DE2825296A1 - Quaternisation of dye bases in absence of solvent - with decomposition of excess alkylating agent with ammonia - Google Patents

Abstract

Organic dye bases are quaternised in absence of solvent and in presence of solid acid acceptor, with subsequent destruction of excess alkylating agent by addn. of ammonia or (NH4)2CO3, and removal of excess basic material by addn. of solid acid and mixing. Pref. 0.5-3(1-1.5) equivs. acid acceptor (pref. MgO) is used per equiv. dye base, which may be of azo, methine or azamethine type. Up to twice, pref. 1.05-1.25 times, the stoichiometric amt. of alkylating agent, esp. dimethyl or diethyl sulphate, is used. The process is applicable and esp. weak, dye bases and the reaction proceeds quickly and quantitatively, the prods. being completely water-soluble.

Description

Process for the aternation of organic dyes

The invention relates to a method for quaternizing dye bases in the absence of solvents.

The quaternization takes place according to the methods of the prior art with alkylating agents generally in solvents in the presence or absence of acid-binding agents.

From DE-OS 27 41 395 it is known that certain dye bases in solid form at temperatures between 30 and 90 ° C to quaternary ammonium salts can be alkylated. The addition of the essentially stoichiometric amounts of alkylating agent takes place in such a way that the reaction mixture during the entire Reaction is free flowing.

The process has the disadvantage that it only uses a few dye bases am-renabar and that any excess alkylating agents used remains in the reaction product.

The task of the present rrfindur.g was to find a method for quaternizing of dye bases to be found, after which in the absence of solvents all, in particular weak dye bases can be converted into quaternary ammonium salts.

#It has been found that organic dye bases can be used with alkylating agents can quaternize in the absence of solvents if you can quaternize carried out in the presence of solid acid-binding agents, then the excess Destroyed of alkylating agents with ammonia or ammonium carbonate and then the excess Compensated in basic substances by adding solid acid.

The method according to the invention also enables weak dye bases to convert quantitatively into quaternary ammonium bases in a rapid reaction. The process products are completely soluble in water.

The method according to the invention is usually carried out so that the dye base is mixed with the acid-binding solid agents and then while the reaction mixture is mixed thoroughly, those for complete quaternization necessary close to alkylating agent optionally adds in portions. if the quaternization has ended, the excess alkylating agent present becomes destroyed by adding ammonia or ammonium carbonate with thorough mixing and then the remaining proportion of basic substances by admixing compensated by solid acids.

Basic azo dyes and basic methine dyes are used as dye bases or basic azamethine dyes.

Alkylating agents - also known as quaternizing agents - sid e.g., alkyl halides, alkyl sulfonates, and dialkyl sulfates. As a quaternizing agent are, for example, to be mentioned in detail: dimethyl sulfate, diethyl sulfate, the methyl, ethyl, Propyl ester of benzene and toluene sulfonic acid, methyl bromide, methyl iodide, ethyl bromide, Ethyl iodide, propyl bromide.

For technical and economic reasons, dimethyl sulfate, Diethyl sulfate, toluene or benzene sulfonic acid methyl ester, ethyl ester, propyl ester, in particular, dimethyl sulfate and diethyl sulfate are preferred.

The amount of alkylating agent depends on that to be alkylated Link. The equivalent to quaternizing nitrogen is used stoichiometrically required amount up to a 2-fold excess of alkylating agent.

It is preferred to use 1.05 to 1.25 times the stoichiometric amount required of alkylating agents.

Acid-binding agents include, for example, alkali carbonates, alkali hydrogen carbonates, preferably magnesium oxide.

The acid binding agent has the task of quaternizing To bind released acid, but also possibly present in the starting materials neutralize acidic components. The amount of acid-binding agents depends therefore generally according to the amount of the compound to be quaternized. Usually one uses 0.5 to 3, preferably 1.0 to 1.5, equivalent, based on dye bases to the acid-binding agents.

Mixing the reaction mixture from the solid to be quaternized Compound, the acid-binding agents and the alkylating agent are carried out in, for example rotating vessels containing grinding media, such as ball mills, rotating tubes, drums in reaction vessels provided with intensive agitators, agitator ball mills, attritors. Ball mills are preferred as reaction vessels.

The quaternization reaction is often exothermic, so that heating of the reaction mixture is not necessary. If the reaction is strongly exothermic, the alkylating agent is advantageously added in portions and / or one , cools the reaction vessel. J in the event that the reaction is only If the reaction time is slightly exothermic or endothermic, the reaction time is shortened by heating the reaction mixture advantageous.

As a rule, it works preferably at temperatures between 10 and 100 between 20 and 60 ° C.

The course of the quaternization can be determined by the usual analytical methods, e.g., by thin layer chromatography. When the quaternization ends is, the excess quaternizing agent is destroyed. For this purpose, the reaction mixture Ammonia or ammonium carbonate added and the whole thing mixed. The excess of ammonate and / or ammonium carbonate and any residue that may be present acid-binding agents - also known as basic substances - is used in the reaction mixture compensated by adding solid acids. Advantageously, raan applies a larger one Amount of solid acid than the stoichiometric amount of the bases present. For example, sodium or potassium hydrogen sulfate, amidosulfonic acid, an acid, Succinic acid, oxalic acid, glutaric acid or mixtures thereof can be considered. flat the When the acids are added, the mixture is thoroughly mixed and homogenized.

