Patent GB-474601-A (GB)
Title: Improvements in the manufacture and production of nitrogenous condensation products
IPC: C08G12/06
Filed: 1936-03-30
Abstract: Resins are produced by condensing formaldehyde in any form with one or more polyalkylene polyamines containing at least one =NH or --NH2 group or their derivatives.  Suitable polyalkylene polyamines include diethylene triamine, triethylene tetramine, tetraethylene pentamine and their higher homologues; mixtures obtained as by-products in the preparation of ethylene diamine from ethylene halides and ammonia; polyalkylene polyamines in which the nitrogen atoms are connected by straight or branched alkylene chains, e.g. 1 : 2-propylene or 1 : 3-butylene, or by chains interrupted by hetero-atoms other than nitrogen, e.g. oxygen, sulphur.  There may also be used substituted polyalkylene polyamines obtained by reacting (e.g. by heating under reflux, preferably in the absence of diluents or solvents) one or more halogenated aliphatic, cycloaliphatic, or naphthenic compounds containing six or more carbon atoms with at least two molecular proportions of polyalkylene polyamine per halogen atom.  Suitable halogenated bodies include alkyl halides such as octyl bromide, dodecyl chloride, octodecyl bromide; chlorination products of the following: hard or soft paraffin wax, ozokerite, middle oils (distillates from mineral oils or from the oils obtained by hydrogenation of coal and the like); alcohols, ketones, ethers saturated or unsaturated acids, e.g. montan wax acids such as those obtained according to Specification 305,552, [Class 2 (iii)], resin and naphthenic acids, and fatty acid mixtures obtained from oxidation of paraffin wax with air, nitric acid, or nitrous gases, beef tallow (examples of such chlorination products are chlordodecyl alcohol and chlorstearic acid used successively in either order, chloroctodecyl alcohol, chlordodecanone, a -chlormethyldodecyl ether, mono- and poly-chlor-oleic, -ricinoleic, or -stearic acids); compounds obtained by addition of halogen or hydrogen halides to unsaturated aliphatic compounds, e.g. mono- and di-chlor undecane, chlorinated oleyl alcohol, chlorination products of liquid or solid olefines from hydrocarbon oil cracking; halogenated polycarboxylic acids (e.g. chloradipic, chlorsebacic, and bromsebacic acids) or their esters, acid halides, or anhydrides; sulphonation, acylation or hydroxy-alkylation products of the foregoing.  Other substituted polyalkylene polyamines may be used, e.g. methyl and butyl derivatives and those obtained by reacting polyalkylene polyamines with aliphatic saturated or unsaturated mono- or polybasic or cyclic acids, or mixtures thereof; with resin acids, e.g. abietic acid; or with reaction products of colophony with maleic anhydride.  Further suitable polyalkylene polyamine derivatives are those in which a nitrogen atom carries a --CO--NH2 or --CS.NH2 group; these may be prepared by reacting on polyalkylene polyamines or their derivatives with cyanic or thiocyanic acid, by treating their salts with cyanates or thiocyanates, by heating them with urea or by reacting on them with carbamic or thiocarbamic acid chloride, preferably in the presence of inert solvents.  The condensation of the polyalkylene polyamines or their derivatives with formaldehyde may be carried out in aqueous media; in other solvents or diluents, e.g. alcohols, esters, or ketones in which case the formaldehyde may be in aqueous solution, and the water may be removed before or during the reaction; in the absence of diluents if the formaldehyde is used as vapour or as trioxy-methylene: the polyalkylene polyamine derivatives may be absorbed on natural or artificial fibres and formaldehyde, e.g. as vapour, allowed to act thereon; or they may be added to spinning solutions, e.g. of viscose, and the spun threads treated with formaldehyde.  There may be present during the reaction other substances which react with formaldehyde, e.g. phenols, aromatic amines, sulphonamides, urea, thiourea, and polybasic acid amides. The products, after drying, are soluble in organic solvents, e.g. alcohols, but insoluble in water: they may be used as additions to lacquers and wax preparations and for waterproofing fibres, e.g. by impregnating (either with the products as such, or successively with the polyalkylene polyamine derivative and formaldehyde) viscose cellulose wool, wet or dehydrated by alcohol; staple fibres of viscose artificial silk which may be obtained according to Specification 443,971, or threads or fabrics therefrom; or threads of viscose artificial cotton.  In examples: (a) triethylene tetramine is condensed with aqueous formaldehyde; (b) condensation products of triethylene tetramine and stearic acid together with adipic acid; montan wax acids alone or with adipic, oxalic, sebacic, or other polybasic acids or the acids obtained by oxidizing paraffin wax; maleic anhydride-colophony condensate; acetic acid; methyl propyl acetic acid; benzoic acid; naphthenic acids; or chlorinated paraffin wax are treated with aqueous formaldehyde; (c) condensation products of triethylene tetramine and stearic acid or adipic acid are treated with paraformaldehyde in alcoholic solution; (d) condensation products of triethylene tetramine and 12-hydroxystearic acid or salicylic acid are treated with trioxymethylene in alcoholic solution; (e) a condensation product of triethylene tetramine and oxalic acid is fused with trioxymethylene; (f) a condensation product of triethylene tetramine and montan wax acids is treated with formaldehyde vapour; (g) triethylene tetramine is condensed successively with montan wax acids and ethylene glycol montanate and treated with aqueous formaldehyde; (h) a condensation product of triethylene tetramine and chlorinated paraffin wax is treated with potassium cyanate followed by aqueous formaldehyde; (i) a condensation product of triethylene tetramine and montan wax acids is treated with potassium cyanate followed by aqueous formaldehyde, trioxymethylene in alcoholic solution, or formaldehyde vapour; (j) a condensation product of triethylene tetramine and montan wax acids is treated with potassium thiocyanate followed by paraformaldehyde; (k) condensation products of triethylene tetramine with dodecyl bromide, adipic acid alone or with montan wax acids, or stearic acid are treated with sodium cyanate followed by aqueous formaldehyde; (l) a condensation product of diethylene triamine and montan wax acids is treated with paraformaldehyde in alcoholic solution.  Samples have been furnished under Sect. 2 (5) as follows: a condensation product of ethylene diamine and b  : b <1>-dichlordiethyl ether is fused with trioxymethylene; tetraethylene tetramine is treated with aqueous formaldehyde; triethylene tetramine is condensed successively with ethylene chloride and chlorinated paraffin wax and treated with aqueous formaldehyde; a condensation product of triethylene tetramine and montan wax is fused with trioxymethylene.  The second Provisional Specification refers to the use, as additions during the condensation of the polyalkylene polyamines or their derivatives with formaldehyde, of polyamino-N-carboxylic and -thiocarboxylic acid amides.