catalyst system for the homopolymerization and copolymerization of alpha-olefins having 2-8 carbon atoms, said catalyst system comprising a cyclopentadienyl Group 6b metal hydrocarbyl compound in which the metal has an oxidation state of +3, said Group 6b metal compound being supported on an inorganic support. The catalyst system my also contain a Group 2 or Group 3 metal alkyl compound.

Cyclopentadienyl group 6b metal alpha-olefin polymerization catalysts

Disclosed is a catalyst system for the homopolymerization of alpha-olefins having 2-8 carbon atoms, said catalyst system comprising a mixed-valent dimeric Group 6b metal compound catalyst precursor wherein one atom of said Group 6b metal is a cyclopentadienyl Group 6b metal hydrocarbyl complex in which the Group 6b metal has an oxidation state +3 and wherein one atom of said Group 6b metal is a cyclopentadienyl alkaryl complex in which the Group 6b metal has an oxidation state +1, said dimeric Group 6b metal compound being supported on an inorganic support. The catalyst system can contain, in addition, a Group 2 or Group 3 metal-alkyl compound.

Disclosed is a catalyst system for the homopolymerization and copolymerization of alpha-olefins having 2-8 carbon atoms, said catalyst system comprising a cyclopentadienyl Group 6b metal hydrocarbyl compound in which the metal has an oxidation state of +3, said Group 6b metal compound being supported on an inorganic support. The catalyst system may also contain a Group 2 or Group 3 metal alkyl compound.

Cyclopentadienyl group 6B metal .alpha.-olefin polymerization catalysts

Disclosed is a catalyst system for the homopolymerization and copolymerization of alpha-olefins having 2-8 carbon atoms, said catalyst system comprising a cyclopentadienyl Group 6b metal compound having at least one oxo, thio, imido or phosphido group bonded directly to the Group 6b metal, and at least one organic radical bonded to the Group 6b metal through a carbon atom, said Group 6b metal compound being supported on an inorganic support. The catalyst system may also contain a Group 2 or Group 3 metal alkyl compound cocatalyst.

Alpha-olefin polymerization catalysts comprising supported

Disclosed is a catalyst system for the homopolymerization and copolymerization of alpha-olefins having 2-8 carbon atoms, said catalyst system comprising a dimeric or tetrameric cyclopentadienyl Group 6b metal compound in which the metal has an oxidation state of +2, said Group 6b metal compound being supported on an inorganic support. The catalyst system may also contain a Group 2 or Group 3 metal alkyl compound cocatalyst.

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Eldersburg, MD, United States of America

Michael John Carney