Albemarle Corporation

Ethyl Corporation

Line-x LLC

David W Owens

John Y Lee

James E Boone

Robert E Farritor

Wesley D Blank

Ronny W Lin

Steven P Diefenbach

John F Balhoff

Charles R Everly

John M Power

Paul L Wiggins

Niomi L Krzystowczyk

Judit Orgad

Mahmood Sabahi

Bruce C Berris

Rajeev S Mathur

Vernon O Brandt

Judit O Orgad

This invention provides aromatic diimines where the diimines have imino groups with at least two carbon atoms, and either are in the form of one benzene ring having two imino groups on the ring, which imino groups are meta or para relative to each other, and in which each position ortho to an imino group bears a hydrocarbyl group, or are in the form of two benzene rings connected by an alkylene bridge and having one imino group on each ring, and in which each position ortho to an imino group bears a hydrocarbyl group. This invention also provides aromatic secondary diamines where the diamines have amino hydrocarbyl groups with at least two carbon atoms, and either are in the form of one benzene ring having two amino groups on the ring, which amino groups are meta or para relative to each other, and in which each position ortho to an amino group bears a hydrocarbyl group, or are in the form of two benzene rings connected by an alkylene bridge and having one amino group on each ring, and in which each position ortho to an amino group bears a hydrocarbyl group. Also provided are processes for forming diimines and secondary diamines from primary diamines, including the aromatic diimines and aromatic secondary diamines of the invention.

Diimines and secondary diamines

This invention provides chain extender compositions. These compositions comprise

Chain extenders

Chloropentafluorobenzene or bromopentafluorobenzene is formed by heating perhalobenzene, C F X where n is 0 to 4, and each X is, independently, a chlorine or bromine atom, with alkali metal fluoride, and an aminophosphonium catalyst (e.g., (Et N) PBr). The resultant chloropentafluorobenzene or bromopentafluorobenzene can be converted into a pentafluorophenyl Grignard reagent or a pentafluorophenyl alkali metal compound. This in turn can be converted into tris(pentafluorophenylborane), which can be converted into a single coordination complex comprising a labile tetra(pentafluorophenyl)boron anion (e.g., a trialkylammonium tetra(pentafluorophenyl)boron complex or an N,N-dimethylanilinium tetra(pentafluorophenyl)boron complex). The complex can be used in the preparation of an active catalyst by mixing the complex with a cyclopentadienyl metal compound containing a Group 4 metal in suitable solvent or diluent so that the cation of the complex reacts irreversibly with a ligand of the cyclopentadienyl compound, and such that the pentafluorophenyl anion forms a non-coordinating ion pair with a resulting cation produced from the cyclopentadienyl metal compound. Alternatively, the tris(pentafluorophenylborane) can be contacted with a metallocene of the formula LMX wherein L is a derivative of a delocalized pi-bonded group imparting a constrained geometry to the metal active site and where L contains up to 50 non-hydrogen atoms, M is a Group 4 metal, and each X is, independently, hydride, or a hydrocarbyl, silyl, or germyl group having up to 20 carbon, silicon, or germanium atoms to form a catalyst having a limiting charge separated structure of the formula LMX&oplus; XA&ominus; wherein A is an anion formed from the tris(pentafluorophenyl)borane.

Halogen exchange reactions in preparing catalysts and their precursors

Fluoroaryl Grignard reagents are produced from a hydrocarbyl Grignard reagent and fluoroaromatic compounds via separate additions of different fluoroaromatic compounds, such that the conversion of hydrocarbyl Grignard reagent to the desired fluoroaryl Grignard reagent is essentially complete, and thus the reaction product is free or essentially free of agents that may negatively affect subsequent reactions. The fluoroaryl Grignard reagents may be further reacted with boron trihalides in order to obtain tris(fluoroaryl)boranes or tetrakis(fluoroaryl)borates.

