CS260634B1 - Unsymmetrical 1: 2 metal complex dyes and method of their preparation - Google Patents

Abstract

Unsymmetrical 1:2 metallocomplex dyes with two sulfo groups based on chromium complexes of constitution I, where the substituents Ai and Az are different and denote —NOz, —Cl, —SO3©, with one of the substituents Ai or Az always denote SOs© and the substituent A3 denotes —H or —Cl, and M denotes Na+ and/or NH4+.

Description

The present invention provides unsymmetrical 1: 2 metal-complex chromium complex dyes of formula I

v and X 3

N - N - C - CONH

wherein A 1 and A 2 are different and denote -NO 2, -Cl, -SO 3 ^- and A 3 is -H, -Cl, wherein each of A 1 or A 2 is -SO 2 ^- and M is Na ⁺ and / or NH 3 ⁺ .

These dyes are new and usable for dyeing wool and polyamide. Textile materials that dye with highly stable olive to brown shades.

Hitherto known metal-complex dyes are prepared as 1: 1 chromium complexes, 1: 2 symmetric chromium or cohesite complexes or 1: 2 unsymmetrical chromium complexes containing one sulfo group per molecule. A disadvantage of 1: 1 metal-complex dyes is their low pull-out from neutral and weakly acid dye baths. A disadvantage of the symmetrical 1: 2 metal-complex dyes is that it is only relatively difficult to achieve the high-light color dyes of the desired shades for dyeing wool and polyamide. The disadvantage of 1: 2 unsymmetrical metal-complex dyes with one sulfo group is their lack of solubility and leveling in conventional dyeing processes.

It has now been found that said drawbacks do not exhibit the 1: 2 metal-complex dyes of the two sulfo groups according to the invention, which is based on an unsymmetrical 1: 2 chromium complex of constitution (I), wherein the substituents A 1, A 2 and A 2 are as previously defined.

The unsymmetrical metal-complex dyes of constitution (I) according to the invention are readily prepared by the reaction of azo dyes of constitution II

A _from OH ^H °

X ^CHj

II ^x VN.-NC-conh (II) where

A 1, A 2 and A 1 are as defined above for the 1: 1 chromium complex of the azo dye of formula (IIIJ)

or by the action of azo compound IV

(IV) to 1: 1 chromium complexes of formula V

where

Α, A2 and As have the above meanings in an alkaline, neutral or weakly acidic environment at temperatures of usually 80 to 100 ° C.

The process for the preparation of unsymmetrical 1: 2 constitutional chromium complexes according to the invention can preferably be carried out in a reaction medium containing ammonium or alkali carbonates. The presence of these substances makes it easier to carry out the complexing reaction in a high concentration of reacting components.

The advantage of the process for the preparation of 1: 2 unsymmetrical chromite complexes of the constitution I according to the invention is the high purity of the dye, since the currently used methods of synthesis of unsymmetrical 1: 2 metallocomplex dyes. both possible symmetrical 1: 2 metal complex dyes. In addition to the high solubility of the dye, the product I is characterized by excellent properties and high light fastness.

The advantage of the process of preparing 1: 2 chromium asymmetric complexes according to the invention is furthermore to achieve high production on a simple production device and to guide the production process so that it is possible to work with waste-free technologies. Another advantage of producing 1: 2 unsymmetrical chromite complexes with two sulfo groups is that it is not necessary to isolate the dye itself before drying.

The invention is further illustrated by the following non-limiting examples.

Example 1

To a suspension of 0.20 mole of 1: 1 chromium complex (III) in 4 L of water was added 0.20 mole of constitution dye (VI)

prepared by azocopulation of diazotized 4-nitro-2-aminophenol-6-sulfoacid to acetoacetanide and the mixture was adjusted to pH 10 by the addition of 22 ml of sodium hydroxide solution c (NaOH) = 10 mol / l to 0.10 moles. was heated at 90-95 ° C for 1.5 h. 40 g of filter clay was added and the reaction mixture was sclerified. After drying the dye solution in a spray drier it was obtained; 210 g of dye of constitution I (where Ai = - —NO2, Az = - SO3, A3 = H), dyeing wool and polyamide textile materials to a khaki shade with high fastness.

Example 2

To a suspension of 0.20 mole of 1: 1 chromium (III) complex in 4 L of water was added 0.20 mole of constitution VII dye.

- CONI-I (VII) prepared by azocopulation of diazotized 6-chloro-2-amino-phenol-4-sulfoacid to acetacetanilide and the mixture was neutralized by addition of 20 ml sodium hydroxide solution c (NaOH) = 10 mol / l to pH = 7.5. 0.10 mol of sodium carbonate was added and the reaction mixture was heated to 95 ^° C for 2 hours. 20 g of filter clay was added and the mixture was sclerified. After drying the dye solution, 200 g of a dye of constitution I (where A 1 = -SO 3 ^- , Az = -Cl, A3 = -H) were obtained, dyeing wool and polyamide textile materials to a high light fast khaki shade.

280034

Example 3

To a suspension of 0.20 moles of a 1: 1 chromium complex of constitution VII

0.20 mol of azo dye of constitution (IV) was added and the mixture was treated with 84 ml of ca 23% aqueous ammonia solution at pH 10. 0.10 mol of sodium bicarbonate was added and the reaction mixture was heated at 90-95 for 3.5 hours. Deň: 32 ° C. After addition of 20 g of filter clay, the reaction mixture was sclerified. After drying the dye solution, 225 grams of constitutional dye (A 1 - = - SO 3 -, A 2 = - NO 2, A 3 = - H) was obtained, dyeing wool and polyamide textile materials to a high shade brown hue.

Claims (3)

1. Unsymmetrical 1: 2 metal-complex dyes with two sulfo groups based on chromium complexes of constitution I 3M where substituents A 1 and A 2? they are different and denote "-NO 2, —Cl, - SO,"; and A3 is -H or -Cl, wherein one of the substituents At or A? denotes --SO 5 and M represents Na ⁺ ε or NH 3. 2. A process for the preparation of unsymmetrical 1: 2 chromium complexes according to claim 1, characterized in that the azo dyes of the formula II wherein A, A2 and A3 are as defined above are reacted with a 1: 1 chromium complex of the azo dye III (III). the azo dye of formula IV is reacted with a 1: 1 chromium complex of the azo dye of formula V And where A 1, A 2, and As are as previously defined. 3. A process for the preparation of asymmetric 1: 2 chromite dye complexes according to claim 2, characterized in that the synthesis of the dyes is carried out in an alkaline, neutral or slightly acidic medium.