CS204071B1 - Reactive triazine complex metal compounds of azo dyes - Google Patents

Description

The present invention relates to reactive triazine metal-complex azo dyes for dyeing cellulosic materials to black shades.

British Patent 985,481 describes 2: 1 chromium-cobalt complexes of azo dyes of the general formula

wherein A represents a nitre-1,2-phenylene radical which may be further substituted by chlorine, methyl or nitro, one symbol X represents hydrogen and the other a sulfo group and Y represents chloro, alkoxy, aryloxy, substituted aryloxy, amino robo substituted amino group. These blends are valuable reactive dyes for dyeing cellulosic fibers to rich blacks.

A disadvantage of the dyes prepared according to said patent is the need to use cobalt salts, for example, cesium sulfate, which are relatively expensive and, in particular, have recently been difficult to obtain. The proportion of cobalt complex in the aforementioned mixtures is between 20 and 50%.

It has now been found that reactive triazine metallocomplex azo dyes of very similar colloistic properties can be obtained at lower production costs if similar mixtures of chromium and ferric complexes are prepared instead of mixtures of chromium and cobalt complexes. Indeed, the cost of iron salts useful in the preparation of ferric complexes is substantially lower than the cost of analogous cobalt salts. Also, in terms of availability, iron salts are much more preferred and, in particular, the most commonly available salt, ferrous sulfate (green vitriol), is practically a waste product.

The present invention provides novel reactive triazine metallocomplex azo dyes of the formula I

wherein one of R 1 and R a is hydrogen and the other is nitro, R 3 is an amino group, C 1 -C 4 alkylamino, phenylamino optionally substituted with methyl or isulfo, C 1 -C 4 alkoxy or phenoxy, and Me is a chromium mixture and iron, having a ratio of 9: 1 to 6: 4.

The dyes of Formula I may be prepared by use of agents providing chromium and iron · o, o ^'j dihydroxyazobarviva formula II

in which R1 and R2 are as defined above, by condensation of the resulting mixture of chromium and ferric complex with a 2: 1 ratio of azo dye to the galley and cyanuric chloride or with triazine derivatives of the general formula III

Cl

III in which R3 is as defined above, and when cyanuric chloride has been used for the condensation, substituting another chlorine atom by reaction with ammonia, aliphatic or aromatic amines or phenols.

The starting o, ^o'-1 dihydroxyazobarviva general formula II are known per se and are described for example in British Pat. No. 965 481. They are prepared in a conventional procedure involving diazotization of 4-nitro-2-aminophenol sulfoxylate · 5-nitro-2- aminophenol and the coupling of the resulting diazonium salt with 1-amino-8-hydroxynaphthalene-3,6-disuiphonic acid in a weakly alkaline medium. For further processing according to the invention, they may be isolated or preferably used without isolation in the form of a solution.

The conversion of the o, o-dihydroxyazo dyes of the formula II to a chromium-ferric complex is carried out by treatment with chromium and iron providing agents, both metallization reactions preferably being carried out in one operation and in one reaction vessel, without intermediate isolation of one or the other. In general, metallization can be accomplished by reacting o, o'-dihydroxyazo dyes with both reagents simultaneously (parallel reactions), but for practical reasons (better analytical control of the metallization process) it is preferable to act sequentially with each agent, regardless of the order in which the metallization is performed. .

The conversion of o, o-dihydroxyazo dyes to complexes with an azo dye to metal ratio of 2: 1 requires, as is well known, 1/2 equivalent metallizing agent. In order to achieve a deep black shade of the reactive dyes of the formula I, a molar ratio of chromium to iron complex relative to one another and thus 1 of the respective metallizing agents 9: 1 to 6: 4 is suitable.

As the chromium-donating agent, chromium acetate, bromine sulfate or potassium chromite alum can be used. as iron-donating agents, salts of both trivalent, for example ferric sulfate, ferric chloride, and divalent iron, for example ferrous sulfate, can be used, both of which produce identical products, namely ferric ferric complexes.

The metallization is carried out by heating an aqueous solution ^. The compound of formula II with the required amount of metallizing agents at a temperature of 40 to 110 ° C and addition of acid-binding substances such as sodium acetate, sodium carbonate or sodium bicarbonate.

