DE2908135A1 - Cationic alkyl imidazolyl-azo aniline dyestuffs - useful for dyeing and printing polyacrylonitrile and acid modified polyamide and polyester textile and in inks - Google Patents

Abstract

New cationic N-alkyl-4-(imidazol-2'-ylazo)aniline dyestuffs are of formula (I). In (I), Y is -NR- CHR3 or -NR- CHR4R5; R is H; R1 and R2 are each lower alk(en)yl or hydroxyalkyl; R3 and r5 are each H or Me; R4 is H Me, Et, OH, MeO or hydroxyethyl or -CHR4R5 is -CH=CH2 or CMe=CH2; and X- is an anion. (I) are used for partic. dyeing and printing polyacrylonitrile (PAN or acid-modified polyamide or polyester textiles. They are also useful in other applications for cationic dyestuffs, e.g. for dyeing and printing cellulose materials, paper and silk, in ball pen and stamp pad inks and in transfer and offset printing. They have good fastness and exhaustion properties and combine well with other dyestuffs.

Description

Cationic dyes

The invention relates to new cationic dyes of the general formula where R1 and R2 independently of one another represent a lower alkyl, alkenyl or hydroxyalkyl radical, p3 represents H or methyl, represents H, methyl, ethyl, hydroxy, methoxy, hydroxymethyl or hydroxyethyl, R5 represents H or methyl or for -CH = CH2 or and X is an anion, their manufacture and use for dyeing and printing natural and sathetic materials.

Lower alkyl and alkoxy groups include, in particular, straight-chain or branched radicals with 1 to 4 carbon atoms.

Lower alkenyl radicals are in particular those with 3 or 4 carbon atoms, especially the allyl, butenyl and i-butenyl radicals.

The anion X can be derived from inorganic and organic acids.

Inorganic anions are, for example, fluoride, chloride, bromide and iodide, perchlorate, hydroxyl, residues of S-containing acids such as hydrogen sulfate, Sulfate, disulfate and aminosulfate; Residues of nitrogen-oxygen acids, such as nitrate; Residues of oxygen acids of phosphorus, such as dihydrogen phosphate, hydrogen phosphate, Phosphate and metaphosphate; Carbonic acid residues such as hydrogen carbonate and carbonate; further anions of oxygen acids and complex acids, such as methosulphate, ethosulphate, Hexafluorosilicate, cyanate thiocyanate, tri- and tetrachlorozincate, tri- and tetrabromozincate, Borate, tetrafluoroborate, and anions of esters of boric acid, such as the glycerol ester boric acid and esters of phosphoric acid such as methyl phosphate.

Organic anions are, for example, saturated or unsaturated anions aliphatic, cycloaliphatic, aromatic and heterocyclic carboxylic acids and sulfonic acids, such as residues of formic acid, acetic acid, chloroacetic acid, cyanoacetic acid, Hydroxyacetic acid, aminoacetic acid, methylaminoacetic acid, aminoethylsulfonic acid, Methylaminoethylsulfonic acid, propionic acid, n-butyric acid, i-butyric acid, 2-methylbutyric acid, 2-ethylbutyric acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, 2-chloropropionic acid, 3-chloropropionic acid, 2-chlorobutyric acid, 2-hydroxypropionic acid, 3-hydroxypropionic acid, O-ethylglycolic acid, thioglycolic acid, glyceric acid, malic acid, dodecyl tetraethylene glycol ether propionic acid, Phenoxyacetic acid, nonylphenoxyacetic acid, n-valeric acid, i-valeric acid, 2,2, 2-trimethyl acetic acid, n-caproic acid, 2-ethyl-n-caproic acid, stearic acid, oleic acid, ricinoleic acid, palmitic acid, n-pelargonic acid, lauric acid, a mixture aliphatic carboxylic acids with 9 to 11 carbon atoms (Versatic acid 911 der Shell), acrylic acid, methacrylic acid, crotonic acid9, propargylic acid, oxalic acid, Malonic acid, succinic acid, adipic acid, pimelic acid, suberic acid, of the mixture of isomers from 2,2,4- and 2,4,4-trimethyladipic acid, sebacic acid, isosebacic acid (mixture of isomers), Tartaric acid, citric acid, glyoxylic acid.

Suitable anions of cycloaliphatic carboxylic acids are, for. B. the anions the cyclohexanecarboxylic acid, cyclohexene-3-carboxylic acid and anions of araliphatic Monocarboxylic acids are z. B. anions of phenylacetic acid, 4-methylphenylacetic acid and mandelic acid.

