DE2010492B - Process for coloring fibers based on acrylonitrile polymers or acrylonitrile polymers - Google Patents

Description

wherein alk is a lower alkyl group, the nucleus A is methyl, methoxy, chlorine, bromine, nitro, amino or acetylamino-substituted or condensed with a benzene nucleus in the 6,7-position, which Core B methyl, methoxy, nitro, chlorine and / or bromine substituted or with a benzene core in 5 ', 6'-position can be condensed, R hydrogen, alkyl up to 4 carbon atoms, nitrile or is phenyl or the nucleus B 'is condensed with a benzene nucleus in the 3', 4'-position and X is a monovalent anion for coloring fibers based on acrylonitrile polymers or copolymers.

The present invention relates to a method for dyeing polyacrylic fibers.

The coloring of fibers based on acrylonitrile polymers or acrylonitrile polymers with the help of basic Dyes, especially methine dyes, are known.

The range of these dyes, however, is poor in industrially easily achievable colors in the reddish-yellow to orange-colored areas that provide vivid color tones, an increased dyeing yield and good fastness properties exhibit. The present invention aims to fill this gap.

This is achieved by using the dyes of the general formulas below

alk

where in the formulas the term alk and the letters A, B, B 'and R have the same meaning as above have.

The reaction medium is a weak organic acid such as acetic or propionic acid. One works near the boiling point. The reaction can be accelerated vigorously and the yields significantly improved if an alkylating agent is added, preferably in a stoichiometric amount or more.
In this case, the loss of alkyl mercaptan is observed, probably as a result of a very reactive methylthiooxonium intermediate. All classic alkylating agents are effective. These include methyl or ethyl sulfate, the alkyl halides, the alkyl aryl sulfonates and, in particular, the methyl or ethyl chlorine or bromoacetates.

In general, the dyestuff is separated by dilution or filtration, if appropriate in the presence by charcoal to remove any impurities, and by precipitating what one is used to add sodium chloride and, if necessary, zinc chloride to the filtrate.

2. One can also use a salt of 3-alkylbenzothiazolium of formula (IV) or (V) condense with a salt of 2-methylbenzopyrylium of formula (VI).

in which alk is a lower alkyl group, preferably

(V)

(VI)

H, C

In the formulas (IV) and (V) the designations alk and A have the same definitions as in the formulas (I) and (II), Y is a monovalent anion, R _{1 is} a chlorine atom or an alkylthio group. In the formula (VI), B has the same meaning as in the formulas (I) and (III), R is a hydrogen atom or an alkyl radical and Z is a monovalent anion, usually the chloroferrate anion Cl ₄ Fe ^e the preferred method of preparing the salts of this type is followed by a known method.

A large number of organic solvents are suitable as the reaction medium. One preferably chooses a water-miscible solvent such as a lower alcohol, a polyalcohol like the glycol, an ester of the latter, dimethylformamide, dimethyl sulfoxide or a weak one organic acid such as acetic or propionic acid.

The reaction often takes place at ordinary temperatures, but it is sometimes necessary to heat to reflux of the solvent. The working time is extremely variable, from a few minutes to several hours, depending on the nature of R ₁ and that of the substituents. The dye formed, which is generally sparingly soluble in the reaction medium, is filtered off, washed with the solvent, then with cold water and dried at moderate temperature or under vacuum.

Some of the pyrylium salts of the formula (VI) are already known, others are new. In general they can be prepared, including an aldehyde of the formula

CHO

OH

(VII)

with a ketone of the formula

CH ₃ -CO-CH ₂ -R

condensed in the presence of a strong mineral acid. As starting materials for carrying out the invention can be mentioned in particular the saws of

2,3-dimethylbenzopyrylium,

2-methyl-3-isopropylbenzopyrylium,

2-methyl-3-butylbenzopyrylium,

2,3-dimethylnaphtho- [b] "pyrylium,

2-methyl-3-isopropylnaphtho- [b] pyrylium,

2-methyl-3-butylnaphtho- [b] pyrylium

and their substituted derivatives.

Dyes with neighboring formulas have already been used by A. I, K i ρ r i a η ο v, A. I. To 1 m a t c h e ν and their collaborators (Journal de Chimie generate russe, vol. 30-1, p. 638, vol. 32-1, p. 383, vol. 33-1, P. 440), but these latter dyes are obtained by various processes with poor Yields obtained were much more difficult to obtain industrially and not lightfast.

Compared to the compounds known from Belgian patent 579 814, in particular the Compounds according to the formulas 14, 17, 33, 35 and 37 are characterized by those used according to the invention Dyes are characterized by a much better lightfastness.

