Patent GB-748016-A (GB)
Title: Process for the manufacture of salts of new hardenable, basic, ternary condensation products
IPC: C08G12/40
Filed: 1952-08-28
Abstract: Water soluble salts, including quaternary ammonium salts, of hardenable basic ternary condensation products are obtained by reacting together simultaneously or in any sequence (a) methylol compounds of amino triazines or urea or their ethers with low molecular alcohols; (b) non-basic aliphatic compounds which contain a carbon chain of at least 7 carbon atoms and a reactive hydrogen atom attached to an oxygen atom, a sulphur atom or a non-basic nitrogen atom; and (c) primary or secondary amines or water soluble salts thereof or such tertiary amines as contain in the molecule a reactive hydrogen atom attached to another hetero atom, i.e. to an oxygen atom, a sulphur atom or another, non-basic, nitrogen atom and converting the resultant bases into water soluble salts, including quaternary ammonium salts, unless salts of primary or secondary amines have been used.  As compounds (b) may be used amides from ammonia or from primary amines, substituted ureas, urethanes, secondary amides, mercaptans, esters of higher molecular alcohol with mercapto carboxylic acids, carboxylic acids, alcohols and N-methylol compounds.  The N-methylol compounds are preferably N-methylol compounds of amides or amide-like compounds.  The compounds (b) preferably contain at least one carbon chain of 16 to 18 carbon atoms.  The compound (c) may be aromatic, hydroaromatic araliphatic, heterocyclic, but preferably aliphatic, primary and secondary amines or their salts. The amines may be mono- or polyamines and may be substituted in the alkyl radical; thus aminocarboxylic acids or sulphonic acids for example alanine or taurine may be used.  As tertiary amines preferably alkanol amines are used.  The molecular ratio of the reactants is dependent upon the number of methylol or methylol ether groups in the component (a).  At least one free methylol group should be present in the end product to ensure that it may be hardened.  Normally one mol. of a compound (a) is reacted with one to two mols. of a compound (b) and one mol. of a compound (c). The final salts may be prepared from inorganic or organic acids. Quaternary salts may be obtained by reacting appropriate tertiary condensation products with dimethyl sulphate or benzyl chloride. The Specification lists a large number of compounds suitable for the components (a), (b) and (c) and gives a large number of examples.  In example 1 a wax-like water soluble product is obtained from acetic acid and the reaction product of triethanolamine and the stearic acid ester of methylated methylol melamine.  In examples 2 and 3 instead of triethanolamine, diethylene triamine and N1N1 diethyl ethylene diamine are used.  In example 4 the acetic acid salt of the reaction product of triethanolamine and the condensation product from methylated methylol melamine and N-methylol stearic acid amide is prepared.  Example 9 describes the preparation of the acetic acid salt of the reaction product of triethanolamine and the condensation product from N methylol octa decyl urethane and methylated methylol melamine.  In example 10 the acetic acid salt of the reaction product of methylol melamine methyl ether with the product from two mols. of stearic acid and one mol. of diethylene triamine is prepared.  A similar product may be prepared from dimethylol urea dimethyl ether. Further examples use as compound (b) part stearic acid and part N-methylol stearic acid amide, and coconut oil fatty acids, and as compound (c), N-hydroxyethylmorpholine and piperidine acetate.  The products of the invention may be used for the waterproofing and other treatment of textiles and leather and for this purpose may be made up into solution together with such compounds as ammonium chloride formic acid and paraffin wax.  Aluminium and zirconium salts may also be added to the treating solutions.  Specifications 611,012 and 662,548 are referred to.ALSO:Water soluble salts, including quaternary ammonium salts, of hardenable basic ternary condensation products are obtained by reacting together simultaneously or in any sequence (a) methylol compounds of aminotriazines or urea or their ethers with low molecular alcohols; (b) non-basic aliphatic compounds which contain a carbon chain of at least 7 carbon atoms and a reactive hydrogen atom attached to an oxygen atom, a sulphur atom or a non-basic nitrogen atom; and (c) primary or secondary amines or water soluble salts thereof or such tertiary amines as contain in the molecule a reactive hydrogen atom attached to another hetero atom, i.e. to an oxygen atom, a sulphur atom or another, non-basic, nitrogen atom and converting the resultant bases into water soluble salts, including quaternary ammonium salts, unless salts of primary or secondary amines have been used.  