Suitable anions of aromatic carboxylic acids are, for example Anions of substituted and unsubstituted benzoic acid, phthalic acid, tetrachlorophthalic acid, 4-hydroxyphthalic acid, 4-methoxyphthalic acid, isophthalic acid, 4-chloro-isophthalic acid, 5-nitro-isophthalic acid, terephthalic acid, nitroterephthalic acid and diphenylcarboxylic acid- (3,4), o-vanillic acid, 3-sulfobenzoic acid, benzene tetracarboxylic acid (1,2,4,5), naphthalenetetracarboxylic acid (1,4,5,8), Biphenylcarboxylic acid (4), abietic acid, phthalic acid mono-n-butyl ester, terephthalic acid mono-methyl ester, 3-hydroxy-5,6,7,8-tetrahydronaphthalene-carboxylic acid- (3), 2-hydroxynaphthoic acid- (1) and anthraquinone carboxylic acid- (2).

Suitable anions of aromatic sulfonic acids are, for example, the anions benzene sulphonic acid, benzene disulphonic acid (1,3), 4-chlorobenzenesulphonic acid, 3-mitobenzenesulphonic acid, 6-chloro-3-nitrobenzenesulfonic acid, toluenesulfonic acid- (4), toluenesulfonic acid- (2), Toluene - @ - sulfonic acid, 2-chlorotoluenesulfonic acid (4), 2-hydroxybenzenesulfonic acid, n-Dodecylbenzenesulfonic acid Colorless anions are preferred. For dyeing from aqueous In the medium, preference is given to those anions which still affect the water solubility of the dye; affect too much. For dyeing from organic solvents are multiple also preferred anions that increase the solubility of the dye in organic Promote solvents or at least not negatively influence them.

The anion is generally by the manufacturing process and the any purification of the crude dye that may have been carried out is given. Generally lying the dyes as zinc chloride double salts, acetates, methosulfates, ethosulfates or Halides (especially as chlorides or bromides). The anions can be known in Way to be exchanged for other anions.

In preferred dyes of the formula I, R1 and R2 are ethyl and especially methyl, R3 for hydrogen, R4 for H, methyl, ethyl, hydroxy or Methoxy and R5 for hydrogen.

The new dyes of the general formula I are produced according to known methods Procedure.

They are obtained in excellent yield by reacting compounds of the formula with amines of the formula In formulas II and III, R1, R2, X, R3, R4 and R5 have the same meaning as in formula I.

R6 denotes a group which can be split off by an amine, e.g. an alkoxy group, an alkyl thio group or a halogen atom.

The dyes of the formula I are also readily accessible by reaction of the compounds II in which R6 is hydrogen, with amines of the formula III in the presence an oxidizing agent, e.g. atmospheric oxygen.

The reactions of II with III can be carried out without a diluent, in aqueous Solution or suspension, in the presence of organic solvents or mixtures thereof take place with water at room temperature or elevated temperature. Lots of connections react between 00C and 20 ° C.

The compounds of the formula 11 are prepared in a known manner by diazotizing and coupling aminobenzenes of the formula in which R6 has the meaning given in formula II, to imidazole and subsequent reaction of the compounds obtained in which R6 has the meaning given in formula II, with alkylating compounds of the formula Rt-X VI or R2-X Vla, in which R1 and R2 have the meaning given in formula I and X is a group providing an anion X, or with oxiranes the formula wherein R8 is hydrogen, methyl or ethyl, prepared Another method for preparing the dyes of the formula I consists in the saponification of compounds of the formula by warming their aqueous suspension or solution with mineral acid.

In formula VIII, R1, R2, R3, R4, R5 and X have those given for formula I. Meaning, Rg means an acyl radical which can be split off by hydrolysis, such as, for. B. acetyl, Propionyl, benzoyl or sulfonyl.

The compounds of the formula VIII are prepared in a known manner by diazotizing and coupling aminobenzenes of the formula in which R3, R4, R5 and Rg have the meaning given for formula VIII, to imidazole and subsequent reaction of the compound obtained in which R3, R4, R5 and Rg have the meaning given in formula VIII, with alkylating compounds of the formula R1-X VI or R2-X VIa, in which R1 and R2 have the meaning given in formula I and X is an anion X supplying Group, or with oxiranes of the formula wherein R8 is H, methyl or ethyl.

Suitable diazo components IV are, for example: aniline, p-anisidine, p-phenetidine, p-n-propoxyaniline, p-i-propoxyaniline, p-butoxyaniline, p-chloroaniline, p-bromoaniline, p-fluoroaniline, p-methyl mercaptoaniline, p-ethyl mercaptoanil in.

Suitable amines III are e.g .: ethylamine, isopropylamine, n-propylamine, n-butylamine, allylamine, ethanol amine, 2-nethoxyethylamine, isobutylamine, sec-butylamine, 1-amino-2-propanol, 1-hmino-3-propanol.

