DE731425C - Process for the production of water-soluble anthraquinone dyes - Google Patents

Description

The present invention relates to a method for the production of new, valuable, water-soluble dyes of the anthraquinone series, which are used for coloring animals Fibers and cellulose esters are very suitable. The new water-soluble anthraquinone dyes are obtained, if you have unsulfonated anthraquinone compounds that contain at least one primary amino group in the anthraquinone or contained in the arylamino radical, with formaldehyde or its polymerization products and a phenol and the intermediates thus obtained undergo sulfonation subject.

To carry out the process of the present invention, the starting compounds used are anthraquinone compounds having at least one primary. Amino group such as i-aminoanthraquinone and its heteronuclear halogen derivatives, i-amino-4-oxy- and -alkoxyanthrachinon, 1, 4-DiammoanthracliiaoiL, 1, 4-diamino-2-bromo-, 2-methyl- and 2-alkoxyanthrachinon, i -Ammo-4-methylarnino- and -hexahydroanilidoanthraquinone, aminoarylaminoaiithraquinones, such as 1-amino-4-anilidoanthraquinone, i-amino-4-m- and -p-toluidoanthraquinone, -4-p-xylidinoanthraquinone, -4-m-chloroanthrachinone -4-pphenylenediaminoanthraquinone, 1-amino-5- and -8-anilidoanthraquinone, and also polyamines, such as i, 4, S, 8-tetraaminoanthraquinone, i-oxy-4, S, 8-triaminoanthraquinone. These compounds contain the amino group in the anthraquinone nucleus.

However, it is also possible to use compounds whose amino group is in the arylamino radical is included. Such compounds are, for example, i-methylamino, I-ethylamino, i-n- and -i-propylaminoanthraquinones, which in the 4-position are the remainder of the p-phenylenediamine wear.

In addition to the simple phenols, substituted phenols such as p-chlorophenol, o- m- and p-cresol (i-oxy-2-, -3- and -4-methylbenzenes), guaiacol (i-oxy-2-methoxybenzene), Dichlorophenols and xylenols (dimethyloxybenzenes), can be used.

For condensation, the three reaction participants are mixed and for a while stirred at normal or slightly elevated temperature. But it can also be used at higher levels Temperatures up to over 100 ° C can be worked. The implementation participants can be mixed in any order; So, firstly, all three implementation participants can be set together, or you can also proceed as follows:

r. The anthraquinone base is dissolved in phenol, and formaldehyde is finally stirred in.

2. The anthraquinone base is mixed with paraformaldehyde and added to the molten phenol, if necessary.

3. Phenol and formaldehyde are mixed, and the anthraquinone base is in entered the liquid mixture.

The condensation is ended when a worked up sample of the reaction mixture becomes with sulfuric acid monohydrate completely sulfonated.

In either case, some of the phenol, reactant and solvent at the same time, through a solvent that is not involved in the reaction, such as benzene. Toluene. Alcohol, to be replaced.

When the condensation has ended, the solvent is removed. This can be done by distillation under reduced pressure or with steam or by pouring the reaction mixture in strongly alkaline water or a saline solution, whereby the reaction product is precipitated. 8n

For sulfonation, the condensation products are converted into sulfuric acid monohydrate dissolved and stirred, if necessary with the addition of some oleum, until samples are soluble in dilute sodium carbonate solution. The dyes are used in more common Way worked up and dried under reduced pressure at low temperature.

The new dyes are, if the amino group is in the anthraquinone nucleus, probably composed as follows:

O NH-CH ₃ - / XX

OH

SO., H

if the amino group is in the aryl radical, they have the composition

O NH-

> -NH-CH

in both cases the anthraquinone and the. Phenol radical to be further substituted can.

They dye wool, silk and cellulose esters in strong tones with valuable properties.

The fastness properties largely agree with those of the dyeings with

fio the underlying aminoanthraquinones in the form of pastes, powders, etc. er

SO ₃ H

holds. It therefore appears that the water-soluble dye changes during the dyeing process for the most part splits with regression of the aminoanthraquinone, so that the aminoanthraquinone is finely divided the fiber can pull up.

example 1

20 kg of I-aminoanthraquinone are stirred with 100 g of phenol at 100.degree. One lets

at the same temperature within one hour 20 kg of formaldehyde (40 percent by volume) run in and stir for a further 2 hours. The melt is now in 10001 Pressed water containing 50 kg of sodium chloride and 45 kg of sodium hydroxide dissolved. The precipitated condensation product is filtered off, taken up in water and with Sulfuric acid neutralized. It is filtered, washed and dried to obtain a brownish-red color Powder that dissolves in alcohol with a scarlet color.

10 kg of the dye base are dissolved in 30 kg of sulfuric acid monohydrate below 20.degree and stirred until a sample is clearly soluble in dilute sodium carbonate solution is. It is pressed into 500 l of sodium chloride solution of 5% »sucks the precipitated Dye off and wash off as much acid as possible with 5% sodium chloride solution. Of the Filter residue is triturated with sodium carbonate until it reacts neutral dried.