The resulting mixture of chromium (III) and ferric complex is suitable for further processing according to the invention isolated from the reaction mixture, for example by precipitation from solution by addition of sodium or potassium salts.

The isolated mixture of chromium (III) and ferric complex is condensed with cyanuric chloride or triazine derivatives of formula (III) after being redissolved in water. Examples of triazine derivatives of general formula III include the condensation products of cyanuric chloride with 1 equivalent of amines, alcohols or phenols, prepared by conventional and known methods. Condensation with cyanuric chloride or triazine derivatives of the formula III is carried out at 0 to 50 ° C ia at pH 4-7, maintained by the addition of substances capable of binding acids, such as sodium carbonate, sodium bicarbonate ¹ sodium carbonate or sodium hydroxide and the addition of surface-active substances or organic solvents such as acetone.

When cyanuric chloride is used for the condensation, the resulting dichlorotriazine derivatives are further condensed with ammonia, aliphatic or aromatic amines or phenols without isolation. This condensation is carried out at an elevated temperature of 20 to 60 ° C and with the addition of acid scavengers.

The final monochlorotriazine dyes are isolated from the reaction mixture by conventional means, for example by precipitation from solution by addition of salts (sodium chloride, potassium chloride or potassium acetate) or by evaporating the entire reaction mixture to dryness in a suitable drying apparatus.

The reactive triazine metal-complex azo dyes prepared according to the invention are novel. They are valuable dyes suitable for dyeing natural cellulose fibers (cotton, flax, hemp) and regenerated cellulose fibers (viscose staple) to rich blacks, which can vary, depending primarily on the chromium / iron ratio, from greenish black to reddish black. New dyes are applied to said textile materials by flocculation or printing in the presence of acid binders. In addition to the desired shade, they are characterized by very good fastnesses. in washing and high stability, in light.

Compared to some of the known, structurally and dye-like properties described, for example, in Brit. No. 985,481, the novel dyes are characterized in particular by lower production costs and easier availability of one of the metallizing agents (ferrous or ferric isoli).

The invention is illustrated by the following examples in which parts are by weight unless otherwise indicated.

Example 1

To 52.8 parts of azo dye sodium salt prepared by coupling diazotized 4-nitro-2-aminophenol with Wamino-8-hydroxynaphthalene-3,6-disulfonic acid in 500 parts of water is added 10 parts of crystalline sodium acetate, 20 parts of chromium-alum. potassium [Cra (SO4) 3]. K2SO4.24 Η2Ό j, the mixture is heated to boiling and boiled under stirring for 3 hours. Then, 2.8 parts of crystalline ferrous sulphate (FeSO 4 .7H 3 O) was added to the reaction mixture and heated at a temperature of 50-60 ° C for 1 hour. The resulting mixture of chromium (III) and iron (III) complex is separated from the solution by the addition of 120 parts of potassium chloride and, after cooling, filtered.

The isolated paste is dissolved in 350 parts of water, the solution is cooled to 0-3 ° C, 18.4 parts of cyanuric chloride are added, and the mixture is stirred for 3 hours while maintaining the pH at 6-7 by adding 10% sodium carbonate solution. After completion of the condensation, excess cyanuric chloride is removed by filtration.

To the solution of the resulting dichlorotriazine derivative was added 17 parts of a 25% aqueous ammonia solution and the mixture was heated at 30 ° C for 2 hours. The pH of the reaction mixture is adjusted to 7 with hydrochloric acid, the dye is separated from the solution by the addition of 180 parts of sodium chloride, filtered off and dried at 70 ° C.

This procedure yields a mixture of dyes of the following structural formulas (in the form of free acids):

about 20%.

The product obtained is a black powder which dissolves well in water to a violet-blue solution, in concentrated sulfuric acid, to a red-violet solution. According to the analysis, it contains a hydrolyzable chlorine atom of 1.0 a7 group. The absorption spectrum of the neutral aqueous solution shows 2 absorption maxima at wavelengths 583 and 631 nm. When applied to cellulosic materials in the presence of alkali, it provides a rich black coloration with very good wash and light fastnesses.

