Patent GB-909604-A (GB)
Title: Improvements relating to polyurethane plastics
IPC: C08G18/64
Filed: 1960-11-28
Abstract: A process for the preparation of polyurethane plastics comprises reacting an organic polyisocyanate with a polyol prepared by condensing a carbohydrate having at least 4 carbon atoms, an oxo compound and an alcohol and/or a phenol.  The three components for the polyol can be reacted simultaneously or in stages.  Preferably at least 0,5 mol. of oxo compound for each monosaccharide unit of the carbohydrate and 0,2 to 4 OH equivalents of alcohol or phenol per mol. of oxo compound are used.  "Carbohydrate" denotes compounds of the formula Cx(H2O)y, i.e. mono di-, tri and polysaccharides, and also formoses.  Some polysaccharides may require preliminary treatment with acid.  Partial acrylation, or alkylation, acetalization and ketalization products or sugar acids or anhydrides can be used.  Aldehydes, ketones, glyoxal, chloral and chloral hydrate are listed as oxo compounds.  The preferred alcohols are those of boiling point above 100 DEG C., e.g. C4 to C18 mono alcohols including chlorhydrins, cyanohydrin, benzyl alcohol and cyclohexanol. Suitable polyhydric alcohols include butane-, butene- and butyne diols, 7,18-dihydroxy-octadecane, cyclohexylmethane derivatives, castor oil, and alkylene oxide adducts of such alcohols.  The condensation reaction can be catalysed by organic or inorganic acids, Lewis acids, ion exchangers, polystyrene sulphonic acids. Phenols specified are phenol itself, cresols, xylenols, butyl-, nonyl, chloro or nitrophenols, resorcinol or its mono-ether, saligenin, triethylphenol and bis(-hydroxyphenyl) alkanes.  The polyisocyanates listed include those containing phosphate, thiophosphate, alkoxy, aryloxy, NO2, Cl groups, and compounds with masked or polymerized isocyanate groups.  The polyols specified can be mixed, for the production of polyurethanes, with polyesters, polyesteramides, polyalkylene ethers and polythioethers, containing OH, NH2, NH, COOH or SH groups.  Cellular polyurethanes are obtained by including water, a halohydrocarbon, azo compounds or low-boiling alkanes in the reaction mixture.  Emulsifiers can be added and also catalysts such as triethylene diamine, N-methyl, ethyl or coro-morpholine, diethylethanolamine, 1-ethyl-4-dimethylaminoethyl piperazine, 3-methoxy-N-dimethylpropylamine, N-methyl-N1-methyl isopropyl propylene diamine, N,N - diethyl - 3 - diethylaminopropylamine, dimethyl benzylamine, molybdenum glycolate, dialkyl tin salts of carboxylic acids and tin alcoholates.  Non-porous products can be obtained by reacting excess polyol with the polyisocyanate and treating the hydroxyl-containing product with an organic peroxide, sulphur or formaldehyde, or by preparing a product containing free NCO groups and cross-linking with polyalcohols, polyamines or amino-alcohols. Coating compositions containing blocked isocyanates are also prepared.  In typical examples (46) a polyhydroxy compound prepared by reacting saccharose, formalin and diethylene glycol in the presence of p-toluene sulphonate is mixed with a polyester from adipic acid, phthalic anhydride, oleic acid and trimethylol propane. After adding permethylated aminoethylpiperazine and aqueous sodium castor oil sulphonate foaming is effected by stirring in 4,41-diphenylmethane diisocyanate; (47) a similar polyhydroxy compound mixed with polypropylene glycol is converted to a foam by addition of dimethyl benzylamine, oxyalkylated polysiloxane, aqueous sodium castor oil sulphonate and polymerized toluylene diisocyanate. (62) a polyhydroxy compound prepared by heating together cane sugar, formalin and phenol in the presence of HBF4 while distilling off water, is triturated with diphenyl-dimethyl-methane-4,41-diisocyanate and the mixture is heated in a press to give a moulding.ALSO:In examples glucose is reacted in the presence of sulphuric acid with (42) isobutyraldehyde and (43) cyclohexanone, to give isobutyrylidene glucose and bis cyclohexylidene glucose respectively.ALSO:A process for the preparation of polyurethane plastics comprises reacting an organic polyisocyanate with a polyol prepared by condensing a carbohydrate having at least 4 carbon atoms, an oxo compound and an alcohol and/or a phenol.  