As compounds (b) may be used amides from ammonia or from primary amines, substituted ureas, urethanes, secondary amides, mercaptans, esters of higher molecular alcohols with mercapto carboxylic acids, carboxylic acids, alcohols and N-methylol compounds.  The N-methylol compounds are preferably N-methylol compounds of amides or amide-like compounds.  The compounds (b) preferably contain at least one carbon chain of 16 to 18 carbon atoms.  The compound (c) may be aromatic, hydroaromatic, araliphatic, heterocyclic, but preferably aliphatic, primary and secondary amines or their salts. The amines may be mono- or polyamines and may be substituted in the alkyl radical; thus amino carboxylic acids or sulphonic acids, for example alanine or taurine may be used.  As tertiary amines preferably alkanol amines are used. The molecular ratio of the reactants is dependent upon the number of methylol or methylol ether groups in the component (a).  At least one free methanol group should be present in the end product to ensure that it may be hardened.  Normally one mol. of a compound (a) is reacted with one to two mols. of a compound (b) and one mol. of a compound (c). The final salts may be prepared from inorganic or organic acids. Quaternary salts may be obtained by reacting appropriate tertiary condensation products with dimethyl sulphate or benzyl chloride. The Specification lists a large number of compounds suitable for the components (a), (b) and (c) and gives a large number of examples.  In example 1 a wax-like water soluble product is obtained from acetic acid and the reaction product of triethanolamine and the stearic acid ester of methylated methylol melamine.  In examples 2 and 3 instead of triethanolamine diethylene triamine and N1,N1-diethyl ethylene diamine are used.  In example 4 the acetic acid salt of the reaction product of triethanolamine and the condensation product from methylated methylol melamine and N-methylol stearic acid amides is prepared.  Example 9 describes the preparation of the acetic acid salt of the reaction product of triethanolamine and the condensation product from N-methylol octadecyl urethane and methylated methylol melamine.  In example 10 the acetic acid salt of the reaction product of methylol melamine methyl ether with the product from two mols. of stearic acid and one mol. of diethylene triamine is prepared.  A similar product may be prepared from dimethylol urea dimethyl ether.  Further examples use as compound (b) part stearic acid and part N-methylol stearic acid amide, and coconut oil fatty acids, and as compound (c), N-hydroxyethylmorpholine and piperidine acetate.  Specifications 611,012, [Group IV (a)], and 662,548 are referred to.ALSO:Creasing and shrinking resistance and a soft handle are imparted to textiles, e.g., of cotton, regenerated cellulose or wool, by treatment with aqueous solutions of water-soluble salts, which may be quaternary ammonium salts, obtained by reacting (1) methylol compounds of aminotriazines or of urea or their ethers with low molecular alcohols with (2) non-basic aliphatic compounds which contain a carbon chain of at least 7 carbon atoms and a reactive hydrogen atom attached to an oxygen atom, a sulphur atom or a non-basic nitrogen atom, and (3) primary or secondary amines or water-soluble salts theeof or tertiary amines which contain in the molecule a reactive hydrogen atom attached to another hetero atom, the resultant bases finally being converted into water-soluble salts if necessary (see Group IV(a)), followed by heating the textiles at an elevated temperature, with or without intermediate drying.  To the treating baths may be added aluminium and zirconium salts, salts of other metals with weak acids, sols of hydrated zirconium dioxide, paraffin wax dispersions, solvents, methylolamides, protective colloids, finishing or matting agents such as methylol ureas, and wetting or softening agents.  In Example 19 cotton gabardine is padded to a take-up by weight of 100 per cent with an aqueous bath which contains ammonium chloride, formic acid and an emulsion of paraffin wax and the acetic acid salt of the reaction product of triethanolamine with the product obtained by reacting methylated methylol melamine and stearic acid.  The fabric is dried and after-treated for five minutes at 120 to 150 DEG C.  Example 20 is similar but omits paraffin wax, and in Example 21 viscose rayon is similarly treated.  Other examples of the salt incude (a) the acetic acid salt of the reaction product of triethanolamine and the product obtained by reacting a highly methylated methylol melamine partly with stearic acid and partly with N-methylol stearic acid amide; (b) the acetic acid salt of the reaction product of triethanolamine with the product obtained by reacting methylated methylol melamine and N-methylol octadecylurethane; (c) the acetic acid salt of the reaction product of methylol melamine methyl ether with the condensation product from 2 mols of stearic acid and 1 mol of diethylene triamine and (d) the acetic acid salt of the reaction product of dimethylol urea dimethyl ether and the condensation product from 2 mols. of stearic a