KR940007328B1 - Method of producing reactive monoazo dyes - Google Patents

Abstract

This relates to a new manufacturing method of a reactive monoazo dye of formula (I). The manufacuring method comprises: A) diazonizing the aromatic amine compd. of formula (II); B) making monoazo compd. of (IV) by coupling with amino compd. of (III) in the presence of sodium carbobenzoate catalyst at 0-20 deg.C and in 2.0-5.0 pH; and C) condensing cyanurate chloride and aromatic amine compd. containing sulfatoethylsulfonate of (IV).

Description

[Purpose of invention]

Process for preparing reactive monoazo dye

Detailed description of the invention

This invention relates to a process for the preparation of the reactive monoazo dyes of the general formula [I] used for dyeing cellulose fibers in yellow.

In the above formula, R ¹ , R ² are each independently hydrogen, methyl, methoxy, ethoxy, carboxyl or sulfonic acid group; R ³ is hydrogen, methyl or sulfonic acid group; A is an acetyl, ureido, propionyl, benzoyl or paratoluenesulfonyl group; X is -CH ₂ CH ₂ OSO ₃ H or -CH = CH ₂ , n is the number of 2 or 3.

As a result of the reaction of unreacted reactants in the manufacture of reactive dyes, the process of salting out and refining has not only resulted in poor fastness and accumulating effect on dyeability, but also a large amount of balance, which is considerable for wastewater treatment. I heard this. In addition, side reactions occur as well as by-products, which are disadvantageous in that each process takes a long time. This problem is due to the failure to properly select the catalyst.

Therefore, an object of the present invention is to select a suitable catalyst to speed up the reaction and at the same time maximize the complete reaction, yield a high yield and a new method for producing a reactive monoazo dye, eliminating the existing filtration, salting and purification process, etc. To provide.

The process according to the invention diazotizes the aromatic amine compound of formula (II) and couples it with the amino compound of formula (III) in the presence of sodium carbonbenzoic acid catalyst at a temperature of 0-20 ° C. and a pH range of 2.0-5.0. Ring to obtain a monoazo compound represented by formula (IV), and then condensed with an aromatic amine compound containing cyanuric chloride and sulfatoethylsulfon group of formula (V), in order. It consists of obtaining a dye.

In the above formula, R ¹ , R ² , R ³ , A, X and n are as defined above.

After diazotizing the aromatic amine compound of general formula (II) according to a known method, general formula (III) is a coupling component in the presence of sodium carbonbenzoic acid catalyst at a temperature of 0-20 ° C. and a pH range of about 2.0-2.5. The amino compound of was prepared by coupling a monoazo compound (lV). The azo compound is then added with sodium bicarbonate or sodium carbonate to adjust the pH to 4-5 and stirred overnight. After neutralizing the pH of the monoazo compound of (IV) in the range of 6.5-6.8, it was made into an aqueous solution, and then condensed with cyanuric chloride at 0-20 ° C, and the aromatic amine compound of general formula (V) at 20-40 ° C. The second condensation to prepare a reactive monoazo compound (I) according to the present invention. During the first condensation and the second condensation, the pH is adjusted to 5-6 and the condensation product is dried directly with a spray dryer to formula (I) To prepare dyes.

Using the reactive monoazo dye according to the present invention, cotton, hemp, and viscose rayon, which are cellulose fiber materials, are absorbed at 20-40 ° C in the presence of neutral salt sodium chloride or sodium sulfate, and are absorbed at 20-40 ° C. Sodium hydroxide, sodium bicarbonate, tribasic sodium phosphate and the like are added and treated at a temperature of 50-60 ° C. to cause staining.

The dyeings are dyed in dark yellow and orange color, and are excellent in wet, washing and light fastness and stable to acid hydrolysis. In addition, after dyeing, there is a small amount of balance and almost no waste water occurs.

Hereinafter, the present invention will be described in more detail with reference to the following examples. In the examples, "parts" means parts by weight.

