CS246533B1 - Preparation method of condensing diasopigments - Google Patents

Description

The invention relates to a process for the preparation of condensation disazopigments of the general formula I

CH5

I co

R - NH - CO - B - N = N - CH - CO - NH - A - (I)

CH3

I co

-NH-CO-CH-N = N-B-CO-NH-R containing admixed disazopigments of formula II,

CH3

AND

WHAT

AND

R 10 OC-B-N = N-CH-CO-NH-A-II

CH3

I co

Ί

-NH-CO-CH-N = N-B-COOR 1 (II) wherein

A and B denote arylene and

R aryl optionally further substituted by non-solubilizing groups and

R1 is alkyl of 2 to 8 carbon atoms.

Principle of preparation of pigments of formula I, i.e. the amide type of the acid of formula III

CH3 CHs

I Whats what

C1CO-BN = N-CH-CO-NH-A-NH-CO-CH-N = NB-COCl (III) with an aromatic amine of formula (IV), R-NH2 (IV) as defined above for A, B and R.

The preparation of the pigments of the formula II, i.e. the ester type, can be carried out by condensation of the dicarboxylic acid dichloride of the formula III with an aliphatic alcohol of the formula V

R1-OH (V) with the meanings given above for A, B and R1.

The products of both types of condensation reactions are disazopigments of yellow shades with very good stability in organic solvents, in migration, in light and especially in the case of amide-type pigments of general formula I characterized by very good thermostability.

Until now, inert aromatic solvents such as toluene, xylenes, chlorotoluenes, chlorobenzene, trichlorobenzenes, nitrobenzene, but most preferably o-dichlorobenzene have been used as a condensation reaction medium for the preparation of the pigments of formula (I). Also disclosed is the use of a mixture of polymeric branched aliphatic hydrocarbons having a carbon number of 6 to 90.

Working with these aromatic solvents, especially chlorine, is very hazardous from the health point of view, as they are generally harmful to the human organism. The recovery of these solvents eliminates the distillation residue, which is disposed of by incineration, which in the case of chlorinated solvents presents considerable problems associated with the disposal of chlorinated waste. A disadvantage of a mixture of polymeric branched aliphatic hydrocarbons having a carbon number of 6 to 90 is the relatively low solubility compared to aromatic solvents and their viscosity. When using the solvents mentioned above, after filtering the pigment from the reaction medium, it is necessary to wash it with a lower water-miscible aliphatic alcohol, on the one hand in order to remove undesirable polar substances which are insoluble in the less polar solvent used for the condensation reaction. the pigment could finally be washed with water. In the production process, this means double solvent management, double solvent recovery, etc.

It has now been found that the disazopigments of the above general formula (I) with an admixture of 5 to 20 mol%. disazopigments of formula II can be obtained using aliphatic alcohols having a carbon number of 2 to 8 as the reaction medium for the condensation reaction of a dicarboxylic acid dichloride of formula III with an aromatic amine of formula IV. The pigments prepared in their color application properties are completely equal to pigments prepared in inert aromatic solvents, while there is no risk to human health caused by the toxicity of the aromatic substances, regeneration is usually less expensive and the wastes do not contain chlorine. Particularly preferred is the use of lower aliphatic alcohols having a carbon number of 2 to 4 (water miscible) since only one type of solvent can be used in the production process.

The invention therefore provides a process for the preparation of condensation disazopigments of the formula I with an admixture of 5 to 20 mol%. disazopigments of formula II wherein A is an arylene radical optionally further substituted by one or two chlorine atoms, methyl, methoxy, ethoxy, trifluoromethyl, or cyano, B is a benzene radical optionally substituted by chlorine, nitro-methyl, methoxy methoxycarbonyl, ethoxycarbonyl or trifluoromethyl, R is aryl optionally substituted with one to three groups such as chloro, bromo, methyl, methoxy, ethoxy, phenoxy, trifluoromethyl, nitro, methoxycarbonyl, ethoxycarbonyl -, cyano, R 1 is an alkyl of 2 to 8, by condensation of 1 mole of the dicarboxylic acid dichloride of formula III with 2 moles of the aromatic amine of formula IV, characterized in that the condensation is carried out at 110-140 ° C in aliphatic alcohol with the addition of calcium or magnesium carbonate or calcium or magnesium oxide to bind the resulting hydrogen chloride.

