DD294394A7 - METHOD FOR THE PRODUCTION OF MONO, DIS, TRETAKIS AND PENTAKISAZO DYES - Google Patents

Abstract

The invention relates to a process for the preparation of mono-, dis-, tetrakis and pentakisazo dyes, which are used in particular for dyeing wool, silk, cotton, viscose staple, rayon and as food colors. The azo dyes are prepared on the basis of sulfanilic as diazo component, using a Sulfanilsaeure obtained by reaction of Anilinhydrogensulfat in the baking process using pyridine and / or picolines and / or triethylamine as a catalyst. As a result, dyes and optical brighteners can be produced which contain no proportions of carbon products and dyes based on aniline, metanilic acid and Anilinsulfosaeure. {Mono-, dis-, tetrakis and Pentakisazofarbstoffe; sulfanilic; caking; Aniline hydrogen sulfate melt; Catalyst; pyridine; picolines; triethylamine; To dye; Wool; Silk; Cotton; Zellwolle}

Description

The following azo dyes can be prepared by the process according to the invention:

a) monoazo dyes • Cl-name Cl number Cl-name Cl number b) disazo dyes Mordant Yellow 10 16540 Acid Red 31 14010 Cl number Mordant Yellow 27 17595 Acid Brown 40 14180 20120 Acid Orange 20 18659 Acid Yellow 4 14600 20170 Acid Orange 7 19020 Acid Yellow 18 15510 20210 19140 Acid Yellow 23 20300 20345 Cl-name Cl number Cl-name 20350 .Mordant Brown 69 27510 Acid Black 5 20480 Acid Orange 24 27790 Acid Black 18 26280 Direct Brown 80 27885 Direct Violet 9 26920 Acid Brown 43 28170 Direct Red 90 27180 Acid Black 16 28190 Direct Violet 63 c) tetraclic azo dyes Acid Black 17 28200 Direct Violet 64 Cl number Acid Black 41 28400 Direct Red 189 35005 Direct Orange 3 29005 Direct Yellow41 35760 Mordant Green 15 Prague Kl 80 213-7-15 Wofanildunkelbraun 36020 Acid Red 56 40215 Cl-name Cl number Cl-name Direct Brown 44 40220 Direct Orange 34 Direct Red 84 40230 Direct Orange 36 Acid Brown 92 40265 Direct Orange 37 Direct Orange 39 40290 Direct Brown 78

d) pentacylazo dyes

Dye according to DD-PS 244349

The inventive use of this particular Sulfanilsäure in the synthesis of azo dyes is particularly suitable for relatively clear and bright colorations, such as. As the dyes Direct Orange 37 and Direct Brown 78 with the CI numbers 40265 and 40290th Despite a Klärfiltration during dye synthesis, it comes with the use of the previously known Sulfanilsäure types easy to quality reductions in the coloration by insoluble particles in the dyeing liquor, which However, in the procedure according to the invention is excluded.

embodiment The invention will be explained below with reference to several examples. example 1

17.3 g of sulfanilic acid prepared by caking aniline hydrogen sulfate with 1% by mass of pyridine are dissolved in

110ml of water by adding

6 g of soda dissolved with stirring. The solution is made by adding ice to a total volume of

Brought 320 ml. After precipitation of the sulfanilic acid with

23 ml of hydrochloric acid (20 ° Bo) is added to this within a period of 30 minutes with a solution of

6.9 g of sodium nitrite in

Diazotized 21 ml of water.

To this suspension, at a temperature of 20 ° C to 25 ⁰ C, a solution of 14.3 g of cresidinin

 64 ml of water and

11.8 ml of hydrochloric acid (2O ⁰ Bo) and stirred vigorously for 3 hours. The suspension is then truncated to a pH of 5 with 72 ml of sodium carbonate solution (12.5% strength) and brought to a pH of 4 after further 3 hours with 4 ml of hydrochloric acid.

