Patent GB-733471-A (GB)
Title: A process for fixing organic compounds on fibrous materials
Filed: 1950-08-25
Abstract: Dyestuffs, softening agents, brightening agents and like water-insoluble organic compounds are fixed on fibrous materials by applying to or forming on the material a water-soluble derivative of the compound containing one or more groups of the formula -SO2-CHR-CR1R2-O-Z-and subjecting the material to the action of an agent of alkaline reaction to form the water-insoluble derivative of the compound.  In the formula R, R1 and R2 each represents hydrogen or a hydrocarbon radical of low molecular weight and Z represents the residue of a polybasic acid, e.g. sulphuric, phosphoric, boric, or a benzene or naphthalene polysulphonic or polycarboxylic acid. The group of the formula given above is converted on the fibre by means of the alkaline agent to a vinyl or substituted vinyl sulphone group -SO2-CR=CR1R2.  Many dyestuffs are specified including azo, nitro, anthraquinone, vat, triphenylmethane, azine and phthalocyanine dyestuffs as well as azo dyestuff components, but azo dyestuffs containing residues of yellow components are excluded; examples are given also of softening and brightening agents having the above-specified esterified hydroxyalkyl sulphone groups, and also agents for increasing the dye-affinity of fibres.  The process may be applied to fibrous materials of wool, silk, artificial protein fibres, nylon, vegetable fibres, regenerated cellulose and cellulose acetate fibres, and also leather, cardboard, paper and the like. The alkalies used to convert the compounds to the insoluble form include sodium carbonate, ammonia, triethanolamine, sodium acetate, soap, diethylamine and sodium hydroxide.  When using an azo coupling component or diazoamino compound containing the above grouping, coupling may be effected on the fibre before or after alkali treatment to form the vinyl sulphone grouping.  When a basic compound containing the above grouping is applied to undyed material, the latter acquires an increased affinity for acid dyestuffs.  In the following examples the process described is followed by alkaline after-treatment: (1) cotton or viscose is printed with a paste of aniline-3-(b -hydroxyethylsulphone) sulphuric ester --> 2:3-oxynaphthoic 2-methoxy-5-vinylsulphonylarylide, thiodiglycol and thickener; (2) as in (1) where the 5-substituent in the arylide is b -hydroxyethylsulphone sulphuric ester; (3) wool is dyed with aniline-3-(b -hydroxyethylsulphone sulphuric ester --> 2:3-oxynaphthoic o-anisidide; (4) wool is dyed with aniline-4-(b -hydroxyethylsulphone)-sulphuric ester --> N-butyl-N-hydroxyethyl-cresidine; butyl may be replaced by methyl or hydroxyethyl; (5) wool is dyed with 2:4-dinitrodiphenylamine-41-(b -hydroxyethylsulphone) sulphuric ester; (6) nylon is dyed with 2-methoxyaniline-5-(b -hydroxyethylsulphone) o-sulphobenzoic ester --> 2:3-oxynaphthoic p-anisidide; (7) nylon is dyed with 2-methoxy-aniline-5-(b -hydroxyisopropylsulphone) sulphuric ester --> 2:3-oxynaphthoic a -naphthylamide; (8) wool is dyed with aniline-4-(b -hydroxyethylsulphone)-sulphuric ester --> diphenylamine; (9) cotton is dyed with o-tolidine \sQ 1-naphthylamine-5-(b  - hydroxyethylsulphone) - sulphuric ester; (10) wool is dyed with 1-amino-4-(21-methoxyanilino - 51 - (b  - hydroxyethylsulphone) sulphuric ester) - anthraquinone - 2 - sulphonic acid; (11) cotton is dyed with 2-methoxyaniline - 5 - (b  - hydroxyethylsulphone) sulphuric ester --> amide of 2:3-oxynaphthoic acid with 2 - amino - 3 - methoxy - dibenzofuran; (12) wool is dyed with a dyestuff as in (10) but without the sulphonic acid group; (13) wool is dyed with aniline-3-(b -hydroxyethylsulphone) sulphuric ester --> b -naphthol; (14) wool is dyed with a dyestuff as in (10) but without the methoxy and sulphonic