The dicarboxylic acid dichloride of the formula III is obtained by the action of thionyl chloride, phosgene or phosphorus trichloride on an intermediate dye which contains two carboxy and two azo groups in its molecule. Diazotinated aminobenzoic acid active ingredients, such as:

3-aminobenzoic acid,

3-amino-4-chlorobenzoic acid,

3-amino-4-methylbenzoic acid,

3-amino-4-methoxybenzoic acid,

3-amino-4-methoxycarbonylbenzoic acid.

Among the passive components for preparing the dyes, bisacetoacetylated 1,4-phenylenediamine derivatives are suitable such as:

1,4-phenylenediamine,

2-chloro-1,4-phenylenediamine,

2-methyl-1,4-phenylenediamine,

2-methoxy-1,4-phenylenediamine,

2-cyano-1,4-phenylenediamine,

2-trifluoromethyl-1,4-phenylenediamine,

2,5-dichloro-1,4-phenylenediamine,

2,5-dimethyl-1,4-phenylenediamine,

2,3-dimethyl-1,4-phenylenediamine,

2-chloro-5-methyl-1,4-phenylenediamine.

Of the aromatic amines of formula IV, aniline derivatives such as 2-, 3-, 4-chloroaniline, 2,5- or 2,4-dichloroaniline, 4-thromaniline, 2-, 3-, 4-methylaniline, xylidines are suitable for condensation. haloalkylanilines such as 3-trifluoromethylaniline, arylanilines such as

4-aminodiphenyl, alkoxy or aryloxyanilines such as 2-ethoxyaniline, 2- or 4-methoxyaniline,

2,5-dimethoxyaniline, 4-aminodiphenyl ether, cyananilines such as 3-cyananiline and aniline substituted with arylcarbamoyl-, arylamino-, acylamino- or methoxycarbonyl such as methyl 2-, 3- or 4-aminobenzo246533, 4- or 3-acetaminoaniline, 4- aminodiphenylamine.

Also suitable are aniline derivatives substituted simultaneously by several different substituents such as:

4-chloro-2-nitroaniline,

2-chloro-4-nitroaniline,

3-chloro-2-methylaniline,

5-chloro-2-methylaniline,

4-chloro-2-methylaniline,

6-chloro-2-methylaniline,

2-chloro-5 methylaniline,

2-chloro-4-methylanine,

3-chloro-4-methylaniline,

4-Chloro-2-trifluoromethylaniline

2-chloro-5-trifluoromethylaniline,

2-chloro-2-methoxyaniline,

2-chloro-4-methoxyaniline,

5-chloro-2-methoxyaniline

4-chloro-2,5-dimethoxyaniline,

5-chloro-2,4-dimethoxyaniline

4-chloro-2-methoxy-5-methylaniline,

2-methoxy-5-methylaniline,

5-Methoxy-2-methylaniline

2-methoxy-5-trifluoromethylaniline,

4-acetamido-3-methoxyaniline,

4-methyl-2-nitroaniline,

2-methyl-5-nitroaniline,

4-methyl-3-nitroaniline,

2-methyl-4-nitroaniline,

4-methoxy-2-nitroaniline,

2-methoxy-5-nitroaniline,

2,5-dimethoxy-4-nitroaniline,

2-methoxy-5-methyl-4-nitroaniline,

2-cyano-4-nitroaniline,

2-phenoxy-5-trifluoromethyl laniline,

2- (4-chlorophenoxy) -4-chloro-5-trifluoromethylaniline,

2- (4-methylphenoxy) -4-chloro-5-trifluoromethylaniline,

2- (4-methylphenoxy) -4-chloro-5-trifluoromethylaniline,

2- (2,4-dichlorophenoxy) -4-chloro-5-trifluoromethylaniline,

2- (4-methoxyphenoxy) -3-trifluoromethylaniline,

2- (4-tert-butylphenoxy) -5-trifluoromethylaniline,

2- (4-isopropylphenoxy) -5-trifluoromethylaniline,

2- (3-chloro-4-isopropylphenoxy) -5-trifluoromethylaniline,

4- (4-chlorophenoxy-aniline),

5-chloro-2- (4-chlorophenoxy) aniline,

5-chloro-2- (4-chlorophenoxy) aniline.

