Patent GB-706717-A (GB)
Title: Process for the production of basic linear polyureas and polyurethanes
IPC: C08G18/28
Filed: 1951-07-24
Abstract: Basic linear polyureas or polyurethanes are prepared by reacting, in a lower aliphatic alcohol, an alcohol soluble aliphatic diprimary polyamine containing at least one secondary amino group in its chain and a polymethylene di-isocyanate or a glycol-bis chlorocarbonate. Included amongst suitable amines are low molecular weight polyamides or polyoxamides having terminal NH2 groups.  Part of the alcohol may be replaced by chlorbenzene, benzene or tetrahydrofurane.  The polymers are soluble in dilute acetic acid and ethanol.  They may be cross linked if desired after spinning and cold-drawing with diethyloxalate, formaldehyde or compounds yielding it on decomposition, diketenes, di-isocyanates, or hexahydro-1, 3, 5-triacrylyl-s-triazine.  The products may be used for forming fibres or films, for animalising textile fibres, for rendering fabric water-repellant or as binders in textile printing (see Group IV (c)). They are preferably used as salts, e.g. acetates in aqueous solution. When used for printing pastes, thickeners may be added, and the polymer may be prepared in presence of a pigment.  In the examples (1) hexamethylene di-isocyanate is reacted with dipropylenetriamine in methanol; (2) hexamethylene di-isocyanate is reacted with diaminodipropyltetramethylenediamine in tertiary butyl alcohol; (3) hexamethylene diisocyanate is reacted with a mixture of diethylenetriamine and hexamethylenediamine in isobutyl alcohol; (4) tetramethylene glycol-bis-chlorocarbonate is reacted with diethylene triamine in ethanol.  Pyridine is present as hydrogen chloride acceptor.  The polyurethane hydrochloride is obtained. Addition of alkali yields the polyurethane; (5) hexamethylene glycol bis chlorocarbonate is reacted in presence of pyridine with diethylenetriamine in ethanol; (6) hexamethylene diisocyanate is reacted in ethanol with a polyoxamide having terminal NH2 groups and prepared from diethyloxalate and diaminodipropyltetramethylene diamine.  (7) Hexamethylenediisocyanate is reacted with a mixture of diethylenetriamine and g , g 1-diaminopropyl methylamine in ethanol. The filtrate from the separated polymer contains low molecular weight compounds and may be used as reaction medium for further batches, thereby increasing the yield; (8) hexamethylene-di-isocyanate is reacted with a mixture of diaminodipropyltetramethylenediamine and g , g 1-diaminopropylmethylamine in ethanol; (9) hexamethylene diisocyanate is reacted with a mixture of dipropylenetriamine and g , g 1-diaminopropylmethylamine in ethanol.  (10) Hexamethylene-di-isocyanate is reacted with a mixture of diethylenetriamine and g , g 1-diaminopropylmethylamine in ethanol. Powdered Hansa Yellow is present during the reaction.ALSO:Polyureas or polyurethanes containing secondary amino groups in their chains (see Group IV(a)) are used as binders in textile printing pastes particularly for cotton and rayon fabrics.  They are preferably used as salts, e.g. acetates in aqueous solution. Thickeners may be added if necessary.  Cross-linking agents for the polymer may be included and the printed surface heated to complete cross-linking.  In examples (7) an aqueous solution of the acetate of the polyurea from hexamethylene diisocyanate and a mixture of diethylenetriamine and g , g -diamino-dipropylmethylamine is mixed with copper phthalocyanine, methyl cellulose, hexahydro-, 1, 3, 5-triacrylyl-s-triazine, and water to yield a printing paste.  (8) The acetate of a polyurea from hexamethylene diisocyanate, spermin and g , g -diaminopropylmethylamine is used as a binder and hexamethylenetetramine as cross-linking agent.  The pigment is unspecified.  (9) The paste is prepared from the acetate of the polyurea from hexamethylene diisocyanate, dipropylenetriamine and g , g \sv-diaminopropylmethylamine, red pigment dyestuff, hexahydro-1, 3, 5-triacrylyl-s-triazine and water.  (10) A polyurea is prepared, in presence of Hanse Yellow powder from hexamethylene diisocyanate, diethylenetriamine and g , g \sv-diaminopropylmethylamine and used in a printing paste.