CS257028B1 - Mixed azocondensation pigments of yellow shades and the method of their preparation - Google Patents

Abstract

Mixed azo condensation pigments of yellow shades of general formula I, where A is an arylene radical with 6 or 10 carbon atoms, optionally further substituted by one or two chlorine atoms, methyl, methoxy, ethoxy, trifluoromethyl, or cyano groups, B is a benzene radical, optionally substituted by chlorine, methyl, methoxy, trifluoromethyl, carbmethoxy, or nitro groups, and R is the residue of a mixture of two or three amines of the benzene type, where the benzene nucleus is substituted by one or more halogen atoms, methyl, carbalkoxy, or acylamino or benzoylamino groups, are prepared by condensing dichlorides of general formula IX with a mixture of amines of general formula III, where A, b, and R have the above meanings, by heating in an inert organic solvent to a temperature of 100 to 160 °C.

Description

The present invention relates to mixed azo-condensation pigments of yellow shades and a process for their preparation.

Yellow shades azo-condensation disazopigments are prepared by condensation of dicarboxylic acid dichlorides with aromatic amines.

Said pigments are used for dyeing polyvinyl chloride, polyurethane, polyethylene and other polymeric substances. Their disadvantage is the need to use pure amines for condensation with dichlorides.

It has now been found that if a mixture of amines is used instead of an amine for condensation with dichlorides, pigments of excellent utility properties are obtained.

Process for the preparation of mixed azo condensation pigments of the formula I

COCH _{3 0} ^0CH 3

R-NHCO-BN = N-CHCOHN-A-NHCOCH-N = NB-CONH-R (I) wherein A is an arylene radical having 6 or 10 carbon atoms, optionally further substituted by one or two chlorine atoms, methyl, ethoxy trifluoromethyl, or cyano, and B is a benzene moiety optionally substituted by chlorine, methyl, methoxy, trifluoromethyl, carbomethoxy, or nitro, and R is a residue of a mixture of two or three benzene-type amines wherein the benzene ring is substituted with one or more halo, methyl, carbalkoxy, acylamino or benzoylamino invention resides in that the dichlorides of formula II Goch _3-OCH3

C10C-BN = N-CHCONH-A-NHCOCH-N = NB-COCl (II), where A and B are as hereinbefore defined, are condensed with a mixture of amines of formula III r-nh ₂ (III), wherein R has the aforementioned by heating in an inert organic solvent to a temperature of 100 to 160 ° C. In many cases, pigments prepared from a mixture of amines have a higher color strength and a higher shade brilliance than pigments prepared from corresponding uniform amines. Condensation of dicarboxylic acid dichlorides of formula II with an amine mixture also yields pigments of superior application properties than pigments of the same chemical composition prepared from the individual components of the mixture by mechanical blending. The main advantage of the new process is the possibility of using a mixture of substituted benzene series amines. These can be prepared at lower production costs, since in the production of amines or the corresponding nitro compounds, purification operations such as crystallization or distillation can be omitted from the production cycle, which are normally included when amines of uniform chemical composition need to be produced.

In addition to mixtures of aromatic amines of this type, i.e. resulting from the technological preparation of these compounds, mixtures of amines prepared artificially by mixing the individual components in the desired ratio can also be used for condensation.

Anhydrous and inert organic solvents such as xylene, chlorobenzene, o- or p-chlorotoluene, o-dichlorobenzene, trichlorobenzene, nitrobenzene or mixtures of such solvents, optionally paraffinic or cycloparaffinic hydrocarbons or organic or inorganic esters or ethers are used as reaction medium. - such as tributyl phosphate.