Suitable diazo components IX are, for example: 4- (N-acetyl-N-ethyl) -aminoaniline, 4- (N-ß-hydroxyethyl-N-acetyl) -aminoaniline, 4- (N-acetyl-N-propyl) -aminoaniline.

The new dyes are suitable for dyeing, printing and mass dyeing of acidic group-containing materials, especially of products that are completely or predominantly of polymerized unsaturated nitriles such as acrylonitrile and Vinylidendicyanid or made of acid modified polyamides or polyesters. They are also suitable for the other known applications of cationic dyes, like dyeing and printing cellulose acetate, coconut, jute, sisal and silk, of tanned cotton and paper, for the production of ballpoint pen pastes and Stamp inks and for use in transfer printing and rubber printing.

The dyeings and prints on the first-mentioned materials, in particular on polyacrylaitrile, are characterized by their very high level of fastness mainly due to very good light, wet, rubbing, decatur, sublimation and perspiration fastnesses.

Furthermore, the new dyes have a very good balancing capacity, which makes it possible without great demands on the dyeing technology without the addition of a retarder to achieve even colors on acrylonitrile fibers even in light tones.

In addition, the new dyes have good drawability and good combinability both with other dyes that migrate well as well as with Dyes with less good balancing capacity.

Example 1 20 g of the dye of the formula obtained by coupling diazotized 4-methoxyaniline onto imidazole, subsequent methylation with dimethyl sulfate, dissolving in water and precipitating with sodium chloride and ZnCl2 are stirred with 20 ml of ethanol. 20 g of an aqueous 50% strength ethylamine solution are added dropwise to this mixture at 40.degree. C. and the mixture is stirred for a further 3 hours at this temperature. The mixture is then cooled to room temperature, diluted with 100 ml of saturated evaporated salt solution and the pH of the mixture is adjusted to 5 with hydrochloric acid. The resulting dye of the formula is then filtered off away. It dyes polyacrylonitrile and acid-modified polyester in a yellowish red shade with very good fastness properties and very good leveling properties.

If the starting dye is alkylated with diethyl sulfate instead of dimethyl sulfate, the dye of the formula is obtained with otherwise the same procedure the polyacrylonitrile dyes a yellowish red with good fastness properties.

Example 2 20 g of the dye of the formula obtained by coupling diazotized aniline onto imidazole, subsequent methylation with dimethyl sulfate, dissolving in water and precipitating with NaCl and ZnCl2 are stirred at room temperature in the presence of atmospheric oxygen with 35 ml of a SOZigen aqueous ethylamine solution until the starting dye is no longer detectable in the thin-layer chromatogram. The mixture is then diluted with 100 ml of saturated evaporated salt solution and the pH is adjusted to 5 with HCl. The dye obtained is then filtered off. It is identical to the product described in Example 1.

Example 3 55.5 g are slowly added to 50 g of 50% strength ethylamine solution conc. Hydrochloric acid.

100 g of the dye of the formula obtained by coupling diazotized 4-chloroaniline onto imidazole, subsequent methylation with dimethyl sulfate, dissolving in water and precipitating with NaCl are stirred in this solution the mixture is heated to 90 ° C. and 50% ethylamine solution is very slowly added dropwise at this temperature until the starting dye is no longer detectable in the thin-layer chromatogram. The mixture is then cooled to room temperature, diluted with 100 ml of saturated evaporated salt solution and the pH is adjusted to 5 with HCl. The dye is then filtered off. It is identical to the dye obtained in Example 1.

If one of the amines mentioned in the following table is used instead of ethylamine in Examples 1, 2 and 3, valuable dyes are also obtained which color polyacrylonitrile in the shades listed: Example No. Amine shade on polyacrylonitrile 4 allylamine yellow. Red 5 n-butylamine scarlet fever 6 n-propylamine scarlet fever 7 isobutylamine bluish. Scarlet 8 aminoethanol yellow. Red 9 isopropylamine yellow. Red 10 2-methoxyethylamine red ii i-amino-2-propanol red 12 i-amino-3-propanol red Example 13 10 g of the dye obtained by coupling diazotized 4- (ethylacetylamino) aniline to imidazole and subsequent methylation with dimethyl sulfate formula are concentrated in 250 ml of water after adding 20 ml. Hydrochloric acid 1 hour.

boiled under reflux. The dye of the formula falls on cooling the end. Its coloristic properties are identical to those of the dye described in Example 1.