The dyes of the formula (I) are particularly suitable for coloring fibers on acrylonitrile polymer or copolymer base, for which they have a very strong affinity. You lend them on in this way strong color tones of great liveliness in the yellow and orange areas. The received Dyeings have excellent general fastness properties.

The following examples are for illustration purposes only, with parts being parts by weight, unless that this is stated otherwise.

example 1

A solution of 3 parts of coumarin-2-thione and 3 parts of 2-methylene-3-methylbenzothiazoline is brought in for 2 hours in a mixture of 20 parts of glacial acetic acid and 3 parts by volume of dimethyl sulfate to boiling. It is diluted with 100 parts of water a little charcoal, filtered and the dye is precipitated by adding 15 parts to the filtrate Adding sodium chloride. It is filtered, squeezed off and dried at a moderate temperature. You get

1.6 parts of dye, the fibers based on acrylonitrile polymer in a very lively and strong golden yellow shade with very good general fastness properties, in particular to light, colors.

Example 2

A mixture of 3 parts of coumarin-2-thione and 3.6 parts of 2-methylene-3,6-dimethylbenzothiazole is brought in for 8 hours in 20 parts of glacial acetic acid and 3 parts of ethyl chloroacetate to the boil. 80 parts of cold water are added and the crystalline water that has formed is filtered off Precipitation, then redissolve in 150 parts of warm water, add a little charcoal, filtered and add 20 parts of sodium chloride to the still warm filtrate. It is allowed to cool, filtered and refined and dries at a moderate temperature. 4.2 parts of the orange dye, the acrylic fibers, are obtained dyes golden yellow with properties similar to those of the dye of Example 1.

Example 3

A mixture of 3.5 parts of chloroferrate of 2,3-dimethylbenzopyrylium is brought in for 10 minutes, 2.3 parts of 3-methylbenzothiazolium-2-sulfonate in 100 parts of glacial acetic acid to the boil. It forms quickly a crystalline precipitate. After cooling, it is filtered and the precipitate is washed with acetic acid until the removal of dark red mother liquors. It is squeezed off and dried under vacuum. You get

3.7 parts orange dye, the acrylic fibers vivid yellow with properties similar to those of the dye of Example 1 stains.

The chlorine ferrate used in this example from 2,3-Dimethylbenzopyrylium can according to Elderfield, "Heterocyclic Compounds", 1951, Vol. II, p. 292, or in the following "manner will:

A mixture of 200 parts by volume of glacial acetic acid, 120 parts of crystallized iron (III) chloride (FeCl ₃ -OK ₂ O), 48.8 parts of salicylaldehyde and 72 parts of methyl ethyl ketone is stirred until it is dissolved. The mixture is stirred and performs in the course of about 4 hours and at a temperature of 15 to 2O ⁰ C 300 parts by volume of concentrated hydrochloric acid. The solution turns red and the benzopyrylium salt begins to crystallize. After stirring for 24 hours at room temperature, the mixture is filtered, washed twice with a mixture of 20 parts by volume of acetic acid and 30 parts by volume of concentrated hydrochloric acid, squeezed off and dried under vacuum. 133 parts of chlorine ferrate from 2,3-dimethylbenzopyrylium are obtained in the form of a reddish crystalline powder. The reddish color is ascribed to a trace of oxidation products, but the crude product is in a state of purity that is sufficient for the manufacture of the dyes.

You can recrystallize this compound from acetic acid in the presence of activated charcoal in preserved in its pure state. Clear, greenish-yellow prisms are obtained; Melting point 106-107 ° C.

if desired, the anion can be exchanged for another anion, for example for reasons of solubility.

Analysis for QjH ₁₁ Cl ₄ FeO:

Calculated:
C 36.98, H 3.08, Cl 39.78, Fe 15.68%;

found:

C 36.9, H 3.32, Cl 40.4, Fe 15.6,
C 37.3, H 3.21, Cl 40.6, Fe 16.0%.

30th

35

In a similar way, you can prepare other pyrylium salts, whereby you can use the salicylaldehyde its halogenated, methylated or methoxylated derivatives or by 2-hydroxy-1-naphthaldehyde replaced, or the methyl ethyl ketone by acetone, methyl isobutyl ketone or methyl amyl ketone replaced. It is sometimes advantageous to use anhydrous, gaseous hydrogen chloride instead of the concentrated one Use hydrochloric acid.