The resulting suspension of the monoazo dyes is filtered off and the filter cake in a 6O ⁰ C warm

Suspension of 45.6 g of nitroflavonic acid in 320 ml of water. By adding 9.2 ml of sodium hydroxide solution (36 ° Bo) is adjusted to a pH of 8 and the volume brought to 500 ml with water. To

Add another 40 ml sodium hydroxide solution (35 ⁰ Bo), the suspension is boiled for 15 hours, then diluted with water to 1.21, to a

Temperaturvon20 ° Cabgekühlt, with

Adjusted to pH 9 with 22 ml hydrochloric acid and mixed with 55 ml chlorinated lye (148 g active Cl / I).

After 2 hours is with

230 g of sodium chloride stirred, filtered off with suction and dried after a further 3 hours.

Colorectal testing of the azo dye gave complete compliance with a trademark of Cl Direct Orange 37 after standing for color strength. Further, no defects were found in the azo dye prepared from the solubility test and determination of insoluble residues.

Example 2

17.3 g of sulfanilic acid, prepared by caking Anilinhydrogensulfat with 1Ma .-% triethylamine, are analogous as

Diazotized in Example 1.

In the suspension of the diazonium compound is a solution of 15.1g a-Naphthylaminin 330 ml of water and

11.2 ml of hydrochloric acid (20 ⁰ Bo) at a temperature of 2O ⁰ C to 25 ° C and with

7.6ml soda solution (12.5%) within 1 hour the pH is brought to 5. It is stirred for 12 hours, the suspension

heated to a temperature of 45 ⁰ C and acidified with 5.3 ml of hydrochloric acid (2O ⁰ Bo). The volume is brought to 1.41 with water and filtered with suction. The filter cake is

stirred with a slurry of 41 g of nitroflavonic acid in 210 ml of water. The suspension is with

Make 8.5 ml of sodium hydroxide solution (35 ^% Bo) slightly alkaline and bring to a volume of 450 ml with water. There are (Bo 35 ⁰⁾ were added further 68 ml sodium hydroxide solution and the suspension is boiled for 20 hours under reflux. Then it will open

a volume of 1.21 and, after cooling, adjusted to 40 pH hydrochloric acid (20 ° Bo) with a pH of 9 and mixed with 42 ml of chlorine (148 g active Cl / I).

After an hour will be with

235g sodium chloride, stirred after a further 3 hours and dried.

Colorectic testing for the azo dye gave complete agreement with a trademark of Cl Direct Brown 78 after its staining for color strength. Further, no defects were found in the azo dye prepared in the solubility test and in the determination of the insoluble residues.

Example 3

17.3 g of sulfanilic acid, prepared by caking Anilinhydrogensulfat with 0.5 wt .-% 2-methylpyridine are analogous as

diazotized in Example 1. The suspension thus obtained is diazotized at a temperature of 10 ⁰ C to the 600 ml sodaalkalischen comprehensive solution of the coupling product of 12.1 g! Added 2,4-dimethylaniline and 11.0 g of resorcinol, with the addition of sodium hydroxide, a pH of above 10 is maintained. To

Termination of the coupling reaction is neutralized, salted out in a conventional manner, filtered off and dried. The coloristic examination of the resulting disazo dyestuff gave complete correspondence with a trademark of CI Direct Orange 24 after being adjusted to the correct color. Furthermore, no defects were found in the azo dye prepared in the solubility test and in the determination of the insoluble residues.

Example 4

17.3 g of sulphanilic acid, prepared by baking aniline hydrogen sulfate with 0.4% by weight of pyridine and 0.4% by weight of triethylamine are diazotized analogously to Example 1. The suspension thus obtained is coupled at a temperature of 20 ⁰ C to 25 ° C analogously to Example 1 on cresidine. The Aminoazofarbstoffsuspension obtained is made alkaline, mixed with nitrate and indirectly diazotized by running in a mixture of ice, hydrochloric acid and water and then slowly at a temperature of 0 ° C to a sodaalkalischen solution of

Add 31.6 g of N-phenyl-I acid.

After completion of the coupling reaction is heated to a temperature of 6O ⁰ C, neutralized, in a conventional manner

salted out, filtered off with suction and dried.

The coloristic examination of the resulting disazo dyestuff, after being adjusted to the correct level, gave complete agreement with a trademark of Cl Direct Violet 9. Furthermore, no defects were found on the prepared azo dye in the solubility test and in the determination of the insoluble residues.