The dicarboxylic acid dichloride of formula (II) is obtained by the chlorination of an intermediate dye which contains two carboxyl groups and two azo groups in its molecule. Diazotized aminocarboxylic acids can be used as active components for the preparation of such dyes. With regard to the application properties of pigments, these are in particular aminobenzoic acids such as:

acid acid acid acid acid acid acid acid acid acid acid

3-aminobenzoic acid,

3-amino-4-chlorobenzoic acid, 3-amino-4-methylbenzoic acid, 3-amino-4-methoxybenzoic acid, 3-amino-6-chlorobenzoic acid, 3-amino-4,6-dichlorobenzoic acid, 3-amino-4-carbomethoxybenzoic acid,

3-amino-4,6-dimethylbenzoic acid, 2-amino-4-chlorobenzoic acid, 2-amino-5-chlorobenzoic acid,

4-aminobenzoic a

4-amino-3-nitrobenzoic acid.

Among the passive components for the preparation of dyes, bisacetoacetyl 1,4-diaminobenzenes seem to be the most suitable as:

1,4- diaminobenzene,

1,4-diamino-2-chlorobenzene,

1,4-diamino-2-methylbenzene,

1,4-diamino-2-methoxybenzene,

1,4-diamino-2-cyanobenzene,

1,4-diamino-2-trifluoromethylbenzene,

1,4-diamino-2,5-dichlorobenzene,

1,4-diamino-2,5-dimethylbenzene,

1,4-diamino-2-chloro-5-methylbenzene

1,4-diamino-2-methoxy-5-methylbenzene or 1,3-diaminobenzene,

1,3-diamino-4-chlorobenzene,

1,3- d.amino-4, β-dichlorobenzene,

1.5- diaminonaftalen,

2,6- diaminonaphthalene a

2.6- diaminonaftalen.

Among the aromatic amine mixtures of the formula III suitable for condensation, these are in particular the mixtures of chlorotoluidines, chloranilines, dichloranilines, bromoanilines, toluidines, aminobenzoic acid esters, xylidines and aminoacylanilides.

These are mainly:

Mixture of 2-methyl-5-chloroaniline a

67:33, as obtained by nitration of 4-chloro-toluene and subsequent reduction of the nitrochlortoluene mixture.

Mixture of 2-methyl-5-chloroaniline,

2-methyl-3-chloroaniline,

2-methylaniline and more chlorinated 2-methylaniline derivatives in a ratio of about 50: 20: 15: 15, as obtained by chlorination of 2-nitrotoluene and subsequent reduction of the nitrochlortoluene mixture.

Mixture of 2-methyl-5-chloroaniline a

70:30 obtained from the previous mixture by partial refining. Mixture of 2-chloro-4-methylaniline a

3-chloro-4-methylaniline as obtained by chlorination of 4-nitrotoluene followed by reduction of the nitrochlortoluene mixture.

Mixture of 2-methyl-4-chloroaniline,

2-methyl-6-chloroaniline a

75:15:10, obtained by chlorination of acetylated 2-methylaniline and desacetylation of the thus obtained mixture.

Mixture of 2-chloroaniline a

35:65 obtained by nitrating chlorobenzene and reducing the nitro compounds. Mixture of 3,4-dichloroaniline a

2,3-dichloroaniline obtained by nitration of 1,2-dichlorobenzene and subsequent reduction of the nitro compounds.

Mixture of 2-bromoaniline and »

40:60 obtained by nitrating bromobenzene and reducing the nitro compounds. Mixture of 2-toluidine

4-toluidine;

3-toluidine in a ratio of about 60 * 36: 4, obtained from toluene by nitration and reduction of the nitrotoluene mixture. Mixture of 2-carbethoxyaniline,

3-carbomethoxyaniline a

4-carbetoxaniline in a ratio of 28: 68: 4, prepared by nitration and reduction of ethyl benzoate.

Mixture of 2-acetaminoaniline a

4-acetaminoaniline in a ratio of 30:70 prepared by nitration of acetanilide in acetic acid medium and reduction of a mixture of nitro compounds, or a mixture of the same substances in a ratio of 8:92 prepared by nitration in sulfuric acid medium and reduction of a mixture of nitro compounds.

Mixture of 2-benzoylaminoaniline a

4-benzoylaminoaniline in similar proportions to the above acetylderivative.

