DE2362330A1 - POLYFLUOROUS ACID AZO DYES - Google Patents

Description

DR. BERG DiPU-ING * STAPF

β MUNICH SO. MAUERKIRCHERSTR. 45

Attorney File 24 492 December 14, 1973

Be / Sch

PROJ) UITS CHIMIQUES UGIHE KUHLMANN Paris / France

"Polyfluorinated Acid Azo Dyes"

Inventor: Jacques PECHMEZE Robert SUREAU

The present invention relates to new polyfluorinated ones acidic azo dyes that are soluble in water; they are for coloring fibers based on natural or synthetic polyamides can be used »

They have the following general formula: 23.C. , -2-

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wherein X is a group -SO ^ H, -PO ₅ Ii ₂ or -PO ₂ H, R ^ is an alkyl radical, X is a hydrogen or halogen atom, an alkyl, alkoxy or nitro group, Z. is a hydrogen atom or a diene chain which forms a naphthalene nucleus with the benzene nucleus, B is an aromatic nucleus, for example a benzene or naphthalene nucleus, which is optionally substituted, m = 0 or 1, R is a hydrogen atom, an alkyl or alkoxy group, R ^ is a hydrogen or chlorine atom, an alkyl, alkoxy, acylamino group or a diene chain which is linked to the benzene nucleus to form a naphthalene nucleus, E ^ is a hydrogen atom, an alkyl, cyanoethyl or hydroxyalkyl group and η = 2 . The alkyl and alkoxy groups preferably have 1 to 5

Carbon atoms. '

Compared to their non-fluorinated homologues, the new dyes show a shift in their maximum absorption to the range of the shortest wavelengths and it is characterized by improved fastness properties compared to Light off.

The new dyes can be prepared in that

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one is the diazo derivative of an amine of the general formula

X ■,

£ N = N - B "^ -NH ₂ (H) '

with a coupling agent of the general formula

N ·. (Ill),

^C 2% - ° ii ^F 2n

wherein X, Y, Z, m, R, R _{x 1} , R 2 and η have the same meanings as above.

Such coupling agents are in French patent application 72 38 896 from 3.110 ^ 1972 for "polyfluoro alkylarylamines et leurs procedes de preparation ".

The dyes according to the invention are suitable for coloring of fibers based on natural or synthetic polyamides. The coloring is carried out under the same conditions like with classic acidic dyes.

In the examples below, they are for explanation only serve, parts are by weight unless otherwise specified. - ""

Example 1 .

17j3 parts of 3-aminobenzenesulfonic acid are added to 200 vol.

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Parts of distilled water with the aid of 5.3 parts of sodium carbonate in solution. 7 parts of sodium nitrite are added. This solution is slowly poured into 120 parts by volume of an aqueous solution of about 6N hydrochloric acid, which has been cooled to 0 to 5 ° C. beforehand. The mixture is stirred for one hour, the temperature being raised to 0 to 5 ° C. The excess sodium nitrite is destroyed by adding sulfamic acid.

The solution of the diazonium chloride is slowly added with stirring to a mixture of 23.9 parts of N-ethyl-N-3-3-4.4.4-pentafl-uorbutylaniline, 25 parts of sodium acetate in 400 parts of crystallizable acetic acid.

After standing overnight, the crystallized dye is filtered and dried. This gives 30.4 parts, corresponding to a 64 / £ strength yield dye of the formula sodium 4 '- (. N-ethyl-N-3.3 ⁱ i ^i' * ⁱ i-pentafluorobutyl.) Amino-benzene-lphenylazo 3-sulfonate. This dye dyes synthetic polyamide fibers in a yellow shade with remarkable fastness properties to light.

The dye, n-butyl, stains under the same conditions instead of the pentafluorobutyl radical, contains synthetic polyamide fibers in a yellow shade with weaker fastness property to light.

In the following table I is a certain number of monoazo dyes ^ which have the 3 · 3 «4» ⁱ J..4-pentafluorobutyl radical

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and were prepared by the method of Example 1, indicated in an exemplary manner '.

In this table, m means meta, ο ortho, ρ para. the Positions refer to the azo group. In all compounds of this table, R = H.

m X 0 Tabel I. Z ^R l H, Color tint on
Polyamide fibers m PO ₃ H ₂ P. H H H- yellow · ■ at
game m SO H 0 Y H H' H "-" ""! » 2 'm ^PO 3H2 0 Ή H H C ₂ H ₅ Il 3 m PO ₃ H ₂ H ¹ H. CH ₃ ^C 2 ^H 5 11 4th * P SO ₃ H H ^: H CH ₃ C ₂ H ₅ ■ ι ·; ■■ VJl m SO ₃ H .OCH ₃ - H CH ₃ C ₂ H ₅ yellow-red 6th Example 9 PO ₃ H ₂ .Cl H H C ₂ H ₅ yellow 7th .Cl 8th YCl

The 4 '- (.. N-ethyl-N-4-h 3.3.4 pentafluorbuty1) amino-2 ^f -methy1-l-phenyIazo-4-sulfonaphtalIn,' which was prepared according to the procedure of Example i, colored polyamide fibers in orange tint. """."''. - _; * ·.

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Example 10

27.7 parts of 4'-aminoazobenzene-3-sulfonic acid are dissolved in 580 parts by volume of distilled water and 55 parts by volume of about 18% hydrochloric acid. 7 _S add 2 parts of sodium nitrite in solution in 20 parts by volume of distilled water, while maintaining the temperature between 0 and 5 g. Stirring is continued for 5 hours at the same temperature.

