Exxon Chemical Patents, Inc.

Exxonmobil Chemical Patents Inc.

Other

Gregory G Hlatky

Howard W Turner

Jo Ann Marie Canich

Jo Ann Canich

Richard R Eckman

Donna Jean Crowther

Richard Allen Fisher

Moses Olukayode Jejelowo

Avinash Chandrakant Gadkari

Henry W Yang

Gary F Licciardi

This invention relates to a catalyst system for the production of polyolefins comprising: (A) a Group IV B transition metal component represented by one of the two general formulae  wherein (CHR) is a cylopentadienyl ring (JR') is a heteroatom ligand in which J is an element with a coordination number of three from Group V-A or an element with a coordination number of two rom Group VI-A of the Periodic Table of Elements, each Q is independently, hydride, C&#x2014;Chydrocarbyl radicals, substituted hydrocarbyl radials wherein one or more hydrogen atoms is replaced by an electron withdrawing group, or C&#x2014;Chydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the group consisting of germanium and silicon, provided that Q is not a substituted or unsubstituted cyclopentadienyl ring, or both Q together may be an alkylidene, olefin, acetylene or a cyclometallated hydrocarbyl; 'y' is 0 or 1; when 'y' is 1, T is a covalent bridging group containing a Group IV-A or V-A element; L is a neutral Lewis base; and &#x201c;w&#x201d; is a number from 0 to 3; (B) an activator compound comprising (1) a cation; and (2) a compatible noncoordinating anion.

Aluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerization

Described are certain tetramethylcyclopentadienyl titanium compounds, catalyst systems comprising such compounds and an activator, and to a process using such catalyst systems for the production of polyolefins, particularly ethylene-&agr;-olefin copolymers having a high molecular weight and high level of &agr;-olefin incorporation.

Tetramethylcyclopentadienyl titanium compounds for ethylene-&agr;-olefin-copolymer production catalysts

A catalyst system comprising a Group 4 transition metal cation having bonded thereto (1) a single cyclopentadienyl ligand or polycyclic derivative thereof, (2) a Group 15 or 16 heteroatom ligand, said single cyclopentadienyl ligand or polycyclic derivative and said heteroatom ligand being covalently bound and bridged to each other, and (3) at least one other ligand selected from the group consisting of hydride, hydrocarbyl, substituted hydrocarbyl, and hydrocarbyl substituted organonometalloid radicals; (b) a compatible non-coordinating anion; (c) a Group 13 element, hydrolyzable Lewis acid compound. The catalyst system is useful for polymerizing olefins, diolefins, cyclic olefins or acetylenically unsaturated monomers, either alone or in combination with each other or with other polymerizable monomers.

Catalyst system of enhanced productivity and its use in polymerization process

An ionic polymerization catalyst system component comprising a stable and bulky anion containing a plurality of boron atoms, such as those selected from the group consisting of polynuclear boranes, carboranes, and metallacarboranes useful for polymerizing olefins, diolefins, or acetylenically unsaturated monomers, either alone or in combination with each other or with other polymerizable monomers is disclosed. A method of using the anion to stabilize ionic catalyst systems during polymerization is also disclosed.

Ionic metallocene catalyst compositions

The invention is generally directed toward a catalyst system useful for polymerizing olefins. The catalyst system of this invention comprises a supported ion-exchange catalyst system.

Polymerization catalyst systems, their production and use

Described are certain mono(cyclopentadienyl) Group IV B metal compounds, catalyst systems comprising such mono(cyclopentadienyl) metal compounds and an activator, and to a process using such catalyst systems for the production of polyolefins, particularly ethylene-.alpha.-olefin copolymers having a high molecular weight and high level of .alpha.-olefin incorporation.

Monocyclopentadienyl metal compounds for

This invention relates to non-Group 4 transition metal compositions useful as olefin polymerization catalysts, wherein the transition metal is in a high oxidation state. The invention further relates to design of new ligand systems and methods of preparing and using the same. Compositions useful as catalyst precursors are neutral transition metal complexes comprising the unique ligand systems of the invention. The inventive compositions may be activated to a catalytic state by ion-exchange reagents or by Lewis acids.

Transition metal olefin polymerization catalysts

This invention relates to processes using non-Group 4 transition metal compositions useful as olefin polymerization catalysts, wherein the transition metal is in a high oxidation state. The invention further relates to design of new ligand systems and methods of preparing and using the same. Compositions useful as catalyst precursors are neutral transition metal complexes comprising the unique ligand systems of the invention. The inventive compositions may be activated to a catalytic state by ion-exchange reagents or by Lewis acids.