Mixture of 2,4-dimethylaniline a

2,6-dimethylaniline obtained by nitration

1,3-dimethylbenzene and reduction of nitro compounds.

The mixed pigments prepared according to the process of the invention are generally yellow. They are widely used because they are thermostable, stable in light and in organic solvents and do not migrate when dyeing softened polyvinyl chloride. They can be used for dyeing polypropylene, polyvinyl chloride, polyethylene, polyacrylonitrile, polystyrene, polyester, polyurethane, rubber for dyeing various copolymers, paints, water-dilutable polymer dispersions and the like.

The following examples illustrate the process of the present invention.

Example 1

The dicarboxydisazo dye prepared by coupling of diazotized 3-amino-4-chlorobenzoic acid with 1,4-bisacetoacetamido-2,5-dimethylbenzene in a molar ratio of 2: 1 is converted to the corresponding dicarboxylic acid dichloride by treatment with chlorinating agents such as thionyl chloride or phosgene. 10.6 g of dry dichloride are stirred in 230 g of o-dichlorobenzene, 4.7 g of a 67:33 mixture of 2-methyl-5-chloroaniline and 2-chloro-5-methylaniline are added. The reaction mixture was heated to 140 ° C and stirred at this temperature for 2 hours. The pigment suspension is filtered while hot, the cake washed with 230 g of hot o-dichlorobenzene, then with 140 g of hot ethanol and finally with 370 ml of hot water. After drying, 12.8 g of a bright yellow pigment is obtained.

Example 2

The dicarboxydisazo dye prepared by coupling of diazotized 3-amino-4-chlorobenzoic acid with 1,4-bisacetoacetamido-2-chloro-5-methylbenzene in a 2: 1 molar ratio is treated with a chlorinating agent such as thionyl chloride or phosgene to the corresponding dicarboxylic acid dichloride. 11.1 g of dry dichloride are stirred in 230 g of o-dichlorobenzene, and 4.7 g of a 67:33 mixture of 2-methyl-5-chloroaniline and 2-chloro-5-methylaniline are added. The reaction mixture is heated to 140 ° C and stirred at this temperature for 2 hours. The pigment suspension is hot filtered, the cake washed with 230 g of hot ethanol and finally with 370 ml of hot water. After drying, 13.6 g of a greenish-yellow pigment are obtained.

Example 3

The dicarboxy disazo dye prepared by coupling of diazotized 3-amino-4-chlorobenzoic acid with 1,4-bisacetoacetamido-2,5-dichlorobenzene in a 2: 1 molar ratio is converted to the corresponding dichloride by treatment with chlorinating agents such as thionyl chloride or phosgene. 11.2 g of dry dichloride are stirred in 230 g of o-dichlorobenzene, 4.7 g of a 67:33 mixture of 2-methyl-5-chloroaniline and 2-chloro-5-methylahiline are added. The reaction mixture was heated to 140 ° C and stirred at this temperature for 2 hours. The pigment suspension is filtered while hot, the cake washed with 230 g of hot o-dichlorobenzene, then with 140 g of hot ethanol and finally with 370 ml of hot water. After drying, 14.2 g of a greenish-yellow pigment are obtained.

»

Example 4

21.8 g of o-dichlorobenzene paste containing 14.2 g of dichloride as in Example 1 was slurried in 350 g of o-dichlorobenzene, the suspension was heated to 140 ° C and a solution of 4.1 g of 2-methyl- was added dropwise over 20 minutes. 5-chloroaniline and 2.1 g of 2-methyl-3-chloroaniline in 40 g of o-dichlorobenzene. The suspension was stirred at 140 ° C for 1.5 hours, the resulting pigment was hot filtered, washed with hot o-dichlorobenzene, ethanol and water. The filter cake was dried to give 17.9 g of a yellow pigment. It is equal to the pigment prepared by the condensation of said dichloride with pure 2-methyl-5-chloroaniline in yield and stability. The shade of the mixed pigment is slightly redder.

