Patent GB-720386-A (GB)
Title: Improvements in the production of nitrogenous condensation products
IPC: C08G12/26
Filed: 1952-08-15
Abstract: Glyoxal monourein or monothiourein of the formula <FORM:0720386/IV (a)/1> where X = O or S is condensed with formaldehyde or a substance which splits off formaldehyde.  The reaction may be carried out in neutral, acid or alkaline aqueous medium or in presence of alcohols which react with the condensate to form ethers, e.g. methanol, ethanol, propanol, butanol, pentanol, allyl alcohol, ethylene glycol or glycerine, or water-soluble partial ethers or esters of polyhydric alcohols, or in the absence of solvents.  In neutral or alkaline medium stable methylol compounds may be formed.  Reaction of the precondensates with acid catalysts yields viscous solutions suitable for adhesives.  The products may be hardened by heating in presence of acid.  Alcohol-modified products form lacquers if desired with other film-forming agents, e.g. cellulose nitrate, alcohol-modified urea resins or alkyd resins.  Substances such as urea, cyanamide, melamine, polyvalent urethanes, or phenols may be included in the reaction mixture. The products may be reacted in acid solution with hydrophobic aliphatic or cycloaliphatic alcohols, e.g. decyl, dodecyl, octadecyl or oleyl alcohol, dioctyl carbinol, diisohexyl carbinol 1,18-octodecanediol, abietinol, isohexylcyclohexanol, decahydronaphthol or monoglycol ethers of these alcohols or mixed alcohols obtained by reduction of high molecular fats or fatty acids, e.g. paraffin wax fatty acids, coconut or palm oil, or alcohols obtained by the oxidation of paraffin wax, from the Oxo synthesis or from hydrogenation products of carbon monoxide. Other suitable reactants are carboxylic acids, e.g. palmitic, oleic, ricinoleic, amines, e.g. laurylamine, octodecylamine, or decamethylene diamine, amides, e.g. oleic acid amide, stearic acid amide or methylamide, sulphonic acid amides, urethanes, mercaptans or isocyanates, e.g. octadecyl isocyanate.  These after-treatments are preferably effected in an inert solvent or diluent, e.g. N-methyl pyrrolidone or dimethyl formamide if desired, mixed with benzene, toluene or carbon tetrachloride or they may be effected in aqueous emulsion.  In examples (1) Glyoxal monourein is condensed with formaldehyde in presence of Ca(OH)2.  Carbon dioxide is fed in and calcium carbonate filtered off. Concentration in vacuo and storing over P2O5 gives crystalline dimethylol compound of glyoxal monourein.  Methylol compounds of glyoxal monourein are also prepared with varying ratios of formaldehyde to monourein.  (2) The product of example (1) is heated with phosphoric acid and n-butanol (3).  A hardened film of the product of example (1) is formed by heating with phosphoric acid (4).  A glyoxal-monourein-formaldehyde condensate is formed in presence of butanol, further heated with phthalic anhydride and butanol, dehydrated azeotropically and mixed with castor oil modified alkyd and TiO2 to form an enamel.  The castor oil modified alkyd may be replaced by a condensate from hexanetriol and adipic acid.  Other examples describe inter alia the use of HCl as curing agent, the addition to the initial reactants of phenol, of urea or of melamine (the product mixed with rye flour yielding an adhesive), blending of the products with a urea-formaldehyde condensate, modification of the condensate with an alcohol mixture obtained by reduction of coconut oil, or with stearic acid amide (addition of a reaction product of ethylene oxide and octadecyl alcohol giving a product readily dispersible in hot water).  Example (10) describes the modification of dimethylol glyoxal monothiourein with a mixture of synthetic alcohols.ALSO:Glyoxal monourein or monothiourein of the formula <FORM:0720386/IV (b)/1> where X=O or S is condensed with formaldehyde or a substance which splits off formaldehyde.  In example 1, glyoxal monourein is heated with aqueous formaldehyde in presence of calcium hydroxide.  Carbon-dioxide is led in, the precipitated calcium carbonate filtered off and the filtrate concentrated in vacuo and stored over phosphorus pentoxide to yield the crystalline dimethylol compound of glyoxal monourein.  Example 10 refers to dimethylol glyoxal monothiourein.