The dicarboxylic acid dichlorides of the formula III can also be condensed with other amines such as:

1-Amino-naphthalene

1-aminoantraquinone, 1-amino-5-chlorantraquinone, 1-amino-5-benzylaminoantraquinone,

4-aminoindan,

5-aminoindan, optionally a mixture of aminoindanes obtained by reduction of nitroisomers after indane nitration.

The pigments prepared by the process according to the invention have a wide application because they exhibit very good thermostability and stability in organic solvents, in migration and in light. They can be used, for example, for dyeing high molecular weight materials such as viscose, cellulose esters and ethers, polyamides, polyurethanes, polyesters, polyvinyl chloride, polyethylene, polypropylene, polystyrene, nitrocellulose based products, natural or synthetic resins such as amidoplasts, alkyd resins, phenoplasts, rubber , lacquers, and silicone products.

The process according to the invention is illustrated in more detail in the following examples:

Example 1

The dicarboxy disazo dye prepared by coupling of diazotized 3-amino-4-chlorobenzoic acid with 1,4-bisacetoacetylamino-2,5-dichlorobenzene in a 2: 1 molar ratio is converted to the corresponding dicarboxylic acid dichloride by treatment with chlorinating agents such as thionyl chloride, phosphorus trichloride or phosgene. 85.4 g of dry dichloride are stirred in 980 g of ethanol in an autoclave, 35.4 g of 5-chloro-2-methylaniline and 11.4 g of calcium carbonate are added. The mixture is heated to 110 ° C and stirred at this temperature and pressure of 4 to 5 bar for 3 hours. After cooling to 60 ° C, the autoclave is opened, the pigment suspension is heated to 75 ° C and filtered. The product is washed with hot ethanol and finally with water. After drying, 94 g of a yellow pigment are obtained.

Example 2

22.4 g of a dicarboxylic acid dichloride prepared from the same components and in the same manner as described in Example 1 is slurried in 260 g of n-butanol, added

9.4 g of 5-chloro-2-methylaniline and 3 g of calcium carbonate. The mixture is heated to boiling, i.e. 117 ° C, with stirring and maintained for 4 hours. Then, the pigment suspension is hot filtered, washed with hot n-butanol and finally hot water. After drying, 26.7 g of a yellow pigment are obtained.

Example 1 a d 3

22.4 g of the dicarboxylic acid dichloride prepared from the same components and in the same manner as described in Example 1 are slurried in 260 g of 2-ethylhexanol, 9.4 g of 5-chloro-2-methylaniline and 3 g of calcium carbonate are added. The mixture was heated to 140 ° C with stirring and held at this temperature for 4 hours. The pigment suspension is filtered while hot, washed with hot 2-ethylhexanol, then hot ethanol and finally with water. After drying, 26.5 g of a yellow pigment are obtained.

Example 4

Dicarboxydisazo dye prepared by coupling of diazotized 3-amino-4-methoxycarbonylbenzoic acid with 1,4-bisacetoacetylamino-2,5-dichlorobenzene in mol. a 2: 1 ratio is converted to the corresponding dicarboxylic acid dichloride by treatment with chlorinating agents such as thionyl chloride or phosgene. 23.8 g of dry dichloride are stirred in 260 g of n-butanol, 9.7 g of 3-trifluoromethylaniline and 3 g of calcium carbonate are added. The mixture is heated to 117 ° C with stirring and stirred at this temperature for 4 hours. The pigment suspension is filtered while hot, the product is washed with hot n-butanol and finally with hot water. After drying, 28.5 g of a yellow pigment are obtained. Example 5

23.8 g of the dicarboxylic acid dichloride prepared from the same components and in the same manner as described in Example 4 are stirred in an autoclave in 260 g of ethanol, 10.7 g of 2,5-dichloroaniline and 3 g of calcium carbonate are added. The mixture is heated with stirring to 110 ° C and stirred at this temperature and pressure of 4 to 5 bar for 3 hours. After cooling to 60 ° C, the autoclave is opened, the pigment suspension is heated to 75 ° C and filtered. The product was washed with hot ethanol and finally with water. After drying, 29.8 g of a yellow pigment are obtained.