Clean generation of a fluoroaryl grignard reagent

Chloropentafluorobenzene or bromopentafluorobenzene is formed by heating perhalobenzene, C,F,X,where n is 0 to 4, and each X is, independently, a chlorine or bromine atom, with alkali metal fluoride, and an aminophosphonium catalyst (e.g., (Et,N),PBr). The resultant chloropentafluorobenzene or bromopentafluorobenzene can be converted into a pentafluorophenyl Grignard reagent or a pentafluorophenyl alkali metal compound. This in turn can be converted into tris(pentafluorophenylborane), which can be converted into a single coordination complex comprising a labile tetra(pentafluorophenyl)boron anion (e.g., a trialkylammonium tetra(pentafluorophenyl) boron complex or an N,N-dimethylanilinium tetra(pentafluorophenyl)boron complex). The complex can be used in the preparation of an active catalyst by mixing the complex with a cyclopentadienyl metal compound containing a Group 4 metal in suitable solvent or diluent so that the cation of the complex reacts irreversibly with a ligand of the cyclopentadienyl compound, and such that the pentafluorophenyl anion forms a non-coordinating ion pair with a resulting cation produced from the cyclopentadienyl metal compound. Alternatively, the tris(pentafluorophenylborane) can be contacted with a metallocene of the formula LMX,wherein L is a derivative of a delocalized pi-bonded group imparting a constrained geometry to the metal active site and where L contains up to 50 non-hydrogen atoms, M is a Group 4 metal, and each X is, independently, hydride, or a hydrocarbyl, silyl, or germyl group having up to 20 carbon, silicon, or germanium atoms to form a catalyst having a limiting charge separated structure of the formula LMX,XA,wherein A is an anion formed from the tris(pentafluorophenyl)borane.

Perfluoroaryl Grignard reagents are produced from a hydrocarbyl Grignard reagent and polyhaloaromatic compounds via separate additions of different polyhaloaromatic compounds, such that the conversion of hydrocarbyl Grignard reagent to the desired perfluoroaryl Grignard reagent is essentially complete, and thus the reaction product is free or essentially free of agents that may negatively affect subsequent reactions. The perfluoroaryl Grignard reagents may be further reacted with boron trihalides in order to obtain tris(perfluoroaryl)boranes or tetrakis(perfluoroaryl)borates.

Clean generation of a perfluoroaryl grignard reagent

Lithiated haloarenes, although useful as intermediates in the synthesis of various end products, can be hazardous to prepare since unstable, shock sensitive compounds can be formed during lithiation of haloarenes. To avoid this problem, a reaction of a polyhaloarene with a hydrocarbyl lithium compound is conducted in the presence of another reactant so that the lithiated haloarene, if formed at all, exists as a transitory intermediate in low concentration. In this way, transitory lithiated haloarene which may be, and presumably is, formed in the reaction is converted into a non-hazardous functionally-substituted haloarene essentially as soon as such lithiated haloarene is formed. Thus, an arene having a halogen atom of atomic number greater than 9 substituted on at least two non-adjacent carbon atoms is concurrently reacted with a non-fluoro halotrihydrocarbylsilane and a hydrocarbyl lithium compound, in proportions such that a haloarene having at least one trihydrocarbylsilyl ring substituent is formed.

Production of silated haloarenes by selective silylation of

An apparatus and process for maintaining the purity of solid/granular product and dispensing high purity granular product from a vessel. A noncontaminating surface is provided by a cup, cylinder, or other structure having a surface of silicon, silicon carbide, silicon nitride, sialon, or similar materials and preferably operates as an angle of repose valve in a pressurized system to prevent contamination by undue contact of the high purity product with conventional gastight valves such as ball valves, butterfly valves, pinch valves, etc.

Angle of repose valve

Production of silicon

An apparatus for maintaining the purity of solid/granular product and dispensing high purity granular product from a vessel. A noncontaminating surface is provided by a cup, cylinder, or other structure having a surface of silicon, silicon carbide, silicon nitride, sialon, or similar materials and preferably operates as an angle of repose valve in a pressurized system to prevent contamination by undue contact of the high purity product with conventional gastight valves such as ball valves, butterfly valves, pinch valves, etc.

Growing community of inventors

Baton Rouge, LA, United States of America

David W Owens