DD201316A1 - METHOD FOR PRODUCING HOMOGENEOUS MIXTURES OF 1: 2 METAL COMPLEX DYES - Google Patents

Abstract

The invention relates to a process for the preparation of mixtures of the 1: 2 chromium and 1: 2 cobalt complexes of monoazo reactive dyes of the formula I in which X = SO &sub3; H, NO & ind2! or CI and Y = NH & ind2! or Z, where Z is the radical of a compound HZ, the aniline, N-methylaniline, N-ethylaniline, o-, m-, p-methylaniline, o-ethylaniline, o-, m-, p-methoxyaniline, aniline o-sulfonic acid, aniline-m-sulfonic acid, aniline-p-sulfonic acid, a sulfonic acid of o-methyl, o-ethyl or o-methoxyaniline or monoethanolamine should be. These mixtures are obtained according to the invention in a so-called one-pot process by initially monoazo dyes of the formula II in aqueous solution by treatment with chromium salts to a certain proportion in the 1: 2 chromium complexes, the remaining amount of monoazo in the medium of chromiumation by treatment with cobalt salts converted into the 1: 2 cobalt complexes and condenses this mixture of metal complexes without intermediate purification with cyanuric chloride, the resulting primary condensation products with ammonia or a compound HZ for the replacement of the second CI atom on the triazine converts formula I and II

Description

The invention relates to a process for the preparation of homogeneous mixtures of 1: 2 ~ δ and 1: 2-Cobaltkomplexeη of .farbstoffen, which in the acid form of I'ormel

(D

correspond. Herein X = SO ₃ H, NO ₂ or Gl and Y = or Z. Z is the radical of a compound HZ which is aniline, N-methylaniline, N-ethylaniline, 0-, m-, p-methylaniline, Äthylanilin, 0-, m-, p-methoxyaniline, aniline-o-suifonsäure, Anilinm-sulfonic acid, aniline-p-sulfonic acid, a sulfonic acid of o-methyl, o-ethyl or .o-Methoxyanilins or monoethanolamine mean.

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Characteristics of the known technical solutions

British Patent Nos. 870,985, 952,461 and 953,710 disclose the pure 1: 2 chromium or 1: 2 Eobaltkomple2: e of monoazo reactive dyes of the above formula. They are suitable for dyeing and printing Gellulosetextilmaterialien, however, give the pure dye complexes when applied only tints of dark reddish purple to greenish dark blue.

Neutral black dyeings on cellulosic textile materials are not available in this way.

From GB-PS 9,551 481 mixtures of the 1: 2-chromium and 1: 2-cobalt complexes of konoazoreaktivfarbstoffen of the above formula are known, with which neutral black Gellulosefärbungen be achieved with excellent fastness properties which is in the acid form of the formula

(H)

corresponds, in which X has the above meanings, in aqueous solution with chromium salts, the resulting 1: 2 chromium complex isolated, washed, the redissolved 1: 2 chromium complex condensed with cyanuric chloride, the resulting primary condensation product with ammonia or a compound HZ further condensed, the dye is isolated and dried.

On a separate apparatus, the corresponding 1: 2 'cobalt complex is prepared in a similar manner. A monoazo dye corresponding to formula II is cobaltized and the inter-purified 1: 2 cobalt complex is then processed as above.

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The resulting 1: 2 chromium and 1: 2 cobalt complexes are now. Finally, mixed in a certain ratio to each other and this mixture used for dyeing or printing cellulosic textile materials, wherein neutral black colorations are achieved.

Object of the invention

The aim of the invention is a comparison with the previous procedure economically favorable production process for homogeneous mixtures of 1: 2 chromium and 1: 2 cobalt complexes of monoazo reactive dyes of the formula I.

Presentation of the «Vesens of the Invention;

It has been found that homogeneous mixtures of the 1: 2 chromium and 1: 2 cobalt complexes of. Monoazoreaktivfarbstoffen of formula I can produce much cheaper if monoazo dyes of formula II in a so-called one-pot process in aqueous solution by treatment with chromium salts to a certain proportion in the 1: 2 chromium complexes, the remaining portion of unreacted Mo dozo dyes in the environment converted the chromation by treatment with cobalt salts in the 1: 2 cobalt complexes and condensing this mixture of metal complexes without intermediate isolation with cyanuric chloride, the resulting primary condensation products with ammonia or a compound HZ further condensed, after which the mixture of metal complex monoazo reactive dyes separated in a known manner and dried becomes.

The resulting homogeneous mixture of the metal-complex monoazo reactive dye e gives, when applied to cellulosic textile products, neutral black dyeings with excellent fastness properties.

The ratio of the 1: 2 chromium to the 1: 2 cobalt complexes in the resulting homogeneous mixtures can vary depending on

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The structure of the monoazo reactive dyes of the formula I vary within wide limits, but is generally within the ratio of 4: 1 to 1: 4.

