KR870000220B1 - Process for the preparation of reactive mono- azo- dye - Google Patents

Abstract

Monoazo dyes of formula(I) and their salts are new. In(I) R1 and R2 are H, Cl, Br, methyl, methoxy, ethoxy, carboxyl, sulphon; A is acetyl, ureid, benzoyl, paratoluenesulphonyl; X is -CH2CH2O SO3H or - CH=CH2. (I) are yellow or reddish-yellow dyes for cellulose. (I) have good solubility properties and give shades of excellent all-round fastness and build-up which are not sensitive to dyeing temp.

Description

Method for preparing reactive monoazo dyes

The present invention relates to a method for producing the following general formula [I] as a reactive dye which is dyed yellow / red to cellulose fibers.

In the form of free acid

In the above formula

R ₁ and R ₂ are hydrogen, chlorine, bromine, methyl group, methoxy group, ethoxy group, carboxyl group and sulfone group

A is an acetyl group, ureide group, propionyl group, benzoyl group, paratoluenesulfonyl group

X is -CH ₂ CH ₂ OSO ₂ H -CH = CH ₂

The present invention is a yellow-red-yellow reactive dye, a dye containing monochlororiagine and vinyl sulfone group, which has high dyeing ability, excellent wet washing fastness and chlorine dog, sweat-light fastness, and the like. It is a dye that is more advanced than conventional reactive dyes, which are not left behind and have easy characteristics for solving wastewater treatment problems.

The manufacturing method of the reactive dye of the said general formula [I] is as follows.

Diazotal of general formula [II]

This diazonium product was converted to aminoalkylaminobenzene-sulfonic acid of general formula [III].

Turn on the capping to obtain the general formula [IV] which is a monoazo compound,

Imanoazo Compounds. [V] is a dichloro-S-triazine azo compound condensed with cyanuric chloride.

By getting

Condensation of an aromatic amine compound of the general formula [V] to the general formula [II] to obtain the general formula [I], or condensation of aminoalkylaminobenzene-4-sulfonic acid and cyanuric chloride represented by the general formula [III] Diazonium diazotized aromatic amine compound of general formula [VI] and general formula [II]

The dichloro-S-triazine monoazo compound represented by the general formula [V] was condensed by condensation, and the aromatic amine compound represented by the general formula [II] was condensed to obtain the monoazo dye represented by the general formula [I]. It can manufacture.

Examples of the aromatic amine compound of general formula [II] used in the present invention are as follows.

1-aminobenzene-3-β-sulfatoethylsulfone

1-aminobenzene-4-β-sulfatoethylsulfone

1-amino-2-methoxybenzene-5-β-sulfatoethylsulfone

1-amino-4-methoxybenzene-3-β-sulfatoethylsulfone

1-amino-2-carboxybenzene-5-β-sulfatoethylsulfone

1-amino-2.5-dimethoxybenzene-4-β-sulfatoethylsulfone

1-amino-2-ethoxybenzenesul-5-β-peytoethylsulfone

Examples of the general formula [III] as the cupping component are as follows.

3-Aminoacetanilide-4-sulfonic acid

3-Aminophenylacetyl-aminobenzene-4-sulfonic acid

3-Aminomethoxyacetylaminobenzene-4-sulfonic acid

3-Aminobenzoylaminobenzene-4-sulfonic acid

3-Aminomethanesulfonylaminobenzene-4-sulfonic acid

3-Aminouraidebenzene-4-sulfonic acid

3-Aminobenzenesulfonylbenzene-4-sulfonic acid

3-Amino-P-tosylaminobenzene-4-sulfonic acid

Referring to the preparation method of the general formula [I] of the present invention in detail.

The aromatic amine compound of the general formula [II] was diazotized according to a known method, and the monoazo compound was subjected to the cumulative reaction with the general formula [III], which is a purifying component, at a pH of 2.0-4.0 at 0-15 ° C. for several hours. IV].

