Patent GB-403977-A (GB)
Title: Manufacture and application of new products useful as assisting agents in the textile and leather industries
Filed: 1932-05-31
Abstract: Products stated to have emulsifying properties are obtained by sulphonating cyclic amidines which are derived from o or peri diamines of the benzene or naphthalene series, and which are substituted in the m -position by an aliphatic residue containing at least three carbon atoms or a hydroaromatic residue.  Before sulphonation the cyclic amidines may if desired be subjected to alkylation, aralkylation or arylation.  In a further modification the same products are obtained by condensing a sulphonic acid of an o-or peri-diamine, in which one amino group may be substituted by an alkyl, aralkyl or aryl group, with an acidylating agent capable of introducing the residue of an aliphatic carboxylic acid containing at least four carbon atoms or the residue of a hydroaromatic carboxylic acid.  The cyclic amidines are obtainable by condensing aliphatic carboxylic acids containing at least four carbon atoms, e.g. butyric, caproic, caprylic, capric, arachic, cerotic and naphthenic acids with o- or peri-arylenediamines.  The following diamines are mentioned: o-toluylenediamine, chlorinated o-phenylenediamines, o-aminodiphenylamines and o-aminomonomethylaniline. o-Nitroamines may also be used as starting materials.  For the alkylation, arylation or aralkylation, chlormethylnaphthalene, alkylhalides, halogenalkylsulphonic acids, chlorhydrins, epichlorhydrins, alkylsulphates and dichlornitrobenzene may be used.  In examples, the following imidazoles and perimidines are sulphonated: m -heptadecylbenzimidazole, m  - undecylbenzimidazole, m -naphthenylbenzimidazole, m  - heptadecyl - N - phenylbenzimidazole, m  - heptadecyl - N - benzyl benzimidazole, m  - heptadecyl - 1 : 2 - naphthimidazole, m  - heptadecylperimidine, m -undecylperimidine and the imidazoles or perimidines obtained from oleic acid or the fatty acids of coconut oil, palm oil, hard fat, soya oil, earthnut oil or bone fat.  In a further example, the sodium sulphonates of the mixture of imidazoles obtained from o-phenylenediamine and a mixture of stearic and palmitic acids are added to molten grain soap.ALSO:Products stated to have wetting, softening, emulsifying, levelling, washing, and similar properties are obtained by sulphonating cyclic amidines which are derived from o or peri diamines of the benzene or naphthalene series, and which are substituted in the m -position by an aliphatic residue containing at least three carbon atoms or a hydroaromatic residue.  Before sulphonation the cyclic amidines may if desired be subjected to alkylation, aralkylation or arylation.  In a further modification the same products are obtained by condensing a sulphonic acid of an o- or peri-diamine, in which one amino group may be substituted by an alkyl, aralkyl or aryl group, with an acidylating agent capable of introducing the residue of an aliphatic carboxylic acid containing at least four carbon atoms or the residue of a hydroaromatic carboxylic acid.  The products may be used in the leather as well as in the textile industry.  The cyclic amidines are obtainable by condensing aliphatic carboxylic acids containing at least four carbon atoms, e.g. butyric, caproic, caprylic, capric, arachic, cerotic and naphthenic acids with o- or peri-arylenediamines.  The following diamines are mentioned: o-toluylenediamine, chlorinated o-phenylenediamines, o-aminodiphenylamines and o-aminomonomethylaniline. o-Nitroamines may also be used as starting materials.  For the alkylation, arylation or aralkylation, chlormethylnaphthalene, alkylhalides, halogenalkylsulphonic acids, chlorhydrins, epichlorhydrins, alkylsulphates and dichlornitrobenzene may be used.  In the following examples, the imidazoles and perimidines are sulphonated with the usual sulphonating agents in some cases with diluents such as tetrachlorethane: (1) m -heptadecylbenzimidazole is sulphonated and neutralised, and if necessary bleached with a hypochlorite, hydrogenperoxide or a permanganate; the product foams readily and may also be used in a soda lye for treating cotton piece goods, and in a bath for wetting woollen yarn: (2) m -undecylbenzimidazole is sulphonated, and the product used for wetting cotton or wool; it may also be added to a mercerising bath for cotton goods containing soda lye and methylcyclohexanol: (3) a m -naphthenylbenzimidazole derived from the mixed naphthenic acids of Baku petroleum is sulphonated: (4) oleic acid and the fatty acids from coconut-oil, palm oil, hard fat, soya oil, earth nut oil and bone fat are used for the preparation of imidazoles or perimidines which are then sulphonated: (5) stearic acid is condensed with o-aminodiphenyl amine and the m -heptadecyl-N-phenylbenzimidazole sulphonated: (6) stearic acid is condensed with N-benzyl-o-phenylenediamine and the m -heptadecyl-N-benzylbenzimidazole sulphonated: (7) m -heptadecyl-1 : 2-naphthimidazole is sulphonated: (8) m -heptadecylperimidine is sulphonated; the neutralised product may be used for washing wool: (9) m -undecylperimidine is sulphonated: (10) m -heptadecylbenzimidazole is treated with benzyl chloride in the presence of sodium acetate, calcium carbonate or sodium carbonate, and the resulting m -heptadecyl-N-benzylbenzimidazole, after purification sulphonated; instead of the benzyl chloride, alkylchloride may be used: (11) o-phenylenediamine is condensed with a mixture of stearic and palmitic acids, the resulting mixture of benzimidazoles treated with benzyl chloride and the product sulphonated: (12) the benzimidazoles derived from oleic acid or the fatty acids of coconut oil or palm oil are benzylated and then sulphonated: (13) the mixture of benzylated benzimidazoles, prepared according to example 11 in the form of their hydrochlorides, is treated first with sodium carbonate and then with benzylchloride whereby the corresponding benzimidazolium chlorides are produced, which are finally sulphonated.  In further examples: (14) stearic acid chloride is condensed with 1 : 8-naphthylene diamine-4-sulphonic acid; (15) woollen piece goods, after being washed in hard water are treated in an aqueous bath with sodium m -undecylbenzimidazolesulphonate to facilitate subsequent dyeing: (16) by mixing the sodium sulphonate of the imidazoles obtained from o-phenylenediamine and a mixture of palmitic and stearic acids, with grain soap, the latter may be used with hard water without the precipitation of calcium soaps: (17) cotton yarn is handled in an alkaline solution of 2 : 3-oxynaphthoic acid anilide containing sodium m -heptadecylbenzimidazole sulphonate and then developed with diazotised-4-chlor-2-amino-1 : 1<1>-diphenylether: (18) hides are chrome tanned, neutralised and then handled in a solution containing sodium m -heptadecylbenzimidazolesulphonate; they are finally stretched and dried.