Compared to the production process known from the prior art, the process according to the invention has the following advantages: By eliminating a separate approach to preparing the 1: 2 cobalt complexes, since they are prepared in accordance with the invention in the environment of ghromization, on the one hand the need for equipment is considerably reduced, on the other hand the present invention the possibility to carry out the 1: 2 chromium complex formation in the presence of an excess of the monoazo dye concerned, apparently to the almost exclusive formation of the desired 1: 2 Ghromkomplexe, so that the previously required intermediate purification of Chromierungsprodukte to separate non-usable Ohromkomplexe no longer required is, which results in a significant simplification of the process. The process according to the invention of the cobaltation of monoazo dyes in the environment of the ghromization reduces the reaction volume, as a result of which larger batches can be run in the same apparatus unit and thus a significantly more favorable space-time yield is achieved. The need for reaction accelerators of metallization, such as. Salicylic acid, for example, is reduced because the amount of salicylic acid used to accelerate the ghromination is completely released after 1: 2 Ghromkomplexbildung and used to accelerate the cobaltation. It is essential for the process according to the invention that the monoazo dyes are subjected to an excess of monoazo dyes which clearly exceeds the ratio of the ghrome to the monoazodye of 1: 2, and the cobaltation of the remaining fraction of monoazo dyes only after completion of 1: 2 -Ghromkomplexbildung is made «

A simultaneous ghromization and cobaltation of the monoazo dyes or also the proportional cobaltation of the monoazo dyes before the 1: 2 ~ Ghromkomplexbildung the remaining portion of the monoazo dyes generally leads to poor

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results, in particular to low color strengths of the final products or also to poor wet fastnesses of the cellulose dyeings carried out with them, which apparently is connected with an incomplete 1: 2 Ghromkomplexbildung under these conditions.

In addition to the abovementioned advantages of the method according to the invention, there are further advantages, such as reducing the need for raw materials such as alkali, hydrochloric acid and sodium or potassium chloride (for salting out), which are given due to the possibility of concentrated driving , which in turn leads to a significant reduction in the salt load of the wastewater. The amount of waste water is significantly lower due to this concentrated Pahrweise, also result for the same reason significant savings in energy sources, such as low-pressure steam, ice or brine.

The following example is intended to further illustrate the invention without limiting it thereto. The parts mentioned therein are parts by weight.

Ausführunpsbeispiel

98.9 parts of 8-amino-2- (5'-nitro-2 ^l -hydroxy-phenylazo) - '1-naphthol-3 _t 6-disulfonic acid are suspended in 400 parts of water and by the addition of hydrochloric acid, a pH of 2.8 set. Then 6 parts of salicylic acid and 19.2 xieile of a basic chromium sulfate with a Cr ₂ O content of 24 to 26 % (Basochrom the VEB hydrogenation Zeitz, BT Völpke) was added and heated to 100 ⁰ O for 3 hours, with the addition of soda the pH is maintained between 2.5 to 3. The mixture is then raised with sodium hydroxide solution the pH to 7. "5 and held for 2 hours at 90 ⁰ G, um.die 1; terminate 2-Ohromkomplexbildung. The solution of the monoazo dye proportionately chromed is cooled to 80 ⁰ C and 4.8 parts of cobalt carbonate, dissolved in dilute hydrochloric acid, added. It is stirred for 2 hours at 75 ⁰ O , wherein the pH is maintained at 9 by means of soda.

232578 6

After completion of the cobaltization, the solution is cooled to 0 ⁰ G, adjusted to pH 7 with hydrochloric acid and 37j added 5 '.Peile cyanuric chloride and 1 part of a wetting agent. The reaction mixture is stirred for 3 hours at 0 to 3 ⁰ C, wherein the pH is maintained by addition of alkali by 7.0. After the condensation 70 parts of ammonia water is added (0.89 g / ml density) and the mixture for 2 hours at 25 ⁰ O stirred. It is heated to 45 ⁰ O, being held by üodazugabe the pH above 8.5. After completion of the condensation, 18 % sodium chloride and 5 % potassium chloride are added and the precipitated homogeneous mixture of the metal-complex monoazo reactive dyes is separated off and dried. With printing pastes prepared on the basis of the dye mixture thus obtained obtained on fabrics made of regenerated cellulose fiber deep black color prints with excellent fastness properties.

Claims (2)

Claim for invention 1. A process for the preparation of homogeneous mixtures of 1: 2-Ghrom- and 1: 2-cobalt complexes of dyes which are in the acid form of the formula HO ₃ S (D in which X = SCLH, NOp or Gl and Y = 1IH ₂ or Z, where Z is the radical of a compound HZ, the aniline, U-methylaniline, N-ethylaniline, o-, m-, p-methylaniline , o-ethylaniline, o-, m-, p-kethoxyaniline, monoethanolamine, aniline-o-sulfonic acid, aniline-m-sulfonic acid, aniline-p-sulfonic acid or a sueflonic acid of o-methyl-, o-Xtbyl-, o-methoxyaniline is, characterized in that dyes of the formula -232578 6 (II) in which X has the abovementioned meaning, are first converted into a 1: 2 chromium complex in aqueous solution in a one-pot process by treatment with chromium salts by known methods, the remaining fraction of the dyes of the formula II subsequently. Treating with cobalt salts by conventional methods in the 1: 2 cobalt complex is converted, then the mixture of the metal complexes with cyanuric chloride to the primary condensation product and this with ammonia or a compound HZ, wherein HZ has the abovementioned meaning, is further condensed. 2. The method according to item 1, characterized in that the chromium and cobalt salts are used in amounts such that the ratio of 1: 2 chroin complex to 1 ^ -Kalt complex in the homogeneous dye mixture is 4: 1 to 1: 4.