Example 14 A fabric made of polyacrylonitrile is coated with a printing paste printed, which was prepared in the following manner: 30 parts of that described in Example 1 Dye, 50 parts of thiodiethylene glycol, 30 parts of cyclohexanol and 30 parts of goat Acetic acid are poured over with 330 parts of hot water and the resulting solution added to 500 parts of Kristallgumni (gum arabic as a thickener). In the end 30 parts of zinc nitrate solution are added.

The pressure obtained is dried, steamed for 30 minutes and then flushed. A yellowish red print with very good fastness properties is obtained.

Example 15 Acid modified polyglycol terephthalate fibers at 20 "C in a liquor ratio 1:40 introduced into an aqueous bath, the per liter 3 to 10 g of sodium sulfate, 0.1 to 1 g of oleyl alcohol polyglycol ether (from 1 mole of oleyl alcohol + 50 moles of ethylene oxide), 0 to 15 g of dimethylbenzyldodecylammonium chloride and 0.15 Contains g of the dye described in Example 6 and with acetic acid to pH 4 until 5 was set. The mixture is heated to 100 ° C. in the course of 30 minutes and this is maintained Bath at this temperature for 60 minutes. The fibers are then rinsed and dried.

A red dyeing with very good fastness properties is obtained.

Example 16 Polyacrylonitrile fibers are at 400C in the liquor ratio 1:40 placed in an aqueous bath containing 0.75 g of 30% acetic acid per liter, 0.38 g of sodium acetate and 0.15 g of the dye described in Example 12 contains. The mixture is heated to the boil within 20 to 30 minutes and the bath is held for 30 to 60 minutes. at this temperature. After rinsing and drying, a red color is obtained with very good fastness properties.

Example 17 From 15 parts of the dye mentioned in Example 1, 15 parts of polyacrylonitrile and 70 parts of dimethylformamide are used to prepare a stock solution, which is added to a conventional spinning solution of polyacrylonitrile and known in Way is spun. A red dyeing with very good fastness properties is obtained.

Example 18 Acid modified synthetic polyamide fibers at 40 ° C in the liquor ratio 1:40 introduced into an aqueous bath, the per liter tO g sodium acetate, d up to 5 g oleyl alcohol polyglycol ether (made from t mol Oleyl alcohol + 50 moles of ethylene oxide) and 0.3 g of the dye described in Example 11 and adjusted to pE 4 to 5 with acetic acid. One heated within from 30 minutes to 98 ° C and keeps the bath at this temperature. Then be the fibers rinsed and dried. A red color is obtained.

Claims (1)

Claims claim 1 dyes of the formula wherein R1 and R2 independently represent a lower alkyl, alkenyl or hydroxyalkyl radical, R3 represents H or methyl, R4 represents H, methyl, ethyl, hydroxy, methoxy, hydroxymethyl or hydroxyethyl, R5 represents H or methyl or for -CH = Cn2 or and X is an anion. Claim 2 dyes according to claim 1, wherein R1 and R2 are methyl or ethyl, R3 for H, R4 for H, methyl, ethyl, hydroxy or methoxy and R5 stand for H. Claim 3 Process for the preparation of dyes according to Claims 1 and 2, characterized in that compounds of the formula with amines of the formula wherein Rl, R2, X, R3> R4 and R5 have the meaning given in claim 1 and R6 is a group which can be split off by an amine, for example an alkoxy group, an alkylthio group or a halogen atom. Claim 4 Method according to Claim 3, characterized in that one in aqueous solution or aqueous suspension, in the presence of organic solvents or their mixtures with water at temperatures between 0 and 1200C, preferably operates at 20 to 95 "C. Claim 5 Process for the preparation of dyes according to Claims 1 and 2, characterized in that compounds of the formula with amines of the formula wherein R1, R2, X, R3, R4 and R5 have the meaning given in claim 1, 1 reacts in the presence of an oxidizing agent. Claim 6 Method according to Claim 5, characterized in that one in aqueous suspension or aqueous solution, in the presence of organic solvents or their mixtures with water at temperatures between 0 and 120 ° C., preferably works at 20 - 900C. Claim 7, method according to claims 5 and 6, characterized in that that the oxidizing agent is atmospheric oxygen. Claim 8 Process for the preparation of dyes according to Claims 1 and 2, characterized in that dyes of the formula in which R1, R2, R3, R4, R5 and X have the meaning given in claim 1 and R9 is a radical which can be split off by hydrolysis, for example an acyl radical, saponified by heating its aqueous suspension or solution with mineral acid. Claim 9 method for dyeing and printing textile materials made of polyacrylonitrile or acid modified polyamide or acid modified polyester, characterized in that dyes according to Claims 1 and 2 are used. Claim 10 Textile materials obtained according to Claim 9.