Patent GB-813486-A (GB)
Title: Diazotizable amine compositions
IPC: C09B41/00
Filed: 1956-06-29
Abstract: A stable diazotizable primary amine composition of pH of at least 7 comprises 10-30 per cent of a diazotizable primary amine compound devoid of solubilizing carboxylic or sulphonic acid groups, an alkali metal nitrite in at least an equimolecular amount relative to the amine compound, 10-50 per cent of a mixture of a non-ionic surface-active agent, containing a polyoxy-alkylene chain and derived from a reactive hydrogen-containing compound, and a water-soluble cationic surfaceactive quaternary ammonium compound, this mixture containing 0.2-1 part of the cationic compound for each part of the non-ionic compound, an amount of an inert organic watermiscible solvent for the amine compound sufficient to yield a stable liquid dispersion, and an amount of water sufficient to keep the nitrite in solution or stable dispersion.  Upon acidification reaction takes place with formation of a solution of a diazonium compound capable of coupling with an azo coupling compound to form an azo dyestuff.  The dispersion is particularly useful for processes of forming azo dyes in situ on fibrous materials or on carriers or substrata.  It may be used in dye printing processes.  Aromatic or heterocyclic primary amines may be used, e.g. aminoazotoluene, 4 - chloro - 2 - nitroaniline, 2,5 - dichloroaniline, 5 - chloro - o - toluidine, 4 - nitro - o - toluidine, 4 - chloro - o - anisidine, 1 - aminonaphthalene, 1 - aminoanthraquinone, dianisidine, aminobenzophenones, aminobenzosulphones, aminodiphenyl ethers, aminocarbazoles, m-phenylene diamine, 3,31 - diaminodiphenylurea, and 3,4-diamino-benzanilide.  Sodium or potassium nitrite may be used. The non-ionic surface-active agent may be obtained by introducing a polyglycol radical having at least two oxyalkylene groups into an organic compound having at least one reactive hydrogen atom, e.g. a water-insoluble carboxylic, sulphonic, or hydroxycarboxylic acid, or an alcohol, phenol, thiol, acid amide, amine, or hydroxylamine. Specified acids are caproic, lauric, palmitic, stearic, oleic, ricinoleic, montanic, abietic, and naphthenic acids and acids produced from waxes and oils or by oxidation from petroleum fractions.  Specified alcohols are hexyl, dodecyl and oleyl alcohols, octadecane diol, abietyl alcohol, alcohol ethers of polyhydric alcohols and branched chain primary alcohols produced by an OXO synthesis.  Specified amines are decyl, octadecyl, diphenyl, N-cyclohexyl-N, mono- and di-alkylol amines, and rosin amines.  Such compounds may be converted into the polyglycol-containing non-ionic surface-active agents by reaction with ethylene oxide, propylene oxide, or halohydrins. The non-ionic agent may contain 2-100 oxyalkylene groups per molecule.  The quaternary ammonium compound preferably contains at least one radical of at least 8 carbon atoms attached to the nitrogen atom and such radical may be saturated or unsaturated and the carbon chain may be interrupted by oxygen, sulphur, or nitrogen, or by aromatic or cycloaliphatic groups.  The anion of the quaternary ammonium compound may be hydroxyl or an inorganic or organic acid radical.  Specified solvents for the diazotizable primary amine are mono- and di-methyl, ethyl, propyl, and butyl formamides, acetamides, methoxyacetamides, and glycolamides, ethylene glycol, diethylene glycol and ethers thereof, dimethyl sulphoxide, N-methyl pyrrolidone, methanol, ethanol, and isopropyl alcohol.  Acidification of the composition to effect diazotization is preferably effected with hydrochloric acid, but sulphuric, phosphoric, formic, acetic, oxalic and other acids may be used.  The coupling component used for forming the azo dye may be a phenol, naphthol, pyrazolone, hydroxybenzofluorenone, benzo-naphthol, or an arylide of 3-hydroxy-2-naphthoic acid or its 5,6,7,8 - tetrahydro derivative, 3 - hydroxy - 2 - anthroic acid, hydroxycarbazole carboxylic acid, acetoacetic acid, benzoylacetic acid, phthaloyl bis-acetic acid, or hydroxydibenzothiophene carboxylic acid.  In examples, stable solutions are obtained by mixing o-aminoazotoluene with a condensation product of castor oil with 40 mols. of ethylene oxide as non-ionic agent; a C8-C18 alkyl dimethyl benzyl ammonium chloride or a condensation product of alkyl amines with 3 mols. of ethylene oxide, quaternized with benzyl chloride, as cationic agent; dimethyl formamide, N-methyl pyrrolidone, diethylene glycol monoethyl ether, or dimethyl sulphoxide as solvent for the amine; sodium nitrite, and water. Similar compositions are prepared in which the diazotizable amine is 4 - chloro - 2 - nitro - ariline, 5 - chloro - o - toluidine, or 4-nitro-o-toluidine.  The compositions are acidified with dilute hydrochloric acid to effect diazotization and the solutions are then diluted and neutralized with sodium acetate.  In another example, cotton is impregnated with a solution comprising 3-hydroxy-2-naphthoic acid b -naphthanilide, formaldehyde, sodium lignin sulphonate, sulphonated castor oil, sodium alkyl naphthalene sulphonate, caustic soda, and water.  The material is squeezed and salt rinsed and then immersed in a diazo solution obtained by acidifying an amine solution comprising o-aminoazo-toluene, dimethyl formamide, ethylene glycol monoethyl ether, castor oil-ethylene oxide condensation product, C8-C18 alkyl dimethyl benzyl ammonium chloride, sodium nitrite, and water.  The cotton is dyed a garnet green shade. Specifications 380,431 and 380,851, [both in Group IV], are referred to.