The dye obtained dissolves in water

a5 ser with red color. This solution becomes Acetate artificial silk dyed in a neutral bath in orange tones.

Similar dyes that also dye acetate rayon orange are obtained from i-amino-5-chloro- and -S-chloroanthraquinone.

Example 2

200 kg of phenol are melted and mixed with 25 kg of formaldehyde of 40 percent by volume. At 40 ^° C., 40 kg of i-amino-4-methoxyanthraquinone are introduced with thorough stirring. The mixture is then stirred for a further 4 hours at the same temperature and the melt is then pressed into a solution of 100 kg of sodium chloride and 90 kg of sodium hydroxide in 2000 l of water.

10 kg of the condensation product are dissolved in 30 kg of sulfuric acid at 20 ° C and stirred for ¹ _J2 hour. A sample is now clearly soluble in dilute sodium carbonate solution. The dye is obtained, as in the first example, by pouring it into salt water and working it up further as indicated there. It dissolves in water blue-red and dyes acetate artificial silk from a neutral bath in beautiful scarlet shades.

With i-amino-4-oxyanthraquinone instead of i-amino-4-methoxyanthraquinone get a bluish red.

Example 3

γόο kg phenol are melted with 1½ kg formaldehyde of 40 percent by volume. At ! ^{4o C.} 20 kg of 1,4-diaminoanthraquinone are added and the mixture is stirred for a further 4 hours. The conversion product is precipitated and processed as in the previous examples.

! 'By sulfonating at 20 ° C in sulfuric acid monohydrate, a dye is obtained j that dissolves in water with a purple color; Acetate rayon is made from this solution in 7 » colored red-violet tones. The dye -aus i, 4-diamino-2-methylanthraquinone stains a similar purple, that of 1,4-diamino-2-bromoanthraquinone a blue-violet, the one from 1,4-diamino-2-m: ethoxyanthraquinone a bluish red.

Example 4

100 kg of p-chlorophenol are melted with 10 kg of i, 4-Diamin.o - 2-methylantbrachinone at 40 ^{3 C.} With thorough stirring, 6 kg of formaldehyde solution of 40 percent by volume are allowed to run in over the course of one hour and are kept at this temperature for a further 2 hours. As in the first examples, the reaction product is precipitated by dilution with alkaline salt water and worked up. Sulphonation in sulfuric acid monohydrate at 20 ° C. gives a dye which dyes acetate rayon from aqueous solution purple. Instead of p-chlorophenol, guaiacol or o-, m- or p-cresol can be used with similar success.

The dyes have the same color as that from p-chlorophenol.

Example 5

20 kg of i-amino-4-methylaininoanthraquinone are mixed with 3 kg of paraformaldehyde and added to 100 kg of molten phenol. The mixture is stirred for 2 hours at 45 ° C. and the melt is pressed into a mixture from 10001 salt water of 5% and 80 kg technical caustic soda. The filtered precipitate is rendered neutral and washed and dried.

The sulfonation takes place as in Example 1. The dye obtained dissolves in water with blue color; his dyeings on acetate rayon are "blue-violet. Also blue-violet colors the dye from i-amino-4-cyclohexylaminoanthraquinone.

Example 6

20 kg i-amino-4-phenylaminoanthrachinon and 100 kg of phenol are heated to solution and cooled to 40 ⁰ C. 10 kg of formaldehyde solution of 40 percent by volume are slowly stirred in and, after a further 2 hours, the melt is pressed into alkaline salt water. The precipitated dye base is as in the previous examples

worked up and sulfonated to a dye that turns blue in water solves. From the neutral solution, expediently in the presence of a wetting and dispersing agent, Acetate artificial silk is dyed in strong reddish blue tones at 80 to 90 ° C. The dyes shown in the same way from i-amino-4- (3'- and ^ '- methyl) -phenylaminoanthraquinone, 1 - Amino - 4 - (2 ', 5'-dimethyl) -phenylaminoanthraquinone color in strong blue tones; the dye off i-Amino-4- (3'-chloro) -phenylaminoanthraquinone gives acetate rayon a strong reddish blue.

Example 7

20 kg i-amino-4- (4'-amino) -phenylaminoanthrachinon are dissolved at ioo ⁼ C in 100 kg of phenol. 20 kg of formaldehyde of 40 percent by volume are allowed to run in slowly and the melt is then pressed into alkaline salt water. The worked up dye base is sulfonated in sulfuric acid monohydrate at 20 ° C. A dye is obtained which is soluble in water with a blue-green color and which dyes acetate artificial silk from a neutral bath blue.

Example 8

20 kg i-amino-S-phenylaminoanthracliinon are introduced at 40 ⁰ C in a mixture "of 100kg phenol and 7 kg of formaldehyde of 40 volume percent. The mixture is stirred for one hour at the same temperature and the l'msetzungserzeugnis precipitated by dilution with alkaline salt water.

