GB993704A - Process for the manufacture of urethanes - Google Patents

Abstract

Urethanes are made by reacting an organic compound containing at least one hydroxyl group with carbon monoxide and with a nitrogenous compound containing at least one non-cyclic group in which a nitrogen atom is directly attached to a single carbon atom and through a double bond to an oxygen or another nitrogen. The hydroxy compounds have the formula R(OH)n or P(OH)n where n is 1 or more, preferably 1 to 3, R is an optionally substituted aliphatic, cycloaliphatic, or araliphatic group, P is an aromatic group containing one or more benzenoid rings which may be fused or joined by single valency bonds, directly or through bridging groups such as oxygen or sulphur atoms, sulphoxide, sulphone or carbonyl groups, or alkylene groups in which the chain may be interrupted by oxygen, or sulphur atoms, sulphoxide, sulphone or carbonyl groups. Many suitable hydroxy compounds are specified. Suitable nitrogenous compounds are organic nitro, nitroso, azo and azoxy compounds or mixtures thereof. The process may be effected at super-atmospheric pressure, e.g. 50-500 atm., at temperatures up to 250 DEG C. Suitable catalysts are metal carbonyls such as a carbonyl, hydrogen carbonyl, halogen carbonyl, hydrocarbon carbonyl, hydrocarbon halogen carbonyl, nitrose carbonyl or cyanocarbonyl of an element in Group VIa, VIIa and VIIIa of the Periodic Table such as Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Ds and Ir.ALSO:Polyurethane polymers are made by reacting polynitro, polynitroso or nitro-substituted azo or azoxy compounds with organic polyhydroxy compounds and carbon monoxide. Linear polyurethanes may be made from diols, dinitro compounds and carbon monoxide or from hydroxynitro compounds and carbon monoxide, whilst cross-linked polyurethane polymers may be obtained directly from di- or poly-nitro compounds, diols or polyols and carbon monoxide. The hydroxy compounds may be optionally substituted aliphatic, cycloaliphatic or araliphatic or aromatic compounds containing one or more benzenoid rings which may be fused or joined by single valency bonds, directly or through bridging groups such as oxygen or sulphur atoms, sulphoxide, sulphone or carbonyl groups, or alkylene groups in which the chain may be interrupted by oxygen or sulphur atoms, sulphoxide, sulphone or carbonyl groups. The process may be effected at superatmospheric pressure at temperatures up to 250 DEG C. Suitable catalysts are metal carbonyls of Group VIa, VIIa and VIIIa of the Periodic Table, e.g. of Cr, Mo, W. Mn, Fe, Co, Ni, Ru, Rh, Os and Ir.