This azo compound is adjusted to pH 5.5-7.0 by adding sodium bicarbonate or sodium carbonate, filtered by salting with sodium chloride or potassium chloride. The azo compound is made into an aqueous solution and subjected to primary condensation with cyanuric chloride at 0-5 占 폚. The compound of formula [V] is subjected to secondary condensation at 20-35 占 폚.

During the first and second condensation, the pH is adjusted to 5-6, and the reaction solution is filtered through salting out with sodium chloride or potassium chloride to obtain a reactive dye of the general formula [I].

Alternatively, the monoazo compound may be condensed with cyanuric chloride as it is without salting the reaction solution.

The new reactive dye of the present invention is absorbed cellulose fiber material cotton, hemp, viscose, etc. at 20-40 ℃ in the presence of neutral salt sodium chloride or sodium lactate, and the acid binder sodium hydroxide, sodium carbonate, sodium bicarbonate Add trisodium phosphate or the like and fix and dye at 50-60 ° C.

The dyeings are dark yellow, orange, red, yellow, etc., and are excellent in wet laundry fastness, chlorine fastness and daylight fastness, and are stable to acid hydrolysis.

In addition, there is almost no balance after dyeing, which makes it easy to treat wastewater.

Referring to the method for producing a reactive dye of the present invention in detail as follows. Herein, "parts" means "parts by weight".

Example 1

14.05 parts of 1-aminobenzene-4-β-sulfateethylsulfone is stirred and dispersed in 130 parts of water, and 15 parts of concentrated hydrochloric acid is added to the mixture, which is then cooled to 3-5 ° C. with ice.

3.5 parts of sodium nitrite are slowly added dropwise at 30 ° C. in an aqueous solution to diazotize and stirred for 1 hour.

Excess sodium nitrite is removed by adding a small amount of sulfamic acid.

11.5 parts of 3-aminoacetanilide-4-sulfonic acid is made into 100 parts of a neutral aqueous solution, and added to the diazonium solution. The mixture is adjusted to pH 3.5-4.0 with sodium bicarbonate to undergo time-curing reaction.

After completion of the cupping reaction, the solution was adjusted to pH 5.5-6.5 with sodium carbonate to obtain an aqueous solution of monoazo dye.

In a separate tank, 9.5 parts of cyanuric chloride in 100 parts of ice water are added and stirred and dispersed at 0-5 占 폚 to obtain a turbid solution.

The above monoazo aqueous solution was added dropwise to this solution and stirred for 2 hours, and the pH was adjusted to 5-6 with sodium carbonate during the condensation reaction and stirred for 1 hour.

Next, 14.1 parts of 1-aminobenzene-3-β-sulfate ethyl sulfone was prepared into 120 parts of an aqueous solution, and added to the primary condensate. The mixture was stirred at a temperature of 20-35 ° C. for 7-8 hours, and then pH 5-6 with sodium carbonate. Control to complete the second condensation reaction.

The reaction solution is added with potassium chloride to separate the dye, filtered and dried. Alternatively, cyanuric chloride and 1-aminobenzene-3-β-sulfateethylsulfone may be first condensed and the monoazo compound may be condensed in the reaction solution.

This dye can be obtained by dyeing the cellulose fiber material in the presence of an acid binder to obtain a deep reddish yellow dye, and excellent in light fastness and wet fastness.

Example 2

14.05 parts of 1-aminobenzene-3-β-sulfateethylsulfone is diazotized in the same manner as in Example 1.

11.6 parts of 3-aminophenyluraide-4-sulfonic acid was made into 110 parts of aqueous solution, and slowly added to the diazonium solution. The mixture was adjusted to pH 3.5-4.0 with sodium bicarbonate and stirred for 10 hours to form a cupping reaction. This cupuring reaction solution was adjusted to pH 5.5-6.5 with carbonate, potassium chloride was added to separate the dye, and the wet cake was dissolved in 280 parts of water.