Transition metal olefin polymerization processes

A polymerization process for olefins, diolefins and/or acetylenically unsaturated monomers is described. The monomers are contacted with an ionic catalyst which comprises a cyclopentadienyl derivative of Group IV-B metals as cation and a compatible non-coordinating anion containing a plurality of boron atoms. Borate, carborate, borane, carborane, metallaborane and metallacarborane compounds exemplify anion sources and dihydrocarbyl-substituted bis(cyclopentadienyl) zirconium compounds exemplify the Group IV-B metal cation sources.

Catalysts, method of preparing these catalysts, and polymerization

A method is disclosed for polymerizing olefins, diolefins, or acetylenically unsaturated monomers containing two or more carbon atoms, either alone or in combination with each other or with other polymerizable monomers, comprising contacting the monomers with an ionic polymerization catalyst comprising (1) a cation derived from a bis(cyclopentadienyl) Group IV-B metal compound by abstracting a ligand to create a positively charged species and (2) a stabilizing non-coordinating anion, said anion being sufficiently labile to permit displacement by the olefin, diolefin and/or acetylenically unsaturated monomer during polymerization. The process provides means of producing narrow molecular weight polyolefin polymers, increasing comonomer incorporation in copolymers and avoiding metal impurities in the polymer products.

An ionic catalyst useful for the polymerization of olefins, diolefins and/or acetylenically unsaturated monomers is described. The catalyst comprises cyclopentadienyl derivatives of Group IV-B metals as cation and a compatible non-coordinating anion containing a plurality of boron atoms. Borate, carborate, borane, carborane, metallaborane and metallacarborane compounds exemplify anion sources and dihydrocarbyl-substituted bis(cyclopentadienyl) zirconium compounds exemplify the Group IV-B metal cation sources. Utility is illustrated for olefin polymerization.

A process for the production of block copolymers of ethylene and an .alpha.-olefin such as propylene by using an ionic catalyst system including a metallocene component and a component having a cation capable of donating a proton and a compatible non-coordinating anion. Novel block copolymers are produced.

Block copolymers from ionic catalysts

Ionic catalyst compositions can be prepared by combining two components. The first component is a bis(cyclopentadienyl) Group IV-B metal complex containing at least one ligand which will combine irreversibly with the second component or at least a portion thereof such as a cation portion thereof. The second component comprises a cation which will irrevesibly react with at least one ligand on the Group IV-B metal complex and a non-coordinating anion. The combination of the two components produces an ionic catalyst composition comprising a cationic bis(cyclopentadienyl) Group IV-B metal complex which has a formal coordination number of 3 and a 4+ valence charge and the aforementioned non-coordinating anion. The anion is (i) labile and can be displaced by an olefin, diolefin or acetylenically unsaturated monomer; (ii) has a molecular diameter about or greater than 4 angstroms; (iii) forms stable salts with reducible Lewis acids and protonated Lewis bases; (iv) has a negative charge delocalized over the framework on the anion or within the core thereof; (v) is not a reducing or oxidizing agent; and (vi) is a relatively poor nucleophile. These ionic catalyst compositions can be used to polymerize .alpha.-olefins, diolefins and/or acetylenically unsaturated monomers, either alone or in combination, to polymers and copolymers.

This invention relates to a process of reducing polyketones to polyalcohols using borohydride salts where the reducing agent is suspended in water.

Reduction of .alpha.-olefin-carbon monoxide copolymers to polyalcohols

The present invention relates to catalysts, to a method for preparing such catalysts, to a method of using such catalysts and to polymeric products produced with such catalysts. The catalysts are particularly useful in the polymerization of - olefins, diolefins and acetylenically unsaturated monomers. The improved catalysts are prepared by combining at least one first compound which is a bis(cyclopentadienyl) derivative of a metal of Group IV-B of the Periodic Table of the Elements capable of forming a cation formally having a coordination number of 3 and a valence of +4 and at least one second compound comprising a cation capable of donating a proton and a compatible noncoordinating anion comprising a plurality of boron atoms, which anion is both bulky and labile, and capable of stabilizing the Group IV-B metal cation without interfering with said Group IV-B metal cation's or its decomposition product's ability to polymerize .alpha.-olefin, diolefins and/or acetylically unsaturated monomers.

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Houston, TX, United States of America

Gregory G Hlatky