PL156707B1 - Method for producing chromium complex of 1:1 6-nitro-2,2-dihydroxyazonaphtalenesulphonic-4 acid - Google Patents

Abstract

Method of producing chromium complex 1: 1 of 6-nitro-2,2'-dihydroxyazonaphthalene-4-sulfonic acid by reaction on 6-nitro-2,2'-dihydroxyazonaphthalene-4-sulfonic acid with trivalent chromium salt such as sulphate and/or alkaline chromium sulphate in acidic aqueous environment above 100 degrees C and under pressure; is characterised in that reaction is conducted using sulphate and/or alkaline chromium sulphate in quantity of 0.9-1.1 gram-atom of Cr, especially 1.00-1.05 gram-atom of Cr, for 1.0 mole of 6-nitro-2,2'-dihydroxyazonaphthalene-4-sulfonic acid, at 110-130 degrees C, with pH=1.0-3.5, especially at pH=1.5-3.0 and reaction mixture volume between 3.0-5.5 dm<3> per 1.0 mole of 6-nitro-2,2'-dihydroxyazonaphthalene-4-sulfonic acid, while temperature of the reaction mixture is raised gradually and kept at least at 115 degrees C level for at least 0.5 hour, and preferably for 1.0-2.0 hours.

Description

The subject of the invention is a method for the preparation of 1: 1 chromium comic strip of 6-nitro-2,2'-dihydroOsyazoeaphthenic acid-4.

6-nitro-2,2'-diiydroxyazrnaftaeβnosufreic acid-4 is a monoazo dye known as CI Mordant Black 1, C, I. 15710, while its 1: 1 chromium complex is a well-known substitute, e.g. for the production of Black ciromokomP ^a ksowθj 2: 3/0. I. Acid Black 52, CI 15711 / and asymmetric mono- and dianic dyes: ohromt0rmplθ0stwyoh 1: 2, especially oiww, browns, broad and blacks.

The method of obtaining rmaw08ny chromium complex 1: 1, known from BIOS 961, p. 168, consists in treating 6-nitro-2,2'-dihydro-aztnaphthalene-4-acid / monoazo dye / chromium formate, obtained by dissolving CrGO3 in formic acid under pressure at the temperature of 115 ° C for 2 hours, with the use of chromium formate in the amount (assuming the achieved yield of the monoaztw8gt dye 85- ^ ^ <^ * 6 of the theory) / corresponding to 1.22-1.29 grams of Cr at 1, 0 mole monoazo dye.

Weeług example given herein latenrowym PRL No. 140 749 nnawwany mono-azo dye complex is carried out in a 1: 1 chromium formate, chromium action, prepared by the reaction ^é Sample of ^{s g} of chromium sulphate with formic acid temppraturze ⁸ ° - ⁹⁰ ° C. ^{M trench} Ea ^that is used chromium in an amount / after conversion, assuming a dye mmoazowego achieves 85-90% of theory / odpowOaαatąoθj 1.12-1.18 gram atom of Cr per mol of dye 1.0 "noszowego, and chrome plating is carried out at a pressure at a temperature of 115-120 ° C and a volume of ^{7, 8} - ⁸ 2 ^{P d} m 1, ^{b 0} mol monoazo arwnika.

The conducted studies have shown that chromium formate is the preferred chromating agent for converting 6-ei.trr-2,2'-di ^^^ y-hydroxyazrnaphthalenesufrerowlgo-4 acid under known conditions into 1: 1 chromium complex / short time, good product quality /, but such a reaction environment is very aggressive and is highly corrosive to the material of pressure equipment, especially steel. In the course of the oycorescence on a similar scale and technical attempts at the synthesis of the discussed comic book with the use of chromium formate, the pressure young showed the corrosive effect of the reaction environment, even in apparatuses made of steel arbor, especially in welded places. As a result, iron compounds were passed into the reaction mixture and the reaction medium became less acidic. Moreover, formic acid exhibits quite strong reducing effect at elevated temperature, causing partial decomposition of monoaErvogo pigment.

