Patent GB-871629-A (GB)
Title: A process for the production of mono-polyurethane addition products of semi-acetals and semi-mercaptals
IPC: C08G18/30
Filed: 1959-04-22
Abstract: Mono- or polyurethanes are prepared by the reaction of mono- or polyisocyanates with semiacetals or semi-mercaptals of general formula:  <FORM:0871629/IV (a)/1> (in which A represents the residue of a mono- or poly-hydric p  alcohol or mercaptan, not containing free -OH or -SH groups respectively, X an oxygen or sulphur atom, R a hydrogen atom or an aliphatic, cycloaliphatic, aromatic or heterocyclic radical, Y a hydrogen atom or -OH group, and n an integer).  The semi-acetals and mercaptals are prepared from alcohols; such as methanol, butanol, isopropyl alcohol, decanol, ethylene and 1, 2-propylene glycol, 1,4-butanediol, 1, 6-hexanediol, thio-diglycol, N-methyl diethanolamine, N, N-diethylaminoethanol, dimethyl ethanolamine, glycerine, pentaerythritol, cyclohexanol and benzyl alcohol, etherification products of hexamethylol melamine with excess polyhydroxy alcohols, cyclic acetals containing hydroxyl groups, N-methylol compounds etherified with polyhydroxy compounds, phenol alcohols, dihydroxyethyl aniline or xylidine, hydroxyethylated xylenol or rescorcinol and reaction products of cyanuric acid chloride with diethanolamine and polyesters, polyethers, polythioethers and polycarbonates; and aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde, benzaldehyde and furfural by mixing at below 30 DEG C. preferably in the absence of solvents and in the case of the preferred formaldehyde at below 20 DEG C., in a proportion of 1 mol per hydroxyl or sulphydryl group, or in excess as paraformaldehyde and high molecular weight products are obtained.  Isocyanates specified are ethyl, cyclohexyl, phenyl, p-methoxyphenyl, p-ethoxyphenyl, toluyl isocyanates and hexamethylene, 1, 4-cyclohexylene, dicyclohexyl 1, 4-, 1-methylbenzene-2, 4-1-methyl-benzene 2, 6-, 1- 4- and 1- 3-phenylene diisocyanates.  The products are crystalline, waxy or liquid compounds which decompose at from 140 DEG -200 DEG C. and are soluble in solvents such as benzene, toluene, acetone, dioxane and tetrahydrofuran.  They are suitable as intermediates in the preparation of plastics and may be used as plasticisers.  Examples describe the reaction of (1) methanol and (2) isopropanol with paraformaldehyde and p-chlorophenyl isocyanate; (3) methanol, ethylene glycol, glycerine, thiodiglycol, 2, 2-dimethyl-1, 3-n-propylene glycol, cyclohexanol, and 1, 4-butanediol with formaldehyde and phenylisocyanate; (4) polyhydroxy methylene glycol semiacetal with phenylisocyanate; (5) methanol and (7) ethylene glycol, paraformaldehyde and a mixture of 1-methylbenzene-2, 4- and -2, 6-diisocyanates; (6) N, N-diethylamino ethanol, paraformaldehyde and 1-methyl benzene-2, 4-diisocyanate; (8) N-dodecyl mercaptan, paraformaldehyde and phenyl isocyanate; (9) methanol, paraformaldehyde and hexamethylene diisocyanate; (10) 2, 21-dimethyl-1, 3-propylene glycol ether of pentamethylol melamine and chloro-N-hexyl isocyanate and (11) methanol, acetaldehyde and p-chlorophenyl isocyanate.ALSO:Mono -or polyurethanes are prepared by the reaction of mono- or polyisocyanates with semi-acetals or semi-mercaptals of general formula:  <FORM:0871629/IV (b)/1> (in which A represents the residue of a monoor poly-hydric alcohol or mercaptan, not containing free -OH or -SH groups respectively, X an oxygen or sulphur atom, R a hydrogen atom or an aliphatic, cycloaliphatic, aromatic or heterocyclic radical, Y a hydrogen atom or -OH group, and n an integer).  The semiacetals and mercaptals are prepared from alcohols; such as methanol, butanol, isopropyl alcohol, decanol, ethylene and 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, thiodiglycol, N-methyl diethanolamine, N,N-diethylaminoethanol, dimethyl ethanolamine, glycerine, pentaerythritol, cyclohexanol and benzyl alcohol, etherification products of hexamethylol melamine with excess polyhydroxy alcohols, cyclic acetals containing hydroxyl groups, N-methylol compounds etherified with polyhydroxy compounds, phenol alcohols, dihydroxyethyl aniline or xylidine, hydroxyethylated xylenol or rescorcinol and reaction products of cyanuric acid chloride with diethanolamine and polyesters, polyethers, polythioethers and polycarbonates; and aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, isobutylaldehyde, benzaldehyde and furfural by mixing at below 30 DEG C. preferably in the absence of solvents and in the case of the preferred formaldehyde at below 20 DEG C., in a proportion of 1 mol per hydroxyl or sulphydryl group, or in excess as paraformaldehyde and high molecular weight products are obtained. Isocyanates specified are ethyl, cyclohexyl, phenyl, p-methoxyphenyl, p-ethoxyphenyl, toluyl isocyanates and hexamethylene, 1,4-cyclohexylene, dicyclohexyl, 1,4-,1-methylbenzene- 2,4-1- methyl-benzene 2,6-, 1-4- and 1-3-phenylene diisocyanates.  The products are crystalline, waxy or liquid compounds which decompose at from 140 to 200 DEG  C. and are soluble in solvents such as benzene, toluene, acetone, dioxane and tetrahydrofuran.  They are suitable as intermediates in the preparation of plastics and may be used as plasticisers.  Examples describe the reaction of (1) methanol and (2) isopropanol with paraformaldehyde and p-chlorophenyl isocyanate (3) methanol, ethylene glycol, glycerine, thiodiglycol, 2,2-dimethyl-1,3-n-propylene glycol, cyclohexanol, and 1,4-butanediol with formaldehyde and phenylisocyanate (4) polyhydroxy methylene glycol semiacetal with phenylisocyanate (5) methanol and (7) ethylene glycol, paraformaldehyde and a mixture of 1-methylbenzene-2,4- and -2,6-diisocyanates (6) N,N-diethylamino ethanol, paraformaldehyde and 1-methyl benzene-2,4-diisocyanate (8) N-dodecyl mercaptan, paraformaldehyde and phenyl isocyanate (9) methanol, paraformaldehyde and hexamethylene diisocyanate (10) 2,21-dimethyl-1,3-propylene glycol ether of pentamethylol melamine and chloro-N-hexyl isocyanate and (11) methanol, acetaldehyde and p-chlorophenyl isocyanate.