acid groups; (15) cotton is dyed with o-dianisidine \sQ 1-naphthol-5-(b -hydroxyethylsulphone) sulphuric ester; (16) wool is grounded with 2:3-oxynaphthoic anilide - 31 - (b  - hydroxyethylsulphone) - sulphuric ester and developed with, e.g. diazotized 4-methoxy-41-aminodiphenylamine or 5-methyl-2 - methoxy - 4 - benzoylamino - aniline; (17) tris - (b  - hydroxyethylsulphonylmethyl)-copper phthalocyanine trisulphuric ester is made by chloromethylating copper phthalocyanine, exchanging chlorine for mercapto, reacting with ethylene oxide or chlorhydrin, acetylating, oxidizing the thio groups to sulphone, hydrolysing the acetyl groups and converting to sulphuric ester; cotton is then dyed with this product; (18) cotton is dyed with 1:5-dihydroxy - 4:8 - di - [3 - (b  - hydroxyethylsulphonyl) - benzoylamino] - anthraquinone disulphuric ester; (19) wool is dyed with 2-methozyaniline - 5 - (b - hydroxyethylsulphone) sulphuric ester --> N-phenyl-g -acid; (20) cotton is printed with the urea of 2-methoxyaniline-5-(b -hydroxyethylsulphone) sulphuric ester --> cresidine, and thiodiglycol; (21) cotton is impregnated with the diazoamino compound from 2 - methoxyaniline - 5 - (b  - hydroxyethylsulphone) sulphuric ester and N-methyltaurine; it is developed with a coupling component after alkali treatment, e.g. with N-phenyl-g -acid, J-acid urea or 1-naphthol-5-sulphonic acid; (22) cellulose acetate is printed with 2-methoxyaniline -5-(b -hydroxyethylsulphone) sulphuric ester --> 1-naphthol-5-sulphonic acid, thiodiglycol, triethanolamine and thickener; (23) leather is dyed in a drum with the dyestuff of (19) and may then be fat-liquored.ALSO:Dyestuff and other textile intermediates containing the grouping <FORM:0733471/IV (b)/1> where R, R1 and R2 each represent hydrogen or a hydrocarbon radical of low molecular weight, and Z is the residue of a polybasic acid such as sulphuric, phosphoric, boric or polysulphonic or polycarboxylic of the benzene or naphthalene series, are prepared as follows: (1) a sulphinic acid is condensed with an alkylene oxide or chlorhydrin such as ethylene, propylene or 1 : 2-butylene oxide or ethylene or propylene chlorhydrin, and the hydroxy group esterified; or (2) a mercaptan is reacted with an alkylene oxide or chlorhydrin, the thio group in the product oxidized to sulphone and the hydroxy group esterified.  Further condensations may be effected to introduce other desired groups into the molecule.  Specified products are 2 : 4- or 3 : 4-dichlorobenzene - b  - hydroxyethylsulphone phosphoric and sulphuric esters, octadecyl b -hydroxyethylsulphone sulphuric ester, and acid esters of 1 : 1 : 1 - trichloro - 2 - di - (b  - hydroxyethylsulphonylphenyl) - ethane, 2 - naphthyl b -hydroxyethyl sulphone, 2 : 3-oxynaphthoic anilide - 31 - (b  - hydroxyethylsulphone), the diazoamino compound from 2-methoxyaniline-5-(b -hydroxyethylsulphone) and N-methyltaurine, condensation products of aminoaryl b -hydroxyethylsulphones with cyanuric chloride, oleic acid chloride and stearyl isocyanate, reaction products of higher amines with chlorophenyl b -hydroxyethylsulphones, sulphones by oxidation of condensation products of chlorinated higher paraffins with mercaptoethanol, the benzimidazole from maleic anhydride and o-phenylenediamine - 4 - (b - hydroxyethylsulphone), the product obtained from 4 : 41-diaminostilbene - 2 : 21 - bis - (b -hydroxyethyl sulphone) and 2 mols. of cyanuric chloride (the further chlorine atoms being exchanged for two hydroxyl and two anilino groups), the reaction products of aryl isocyanates with 4 : 41-diaminostilbene - 2 : 21 - bis - (b  - hydroxyethylsulphone) and 2 - stearyl - 3 - methyl - 6 - (b  - hydroxyethylsulphonyl)-benzimidazole.  An arylide is made by condensing 2-hydroxy-3-naphthoyl chloride with 2 - methoxy - 5 - vinylsulphonylaniline.