The three components for the polyol can be reacted simultaneously or in stages.  Preferably at least 0.5 mol of oxo compound for each monosaccharide unit of the carbohydrate and 0.2 to 4 OH equivalents of alcohol or phenol per mol of oxo compound are used. "Carbohydrate" denotes compounds of the formula Cx(H2O)y i.e. mono di-, tri and poly-saccharides, and also formoses.  Some poly-saccharides may require preliminary treatment with acid. Partial acylation, or alkylation, acetalisation and ketalization products or sugar acids or anhydrides can be used.  Aldehydes, ketones, glyoxal, chloral and chloral hydrate are listed as oxo compounds.  The preferred alcohols are those of boiling point above 100 DEG C. e.g. C4 to C18 mono alcohols including chlorhydrins, cyanohydrin, benzyl alcohol and cyclohexanol.  Suitable polyhydric alcohols include butane-butene- and butyne diols, 7, 18-dihydroxyocta-decane, cyclo-hexylmethane derivatives, castor oil, and alkylene oxide adducts of such alcohols.  The condensation reaction can be catalysed by organic or inorganic acids, Lewis acids, ion exchangers, polystyrene sulphonic acids. Phenols specified are phenol itself, cresols, xylenols, butyl-,nonyl, chloro or nitrophenols, resorcinol or its mono-ether, saligenin, triethyl-phenol and bis-(hydroxyphenyl) alkanes.  The poly-isocyanates listed include those containing phosphate, thiophosphate, alkoxy, acryloxy, NO2, Cl groups, and compounds with masked or polymerized isocyanate groups.  The polyols specified can be mixed, for the production of polyurethanes, with polyesters, polyesteramides, polyalkylene ethers and polythioethers, containing OH, NH2, NH, COOH or p  SH groups.  Cellular polyurethanes are obtained by including water, a halohydrocarbon, azo compounds or low-boiling alkanes in the reaction mixture.  Emulsifiers can be added and also catalysts such as triethylene diamine, N-methyl, ethyl or coco-morpholine, diethyl-ethanolamine, 1-ethyl-4-dimethylamino-ethyl piperazine, 3-methoxy-N-dimethyl-propylamine, N-methyl-N1-methyl isopropyl propylene diamine, N, N-diethyl-3-diethyl-aminopropylamine, dimethyl benzylamine, molybdenum glycolate, dialkyl tin salts of carboxylic acids and tin alcoholates.  Non-porous products can be obtained by reacting excess polyol with the polyisocyanate and treating the hydroxyl-containing product with an organic peroxide, sulphur or formaldehyde, or by preparing a product containing free NCO groups and cross-linking with polyalcohols, polyamines or aminoalcohols. Coating compositions containing blocked isocyanates are also prepared.  In typical Examples (46) a polyhydroxy compound prepared by reacting saccharose, formalin and diethylene glycol in the presence of p-toluene sulphonate is mixed with a polyester from adipic acid, phthalic anhydride, oleic acid and trimethylol propane. After adding permethylated aminoethyl piperazine and aqueous sodium caster oil sulphanate foaming is effected by stirring in 4, 41-diphenylmethane diisocyanate; (47).  A similar polyhydroxy compound mixed with polypropylene glycol is converted to a foam by addition of dimethyl benzylamine oxyalkylated polysiloxane, aqueous sodium caster oil sulphonate and polymerized toluylene diisocyanate.