Dyes of similar properties are obtained when methylamine, aniline, o- or p-toluidene, n or aniline-3-sulfonic acid is used instead of ammonia to replace the second chlorine atom.

Example 2

To 52 parts of azo dye prepared by coupling diazotized 5-nitro-2-aminophenal with 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 500 parts of water was added 10 parts of crystalline sodium acetate, 4.2 parts of gelatinous sulfate. and the mixture was heated at 70 ° C for 1 hour. 17.5 parts of potassium chromium alum are then added, the mixture is heated to boiling and maintained at this temperature for 3 hours. The resulting mixture of chromium (III) and ferric complex is separated from the solution by the addition of 120 parts of sodium chloride and, after cooling, is filtered off.

The isolated paste was dissolved in 350 parts of water, a solution of 31 parts of 2,4-dichloro-6- (3-sulfoanilino) -triazine sodium salt in 150 parts of water was added and the mixture was heated to 45 ° C for 3 hours while maintaining ipH 6 to 7 with 10% sodium carbonate solutions.

After completion of the condensation, the dye is isolated by evaporating the reaction mixture to dryness.

This procedure yields a mixture of dyes of the following structural formulas (in the free acid farm):

The product obtained is a black powder, which dissolves in water, into a blue solution, in concentrated sulfuric acid, to a chip-violet solution. According to the analysis, it contains 1.02 hydrolysable chlorine atoms per azo group. The absorption spectrum of the neutral aqueous solution shows 2 absorption maxima at 593 and 649 nm. When applied to cellulosic materials in the presence of alkali, it provides a rich black coloration with very good wash and light fastnesses.

A dye of very similar properties is obtained when the same molar amount of 2,4-dichloro-S- (4-sulfoanilino) -s-triazine is used in place of 2,4-dichloro-6 (3-sulfoanilino) -5-triazine.

Example 3

To 52.8 parts of azo dye sodium salt prepared by coupling diazotized 4-nitro-2-aminophenol with 1-amino-8-hydroxy-naphthalene-1,3,6-disulfonic acid in 500 parts of water is added 10 parts of crystalline sodium acetate, 2 | 2 5 parts of chromium-potassium alum, 1 part of ferric chloride and the mixture was heated to boiling for 3 hours. The resulting mixture of chromium (III) and ferric complex is separated from the solution by the addition of 110 parts of sodium chloride and, after cooling, filtered.

The recovered paste was dissolved in 350 parts of water are added 18 parts of 2,4-dichloro-6-methoxybriazinu and the mixture was stirred for 2 hours at 20 ° C while maintaining pH 6-7 by adding 10 ^I0 / o sodium carbonate solution. After completion of the condensation, the dye / precipitates out of solution by adding 160 parts of sodium chloride, filtered and dried at 70 ° C.

This procedure yields a mixture of b-derivatives of the following structural formulas (in the form of free acids):

och ₃

The product obtained is a black powder which dissolves in water into a violet-blue solution, in concentrated sulfuric acid on a worm, a non-violet solution. It contains 0.94 hydrolysable chlorine atoms per 1 azo group. The absorption spectrum of the neutral aqueous solution shows 2 absorption maxima at wavelengths 572 and 621 nm. When applied to cellulosic materials in the presence of alkali, rich black coloration provides very good wash and light fastnesses.

Dyes of similar properties are obtained when the same molar amounts of 2,4-dichloro, R-6-ethoxy-s-triazine, 2,4-dichloro-6- are used for condensation instead of 2,4-dichloro-6-methoxytriazine. (2-ethoxyethoxy) -s-triazine or 2,4-dichloro-6-phenoxy-s-thiriazine.

Claims (1)

SUBJECT VYNALEZU Reactive triazine metallocomplex azo dyes of the formula I in which one of R 1 and R 2 is hydrogen and the other is nitro, R 3 is amino, C 1 -C 4 alkylamino, phenylamino optionally substituted with methyl or sulfo, C 1 -C 4 alkoxy or the phenoxy group and the Me symbol denote a chromium-iron mixture having a ratio of 9: 1 to 6: 4.