Example 5

17.3 g of sulfanilic acid prepared by caking aniline hydrogen sulfate with 0.5% by mass of 3-methylpyridine and 0.5% by mass.

Triethylamine are diazotized analogously as in Example 1 and coupled to cresidine. In this suspension, a filter-moist paste in an amount of

Stirred 25.7 g of an aminoazo dye, by diazotizing p-nitraniline, dome on silicic acid in sodaalkalischer

Solution, reduction of the nitro group with sodium sulfide solution at a temperature of 20 ° C, acidification, clarification and salting out was obtained. The volume is adjusted to 1000 ml and phosgenated at a temperature of 25 ⁰ C, wherein the pH is gradually brought to 8 by adding portions of sodium hydroxide solution. The obtained azo dye solution is salted out in a conventional manner, filtered and dried.

The coloristic examination of the resulting disazo dyestuff gave complete correspondence to a commercial grade of Cl Direct Yellow 41 after being adjusted to its own color. Furthermore, no defects were found in the azo dye prepared in the solubility test and in the determination of the insoluble residues.

Example β

17.3 g of sulphanilic acid prepared by caking aniline hydrogen sulfate with 0.7Ma .-% of pyridine and 0.3Ma .-% 4-methylpyridine are diazotized analogously as in Example 1 and at a temperature of 1O ⁰ C within 2 hours

in a soda-alkaline solution in an amount of 28.4 g of 3-carboxy-1- (p-sulfophenyl) -5-pyrazolone.

After completion of the reaction is heated to a temperature of 6O ⁰ C, neutralized and in conventional Salted out, filtered off and dried.

The coloristic examination of the monoazo dye obtained gave complete correspondence with a trademark of Cl Acid Yellow 23 after being adjusted to color strength. Furthermore, no defects were found in the azo dye prepared in the solubility test and in the determination of the insoluble residues.

Example 7

17.3 g of sulphanilic acid, prepared by baking aniline hydrogen sulfate with 0.5% by weight of pyridine, 0.2% by weight of 2-methylpyridine and 0.7% by weight of triethylamine are analogously diazotized as in Example 1.

The suspension thus obtained is at a temperature of 1O ⁰ C to 800 ml comprehensive sodaalkalischen solution of the coupling product of 19.9 g of diazotized picric acid and

11.0 g of resorcinol, wherein a pH of more than 10 is adjusted by the addition of sodium hydroxide solution. The volume is set to 1.81. The obtained Disazofarbstoffsuspension is by the addition of sodium hydroxide solution (36 ° Bo) at a

Temperature of 70 ° C brought into solution and by adding a concentrated solution of

28 g of FeSO ₄ .7H ₂ O converted into the metal complex dye. This dye is salted out, filtered off and dried. The coloristic examination of the resulting disazo dyestuff revealed complete agreement with a trademark of Prague Kl 80 213-7-15 Wofanil dark brown after being adjusted to the correct color. Furthermore, no defects were found on the prepared azo dye in the solubility test and the determination of the insoluble residues.

Example 8

17.3 g of sulphanilic acid, prepared by baking aniline hydrogen sulfate with 0.7% by weight of 3-methylpyridine are diazotized analogously to Example 1.

The suspension thus obtained is 23.7 g of 1-aminonaphthalene-7-sulfonic acid _(at a temperature of 1O ⁰ C in a weakly acetic acid suspension which was prepared by dissolving with 12 ml of sodium hydroxide in 500 ml of water and precipitating with 10 ml of glacial acetic acid, entered.

After completion of the coupling reaction is dissolved by addition of sodium hydroxide, mixed with nitrite and by Ingestion in an ice-water-hydrochloric acid mixture indirectly diazotized.

In this suspension, a solution of aniline-cu-methanesulfonic acid, which was prepared from 9.3 g of aniline with formalin and bisulfite, registered. The coupling reaction is by neutralization to

Completed brought a soda excess and cleaved by boiling the ω-Methansulfonsäuregruppe. It

is neutralized, salted out and intermediately isolated. After re-slurrying, the pH becomes 5.6

adjusted and made a volume of 21, phosgenated at a temperature of 2O ⁰ C, wherein the pH is maintained by adding portions of sodium hydroxide solution.