Example 4

A mixture of 3.5 parts of chloroferrate of 2,3-dimethylbenzopyrylium is brought for 5 hours, 3.5 parts of sulfomethylate of 2-methylthio-3-methyl-6-nitrobenzothiazolium in 100 parts glacial acetic acid to boiling. It is allowed to cool, filtered, and the precipitate is taken up in 50 parts of boiling ethanol on to excrete the red contamination, filtered, washed with ethanol and dried at moderate Temperature. 3 parts of orange dye are obtained in the state of chlorine ferrate, the acrylic fibers are orange-yellow with very good general fastness properties. ten colors.

The following table comprises additional examples of the dyes of formula (I) of the invention wherein alk is CH ₃ , the core substituents A, B and B 'are as indicated in the second column. With regard to the fibers, the anion does not play a coloring role and is Cl®, ZnCIf or Cl ₄ Fe ⁶ , depending on the manufacturing method used. When

at
spat Substituents Shades
on acrylic fibers 5 6-methoxy Golden orange 6th 6-chlorine Golden yellow 7th 3'-methyl-8'-methoxy yellow 8th 6-nitro-3'-methyl- yellow 8'-methoxy 9 3'-methyl-5 ', 6'-benzo Lively
Orange 10 5,3'-dimethyl yellow 11th 6-methyl-6'-bromo Golden orange 12th 6-methoxy-6'-bromo orange 13th 6-chloro-6'-bromo orange 14th 3'-methyl-6'-bromo Golden yellow 15th 3'-methyl-6'-chloro Lively Yellow-green 16 6,7-benzo-6'-bromo Lively orange 17th 6-methoxy-3'-methyl Golden yellow 18th 6,3'-dimethyl Golden yellow 19th 5-methoxy-3'-methyl Golden yellow 20th S-methoxy-o-acetylamino- orange 3'-methyl 21 5-chloro-3'-methyl yellow 22nd 6-chloro-3'-methyl Golden yellow 23 6'-bromine Golden yellow 24 6'-chlorine Golden yellow 25th 6,6 ', 8'-trimethyl Golden orange 26th 6-methoxy-6 ', 8'-dimethyl orange 27 6-chloro-6 ', 8'-dimethyl Golden orange 28 6,7-benzo-6 ', 8'-dimethyl orange 29 . 6,7-benzo-3'-methyl orange 30th 6-methyl-7'-methoxy vermilion 31 6,7-benzo-7'-methoxy orange 32 6,7'-dimethoxy orange 33 6-chloro-7'-methoxy orange 34 6-methyl-3 ', 4'-benzo- Golden yellow 7'-methoxy 35 6-methoxy-3 ', 4'-benzo- yellow 7'-methoxy 36 6-chloro-3 ', 4'-benzo- Golden yellow 7'-methoxy 37 6-methyl 1-3'-phenyl Golden yellow 38 6-methoxy-3'-phenyl Golden orange 39 6-chloro-3'-phenyl Golden orange 40 6-methyl-8'-methoxy Golden yellow 41 6,8'-dimethoxy Golden orange 42 6-chloro-8'-methoxy Golden yellow 43 6,7-benzo-8'-methoxy orange 44 6-methyl-6'-nitro Golden yellow 45 6-methoxy-6'-nitro Brownish yellow 46 6-chloro-6'-nitro yellow 47 6,7-benzo-6'-nitro Yellow chamois

continuation

at
game Substituents Shades
on acrylic fibers 48
49
50
51 6 ', 8'-dimethyl
7'-methoxy
8'-methoxy
3'-phenyl Golden orange
orange
Golden yellow
Golden orange

IO

at
game Substituents Shades
on acrylic fibers 52
53
54
55 6'-nitro
3 ', 4'-benzo-7'-methoxy
3'-isopropyl
3'-n-butyl yellow
Golden yellow
Golden yellow
Golden yellow

209524/468

Claims (1)

Claim: Use of the common formula alk is a methyl or ethyl group, the nucleus A is methyl, methoxy, chlorine, bromine, nitro, amino or acetylamino substituted or with a benzene nucleus methine dyes of the all-in 6,7-position can be condensed, the nucleus B j can be methyl-, methoxy-, nitro-, chloro- and / or bromine-substituted or condensed with a benzene nucleus in the 5 ', 6'-position, R hydrogen atom, alkyl with is up to 4 carbon atoms, nitrile or phenyl or the nucleus B 'is condensed with benzene in 3', 4'-position ίο, and X is a monovalent anion, for coloring fibers based on acrylonitrile polymers or copolymers. The dyes of the formula (I) can be prepared by two different processes: 1. You can after a first reaction, a 2-methylene-3-alkylbenzothiazoline of the formula (II) condense with a coumarin-2-thione of the formula (III).