Next, 9.5 parts of cyanuric chloride were added to 100 parts of ice water in a separate tank, and the mixture was stirred and dispersed at 0-5 ° C. The aqueous solution was slowly added dropwise to the dispersion, stirred for 2 hours at the same temperature, and condensed by adjusting the pH to 5-6.

14.1 parts of 1-aminobenzene4-β-sulfatoethylsulfone was made into 120 parts of an aqueous solution, and added to the above condensation mixture. The mixture was condensed at a temperature of 20-35 ° C. and adjusted to pH 5.5-6.5 with carbonate, followed by stirring for 12 hours. Let's do it.

When the reaction is completed, sodium chloride is added, dyed, filtered and dried.

When the dye is dyed and fixed in the presence of an acid binder on the cotton according to a conventional method, a yellow dye having excellent fastness can be obtained.

Example 3

15.6 parts 1-amino-2-methoxybenzene-5-β-sulfatoethylsulfone was diazotized in the same manner as in Example 1 and 11.5 parts 3-aminoacenilide-4-sulfonic acid was made into 100 parts of aqueous solution. Add slowly to the diazonium solution and adjust the pH to 3.5-4.0 with bicarbonate, stirring stirred for 8 hours.

This cupuring solution is adjusted to pH 6.0-6.5 with carbonate.

9.5 parts of cyanuric chloride were added to 100 parts of ice water for condensation reaction in the following tank, and the mixture was stirred at 0-5 ° C. to the dispersion. Adjust to condensation.

14.1 parts of 1-aminobenzene-3-β-sulfatoethylsulfone is made into 120 parts of an aqueous solution and added to the condensation reaction product. The second condensation reaction is performed at pH 5-6 at 20-35 ° C.

After the condensation reaction is completed, sodium chloride is added to salt the product and filtered. This dye is dyed reddish yellow on cotton.

Example 4-58 listed below can be made in the same manner as Example 1-3.

Example 59

17.05 parts of 1-amino-2.5-dimethoxybenzene-4-β-sulfatoethylsulfone was diazotized in the same manner as in Example 1, and 11.5 parts of 3-aminoacetanilide-4-sulfonic acid was used as an aqueous solution. The diazo solution is added to the cupper, adjusted to pH 3.5-4.0 with bicarbonate, stirred for 8 hours, and then adjusted to pH 6.0-6.5.

9.5 parts of cyanuric chloride was added to 100 parts of ice water, and the mixture was stirred and dispersed. The stocking liquid was added thereto, adjusted to pH 5-6 at 0-5 ° C., and condensation reaction was carried out to obtain 14.1 parts of 1-aminobenzene-3-β-sulfate ethyl sulfone. Condensation reaction at 20-35 ° C. and pH adjustment by addition of carbonate to 5-6.

This dye is dyed reddish color when cotton is dyed according to the conventional method.

Example 60

14.05 parts of a 1-aminobenzene-4-β-sulfatoethylsulfone were diazotized in the same manner as in Example 1 and the cupping component was prepared using 14.6 parts of 3-aminobenzoylaminobenzene-4-sulfonic acid. 9.5 parts of cyanuric chloride and 14.1 parts of 1-aminobenzene-3-β-sulfatoethylsulfone in an equimolar ratio are condensed.

This dye is dyed red yellow.

Claims (1)

The diazotization product which diazotized the aromatic amine of general formula (II) couple | bonds the aminobenzene sulfonic acid of general formula (III), and obtains the monoazo compound of general formula (IV), and the compound of general formula (IV) is chlorinated. By condensation with cyanuric to give the diclo-S-lotriazin azo compound of formula (V), and then to the aromatic amine compound of formula (II) to condense the reactive monoazo dye of formula (I). How to make:

(Wherein R ₁ and R ₂ are hydrogen, chlorine, bromine, methyl group, methoxy group, ethoxy group, carboxyl group or sulfone group; A is acetyl group, ureide group, propionyl group, benzoyl group or paracoluene Sulfonyl group; X is -CH ₂ CH ₂ ○ SO ₃ H or -CH = CH ₂