Patent GB-424076-A (GB)
Title: Improvements in the manufacture and production of resinous condensation products
IPC: C08G12/22
Filed: 1933-10-14
Abstract: Resinous products are obtained by condensing amides and/or thioamides of polyamino-N-carboxylic acids with formaldehyde, its polymers, substances liberating formaldehyde or mixture thereof in the presence or absence of solvents and/or condensing agents. Suitable amides or thioamides include hydrazine dicarboxylic acid diamide, ethylenediamino - N - N<1> - dicarboxylic acid amide, putrescine-N-N<1>-dicarboxylic acid amide, phenylenediamine - N - N<1> - dicarboxylic acid amide, benzidine-N-N<1>-dicarboxylic acid amide, phenylenediamine - N - N<1> - dicarboxylic acid amide, benzidine-N-N<1>-dicarboxylic acid amide, or the corresponding thioamides, amides or thioamides of polyamino-N-carboxylic acids in which the N-carboxylic acid amide group is combined with radicles of polybasic acids such as carbonyl di-urea or adipinyl di-urea or in which the carbon chain is interrupted by other atoms or atomic groups such as oxygen, sulphur or imino groups such as diethylenetriamine-N-N<1>-dicarboxylic acid diamide.  The products may be hardened by heating.  The condensation may be carried out in acid, neutral or alkaline media, in the presence of organic compounds such as alcohols, esters, butyl alcohol, ethyl alcohol or a glyceride of linseed oil fatty acids and in the presence of substances capable of forming condensation products with formaldehyde such as phenols, aromatic amines, urea, thiourea or amides or thioamides of dicarboxylic acids.  The products may be moulded with or without the addition of hardenable resins such as phenol-formaldehyde resins, alkyd resins, urea-formaldehyde resin, or resins derived from polycarboxylic acid polyamides and formaldehyde and with or without fillers such as cellulose, wood meal or asbestos and dyestuffs. Fusible intermediate products are suitable as raw materials for lacquers such as nitrocellulose lacquers and as impregnating agents for fibrous materials such as artificial silk to render them proof against creasing.  In examples: (1) hydrazine dicarboxylic acid diamide is condensed with aqueous neutral formaldehyde; (2) ethylenediamine-N-N<1>-dicarboxylic acid diamide is condensed with aqueous formaldehyde, neutral or with the addition of a substance having an acid reaction such as hydrochloric acid, ammonium salts or acid phosphates; (3) ethylenediamine-N-N<1>-dicarboxylic acid diamide is condensed with aqueous formaldehyde in the presence of formic or boric acids and artificial silk is treated with the aqueous solution of the condensation product and dried; the artificial silk may be treated with an aqueous neutral solution of the condensation product and after treated in an acid bath; (4) ethylenediamine-N-N<1>-dicarboxylic acid dithioamide is condensed with aqueous formaldehyde in the presence of potassium carbonate; (5) heptamethylenediamine - N - N<1> - dicarboxylic acid diamide is heated with trioxymethylene with or without the addition of linoleic acid monoglyceride, aqueous formaldehyde in the presence or absence of potassium carbonate or a solution of trioxymethylene in butanol. Specification 413,345 is referred to.  Amides or thioamides of polyamino-N-carboxylic acids may be prepared by the action of carbamic acid chloride or thiocarbamic acid chloride on polyamines, intramolecular rearrangement of the cyanates or thiocyanates of polyamines obtained by the action of cyanic acid or thiocyanic acid on the free polyamines or by the reaction of cyanates or thiocyanates with the salt of polyamines. The thioamides may also be obtained by the action of ammonia on compounds containing the group-NCS more than once in the molecule. In examples: (1) hydrazine dicarboxylic acid diamide is obtained from hydrazine sulphate and potassium cyanate, and (5) heptamethylenediamine - N - N<1> - dicarboxylic acid diamide is obtained by the oxidation of train oil fatty acids with nitric acid followed by the Hofman degradation by means of chlorine liquor of the corresponding dicarboxylic acid diamides to yield heptamethylenediamine which is heated in the form of its hydrochloride with potassium cyanate.