Patent GB-933482-A (GB)
Title: Reaction products of ketones with covalent inorganic isocyanates
Inventor: FIELDING HAROLD CROSBIE
IPC: C08G18/30
Filed: 1960-04-29
Abstract: The invention comprises the products of reaction between phosphorus triisocyanate, phosphoryl triisocyanate or silicon tetraisocyanate and ketones having one or more hydrogen atoms attached directly to one or both of the carbon atoms next to the carbonyl group. Specified ketones are acetone, methyl ethyl ketone and acetophenone. When the ketone used contains a hydrogen atom or atoms attached to only one of the carbon atoms next to the carbonyl group the products are not polymeric and may contain one or more free isocyanate groups which are able to take part with further reactions, e.g. with alcohols to give urethanes or with amines to give substituted ureas. When the ketone contains a hydrogen atom or atoms attached to both of the carbon atoms next to the carbonyl group polymeric compounds can be formed, thus acetone and P(NCO)3 or P(O)(NCO)3 can yield products containing the probable structures <FORM:0933482/IV(a)/1> or <F\2> and these can be obtained in the form of hard resins which adhere strongly to glass and may be used for bonding glass fibres.  The reaction between the isocyanates and ketones is suitably effected by refluxing the reactants under atmospheric pressure in the absence of moisture and if the ketone is normally a solid an inert organic solvent, e.g. benzene or toluene, may be used.  In examples: (1) phosphorus triisocyanate is reacted with acetone to yield a solid product which on melting forms a hard brittle resin which adheres strongly to glass fibres; (2) silicon tetraisocyanate is reacted with acetophenone to yield a pale yellow insoluble and infusible powder and a brown resinous product.ALSO:The invention comprises the products of reaction between phosphorus triisocyanate, phosphoryl triisocyanate or silicon tetraisocyanate and ketones that have one or more hydrogen atoms attached directly to one or both of the carbon atoms next to the carbonyl group.  Specified ketones are acetone, methye ethyl ketone and acetophenone.  When the ketone used contains a hydrogen atom or atoms attached to only one of the carbon atoms next to the carbonyl group the products are not polymeric and may contain one or more free isocyanate groups which are able to take part in further reactions, thus acetophenone and phosphorus triisocyanate give products which may have the structure (C6H5COCH2CONH)3P or (C6H5COCH2CONH)nP(NCO)3-n wherein n is 1 or 2 and the latter may take part in further reactions e.g. with alcohols to give urethanes or with amines to give substituted ureas.  When the ketone is one, e.g. acetone, which contains a hydrogen atom or atoms attached to both of the carbon atoms next to the carbonyl group polymeric compounds can be formed (see Group IV(a)).  The reaction between the isocyanates and ketones is conveniently effected by refluxing the reactants under atmospheric pressure in the absence of moisture and if the ketone is normally solid an inert organic solvent, e.g. benzene or toluene may be used.  Examples are given for the reaction of phosphorus triisocyanate with (1) acetophenone to yield a product which may be further reacted with ethanol or butylamine, or with water, carbon dioxide, and nitrogen being evolved in the latter case, and (2) with acetone to yield a solid product which on melting formed a hard brittle resin.