Consecutive of these phenomena are: decrease in the reaction by 10-20% and contamination of the product with sparingly soluble complexes and / or salts of iron with a moeoazium dye,

156 707 as well as the undesirable 1: 2 chromium complex of the monoazo dye, which in many cases makes it impossible to use the obtained 1: 1 chromium complex for the synthesis of asymmetric 1: 2 chromocomplex dyes. Moreover, with the necessary purification of the wastewater after filtration of the chromium complex 1: 1, by the inclusion of chromium in the form of vorarotate with the addition of sodium hydroxide solution and filtering off the sludge, the obtained chromium hydroxide slurries are heavily contaminated with co-precipitating iron hydroxide. The utilization of such shamms is significantly limited, and their management is additionally made difficult by their non-standard nature.

Detailed tests of the corrosivity of acid-resistant steels in the environment of the chromium-plating reaction carried out with the use of chromium formate in the known way have shown that only the hard-to-reach steel KO17N13MeT is resistant. Emitted pressure devices with an undamaged surface or with ceramic lining can also be used, but the surface of the agitator should be adequately protected.

There is also known a general method of converting o, o ^{, -} dihydroxy dyes into their 1: 1 chromium complexes by treating these dyes in an acidic aqueous medium with an excess of inorganic trivalent chromium salts, such as e.g. fluoride, chloride, carbonate, sulphate at the boiling point. or at a temperature above 100 ° C under low pressure. However, closer studies show that the chromium plating process for the compounds described in the present invention is always carried out in the presence of organic reaction promoters, such as, for example, tartaric, citric, glycolic acid, preferably formic acid or oic acid / patents: EP 156,768, GDR 148,783 /.

As a result of the conducted research, it was unexpectedly found that the chromating reaction of 6-nitro-2,2'-dihydroxyazoneαftaatrosulrnegr-4 to kn ^ pp ^ chromium x 1: 1 can be carried out with a very good efficiency / over 9OS6 theory / using chromating agents as : sulphate and / or basic chromium sulphate without the need to catalyze it with organic adjuvants, if the process is carried out using a pressure method under certain conditions of temperature, pH and volume:!. The duration of the reaction is slightly longer, the corrosive environment is insignificant, and the yield of the obtained product is higher than in the known method carried out in an apparatus resistant to the corrosive effect of chromium formate.

According to the method of the invention, 6-nitra-2, 2'-dihydroc3kαzonaftaeerosultrium-4 is transformed into a 1: 1 chromium complex by the action of sulfate and / or basic chromium sulfate, used in an amount corresponding to 0.9-1.1 grams of Cr atom, especially 1, 00-1.05 gram atom of Cr per 1.0 mole of monoazo dye, at 110-130 ° C, at pH = 1.0-3.5. The pup is naked at pH = 1.5-3.0 and in the volume of the reaction mixture in the range of 3.0-5.5 dm per 1.0 mol of monoazo dye, the temperature of the reaction mixture is gradually increased and maintained not below 115 ° C at time of at least 0.5 hours, preferably 1.0-2.0 hours.

The 1: 1 chromium complex of 6-π1ζμ-2,2 '-dihydrocakaionaphthalene-4-acid, obtained by the method according to the invention, can be used for further reactions, e.g. for the synthesis of 1: 2 asymmetric chromocomplex dyes without straining in the form of a suspension, which is a mixture of po ^ ak ^ jna after his w / t '^ on ^^ n: iu. The 1: 1 chromium complex obtained by the method according to the invention may also be greasy, after possible shaving and / or cooling the reaction mixture by filtering, and the effluent obtained may be sent as a medium in the next reaction of 6-nitro-2,2 acid. '-dihyaroxyazonaphthalenesulronooego-4 into a 1: 1 chromium complex, after adding water and a chromating agent if necessary. The use of the odor as the reaction medium can be repeated two times successively without degrading the quality of the resulting 1: 1 chromium complex.

