Patent GB-613020-A (GB)
IPC: D06M13/184
Abstract: Fibre-forming polymers containing 1.2.4-triazole rings are made by heating a mixture containing a dicarboxylic acid and a base consisting of ammonia and hydrazine and/or containing substances which on hydrolysis yield such acid and base, there being present for each mol. of dicarboxylic acid more than two mols. of base, combined or uncombined, of which more than one consists of hydrazine, and continuing the heating until a polymer is produced. Particularly, the polymers may be made by heating together a diamide and a dihydrazide of a dicarboxylic acid together with hydrazine, the amount of hydrazine present, combined and uncombined, being more than one mol. for each dicarboxylic acid residue present (e.g. up to 10 per cent excess hydrazine), and continuing the heating until a polymer is produced.  Up to one mol. of base may be replaced by a compound of that base with a monobasic acid.  Polymers containing 4-amino-1.2.4-triazole rings may be made from dicarboxylic acids or anhydrides with more than two moles. of hydrazine alone.  Alternative combinations of starting materials specified are (1) mono-amide mono-hydrazide of a dicarboxylic acid with free hydrazine; (2) dicarboxylic acid, ester, e.g. methyl, ethyl, or phenyl ester, or anhydride, hydrazine and ammonia; (3) dicarboxylic dinitrile and hydrazine; (4) dicarboxylic dihydrazide, diester and ammonia; (5) dicarboxylic diamide, diester and hydrazine; (6) dicarboxylic mono-amide-monoester and hydrazine; (7) dicarboxylic mono-hydrazidemonoester and ammonia.  Also, the reaction may be carried out in two stages, e.g. dicarboxylic diester with a little more than one mol. of hydrazine, and then with ammonia, or in the reverse order.  Dicarboxylic acids specified are succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, diphenic, phenylene-1.4-diacetic, diglycollic, N - methyl - imino - diacetic. Compounds with monobasic acids specified, i.e. monobasic acid hydrazides or amides, are acetyl, propionyl, or lauryl hydrazine. The melting point of the products is higher the higher the ratio of hydrazine to ammonia employed, and while those melting above 240 DEG C. are insoluble in cold methanol, those melting below 240 DEG  C. are soluble.  The condensation is carried out at 200-300 DEG  C., preferably 230-280 DEG  C., in a diluent or without.  The presence of water prevents resinification which may result from cross-linking. The viscosity of the polymer may be stabilized by hydrolysing the terminal hydrazide groups, e.g. with aqueous hydrochloric acid.  The polymers may be made into filaments by melt-spinning at 10-30 DEG  C. above the melting point of the polymer, mixed with sulphonamide, phenolic, urea or thiourea plasticisers, or by wet or dry spinning of solutions in formic or acetic acids or phenolic solvents.  The filaments may be cold-drawn.  The polymers may be used for softening or coating, and may be mixed with cellulose acetate, aceto-butyrate, butyrate, keto-stearate, ethyl cellulose, oxyethyl cellulose, oxyethyl cellulose acetate, benzyl cellulose, and other cellulose derivatives, plasticizers, or softening agents, dyestuffs or pigments.  In examples: (1) and (2), debacic diamide and sebacic dihydrazide are heated with hydrazine hydrate in varying proportions, and (3) hydrazine sebacate, and (4) sebacic acid are heated with different proportions of hydrazine hydrate.  In example (5), the product of (3) is melted with o-phenylphenol and m-cresol under nitrogen, and spun.