After salting out, the dye is filtered off with suction and dried.

The coloristic examination of the tetrakisazo dye obtained gave complete conformity with a trademark of Cl Direct Red 84 after being adjusted to the correct color. Furthermore, no defects were found in the azo dye prepared in the solubility test and in the determination of the insoluble residues.

Example 9

28g 4,4'-diaminodiphenylamine-2-sulfonic acid at a temperature of 10 ° C aca.

400 ml of water blsdiazotiert and in a sodaalkalischen solution

48 g of 2-amino-8-hydroxynaphthalene-6-sulfonic acid, coupled at a temperature of 10 "C (total volume about 850 ml).

The resulting disazo dye is added at a temperature of ⁰ ° C by addition of hydrochloric acid and nitrite within

Bisdiazotiert 30min and by rapid addition of a sodaalkalischen solution of

19g 1,3-diaminobenzene-4-sulfonic acid coupled on one side (temperature maximum 5 ⁰ C, volume 1300ml). 17.5 g of sulphanilic acid, prepared by baking aniline hydrogen sulfate with 1.2% by weight of triethylamine, are prepared analogously as in

Example 1 diazotized. The suspension thus obtained is added to the o. G. Diazotrisazoverbindungslösung given and by adding 150 parts

12.5% Sodalösung completed the coupling reaction, with a weakly alkaline suspension was formed. The

remaining diazonium group was coupled by adding a sodium carbonate solution of 17 g of acetoacetanilide in 80 ml of water. At a temperature of 10 ⁰ C, the reaction is complete after 16 hours, and it is by the addition of

Salted out 80 g of sodium chloride, heated to a temperature of 6O ⁰ C, filtered off with suction and dried.

The coloristic examination of the obtained Pentakisazofarbstoffes showed after standing on type color complete agreement with a trademark according to DD-PS 244349. Further, no deficiencies were found on the prepared azo dye in the solubility test and the determination of insoluble residues.

Example 10 Under the same conditions as in Example 9, the dye is prepared according to DD-PS 244 349, only with the Difference, that a Sulfanilsäure is used, which by caking Anilinhydrogensulfat with 0.5Ma .-% pyridine and

0.2 wt .-% of 3-methylpyridine was obtained as a catalyst mixture.

The coloristic examination of the obtained Pentakisazofarbstoffes resulted in position on type strength complete agreement

with a trade mark according to DD-PS 244349. Further, on the prepared azo dye in the solubility test and the

Determination of insoluble residues no deficiencies detected. Verglelchsbelsplel 1 Under the same conditions as in Example 1, with only a commercial sulfanilic acid, the azo dye Cl Direct Orange 37 made. In the coloristic evaluation, dark particles were observed on the dyeings. The dye did not match the

quality requirements and was evaluated as a committee. Based on the results of the solubility test and dor

Determination of the insoluble residues, the dye was classified as unsalable. Verglelchsbelsplel 2 Under the same conditions as in Example 2, with only a commercial sulfanilic acid, the azo dye Cl Direct Brown 78 produced. In the coloristic evaluation, dark particles were observed on the dyeings. The dye did not match the

quality requirements and was evaluated as a committee. Based on the results of the solubility test and the

Determination of the insoluble residues, the dye was classified as unsalable. Comparative Example 3 Under the same conditions as in Example 1, with only a commercial sulfanilic acid, the azo dye Cl Direct Orange 37 produced, wherein before the addition of ice additionally a clarifying filtration is performed. The coloristic evaluation of the azo dye showed a high degree of agreement with respect to type strength

a trademark of Cl Direct Orjnge 37.

Based on the results of the solubility test and the determination of the insoluble residues, the dye was used as

not marketable.

Comparative Example 4 Under the same conditions as in Example 2, with only one commercially available sulfanilic acid, the azo dye Cl Direct Brown 78 produced, wherein before the addition of ice additionally a clarifying filtration is performed. The coloristic Evaluation of the azo dye showed a high degree of agreement with one according to type strength Trademark of Cl Direct Brown 78. Based on the results of the solubility test and the determination of the insoluble residues, the dye was used as

not marketable.