Sulfonation with sulfuric acid monohydrate at 20 ° C. gives a water-soluble one Dye that dyes acetate rayon bright red.

The dye from i-amino-S-phienylamine-oanthraquinone turns bluish red.

Example 9

45 x 20 kg 1,4, 5, 8-tetraaminoanthraquinone and 100 kg of phenol are stirred at 100 ° C. 25 kg of formaldehyde of 40 percent by volume are allowed to run in within one hour, stir for a short time and press the melt into alkaline salt water.

The worked up and dried dye base is dissolved in sulfuric acid monohydrate sulfonated. The dye dissolves in water with a green-blue color; he dyes acetate rayon clear blue.

The dye from 1, 4, 5-triamino-8-oxyanthraquinone also colors blue.

Example 10

20 kg of ι-methylamino-4- (4'-amino) -phenylaminoanthraquinone are dissolved in 100 kg of phenol at -80 ° C. To this melt lets slowly run in 10 kg of formaldehyde solution of 40 percent by volume and stir briefly Time to continue at the same temperature. The melt is then put into a solution of 50 kg of sodium chloride and 40 kg of sodium hydroxide in 10001 of water, filtered and washes with salt water of 5 ° / ", takes up the filter material again in 1000 l of water and add hydrochloric acid or sulfuric acid until the reaction is weakly acidic. Filter the precipitated base, washed with water and dried at low temperature.

10 kg of the base obtained are dissolved in 50 kg of sulfuric acid monohydrate at 20 to 25 ^° C. and V is stirred for _{2 hours.} If after this time a sample is not clearly soluble in dilute sodium carbonate solution, ι o kg "2 / percent oleum are added. After the sulfonation is complete, 500 liters of water are poured out, the dyestuff which has separated out is suctioned off and washed out with water. The filter cake is then kneaded with so much sodium carbonate that just a weak alkaline reaction remains, and then dried.

The dye dissolves in water with blue-green, in concentrated sulfuric acid with steel blue color: ■ its aqueous solution gives acetate rayon a very real blue-green color.

Example 11

20 kg i-methylamino-4 (4'-amino) -phenylaminoanthrachinon are stirred with 100 kg of phenol and 10 kg of formaldehyde of 40 volume percent for 8 hours at 40 ⁰ C. The work-up and sulfonation are carried out as in Example 10. The same dye is obtained.

Example 12

100 kg of phenol were melted with 10 kg of formaldehyde solution of 40 volume percent at 40 ⁰ C. 20 kg of i-methylamino-4- (4'-amino) -phenylaminoanthraquinone are stirred in and kept at this temperature for 8 hours. The worked-up dye base provides the same dye as Examples 10 and 11 on sulfonation.

Example 13

Dissolve 20 kg i-methylamino-4- (4'-amino) -phenylaminoanthrachinon at 100 ⁰ C in 100 kg of o-cresol, cooled to 20 ⁰ C, and 10 can be kg of formaldehyde solution of 40 \ 7 "accrue olumprozent. After stirring for several hours The batch is pressed into a solution of 50 kg of sodium chloride and 40 kg of sodium hydroxide in 1000 liters of water and filtered. The processed dye base is sulfonated as indicated in Example 10. The dye obtained is

Substance dissolves in water with a bluish-green tinge, in concentrated sulfuric acid with a purple tinge steel blue color and dyes acetate rayon from aqueous solution while maintaining structure acetylated cotton yarn and acetyl cellulose films in very real blue-green tones.

Similar dyes are obtained if, in this example, the o-cresol by the technical Mixture of m- and p-cresol, by guaiacol, p-chlorophenol, 2,4-xylenol or 3, 4-dichlorophenol is replaced.

The dyes dye in the same blue-green shades as the dye from o-cresol.

Example 14

A mixture of 2, 6 kg trioxymethylene with 20 kg of i-ethylamino-4- (4'-amino) -phenylaminoanthrachinon is .eingerührt in 100 kg of molten phenol at 50 ⁰ C and held at this Temperatuf until no starting material is detectable. The processed condensation product is, as described in Example 10, sulfonated in sulfuric acid monohydrate, the sulfonic acid is precipitated with water, suction filtered, redissolved neutrally - and salted out. The dye obtained dissolves in concentrated sulfuric acid with a gray color, in hot water with a greenish blue color and stains acetate rayon a strong blue-green.

Similar dyes that also dye acetate rayon blue-green are identified with i-n- and -i-propylamino-4- (4'-amino) -phenylaminoanthraquinone obtain.

Claims (1)

Claim: Process for the preparation of water-soluble anthraquinone dyes, thereby characterized in that one unsulfonated anthraquinone derivatives, the. at least one primary amino group in the Contained in anthraquinone or in the arylamine nucleus, with formaldehyde or its polymerisation products and a Treated phenol and sulfonated the intermediate products thus obtained.