DE1272476B - Process for the preparation of anthraquinone dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C09b

German class: 22 b-3/02

Number: 1 272 476

File number: P 12 72 476.4-43 (B 82345)

Filing date: June 10, 1965

Opening day: July 11, 1968

It has been found that valuable dyes of the 1 - aminoanthraquinone - 2 - sulfonic acid series, which are used in Carrying a substituted amino group in the 4-position is obtained when l-amino-4-halogenanthraquinone-2-sulfonic acids are used or their salts with mono- or diamines of the dihydro or tetrahydro compounds of the di- or trimeric cyclopentadiene.

As mono- or diamines of the dihydro or tetrahydro compounds of di- or trimeric cyclopentadiene for example:

H ₇ N

H, N

H ₇ N

H ₉ N

H ₇ N-

H ₇ N

/ NH ₇

CH ₇

, NH ₇

CH ₇

NH ₇

Process for the production of Anthraquinone dyes

Applicant:

Aniline & Soda Factory in Baden Aktiengesellschaft, 6700 Ludwigshafen Named as inventor: Dr. Fritz Graser, Ludwigshaferr; Dr. Hans Eugen Kiefer, 6706 Wachenheim

These amines can e.g. B. after the Ritter reaction from the di- or trimer of cyclopentadiene can be obtained. The double bond contained in the monoamines can, if desired, in a customary manner Way to be hydrogenated. The preparation of the compounds mentioned is detailed in the German Patents 1,215,145 and 1,239,302 and in French patent 1,482,396.

The 1 - amino - 4 - halogenanthraquinone - 2 - sulfonic acids used for the reaction with the named amines ζ. B. l-amino-4-chloro- or preferably 1 -Amino ^ -bromoanthraquinone ^ -sulfonic acid or its salts. It is advantageous to go there of water-soluble salts, for example the alkali metal salts such as the sodium or potassium salts of these sulfonic acids. The reaction is expediently carried out in the presence of hydrogen halide binding agents Means, e.g. B. of sodium or potassium carbonate, sodium bicarbonate, sodium acetate or secondary sodium phosphate, and in the presence of copper or copper compounds, e.g. copper salts, such as copper sulfate, copper (I) chloride or copper acetate, in aqueous, aqueous-alcoholic or alcoholic Liquid or in other water-miscible organic solvents such as dimethylformamide, Dioxane, mixed with water, optionally in the presence of dispersants, for example the sodium salt of the condensation product of / S-naphthalenesulfonic acid and formaldehyde, the end. In particular, low molecular weight alcohols such as methanol or Ethanol, into consideration.

The reaction takes place even at a moderately elevated temperature. It is expedient to work at a temperature of from 60 to ^100.degree. C., preferably from 70 to 100.degree. In most cases, the

m 569/51 «

Settlement completed within 4 to 24 hours. When using the i-amino ^ -bromoanthraquinone ^ -sulfonic acid or their water-soluble salts, a reaction time of 1 to 8 hours is usually sufficient.

It is expedient to start from stoichiometric amounts of the reaction participants. However, it is 1.2 to 3 times the equivalent amount of the amine, based on l-amino-4-halogenanthraquinone-2-sulfonic acids, is advantageous or their salts. However, a larger excess of amine is not harmful. Also with an excess of 1-amino-4-halogenanthraquinone-2-sulfonic acid implementation takes place.

Of particular technical interest are the dyes from the amines, in particular from the Monoamines of tetrahydro-, preferably dihydrotricyclopentadiene.

The new dyes, which are available in various forms, for example as alkali metal salts, such as sodium or potassium salts, as amine salts, such as hexamethylenediamine salts, di- or tetrahydrodi- or tricyclopentadienylamine salts, as internal salts or as free acids, optionally in finely divided form State, from a weakly alkaline bath, but advantageously from a neutral or weakly acidic bath, can be applied, deliver on structures such. B. foils, films and textiles, such as threads, fibers, Flakes, woven and knitted fabrics of all kinds, blue dyeings. They are particularly suitable new dyes for dyeing textiles made of linear polyamides, such as polycaprolactam, polycapryllactam, Polyhexamethylene diamine adipate or polycondensed ω-aminoundecylic acid. The on the The strong and uniformly reddish-tinged blue colorations obtained from the fibers mentioned are distinguished by the fact an extraordinarily bright shade and very good wet fastness properties. Textile goods from Wool or silk also dye the dyes obtainable according to the invention in bright blue Tones. The dyes are also suitable for printing on the textile material mentioned above. In some In some cases it is advantageous to mix the new dyes with one another or with others use known dyes.

The dyes can be dissolved or finely divided in the baths and printing pastes.

The dye baths and printing pastes can also contain wetting agents, such as the sodium salt of disulfonimide from heavy gasoline, adjusting agents such as sodium chloride and sodium sulfate, and others, in such Mixtures of customary auxiliaries, for example polyoxyalkyl ethers, such as the reaction product of 1 mol Octadecyl alcohol and 25 moles of ethylene oxide or the sodium salt of the acid sulfuric acid ester Addition product of about 80 moles of ethylene oxide to 1 mole of sperm oil alcohol. Also can Substances may be present that give the mixtures a weakly alkaline, neutral or acidic reaction to lend. Such substances can also change their mixtures during their use original pH value can be added. The presence of a distribution agent is particularly advantageous, for example a lignosulfonic acid salt or the condensation product of naphthalene-2-sulfonic acid and formaldehyde, in amounts up to about 150%. based on the weight of the dyes. The printing pastes also contain thickeners such as British gum, tragacanth and Crystal rubber.