In the process according to the invention, the quaternization of the dye bases can be carried out also in the presence of the adjusting agents usually contained in the merchandise and other additives. The adjusting agents and the other additives can also be added after the quaternization and then the mixture is homogenized will. In these cases, the finished commodity is obtained directly from the dye base.

The following examples are intended to add to the process according to the invention explain. The parts and percentages relate to weight. J example 1 One fills 157 parts of color base, which by diazotization of ß - @ aphthylamine and domes was obtained on 2.3.3.-trimethylindolenine, 12 parts of magnesium oxide and 76 parts Put dimethyl sulfate in a ball mill and grind for 20 hours. Then give another 12 Parts of magnesium oxide and 86 parts of dimethyl sulfate and continues the grinding process, until a sample on a thin layer chromatogram indicates the end of the reaction, which is the case after another 20 hours. By every four hours: it mixes grinding only one after the other 30 parts of ammonium carbonate and 250 parts of tartaric acid. Man receives a dye powder. The dye gives a comparison on polyacrylonitrile fabrics to the same dye produced by prior art processes only a little bit more natural colorings, while the color purity and pearl effect remain entirely to match.

Example 2 58 parts of the diazotized 3-amino-1,2,4-triazole and 2-phenylindole available azo dye with 3 parts of magnesium oxide and 60 parts of dimethyl sulfate were ground in a ball mill overnight. Then grind one 5 hours lanb with 20 parts of 25 percent aqueous ammonia solution and then with 150 parts of tartaric acid (duration: 5 hours). The powdery dye thus obtained largely agrees with the process in terms of shade, purity and fastness properties prior art dye C.I. Basic Yellow 25, C.I. Mr. 11450, match.

Example 3 184 parts of that from diazotized 3-amino-1,2,4-triazole and @, N-dibenzylaniline available p-aminoazo dye with 24 parts of magnesium oxide and 2 portions of 76 parts each of dimethyl sulfate for 20 hours long ground in a ball mill Then add 30 parts of ammonium carbonate, grinds for four hours and finally mixes in 200 parts of sulfamic acid. A dye powder is obtained which has a nuance, purity of hue and in the fastness properties largely with the comparison dye prepared in a conventional manner C.I. Basic Red 50, matches.

Example 4 165 parts of azo dye prepared by diazotization 2-aminothiazole and coupling to 1-methyl-2-phenylindole are used for 24 hours Ground 12 parts of magnesium oxide and 76 parts of dimethyl sulfate (ball mill). To Addition of 15 parts of ammonium carbonate, the milling is continued for two hours.

Finally add 150 parts of WeinsSure and grind again for three hours. The dye powder obtained dyes polyacrylonitrile fabric slightly bluer than the conventionally prepared comparative dye C.I. Basic Red 29, C.I. No. 11460.

Example 5 62.5 parts of that from diazotized 2-amino-6-methoxybenzthiazole and N, N-dimethylaniline available dye base are mixed with 10 parts of magnesium oxide and 62 parts of dimethyl sulfate were ground in a ball mill for 12 hours. Then destroyed the excess of the alkylating agent by grinding with 16 parts of ammonium carbonate and then grinds in 100 parts of sulfamic acid. The dye obtained is identical to the dye prepared by prior art processes C.I. Basic Blue 54, C.I. No. 11052 in shade, purity, solubility and in the Reserve of accompanying fabrics made of acetate or perlon equal.

Example 6 works as described in Example 5, but gives for the dye base 10 parts of magnesium oxide and 750 parts of dextrin.

the dye C.I. Basic Blue 54, C.I. No.

11052, also in excellent quality, directly in line with the standard of the merchandise.

EXAMPLE 7 A bottle made of polyethylene with a volume of 5 liters is filled 20 porcelain balls with a diameter of 30 mm, 133.5 parts coupling product from diazotized 2-amino-6-methoxy-benzothiazole and N-ethyl-N-ß-hydroxyethyl aniline, 9 parts of magnesium oxide, 600 parts of dextrin and 75 parts of dimethyl sulfate and rolls the sealed bottle on a roller board overnight. The alkylation process is finished. 16 parts of ammonium carbonate are added and the mixture is ground for a few hours until the Excess alkylating agent is destroyed and grinds 100 parts of sulfamic acid a.

The dye powder obtained is of excellent quality outperforms identical dye C.I. basic Blue 41, C.I. No. 11154, due to better solubility and a slightly better reserve on accompanying fabrics made of acetate or perlon.

Claims (4)

Patent claims J {1 method for quaternizing organic dye bases with alkylating agents in the absence of solvents, characterized in that that the quaternization is carried out in the presence of solid acid-binding agents, then the excess of alkylating agent with ammonia or ammonium carbonate destroyed and then the excess of basic substances by adding more solid Acids compensated. 2. The method according to claim 1, characterized in that 0.5 up to 3 equivalents of acid binding agent - based on the dye base. 3. The method according to claims 1 or 2, characterized in that that up to 2 times the stoichiometrically required amount of alkylating agent applies. 4. The method according to claims 1 to 3, characterized in that that the solid acids sodium hydrogen sulfate, xalium hydrogen sulfate, amidosulfonic acid, Tartaric acid, succinic acid, oxalic acid, glutaric acid or mixtures thereof are used.