Example 1

14 parts of concentrated hydrochloric acid was added to 45.6 parts of 2-aminonaphthalene-3,6,8-trisulfonic acid in 230 parts of water, and stirred for 2 hours. Then, 100 parts of ice water was added, followed by cooling, 8.2 parts of sodium acetate, and stirred for 4 hours.

5.8 parts of sodium carbonate was added to adjust the pH to 3, 1.0 part of sodium carbon benzoic acid was added, 18 parts of ureidoaniline was dispersed together with 120 parts of water and 12 parts of sodium bicarbonate, heated to 70 ° C, cooled to l5-20 ° C, and then diazotized solution Add, adjust pH to 4-5 and stir overnight.

Separately, 22.6 parts of cyanuric chloride and a dispersant are added to 220 parts of ice water, and the mixture is stirred to form a suspension. The reaction solution was added thereto, reacted at 0-20 占 폚, 8 parts of sodium carbonate was added, neutralized, and heated to 20 占 폚.

1-Aminobenzene-4-β-sulfatoethylsulfonic acid is added, neutralized, stirred, heated to 40 ° C, and dried with a spray dryer. 200 parts of drying amount were obtained.

Example 2

Cyanuric chloride and 1-aminobenzene-4-β-sulfatoethylsulfonic acid were simultaneously added to the compound of formula (IV) synthesized according to the method described in Example 1, and then reacted. Neutralize to 6.5-6.8 and dry with a spray dryer.

Example 3-31

The examples in which the monoazo coupling component is different from β-sulfatoethylsulfone according to the procedure of Example 1 are shown in the following table.

Example 32

This example relates to a comparative example without a catalyst.

14 parts of concentrated hydrochloric acid was added to 45.6 parts of 2-aminonaphthalene-3,6,8-trisulfonic acid in 230 parts of water, and stirred for 2 hours. Then, 100 parts of ice water was added, followed by cooling, 8.2 parts of sodium acetate, and stirred for 4 hours.

5.8 parts of sodium carbonate was added to adjust the pH to 3, 18 parts of ureidoaniline was dispersed together with 120 parts of water and 12 parts of sodium bicarbonate, heated to 70 ° C., cooled to 15-20 ° C., and then added to the diazotized solution and the pH was adjusted to 4.4-. Adjust to 4.5 and stir overnight.

Sodium chloride is added to this solution to precipitate crystals, suction filtration, and dissolve in 240 parts of water.

Separately, 22.6 parts of cyanuric chloride and a dispersant are added to 220 parts of ice water, and the mixture is stirred to form a suspension.

After adding and reacting the above reaction solution, the reaction mixture was neutralized with 8 parts of sodium carbonate, heated to 20 ° C, and added with 1-aminobenzene-4-β-sulfatoethylsulfonic acid. Then, the mixture was stirred and heated to 40 ° C., and then 300 parts of sodium chloride was added to precipitate crystals. The crystals were filtered off by suction, and dried at 60 ° C. to obtain 160 parts of dry amount.

According to this embodiment it can be seen that there is a problem that the yield is not only about 20% lower than the case of using the catalyst according to the present invention, the reaction time is long, and the process is long.

Claims (1)

The aromatic amine compound of formula (II) is then diazotized and coupled with an amino compound of formula (III) in the presence of a sodium carbonbenzoic acid catalyst at a temperature of 0-20 ° C. and a pH range of 2.0-5.0 to formula (IV) The monoazo compound represented by) is obtained, and then condensed with cyanuric chloride and an aromatic amine compound containing a sulfato-episulfon group of general formula (V), in order to prepare a reactive monoazo dye of general formula (I). How to: In the above formula, R ¹ , R ² are each independently hydrogen, methyl, methoxy, ethoxy, carboxyl or sulfonic acid group; R ³ is hydrogen, methyl or sulfonic acid group; A is an acetyl, ureido, propionyl, benzoyl or paratoluenesulfonyl group; X is -CH ₂ CH ₂ OSO ₃ H or -CH = CH ₂ : n is the number of 2 or 3.