Compared to dyes known from German patents 1 018 569 and 1 117244, Dyes produced according to the invention result in dyeings with better waterfastness and clearer color Hue.

Compared to the dyes described in German Patent 1115 215 stand out the new dyes on polyamide material due to their significantly better water and perspiration fastness and better wash fastness. They also dye polyamide at different pH values (pH 4, 7 and 9) practically equally strong, while z. B. the dye of Example 1 of said German Patent specification has its optimal drawability only in the acidic range. According to the invention Process using diamines obtainable dyes which still have a free amino group in the cycloalkyl radical are also suitable for dyeing and printing cellulose textile materials with the use of polyfunctional reactive compounds, for example according to the Procedure of the German Auslegeschrift 1155 088.

The parts and percentages given in the examples are weight units.

example 1

13.5 parts of the sodium salt of l-amino-4-bromoanthraquinone-2-sulfonic acid and 11 parts of dihydrotricyclopentadienylamine of the formula

H ₇ N

are heated in a mixture of 150 parts of water and 175 parts of methyl alcohol together with 7.1 parts of anhydrous sodium carbonate and 0.4 parts of copper (I) chloride for 5 hours with stirring at 75 to 8O ⁰ C. The reaction mixture is then acidified with dilute mineral acid until the reaction is weakly Congo acidic, and the reaction product is filtered off with suction and washed extensively with hot water. If necessary, for further purification, the dye is stirred with boiling hot, weakly sodium carbonate or soda-alkaline water (pH about 9), acidified again with dilute mineral acid until a weakly Congo-acidic reaction, sucks off hot and washed extensively with hot water. A blue dye is obtained in good yield which dyes polycaprolactam fabrics in bright blue, strong shades with very good fastness properties.

If, instead of the dihydrotricyclopentadienylamine, equal parts of tetrahydrotricyclopentadienylamine are used the formula

CH, CH

H, N

in this way a very similar dye is obtained.

A dyebath contains 1 part of that obtained according to Example 1, paragraph 1, in 4000 parts of aqueous mixture Dye, 2 parts of the sodium salt of the acidic

Sulfuric acid ester of a reaction product

1 mole of sperm oil alcohol and 80 moles of ethylene oxide and

2 parts ammonia (30%).

100 parts of a knitted fabric made of polycaprolactam and are brought into this bath at boiling temperature stains for 1 hour at this temperature. 4 parts of ammonium sulfate are then added and the mixture is treated the material to be dyed for a further 30 minutes at boiling temperature. The textile goods are then rinsed and dried. A deep, reddish blue coloration of good fastness to light, water, perspiration and washing is obtained. Polyhexamethylene diamine adipate and polycondensed cu-aminoundecylic acid are also used in the same way Dyed in strong, brilliant red-tinged blue tones of good light and wet fastness.

A printing paste consists of 30 parts of the dye of Example 1, paragraph 1, 30 parts of thiodiethylene glycol, 500 parts of crystal rubber (1: 2), 30 parts of phenol and 410 parts of water. Polyamide fabric based on ω-aminoundecanoic acid is printed with this paste, dried and steamed for half an hour. It is then rinsed and ^{soaped for 10 minutes at 50 °} C. with a solution of 0.5 part of Marseille soap in 1000 parts of water. A brilliant, reddish blueprint of good lightfastness, waterfastness and washfastness is obtained.

Fabrics made of polycaprolactam or polyhexamethylene diamine adipate can also be printed.

Example 2

38.2 parts of 1-amino-4-bromoanthraquinone-2-sulfonic acid and 26 parts of dihydrodicyclopentadienylamine the formula

H, N

are in a mixture of 400 parts of water and 90 parts of methyl alcohol together with 30 parts anhydrous potassium carbonate and 1.2 parts of crystallized copper sulfate for 6 hours with stirring Heated between 75 and 80 ° C. After cooling, the reaction mixture is diluted with mineral acid acidified to the weak Congo acid reaction, the reaction product sucked off and extensively first washed with cold to moderately warm water, then with hot water. If necessary, will further purified as indicated in Example 1. A blue dye is obtained in good yield, of wool and fabrics made of polyhexamethylene diamine adipate in bright blue tones with good to very good good fastness properties.

Used instead of dihydrodicyclopentadienylamine a tetrahydrodicyclopentadienylamine of the formula

H, N

CH

or the formula

NH,

CH

in this way one obtains very similar dyes. The last-mentioned amine can be obtained from dihydrodicyclopentadiene via the Ritter reaction.

Example 3

20.2 parts of the sodium salt of l-amino-4-bromoanthraquinone-2-sulfonic acid and 15.6 parts of tetrahydrotricyclopentadienylenediamine of the formula

H, N

NH,

are in a mixture of 220 parts of water and 270 parts of methyl alcohol with 5.5 parts of sodium carbonate and 0.7 parts of copper (I) chloride heated to boiling with stirring for 6 hours. One works the reaction mixture as described in Example 1 and receives a blue dye, the tissue from Polycaprolactam dyes bright blue with good fastness properties. On cotton you get with use of reactive polyfunctional compounds, e.g. B. according to the procedure of the German interpretative document 1155 088, blue dyeings with good fastness properties.

Claims (1)

Claim: Process for the production of anthraquinone dyes, characterized in that that one l-amino-4-halogenanthraquinone-2-sulfonic acids or their salts with mono- or Diamines of the dihydro or tetrahydro compounds of di- or trimeric cyclopentadiene implements. Considered publications:
German Auslegeschriften No. 1 018 569, 1117 244. When the application was announced, a coloring table with explanations was laid out. 109 569/516 7. U O Bundesdruckerei Berlin