The conversion of the monoazo dye to the 1: 1 chromium complex according to the invention is characterized by a weakly corrosive reaction medium, so that the process can be realistic in an apparatus made of any acid-resistant steel, e.g., readily available H-17 steel.

The method v: according to the invention provides, under technical conditions, easier preparation of the 1: 1 chromium complex of 6-η1ί ^ -2.2 '' -a: UlyaΓokskrionaftale nosulfonic acid-4 with a good quality ensuring the suitability for the production of asymtric mono- and 1: 2 dihydro-complex dyes.

156 707

The invention is illustrated by the following examples in which parts and percentages are parts and percentages by weight and degrees of temperatures are given in degrees Celsius:

EXAMPLE 1 To 300 parts of water with a temperature of 80-90 °, 20.6 parts of chromium sulfate are added and the mixture is stirred until the chromium sulfate is completely dissolved. 43.9 parts of 6-nitro-2,2'-dihydroxyazonaphthaenesulfine-4 acid are added to the solution obtained and the pH of the suspension is adjusted to 2.0-3.0 with the possible addition of sodium hydroxide or sulfuric acid. After thorough homogenisation the suspension was heated at camera acid-resistant to a temperature of 115-125 ° C and stirred at this temperature for 2.0 hours and the reaction zakończenl-romowea f ^{i n} a. ° inside ^y Muje ^0.4 dm ^{P y} suspensions containing ^ą cej ^0.09 7 moles of 1: 1 chromium complex of 6-nitro-2,2 * -dihydioxyazoaaphthalβnosulfanic acid-4.

Example II. The method described in Example 1 is followed, using instead

20.6 parts of chromium sulphoate 16.8 parts of basic chromium slarosan in the form of a commercial product named (Chromi J-33 according to BN-78 / 7761-03. Z ^ a ^ in ^^ after cooling, the reaction is filtered at 30 ° 150 parts of a paste containing 0.092 moles of the 1: 1 chromium complex of the acid 6 - ^^ tr-2.2 * -diiydrokβyazonaftallmosull'onfwβgo-4 are obtained.

Example III. The procedure described in Example 2 was followed, using instead of water the effluent obtained by filtration of the previously prepared chromium complex 1: 1 and using 16.5 parts of Chromium J-33. 160 parts of a paste are obtained containing 0.093 mol of a 1: 1 chromium complex of 6-nitro-2.2'-dihytfokya Bonaphthalβ-4-nosulfanic acid.

Department of Publishing of the UP RP. Circulation of 90 copies

Price PLN 5,000.

Claims (1)

Patent claims The method of preparation of chromtwagt 1: 1 complex of 6-nitrile-2,2-dihydroxyshonaf talent3ulphonateagt-4 by treating 6-nitro-2,2'-dihydroxyazonaphtheansulphinic acid-4 by trivalent chromium salts such as sulphate and / or basic chromium sulphate in acid in an aqueous medium at a temperature above 100 ° C under pressure, characterized in that the reaction is carried out with the action of sulfate and / or basic chromium sulfate, used in an amount corresponding to 0.9-1.1 gram atom of Cr, especially 1.00-1.05 gram atom Cr, per 1.0 mol of 6-nitro 22.2 * ddiyydroksyaEonaphthaletosulfoo-4 acid, at a temperature of 11O-13O ° C, at a pH = 1.0-3.5, especially at pH = 1.5-3.0 and in volume the reaction mixture within 3 -5 ⁰ »5 <the ^{p 1,} 0 mol Ikwasu ^6-nitro-2, 2-di * ^hy droksyazonafttlβno ^ u ^f f ^onowlgt-4, wherein the reaction temperature is gradually raised and maintained not below 115 ° C for at least 0.5 hours, preferably 1.0-2.0 hours. * * *