Patent GB-867156-A (GB)
Title: New condensation products and a process for producing them
IPC: C08G18/80
Filed: 1959-06-19
Abstract: A process for the production of condensation products comprises reacting one or more monoisocyanates and/or one or more polyisocyanates with one or more compounds each containing one or more linear and/or cyclic acetal groups in the presence of a Friedel-Crafts catalyst.  The acetal reacts as a bifunctional compound, the use of a monoisocyanate giving a product containing at least two urethane groups, and polyisocyanates giving products containing more urethane groups and possibly free isocyanate groups. The products can be used in combination with polyhydroxy compounds as stoving lacquers and those which contain free isocyanate groups can be used in the manufacture of lacquers, foam materials and coatings. The acetals can be derived from formaldehyde, acetaldehyde, propionaldehyde, butyric aldehyde, b -chloro-acetaldehyde, benzaldehyde and naphthaldehyde.  As hydroxy compounds for reaction with these aldehydes there can be used unsubstituted or substituted saturated or unsaturated monohydric alcohols, phenols, and reaction products of these with alkylene oxides, epichlorhydrin or styrene oxide; polyhydroxy compounds such as polyhydric alcohols or phenols and their reaction products with alkylene oxides, styrene oxide, epichlorhydrin and tetrahydrofuran; OH-terminated polycondensates of alkylene oxides; esters, e.g. glycerine monomethyl methacrylate, polymers and copolymers thereof; castor oil, phthalic acid bis-glycol ester, ricinoleic glycol ester; polyesters, polythioethers, completely or partially saponified polyvinyl acetates; reaction products of amides and alkylene oxides.  a -Alkoxytetrahydrofurans, a -alkoxytetrahydropyrans, and reaction products of alcohols and phenols with polyoxy compounds such as glyoxal, malonic dialdehyde, succindialdehyde and benzene-p-dialdehyde also are suitable. Halogen, ester, amide, nitro, ether, thioether, sulpho, carboxyl, urethane and heterocyclic groups may be present.  Lists are given of specific acetals, mono and polyisocyanates, FriedelCrafts catalysts and hydrocarbon, chlorohydrocarbon, ether, ester and ketone solvents for the reaction mixture.  In typical Examples (1) equimolar amounts of formaldehyde dimethyl acetal and phenyl isocyanate are reacted in the presence of BF3-etherate at temperatures from 60 DEG  to 170 DEG C. with distillation of methylal and methanol.  The product (not containing NCO groups) in glycol monomethyl acetate is mixed with ethyl acetate solution of an adipic acid/phthalic acid/trimethylol propane polyester and a layer is stoved on a metal surface to give a hard film; (4)m- or p-phenylene diisocyanate is used as the isocyanate in similar reactions; (8) a mixture of phenyl isocyanate and m-phenylene diisocyanate is reacted similarly; (16) monophenyl urethanes of mixed 2, 4- and 2, 6-toluylene diisocyanates and the acetal are reacted similarly the product (containing 3,15% isocyanate and 11,95% of isocyanate which can be split out) being mixed with an adipic acid/trimethylol propane/butylene-1, 3-glycol polyester to give a stoving lacquer; (17) an isocyanate from polypropylene glycol and excess toluylene diisocyanates is reacted with the same acetal as before; (18) polyoxymethylene and toluylene diisocyanates are reacted; (19) 4-phenyl-m-dioxane.  Specification 798,209 is referred to.ALSO:A process for the production of condensation products comprises reacting one or more polyisocyanates and/or one or more monoisocyanates with one or more compounds each containing one or more linear and/or cyclic acetal groups in the presence of a Friedel Crafts catalyst.  The use of a monoisocyanate gives a product containing at least two urethane groups and polyisocyanates yield products containing more urethane groups and in some cases free isocyanate groups.  The products can be used in combination with polyhydroxy compounds to form stoving lacquers (see Group IV(a)). The acetals can be derived from aldehyde, acetaldehyde, propionaldehyde, butyraldehyde, b -chloroacetaldehyde, benzaldehyde, naphthaldehyde, glyoxal, malonic dialdehyde, succindialdehyde, and benzene p-dialdehyde. As hydroxy compounds for reaction with these aldehydes there can be used unsubstituted or substituted saturated or unsaturated monohydric and polyhydric alcohols, phenols and the reaction products of these with alkylene oxides, styrene oxide, or epichlorhydrin; OH-terminated polydensates of alkylene oxides; esters, e.g. glycerine monomethylmethacrylate; castor oil, phthalic acid bis glycol ester, ricinoleic glycol ester; polyesters, polythioesters, completely or partially saponified polyvinyl acetate; reaction products of amines and alkylene oxides.  a -Alkoxytetrahydrofuran or a -alkoxy tetrahydropyrans are also suitable acetals.  Halogen, ester, amide, nitro, ether, thioether, sulpho, carboxyl, urethane and heterocyclic substituents may be present in the acetals.  In a typical Example 1 equimolecular amounts of formaldehyde dimethyl acetal and phenyl isocyanate are reacted in the presence of BF3-etherate at temperatures from 60 to 170 DEG C. with distillation of excess methylal and methanol from the mixture. The product is free from NCO groups and is an addition product of 2 mols of phenyl isocyanate and the acetal.  Specification 798,209 is referred to.