CS238094B1 - Method of preparing 2: 1 metal complex dyes - Google Patents

Abstract

The purpose of the invention was to simplify the production of symmetrical 2:1 metal complex dyes, in particular their preparation without isolating intermediates. The purpose was achieved by carrying out the azo coupling in the presence of carbonates and/or bicarbonates of alkali metals or ammonium, and the chromization is carried out with a reagent containing chromium dichromate.

Description

The invention relates to a process for the preparation of metal-complex dyes, wherein the central metal is a chromium atom, consisting of a consecutive reaction of water-soluble azo compounds of the general formula:

wherein X is hydrogen and / or -NOg

I »

Y is a 1-naphthyl or 2-naphthyl 1-phenyl-3-methyl-5-pyrazolone group, prepared in general by azocopulation of diazotizing components of formula:

wherein X is hydrogen and / or -NOg as described above with the coupling components Y and subsequent cp.

-2238 094

Methods known for preparing the aforementioned type 2: X metallocomplex dyes are based on the azocopulation of the starting components at relatively low temperatures in an alkali hydroxide environment, where side reactions are performed whose products greatly impair the coloristic properties of the final dyes. As a result, the products of these side reactions have to be removed from the reaction mixture. The dyeing is generally carried out with chelating agents, most often chromsalicilic acid or other trivalent chromium compounds under extreme conditions. The disadvantages of these hitherto known methods for the preparation of symmetrical metal-complex azo dyes are the necessity of isolation of the azo dye and the final metal-complex dye, the lack of preparation of special chromating agents, or the need for high-temperature and pressure chromating.

It has now been found that the above disadvantages are overcome by the process for preparing the metal-complex dyes of formula X

O // 0,5-Ο-ν = / ν-γ Y — A / = V. Qx where X is hydrogen and / or grouped?

Y is 1-naphthol and / or 2-naphthoxyl-1-phenyl-3-methyl-5-pyrazolone and the azocopulation of the diazotization component is 1-diazo-2-naphthol-4-sulfonic acid and / or 6-nitro- 1-diazo-4-sulfonic acid with a coupling component which is 1-naphthol and / or 2-naphthol or 1-phenyl-3-methyl-5-pyrazolone and chromating the resulting reaction product according to the invention by carrying out the azocopulation ae in the presence alkali metal carbonates and / or hydrogen carbonates;

The ammonium salt with the diazotizing component in the form of the ammonium salt and the chromation of the reaction product is carried out with a chromium dichromate reagent.

It is an advantage of the process according to the invention that in the presence of alkali metal and ammonium carbonates or bicarbonates, the azocopulation reaction of the starting diazonium salts can be optimally achieved at reaction temperatures of 40 to 10 ° C, chemical products being highly pure corresponding compounds. starting coupling copolymers (1-naphthol and / or 2-naphthol) in the form of an emulsion prepared in aqueous solutions of mixtures of alkali hydroxides with alkali carbonates, optionally in the presence of suitable emulsifiers * at 95-100 ° C and starting diazotization components neutralized with aqueous ammonia solution A further advantage of the process according to the invention is the possibility of carrying out azo dye synthesis at high starting concentrations of the reactants, which is particularly advantageous for the subsequent chromium metallization.

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It has also been found that the reaction medium containing carbonate, bicarbonate and ammonium ions creates favorable conditions for the metallization of azo dyes directly in the reaction mixture with a chromating agent containing chromium dichromate, the application of which makes it possible to prepare 2: 1 metallocomplex compounds. At the same time, the temperature of the chromating process for a maximum of 30 to 90 minutes does not exceed the boiling point of the reaction mixture, and there is no need to prepare commonly used chromium coordination compounds with salicilic acid. , where only coordinating compounds are formed containing two molecules of the starting azo dye and one central chromium atom »

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Advantages of the process for the preparation of symmetrical metal-complex azo dyes according to the invention are the highly selective and rapid course of azo copulation and metallation reactions, which in industrial applications allows to minimize equipment requirements, high production process productivity, waste-free technology management and production process continualization.

Example 1

175 parts by weight of 1-phenyl-3-methyl-5-pyrazolone are dissolved in 1500 parts by weight at 60 ° C. parts of water using 95 rm. 1000 parts of an aqueous suspension containing 250 parts of 1-diazo-2-naphthol-4-sulfonic acid are added with stirring, and the reaction mixture is heated to a temperature of 60 to 70 ° C. After this time, 500 parts of a chromating reagent prepared by mixing 75 parts of potassium dichorate, 120 parts of scalic acid and 305 parts of water are added to the reaction mixture. 90-95 ° C.Vzniklá reaction is further heated at 95-100 ° C wherein _R occurs quantitatively transfer complex azo dyes formu.Po kleraci reaction mixture. The dye solution is dried. 560 parts of a 2: 1 metal-complex dye are obtained, dyeing wool and polyamide textile materials to a red hue.

Example. 2

144 parts by weight of 2-naphthol are emulsified at 1,500 parts by weight of water at 95 DEG C. with 20 parts of sodium hydroxide and 95 parts of sodium carbonate and 1 part of sodium dodecylbenzenesulfonate. The emulsion thus prepared is mixed with 1200 parts of a suspension containing 300 parts of 1-diazo-2-naphthol-6-nitro-4-sulfonic acid neutralized with aqueous ammonia to pH 4.5 with stirring. After mixing the reactants, the temperature of the reaction mixture the resulting azo dye is chromium-plated with 500 parts of the chromating agent prepared according to the example and for 30 minutes at the boiling point of the reaction mixture. After the reaction mixture is cured, the dye solution is dried,

-5238, thereby obtaining 720 parts of the metal-complex dye, dyeing the wool and polyamide materials to a deep black tint.

Example 3

590 parts of a 2: 1 metalconjlex dye that dyed wool and polyamide textile materials to a reddish brown shade were prepared in the same manner as in Example 1, except that 300 parts of 1-diazo-2-naphthol-4-sulfonic acid was used instead of 250 parts. parts of 1-diazo-2-naphthol-6-nitro-4-sulfonic acid.

Example 4

675 parts of a 2: 1 metal-complex dye dyeing wool and polyamide textile materials to a dark blue shade were prepared in the same manner as in Example 2, except that 300 parts of 1-diazo-2-naphthol-6-nitro-4-sulfone 250 parts of 1-diazo-2-naphthol-4-sulfonic acid are used.

Claims (1)

BACKGROUND OF THE INVENTION 238 094 A process for the preparation of 2: 1 metal-complex dyes of the general formula X wherein X is hydrogen and / or NO ₂ Y is a 1-naphtholyl or 2-naphtholino-1-phenyl-3-methyl-5-pyrazolone group by azocopulation of the diazotization component, which is 1-diazo-2-naphthol-4-sulfonic acid and / or 6-nitro- 1-diazo-4-sulfonic acid with a coupling component which is 1-naphthol and / or 2-naphthol or 1-phenyl-3-methyl-5-pyrazolone, and by chromating the resulting reaction product, characterized in that the azocopulation is carried out with The presence of an alkali metal or ammonium carbonate and / or bicarbonate with a diazotizing component in the form of an ammonium salt and the chromocation of the reaction product and the azocopulation is carried out with a chromium dichromate reagent.