Example 5

11.2 g of the dry dichloride of Example 3 are stirred in 230 g of o-dichlorobenzene, 4.7 g of a 50:50 mixture of 2-methyl-5-chloroaniline and 2-methyl-3-chloroaniline are added. The reaction mixture was heated to 140 ° C and stirred at this temperature for 2 hours. The pigment suspension is filtered while hot, the cake washed with 230 g of hot o-dichlorobenzene, then with 140 g of hot ethanol and finally with 370 ml of hot water. After drying, 14.1 g of a yellowish pigment with a higher brilliance than the uniform amines are obtained.

Example 6

Following the same procedure as in Example 5, using a 25:75 mixture of 2-methyl-5-chloroaniline and 2-methyl-3-chloroaniline, a bright greenish-yellow hue pigment is obtained which is purer than with uniform amines.

Example 7

Following the same procedure as in Example 5, using a 75:25 mixture of 2-methyl-5-chloroaniline and 2-methyl-3-chloroaniline, a yellow pigment was obtained with high hue brilliance against pigments prepared from uniform amines.

Example Diazokomponenta Bisacetoacetyl diamine and components Mixture of condensation amines 8 3-Amino-4-methylbenzoic acid 2,5-dimethyl-1,4-phenylenediamine 2-methyl-4-chloroaniline, 2-methyl-6-chloroaniline and 2-methylaniline in ratio 75:15:10 9 3-Amino-4-methyl- benzoic acid 2-chloro-1,4-phenylenediamine. 2-chloroaniline- and 4-chloro- aniline in a ratio of 35:65 10 3-Amino-4-carb- methoxybenzoic acid 2-methyl-5-methoxy-1,4-phenylene- diamine 2-Carbethoxyaniline 3-carbetoxylinin and 4-carbethoxyaniline in ratio 28: 68: 4

continued table

Example Diazokomponenta Bisaoetoacetyl diamine azo components Mixture of condensation amines 11 2-Amino-5-chloro henzoic acid 2-cyano-1,4-phenylenediamine 2-acetaminoaniline a 4-acetaminoaniline in a ratio of 30:70 12 3-Amino-4,6-di- chlorobenzoová acid 4-chloro-1,3-phenylenediamine 2-methyl-5-chloroaniline a 2-methyl-3-chloroaniline 70:30 13 3-Amino-4-methoxy- benzoová acid 1,4-phenylenediamine 2-methyl-5-chloroaniline and 2-methyl-3-chloroaniline in a ratio of 70:30 14 3-amino-4-carb- methoxybenzoová acid 1,5-diaminonaphthalene 2-bromoaniline and 4-bromo- aniline in a 40:60 ratio 15 Dec 4-Amino-3-nitro- benzoic acid 1,4-diamino-2-trifluoromethylbenzene 2-benzoylaminoaniline and 4-benzoylaminoaniline

in a ratio of 30:70

Claims (2)

I will invent the object 1. Mixed azo condensation pigments of yellow shades of the general formula I COCH, COCH, I ^{* 1 2 3} I ³ R-NHCO-BN = N-CHCOHN-A-NHCOCH-N = NB-CONH-R (I) wherein A is an arylene residue of 6 or 10 carbon atoms, optionally further substituted with one or two chlorine atoms, methyl, methoxy and ethoxy, trifluoromethyl, or cyano, and B is a benzene moiety optionally substituted with chloro, methyl, methoxy, trifluoromethyl, carbomethoxy, or nitro, and R is a residue of a mixture of two or three benzene-type amines wherein the benzene ring is substituted with one or more halogen atoms, methyl, carbalkoxy or acylamino or benzoylamino. 2. A process for the preparation of mixed azo condensation pigments according to claim 1, characterized in that the dichlorides of the general formula II COCH ₀ COCHI 3 I 3 C1OC-B-N = N-CHCONH-A-NHCOCH-N = N-B-COCl (II) wherein A and B are as defined in point 1 are condensed with a mixture of amines of formula III R-NH ₂ (III), wherein R is as defined in item 1, by heating in an inert organic solvent to a temperature of 100 to 160 ° C.