Patent GB-872523-A (GB)
Title: Polyether condensates from poly-(n-methylol) compounds and polyhydric alcohols
IPC: C08G67/00
Filed: 1957-08-28
Abstract: Polyethers preferably with a molecular weight of at least 750 and containing one or more chains having terminal hydroxyl and/or methylol groups, said chains comprising at least two nitrogen atoms, have a radical containing at least one ether or thioether bridge joined to a carbon chain of more than two carbon atoms linked to at least one of the nitrogen atoms by means of a -CH2O- grouping.  They are produced by condensing under acid conditions preferably in an organic solvent a poly-N-methylol compound, or an ether thereof with a monofunctional alcohol, with a polyhydric alcohol containing at least one ether or thioether bridge connected to a carbon chain having more than two carbon atoms.  Suitable poly-(N-methylol) starting materials are the methylol derivatives of urea, thiourea, methylene diurea, methylene dithiourea, diurea, dithiourea, hydrazodicarbonamide, melamine, hydrazodicarboxylic acid esters, ethylene urea, ethylene thiourea, or mixtures thereof with one another or with poly-methylol derivatives of substances such as guanidine, dicyandiamide, diurethanes, hexamethylene diurea. Suitable polyhydric alcohol starting materials are the hydroxyethyl derivatives of tri-, tetra-, penta- or hexamethylene glycols of glycerol, trimethylol propane, or pentaerythritol; the mono-fatty acid esters of hydroxy-ethylated polyhydric alcohols, polytetrahydrofurane, adducts of ethylene or propylene oxide with 4, 41-dihydroxydiphenyldimethylmethane or with 4, 41-dihydroxydiphenylsulphone, or hydroxyethylated derivatives of glycol urethanes, of thiodiglycol, or of polyethers.  Polyhydric alcohols not containing ether or thioether bridges may be used together with those of the invention. Preferably the methylol starting materials are prepared in presence of the polyhydric alcohol with which they are to be reacted.  Water formed in the reaction is removed azeotropically or by distillation at low pressure.  When using simple ethers of the polymethylol starting materials, alcohol is split out instead of water.  Small amounts of urea may be added to prevent crystallization of the products of the invention.  Terminal hydroxyl and/or methylol groups in the polyethers of the invention may be etherified with a monohydric alcohol or with diethanolamine, or the products of the invention may be reacted with poly-isocyanates to produce rubbery or cellular poly-urethanes as in U.S.A. Specification 2,764,565.  NH groups within the polymer chains may be treated to form methylol side chains which react with, for examples, methacrylic acid amide.  In the Examples (1) and (2) urea and formaldehyde are condensed in presence of alkali and of butane -b , b 1-dihydroxydiethyl ether, the reaction mixture is acidified and heated to remove water and form polyethers.  Example (3) is similar but some hexanetriol is admixed with the butane-b , b 1-dihydroxydiethyl ether.  Example (4) is similar to (1) but uses less dihydric alcohol initially and adds some hydroxyethylated-4, 41-dihydroxydiphenyldimethylmethane before the etherification step. If desired part of the butane-b , b 1-dihydroxydiethylether used as solvent for the methylol urea formation may be replaced by hydroxyethylated trimethylolpropane, or by an esterification product from one mol of hydroxyethylated trimethylol propane and one mol of oleic acid, or by a tetrabutylene glycol polyether.  Example (5) is also similar to (1) but some thiodiglycol is present in the initial reaction medium.  Example (6) describes etherification of tetramethylol hydrazodicarbonamide with butane dihydroxyethyl glycol. Example (7) is similar to (1) but uses thiourea or ethylene urea in place of urea.  Example (8) describes the transetherification of dimethylol urea dimethyl ether with butane-b , b 1-dihydroxyethyl ether.  Example (9) is similar to (8) but uses dipropylene glycol as the polyhydric alcohol.