CS260627B1 - Non-symmetrical 1 to 2 metallocomplex dye stuffs and method of their preparation - Google Patents

Abstract

Unsymmetrical 1: 2 metal complex dyes with two chromium-based sulfo groups complexes of constitution I where substituents Ai and Az are different and denote —NO2, —Cl, —SO3, with one of the substituents M + is Na + and / or NH4 + Constitution I

Description

SUMMARY OF THE INVENTION The present invention provides unsymmetrical 1: 2 metal-complex dyes based on the chromium complex of Formula I

where A 1 and A? they are different and denote -NO 2, -Cl, -SO 3, wherein each substituent is -SO 3 ^- and M ⁺ is Na ⁺ and / or /ι ⁺ .

These dyes are new and usable for dyeing woolen and polyamide textile materials, which dye highly stable blue to gray shades.

The hitherto known metal-complex dyes are prepared as 1: 1 chromium, 1: 2 symmetric and 1: 2 asymmetric complexes containing one sulphosucline 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 symmetrical 1: 2 metal-complex dyes is that it is difficult to achieve the high lightfast 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 equalization in conventional dyeing processes.

It has now been found that said drawbacks do not exhibit 1: 2 metal-complex dyes having 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 and A 2 are as previously defined.

The unsymmetrical metal-complex dyes of constitution (I) according to the invention are readily obtainable by the action of compounds of constitution (II),

3M '(I) wherein A 1 and A 2 are as previously defined for the 1: 1 chromium complex of formula

(III) or by treatment with an azo compound of formula (IV)

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

N = N (V).

(II) wherein A 1 and A 2 are as previously defined in an alkaline, neutral or weakly acidic environment at temperatures usually 80 to 100 degrees Celsius.

The process for the preparation of unsymmetrical 1: 2 chromium complexes of constitution (IJ according to the invention) can be carried out advantageously with a reaction medium containing ammonium or alkali carbonates, the presence of which allows the complexing reaction to be easily carried out in a high concentration of reacting components.

The advantage of the process for the preparation of 1: 2 unsymmetrical complexes of 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. possible symmetrical 1: 2 metal complex dyes. In addition to the high solubility of the dye, the product (1j) has excellent coloristic properties and high light fastness.

The advantage of the process of preparing 1: 2 chronic asymmetric complexes according to the invention is furthermore to achieve high production on a simple production equipment and to guide the production process so that it is possible to work with waste-free technologies. A further 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 0.02 moles of a 1: 1 chromium complex of formula (V) (A 1 = NO 2, A 2 = -SO 5) in 400 ml of water was added 0.02 mol of azo compound of constitution (IV) and adjusted to pH 10 with sodium hydroxide solution. the mixture was heated to 90-95 ° C and held at this temperature for 1 hour. The resulting dye solution was sclerated and dried. 22.5 g of a dye of the formula I (A1 - - NO2, A2 = --SO3) were obtained, dyeing wool and polyamide textile materials to a bluish gray shade with high light fastness.

Example 1 a d 2

To a suspension of 0.02 mole of the 1: 1 chromium complex of formula (III) in 400 ml of water was added 0.02 mole of the azo compound of constitution (Π) (Ai = —NO2, A2 = —SO3-) and the pH was adjusted with 1.2 ml sodium hydroxide solution c (NaOH) 10 mol / l. The reaction mixture was heated to 90-95 ° C and held at this temperature for 1 hour. The resulting dye solution was sclerated and dried. 22.5 g of a dye of the formula I (A1 = -NO2, A1 = = -SO3) were obtained, i.e. the same constitution as in Example 1.

Example 1 a d 3

To a suspension of 0.02 mole of the 1: 1 chromium complex of formula (III) in 400 ml of water was added 0.02 mole of the azo compound of constitution IV (A 1 = -Cl, A 2 = -SO 3 -). The pH of the reaction mixture was adjusted to 10 with 10 N sodium hydroxide solution (NaOH), 0.02 mol of sodium hydrogen carbonate was added, and the reaction mixture was heated at 90-95 ° C for 2 hours. The resulting dye solution was sclerated and dried. 18 g of dye of formula (I) (Al - —Cl, A2 = —SO3-) were obtained, dyeing wool and polyamide textile materials to a reddish-blue hue with high light fastness.

Claims (3)

OBJECT OF THE INVENTION 1. Unsymmetrical 1: 2 metal-complex dyes with two sulfo groups based on chromium complexes of constitution I (I) where the substituents A 1 and Aa are different and denote —NO2, —Cl, - SO3, where each substituent denotes —SO3 ^- and M ⁺ is Na ⁺ and / or NH 4 ⁺ . 2. A process for the preparation of unsymmetrical 1: 2 chromium complexes according to claim 1, characterized in that the azo compounds of the formula II or the azo dyes IV ' ^A Z OH are reacted with a 1: 1 chromium complex of the azo dyes V meaning is reacted with a 1: 1 chromium complex of formula III '/ \ / ' ^z \ N O (41) wherein A 1 and A 2 are as defined above. 3. A process for the preparation of asymmetric 1: 2 chromium complexes according to claim 1 or 2, characterized in that the synthesis of the dyes is carried out in an alkaline, neutral or slightly acidic medium.