Patent GB-851668-A (GB)
Title: Improvements in or relating to the production of polyurethanes
IPC: C08G18/62
Filed: 1959-04-01
Abstract: A process for the preparation of a polyurethane resin comprises reacting an organic polyisocyanate or polyisothiocyanate with a resinous polyol which is a copolymer of an ethylenically unsaturated monohydric alcohol and an alkenylsubstituted aromatic compound and/or a polyhydroxy-containing derivative of the copolymer.  Alcohols mentioned are allyl, chlorallyl, methallyl and beta-phenallyl alcohols.  Suitable alkenyl-substituted aromatic compounds are styrene, or p-chlorostyrene, a -methylstyrene, p-methoxystyrene, p-butylstyrene, p-octylstyrene, vinyl toluene, 2, 5-dibutylstyrene, b -vinyl-naphthalene and 2, 4-dichlorostyrene.  The copolymers are preferably prepared by heating the monomers at 100 DEG  to 250 DEG C. in the presence of a peroxide having a decomposition temperature of above 90 DEG C., the alkenyl-substituted aromatic compound being added in small increments.  Suitable catalysts are hydrogen peroxide, di-tertiary butyl peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, paramenthane hydroperoxide and tertiaryl butyl perbenzoate.  The polyhydroxy derivatives can be those obtained by reacting the copolymers with for example, ethylene or propylene oxides, suitably in the presence of a boron trifluoride complex or by reacting all but two of the other OH groups of the copolymer with acids, anhydrides, alkylene oxides and other alcohols.  The polyhydroxy esters of a large excess of the copolymers with phthalic, terephthalic, isophthalic, adipic, succinic, 1, 20-eicosanedioic, 1, 14-tetradecanedioic, cyclohexanedicarboxylic, tetrachlorophthalic and maleic acids are suitable.  A number of polyisocyanates and polyisothiocyanates and their partial reaction products with polyhydric alcohols are listed.  Monoisocyanates may be added with the polyisocyanates. Reaction with the polyisocyanates can be effected in the presence of catalysts such as triethylamine, benzyldimethylamine, tributylamine and methyldiethanolamine and of diluents such as benzene, toluene, cyclohexane, hexane, heptane, methyl isobutyl ketone or diamyl ketone.  In preparing formed materials a prepolymer may first be formed or all the reactants including a minor amount of water, catalyst and surface-active agent are mixed together.  In examples (1) an allyl alcohol-styrene copolymer is dissolved in toluene and toluene disocyanate is added to give an air-drying coating composition; (5) a similar coating is prepared using a propylene oxide adduct of an allyl alcohol-styrene copolymer.ALSO:A process for the preparation of a polyurethane resin (which may be foamed or cellular) comprises reacting an organic polyisocyanate or polyisothiocyanate with a resinous polyol which is a copolymer of an ethylenically unsaturated monohydric alcohol and an alkenyl-substituted aromatic compound and/or a polyhydroxy-containing derivative of the coploymer.  Alcohols mentioned are allyl, chlorallyl, methallyl and beta-phenallyl alcohols.  Suitable alkenyl-substituted aromatic compounds are styrene, p-chloro-styrene, a -methylstyrene, p-methoxy-styrene, p-butylstyrene, p-octyl-styrene, vinyl toluene, 2, 5-dibutyl-styrene, b -vinylnaphthalene and 2, 4-dichlorostyrene. The polyhydroxy compounds can be those obtained by reacting the copolymers with alkylene oxides or by reacting all but two of the OH groups with acids, anhydrides, alkylene oxides or other alcohols.  The polyesters of a large excess of copolymer with phthalic, terephthalic, isophthalic, adipic, succinic, 1, 20-eicosanedioic, 1, 14-tetradecanedioic, cyclohexane dicarboxylic, tetrachlorophthalic, and maleic acids are suitable. A number of suitable polyisocyanates and poly-isothiocyanates are listed. Monoisocyanates may also be reacted.  Reaction can be effected in the presence of catalysts such as triethylamine, benzyldimethylamine, tributylamine and of diluents such as benzene, toluene, cyclohexane, hexane, heptane, methyl, isobutyl ketone or diamyl ketone.  In preparing foamed materials a prepolymer may first be formed or all the reactants including a minor amount of water, catalyst and surface-active agent are mixed.  In Example (10) one equivalent of an adduct of propylene oxide with a copolymer of styrene and allyl alcohol is reacted with three equivalents of toluene diisocyanate. After cooling, water and an amine catalyst are added and the mixture is heated at 25 DEG C. in a mould to give a cellular product.