Patent GB-421117-A (GB)
Title: Improvements in the manufacture and production of organic dyestuffs
IPC: C09B69/00
Filed: 1933-05-06
Abstract: Dyestuffs are produced in substance or on the fibre by a process which includes the step of interaction, at above about 60 DEG  C., at any stage in the production of the dyestuff, between an intermediate compound or dyestuff containing at least one reactive hydrogen atom in its molecule and such an amount of an alkylene oxide that the reaction product contains at least one radicle with at least four carbon atoms, such radicle containing at least one ether-oxygen bridge and at least one free hydroxy group. Alternatively, such radicles are introduced into the intermediate compound or dyestuff by condensation with aliphatic compounds already containing such a radicle, e.g., tri- or tetra-ethylene glycol or polymerised glycerol or halogen compounds thereof.  The resulting dyestuffs, as compared with the dyestuffs not containing the said radicle, are more readily dispersed or dissolved in water.  The free hydroxy groups in the finished dyestuffs may be esterified with phosphoric or sulphuric acid.  The following intermediate compounds or dyestuffs are specified as reactants:--a -- and b -- aminoanthraquinones, 1 : 4- and 1:5:diaminoanthraquinones, and acylation or sulphonation products of these still retaining reactive hydrogen, di- and tri-hydroxyanthraquinones, mono- and di-hydroxy- and mono- and di-amino-benzanthrones, hydroxy- or aminodibenzanthrones, other vat dyestuffs containing hydroxy, carboxy or amino groups, e.g., those of the indigo or thioindigo series, aminoazobenzene, azo or triphenylmethane dyes containing hydroxy, carboxy, amino or imino groups, intermediates for the preparation of triphenylmethane dyes, coupling components for azo dyes, e.g., amines, phenols and naphthols, such as p-toluidine, p-xylidine, o-anisidine, m-phenylenediamine, m-toluylenediamine, a -naphthylamine, p-aminophenol, aminonaphtholsulphonic acids and salicylic acid, diazo components for azo dyes, e.g., m-phenylenediamine, benzidine, tolidine, dianisidine, 3 : 3<1>-diaminoazobenzene, and anthranilic acid, the amino group to be diazotized being protected during the reaction or being introduced subsequently by reduction of a nitro group.  Specified alkylene oxides are ethylene oxide and propylene oxide; the Provisional Specification refers also to the use of hexylene and dodecylene oxides.  The condensation with the intermediate compound may be effected in presence of neutral acid or alkaline catalysts, such as bleaching earths, mineral acids, alkali metal hydroxides or alcoholates, ammonia, sodium chloride or acetate. The alkylene oxides or polymerized glycols may react first with compounds, such as monochloracetic acid or glycol chlorhydrin, containing a readily exchangeable halogenatom in addition to a readily reactive hydrogen atom, the products being then further reacted with the intermediate compounds or dyestuffs.  The finished dyestuffs may be employed for dyeing in hard water and, in cases where the affinity for the fibres is slight, deep dyeings or prints may be obtained by applying the dyestuffs, or the components for their production upon the fibres, with the use of elevated temperatures or with the addition of assistants, e.g., Glauber's salt, formic or acetic acid, sulphite waste liquor, soaps, turkey red oils, sulphuric esters of higher alcohols, condensation products of fatty acids with amino-alkyl- or hydroxy-alkylsulphonic acids or reaction products of ethylene oxide with higher alcohols, or by pre-treatment of the fibrous material with tannin, phenolic compounds, tanning substances, sulphurized phenols or their sodium salts or other substances capable of fixing the dyestuffs or components in insoluble form upon the fibres.  The dyeings may also be after-treated with tannin, reduction products of phosphotungstomolybdic acid or metal salts to improve the fastness to water, washing and light.  Alternatively the dyestuffs may be pre-treated with metal salts.  The dyestuff products are also suitable for colouring fats, oils, waxes, soaps, organic solvents and cellulose ester or other varnishes and in some cases for printing paper or colouring sizes.  The following examples of the manufacture and application of the dyestuffs are given.  (1) A mixture of 1 : 4-diamino-anthraquinone, sodium chloride, benzene and ethylene oxide is heated with stirring at 120--130 DEG  C., for 15 hours under pressure, the benzene is distilled off and the residue is extracted with boiling water, the aqueous solution being evaporated and the residue dried in vacuo; the product dyes a tannin-mordanted mercerised cotton yarn a dark grey shade which, on after-treatment with copper chloride and acetic acid, is fast to washing; it is also applicable for colouring linseed oil, the oil so coloured being suitable, with or without addition of siccatives, for sizing a viscose or acetate artificial silk warp for identification purposes in weaving.  (2) m-Phenylenediamine (1 mol.) is treated at about 100 DEG  C., under pressure, in presence of a small proportion of sodium alcoholate, with ethylene oxide (7 mols.) until all the ethylene oxide has been absorbed and the product is applied in a bath treatment to tannin-mordanted viscose artificial silk, which is then treated with a solution containing the tetrazo compound of Fast blue salt B, and a condensation product of ethylene oxide (20 mols.) with oleyl alcohol (1 mol.) to obtain a deep violet-red dyeing, fast to rubbing; alternatively the dyestuff may first be prepared in substance; the dyeings may be made fast to water by after-treatment in a bath containing tannin, sodium chloride and acetic acid.  (3) A mixture of aminoazobenzene, sodium chloride, benzene and ethylene oxide is heated with stirring at 120--130 DEG  C., for 15 hours under pressure, the benzene is distilled off and the dyestuff is extracted from the residue as in (1); the product gives olive green dyeings on viscose artificial silk or natural silk mordanted with tannin and yellow dyeings on wool; the condensation product from aminoazobenzene, (1 mol.) and ethylene oxide, (6 mols.) colours olein olive green when heated therewith at 120 DEG  C., in a closed vessel with addition of a small proportion of caustic soda solution.  (4) 1 : 4-Diaminoanthraquinone (1 mol.) is heated at 120 DEG  C., with ethylene oxide (5 mols.) in presence of 1 per cent of sodium chloride to obtain a blue dyestuff readily dispersible in water; acetate artificial silk is dyed a bluish violet, very fast to rubbing, by treatment for 1 hour in a bath at 70 DEG  C., containing 5 per cent. of the dyestuff, preferably with an addition of soap or of the reaction product from ethylene oxide (20 mols.) and oleyl alcohol (1 mol.).  (5) m-Phenylenediamine (1 mol.) is heated at about 100 DEG C., with ethylene oxide (7 mols.) in presence of a small proportion of caustic soda solution and the product is coupled with tetrazotized fast blue salt B to obtain a resinous red-violet dyestuff, soluble in water; this gives deep blue-black dyeings capable of a good gloss on tanned sheep leather; if the tetrazotized Fast blue salt B is replaced by diazotized 2 : 5 : 7 - amino - naphtholsulphonic acid, the product gives deep dark red dyeings on chrome-tanned leather; similar water-soluble dyestuffs are obtainable by similarly condensing p-aminophenol (1 mol.) with monochloracetic acid (1 mol.) and ethylene oxide (6 to 8 mols.) and coupling the product with diazotized aniline or its derivatives, e.g., m-nitraniline.  (6) A mixture of 2-aminoanthraquinone, sodium chloride, benzene and ethylene oxide is heated with stirring at 120--130 DEG  C., for 15 hours under pressure, the benzene is distilled off and the dyestuff is extracted from the residue as in (1); the water-soluble viscous red-brown product may be mixed into a melted montanic acid glycol ester or beeswax to obtain a brick red wax suitable for candles.  (7) Natural silk or viscose artificial silk mordanted with tannin is subjected to a bath treatment with a solution of the condensation product of example (2) from m-phenylenediamine (1 mol.) and ethylene oxide (7 mols.) and is then treated with a solution of tetrazotized Fast red salt GL to obtain red-brown dyeings fast to water; if the condensation product is replaced by one from o-anisidine (1 mol.) or p-xylidine (1 mol.) and ethylene oxide (10 mols.), the dyeings are golden yellow to orange; if the tetrazo component is replaced by diazotized p-nitraniline --> 2 : 5-dimethoxyaniline, the dyeings are brown-black; a bath containing a water-soluble azo dyestuff prepared in substance (cf example 5) with the use as coupling component of the above condensation product from m-phenylenediamine and ethylene oxide may be used at room temperature for colouring a paper mass, previously treated with tannin, comprising 2 parts of wood pulp, 1 part of sulphite cellulose and small additions of resin soap and aluminium p  sulphate.  (8) Oak or beech wood is coloured grey or red by immersion in an aqueous solution of the dyestuff of example 1 or example 6 respectively.  (9) Viscose artificial silk rope ware is treated with a solution containing a condensation product from m-phenylenediamine (1 mol.) and a polyglycerol (2 mols.), of molecular weight about 462, which has been treated with gaseous hydrochloric acid, and the material is developed with tetrazotized Fast blue salt B to obtain chestnut brown dyeings very fast to rubbing; if the condensation product is coupled with diazotized 2 : 5 : 7 - aminonaphtholsulphonic acid, the sodium salt of the resulting dyestuff gives level red-violet dyeings on viscose artificial silk from a Glauber's salt bath.  Specifications 11930/09, 26336/10, [both in Class 2 (iii)], 380,431, and 380,851 are referred to.ALSO:Dyestuffs containing at least one radicle with at least four carbon atoms, such radicle containing at least one ether-oxygen bridge and at least one free hydroxy group, an