The resulting solution of the diazonium chloride is poured into a solution of 28.1 parts of N-ethyl-N-3.3.4.4.4-pentafluorobutyl-m-toluidine in 400 parts by volume of crystallizable acetic acid, the solution being obtained by adding sodium acetate buffers.

After the coupling has ended, the dye is precipitated by adding sodium chloride, filtered and washed with a saturated sodium chloride solution and dries.

60.4 parts of a mixture are obtained, the 80% dye namely the sodium salt of /ΐ-(N-äthyl-N-3'.3'.4'.4 ·. 4 · pent af luorbutyl) amino-2-methyl -benzo 1.7- ^ l azo 4 ') - / contains fenzolazo-benzene-3-sulfonic acid7 and $ 20 sodium chloride. The yield is Sl% of the theoretical amount. This dye dyes synthetic polyamide fibers in a red shade with very good fastness properties to light.

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_ ₇ . 7362330

The dye homologue that uses the n-butyl radical instead of the Has pentafluorobutyl radicals, dyes synthetic polyamide fibers Bordeaux red with mediocre fastness properties compared to light.

Example 11 '-

The procedure is as in Example 10, but after coupling the N-Ethy 1-N-3.3.4 .A is replaced . 4-pentafluorbuty1-mt oluidine by 30.6 parts of N-cyanoethyl-N-3.3 .. U. H. 4-pentafluorobutyl-mtoluidine. With a yield of-.605? compared to the theoretical yield, the dye as the sodium salt of / ¥ - (N-ethyl-N-3 ¹ -3'.4 * , M \ .W- pentafluorobuty1) amino-2-methy! benzene / - (l azo 4 γ -_ / Fenzola2obenzol-3-sulfonic acid_ /, which dyes synthetic polyamide fibers in scarlet red with very good fastness properties to light.

The dye homologue in which the pentafluorobutyl radical is replaced by the n-butyl radical, dyes synthetic polyamide fibers in a red shade with mediocre fastness properties to light.

Example 12

7.3 parts of 3-aminobenzenesulfonic acid are fried in 20 parts by volume of distilled water and 10 parts by volume of 30 % sodium hydroxide solution. After dissolving, the total volume is brought to 100 parts by adding distilled

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Water and gives 6.9 parts of sodium nitrite solution in 10 Share by volume with distilled water.

The resulting solution is poured into a mixture of 7 ^ parts of crushed ice and 50 parts of about 30 minutes 18 # hydrochloric acid, keeping the temperature between 0 and 5 C. After stirring for 30 minutes, the excess is destroyed of nitrous acid by adding sulfamic acid.

On the other hand, is placed 1 ^ 4.1 parts Qt, naphthylamine, dissolved in 110 parts by volume distilled water and 20 volts ropes about lSjSiger hydrochloric acid »by heating to boiling is allowed to cool to 70 ⁰ C and decreases to 60 ° C with the addition of distilled Water,

75 parts of ice are added to the solution of the diazo derivative Metanilic acid. Ok-naphthylamine solution is quickly poured in and stirs 3 hours. After the coupling is complete, the dye prepared first is by adding 24 parts by volume of a 30 # sodium hydroxide solution brought into solution. 16.5 parts by volume of a 50 # strength sodium nitrite solution are added and then pours quickly. 60 parts by volume of 18 # hydrochloric acid. Man filters the diazonium chloride, then pastes again in 80 Parts by volume of distilled water and 30 parts of crushed ice. You bring the total volume to 250 parts distilled water.

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The suspension of the diazonium salt is poured into a solution of 28.1 parts of N-ethyl-N-3.3.4.4.4-pentafluorobutyl-mtoluidine in 400 parts by volume of crystallizable acetic acid. During the pouring in, the p n value is kept at 4 to 4.5 by adding sodium acetate. :

When the coupling is complete, the dye is salted out by adding 58.5 parts of sodium chloride, filtered and washed with a 24 $ solution of sodium chloride and dry.

The dye is obtained in the form of the sodium salt of the /? - (N-ethyl-N-3 ^f .3'.4'.4 ».4'-pentafluorobutyl) amino-2-methylbenzene- <l- azo-4 '^ -Vnaphthalene-azobenzene-3-sulphonic acid /, which dyes synthetic polyamide-based fibers in reddish-brown with good lightness properties.

The dye homologue in which the 3.3.4,4.4-pentafluorobutyl radical is replaced by the n-butyl radical, dyes synthetic Brown colored polyamide fibers with poor light fastness properties.

(Patent claims)

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Claims (2)

- ίο - Patent claims: Λ . Compounds of the general formula - ^X R Ro τ- Ν wherein X is a -SO ^ H-, -PO ₅ II ₂ - or -P-0 ₂ H- group, where R ^ is an alkyl radical, Y is a hydrogen or halogen atom, an alkyl, alkoxy or nitro group, Z is a hydrogen atom or a diene chain which forms a naphthalene nucleus with the benzene nucleus, B an aromatic, optionally substituted nucleus, m = 0 or 1, R a hydrogen atom, an alkyl or alkoxy group, R ^, a hydrogen or chlorine atom, a Is an alkyl, alkoxy, acylamino group or a diene chain which is bonded to the benzene nucleus to form a naphthalene nucleus, R _{2 is} a hydrogen atom, an alkyl, cyanoethyl or hydroxyalkyl group and η = 2. 2. Process for the preparation of compounds according to claim 1, characterized in that that one is the diazo derivative of an amine of the general formula f-N = N-B -11- 409825/1 U2 with a coupling agent of the general formula where in the formulas X, X, Z, m, R, R., R ₂ , η have the same meanings as under 1., coupling. 3- "Use of the compounds according to claim 1 for dyeing of natural and synthetic polyamide fibers. 0 9 8 2 5/1 1 l> 2