Patent GB-868080-A (GB)
Title: Process for the manufacture of hardenable condensates from modified ureas and aldehydes
Inventor: ORTHNER LUDWIG
IPC: C08G12/04
Filed: 1957-11-01
Abstract: Hardenable condensation products are produced by treating an amine having at least three amino groups to introduce at least two urea groups into it, reacting the product with a long chain compound containing a functional group which reacts with amino or carbonamide groups, and converting the product so obtained into a methylol or substituted methylol derivative by reaction with an aldehyde. Suitable polyamines are diethylene triamine, triethylene tetramine, tetraethylene pentamine, dipropylene triamine, tripropylene tetramine, tetrapropylene pentamine, polyamino benzenes, polyamino naphthalenes, and products obtained by reacting alcohols or amines with acrylonitrile and reducing the product.  Introduction of urea groups into the amine may be effected with urea, nitro-urea or potassium cyanate.  Suitable long chain compounds are carboxylic acids, esters, anhydrides, halides or azides, carbamide chlorides, isocyanates, chlorcarbonic acids or methylol compounds.  The chains contain 10-18 carbon atoms and may be interrupted or substituted by aromatic, cycloaliphatic or heterocyclic radicals or hetero atoms. Mentioned are stearic acid-N-methylol amide, octadecyl-N-methylol urethane, octadecylchloromethyl ether.  If desired the poly-amine may be reacted with the long chain compound before the conversion of amino to urea groups.  The products are preferably reacted with formaldehyde.  Acetaldehyde and glyoxal are also mentioned. The methylol groups may be etherified by reaction with alcohols, e.g. methyl, ethyl, propyl or butyl alcohol in acid medium.  The products of the invention may be applied in aqueous media with acid catalysts to paper, textiles or leather, dried and cured at 80 DEG -170 DEG C. Suitable catalysts are lactic acid, glycollic acid, ammonium nitrate or aluminium sulphate.  They may be used together with other aminoplasts, polyvinyl acetate, polyvinyl propionate, polyacrylic esters, polyvinyl alcohol, polyacrylic amide, starch, glue, water-soluble cellulose derivatives, paraffins, or waxes.  In Examples (1) diethylene triamine is heated with urea, and the product with stearoyl chloride and then with formalin; (2) is similar using octadecyl isocyanate in place of stearyl chloride.  The aqueous emulsion of product is used with hexamethylol melamine and ammonium nitrate; (3) Triethylene tetramine was heated with stearic acid and then with urea and the product with paraformaldehyde; (4) Triethylene tetramine was condensed with urea, octadecyl isocyanate and then formalin; (5) is similar to (4) with stearic acid-N-methylol-amide in place of octadecyl isocyanate; (6) Dipropylene triamine was condensed with urea followed by octadecyl isocyanate and formalin.  The product was etherified with methanol and the white paste mixed with paraffin and xylol, and diluted, if desired, with water; (7) Tripropylene tetramine was heated with tetradecyl chloride, then with potassium cyanate and then with formalin or glyoxal; (8) Dipropylene monoethylene tetramine was condensed with urea and then with a mixture of stearyl and palmitoyl chlorides, followed by formalin; (9) Tetraethylene pentamine was heated with urea, with octadecyl isocyanate and then with formaldehyde.  The aqueous emulsion was mixed with paraffin xylene and an emulsifier.  Uses: The products are used for making paper, leather or textiles water-repellent, giving a soft handle to textiles and giving wet strength to paper.ALSO:Methylol or substituted methylol derivatives of substances prepared by treating polyamines in either order with substances to introduce urea groups and with long-chain substances containing groups which react with amino or with carbonamido groups (see Group IV(a)) are used as aqueous pastes or emulsions to treat textiles to make them, after drying and curing, water-repellent, soft and resistant to scraping or shrinking.  In an example cotton poplin is impregnated with an aqueous emulsion of ammonium nitrate and a paste obtained by treating diethylene triamine with urea and then with stearyl chloride and formalin.  After drying and heating the fabric has a soft and full handle not affected by repeated washing.