Claims (1)

Process for the preparation of mono-, dis-, tetrakis- and pentakisazo dyes based on sulphanilic acid as diazo component, characterized in that a sulphanilic acid is used which is obtained by reaction of an aniline hydrogen sulfate in the baking process using pyridine and / or picolines and / or triethylamine was obtained as a catalyst. Field of application of the invention The invention relates to a process for the preparation of mono-, di-, tetrakis- and pentakisazo dyes, which are used in particular for dyeing wool, silk, cotton, rayon, rayon and as food colors. Characteristic of the known technical solutions It has long been known, for the synthesis of azo dyes, to use sulphanilic acid as active component (Colourindex, Second, Edition, Yorkshire, 1956, Vol. 3, pp. 3038 to 3340 and 3780). The sulphanilic acid is thereby dissolved alkaline and then precipitated either with acid to a fine suspension which is reacted with nitrite or mixed with nitrite and diazotized by stirring in acid and reacted as a diazonium salt solution with a couplable substance (Fierz-David / Blangey, Farbchemie, 5 Aufl., Vienna 1943, p.237 and 249). Technical sulphanilic acid mostly contains insoluble carbonates and aniline as well as traces of metanilic acid and aniline disulfonic acid. The Kohlungsprodukte cause in dyeing impurities and the aniline reduced by forming other colored dyes with other fastnesses, drawability, etc., the performance characteristics of the articles colored with these azo dyes. Since the sulphanilic acid must be dissolved alkaline prior to diazotization, the carbon particles are removed from this solution by Klärfiltration and the aniline excess by steam distillation. However, the clarification filtration is a very time-consuming process for this particular application, since the carbon particles are very finely divided and alkaline filtrations already run very slowly anyway. It is therefore necessary to work with complex, large-area filter presses. Even more complicated than the clarification is the removal of aniline excess by steam distillation. The entire solution must be heated to a temperature of about 100 ⁰ C and cooled again to a temperature of almost ^{0 0} C prior to the diazotization reaction. In addition, aniline-containing wastewater, which represent an additional environmental impact. For these reasons, aniline-free sulfanilic acid is required by the dye manufacturers. The carbon products are removed during the dye production by Klärfiltration. It is already known (for example DE-OS 3114832), by modifying the production process for sulfanilic acid to keep the proportion of coal products, aniline, metanilic acid and Anilindisulfosäuro as low as possible or completely to prevent. However, this has hitherto only been possible by means of high additional expenses which have an adverse effect on the price of the sulphanilic acid and the azo dyes. Aim of the egg The aim of the invention is to improve the quality of the azo dyes, to reduce the technical-economic production costs and the production costs and to avoid additional environmental pollution. Explanation of the essence of the invention The object of the invention is to provide a process for the preparation of mono-, dis-, tetrakis and Pentakisazofarbstoffen on the basis of sulfanilic acid as a diazo component, which are obtained without cleaning the Sulfanilsäurelösung azo dyes that no shares of coal products and dyes Base of aniline, metanilic acid and aniline disulfonic acid. According to the invention the object is achieved in that a Sulfanilsäure is used, which was obtained by reaction of Anilinhydrogensulfat in the baking process using pyridine and / or picolines and / or triethylamine as a catalyst. The sulfanilic acid prepared in this way is particularly suitable for the preparation of azo dyes, since it contains no carbon products and no free aniline, metanilic acid and aniline disulfonic acid fractions. In contrast to other sulphanilic acids, this sulphanilic acid still contains the added catalytic compounds pyridine and / or picolines and / or triethylamine, which, however, have no detrimental effects on the preparation of the azo dyes. It is of particular advantage even if pyridine is used as catalyst in the preparation of the sulfanilic acid, since it is known (Zollinger, Azo and Diazo Chemistry, Interscience Publishers, New York / London, 1961, p 250 to 253), this compound in the preparation of azo dyes acts as a coupling accelerator. The high purity of the sulfanilic acid used makes it possible to dispense with additional purification operations during the synthesis of the azo dyes. As a result, the production costs can be significantly reduced. The manner of diazotization of sulfanilic acid, whether after precipitation with acids as a finely divided suspension, by reaction with nitrite and acid, or indirectly by allowing a mixture of alkaline sulfanilic acid and nitrite solution to an excess of acid, does not matter.