Example 1 a d 6

Dicarboxydisazo dye prepared by coupling diazotized 3-amino-4-chlorobenzoic acid with 1,4-bisacetoacetylamino-2-chloro-5-methylbenzene in mol. a 2: 1 ratio is converted to the corresponding dicarboxylic acid dichloride by treatment with chlorinating agents such as thionyl chloride or phosgene.

36.3 g of dry dichloride are stirred in 550 g of ethanol in an autoclave, 11.6 g of 3-chloro-2-methylaniline and 5 g of calcium carbonate are added. The mixture is heated to 115 degrees Celsius with stirring and held at this temperature and pressure of 4 to 5 bar for 4 hours. After cooling to 60 ° C, the autoclave is opened, the pigment suspension is heated to 75 ° C and filtered. The product was washed with hot ethanol and finally with water. After drying, 48.5 g of a yellow pigment are obtained.

Example 7

A dicarboxy disazo dye prepared by coupling diazotized 3-amino-4-chlorobenzoic acid with 1,4-bisacetoacetylamino-2,5-dimethylbenzene in mol. a 2: 1 ratio is converted to the corresponding dicarboxylic acid dichloride by treatment with chlorinating agents such as thionyl chloride or phosgene. 25 g of dry dichloride are stirred in an autoclave in 395 g of ethanol, 11 g of 5-chloro-2-methylaniline and 3.5 g of calcium carbonate are added. The mixture is heated to 120 ° C with stirring and stirred at this temperature and pressure 0 45 to 0.55 MPa for 6 hours. After cooling to 60 ° C, the autoclave is opened, the pigment suspension is heated to 75 ° C and filtered. The product was washed with hot ethanol and finally with water. After drying, 30 g of a yellow pigment are obtained.

The same result is obtained when magnesium carbonate, magnesium oxide or calcium oxide is used instead of calcium carbonate under otherwise the same conditions as in the examples.

Claims (1)

PftEDMET Process for the preparation of condensation dlsazopigments of the formula I containing 5 to 20 mol% in admixture. disazopigments of formula II, COCHs R-NHCO-B-N = N-CHCONH-ACOCH 3 AND AND -NHCOCH-N — N-B-CONH-R (I) COCHg R1-OOC-B-N = N-CHCONH-ACOCH3 -NHCOCH-N = N-B-COO-R 1 (II) wherein A is an arylene radical, optionally further substituted by one or two chlorine atoms, methyl, methoxy, ethoxy, trifluoromethyl or cyano, B is arylene, optionally substituted with chlorine, methyl, methoxy, trifluoromethyl, methoxycarbonyl, ethoxycarbonyl, or nitro, R is aryl, optionally substituted once INVENTION with up to three groups such as chloro, bromo, methyl, methoxy, ethoxy, phenoxy, trifluoromethyl, nitro, methoxycarbonyl, cyano, acylamino, arylamino, alkylcarbamoyl, or arylcarbamoyl, R1 is an alkyl having 2 to 8 carbon atoms, condensed with 1 mole of the dicarboxylic acid dichloride of formula III, COCH3 COCH3 C1CO-B-N = CH-CO-NH-A-NH-CO-CH = N-B-COC1 (III) where A and B are as defined above with 2 moles of the aromatic amine of formula IV, R-NH 2 (IV) wherein R is as defined above, characterized in that the condensation is carried out at 110 to 140 ° C in an aliphatic alcohol having a carbon number of 2 to 8 with addition of calcium or magnesium carbonate or calcium or magnesium oxide for binding the formation of hydrogen chloride.