DE1014519B - Process for coloring polymers or copolymers made from acrylonitrile or asymmetric dicyanaethylene - Google Patents

Description

Process for coloring polymers or copolymers of acrylonitrile or. Asymmetric dicyanethylene additive to patent application F 191881Vc / 8m ( Auslegeschrift 1011396) The subject of patent application F 19 188 IV c / 8 m is a process for dyeing polymers or copolymers of acrylonitrile or asymmetric dicyanethylene by using sulfonic acid and carboxylic acid group-free monoazo dyes, which have at least one non-aromatically bound tertiary amino group or quaternary ammonium base.

In further processing of the inventive idea on which the main patent is based it has now been found that such sulfonic acid and carboxylic acid group-free Monoazo dyes are advantageously suitable for dyeing polyacrylonitrile fibers that contain at least contain a non-aromatically bound primary or secondary amino group in the molecule. Here, the primary or secondary amino group can, for example, via an alkyleneamino radical be bound to an aromatic nucleus.

The monoazo dyes used in the present invention can, for example the benzene-azo-benzene series, the benzene-azo-naphthalene series, the benzene-azo-arylpyrazolone series or belong to the benzene-azo-acyl acetic acid-arylamide series. They are known after Methods prepared by coupling diazotized amines with azo components. Here can either be the non-aromatically bound primary or secondary amino group be contained in the diazo or in the azo component.

Such dyes can also be used that have more than one contain non-aromatically bound primary or secondary amino group in the molecule. In addition to these groups, the azo dyes can also contain other groups in azo chemistry have customary substituents, with the exception of sulfonic acid and carboxylic acid groups.

For the preparation of the azo dyes used according to the invention for example, the following diazotized amines are suitable: 1-amino-4-methylbenzene, 1-amino-2, 4-dicyanobenzene, 1-amino-2, 4-dicyan-6-methylbenzene, 1-amino-3-chloro-4-cyanobenzene, 1-amino-2, 4-dichlorobenzene, 1-amino-4-methoxybenzene, 1-amino-3, 5-dichloro-4-cyanobenzene, 1-Amino-2-cyano-4-chlorobenzene, 1-amino-4-nitrobenzene, 1-aminobenzene-4-carboxylic acid methyl ester.

Suitable coupling components are, for example, 1-oxy-4-methylbenzene, 2-oxynaphthalene, 2-oxynaphthalene-3-carboxylic acid methyl ester, 1-phenyl-3-methylpyrazolone- (5), py-tetrahydro-3, 6'-dioxy-7, 8, 1 ', 2'-benzoquinoline, N-methyl-N-ß-aminoethyl-aminobenzene, 1- (N-ethyl-N-aminomethyl-amino) -3-methylbenzene, 1- (N-ß-methylamino-ethyl-amino) -3-methylbenzene, 1- (N-ethyl-N-ß-methylamino-ethyl-amino) -3-methylbenzene, 1- (N-ethyl-N-ß-aminoethyl-amino) -3-methylbenzene, 1- (N-ß-aminoethyl-amino) -3-methylbenzene.

The monoazo dyes used by the process with non-aromatic bonded primary or secondary amino groups are in the form of their salts in water easily soluble.

The dyes are used in a conventional manner, e.g. B. from acidic solution if necessary using a dispersant, dyed onto the polyacrylonitrile fiber. The dyeings obtained in this way are distinguished by good fastness properties. Example 1 1 g of the dye on diazotized 1-amino-2, 5-dicyanobenzene and 1- (N-β-methylamino-ethyl-amino) -3-methylbenzene is clearly dissolved as chloroacetic acid salt in 31 water and the solution with 3 g of 30% Acetic acid added. Then 100 g of polyacrylonitrile fibers are put into the dyebath at 40 to 50 °, brings the bath to 100 ° within 40 minutes and boils 1 Hour. A clear, yellowish orange dyeing with good washfastness and lightfastness is obtained.

In the same way, dyeings with good fastness properties are obtained on polyacrylonitrile fibers using the dyes in the table below: 'Example' .- Dye Hue of the dye on polyacrylonitrile fiber NC / C2Hb ,. 2 N = N - "- @ N \ Orange C2H4NH - CH, CN CH3 H "'3 - - NC -CD - N = N -C> --- N / strong reddish orange _ - I. _ ._ (C@H.NH. CH, CN CH3 - 1 c i 4 4 N @ yellowish red . ((. C, H4NH-CH3 _ - -` C- N CH3 H 5 N = NN strong yellowish orange (C2H4NH # CH3 CN C 113 Cl (- C2 H5 6th N = NN \ Orange (C2H4NHCH3 CN CH, H 7 N - C N = N N Yellowish orange " _ (C2H4NH-CH3 G1 CH3 N = C C2 H6 8 @@ - N = N N orange C2H4NH, C = N CH3 H 9 N _ - _. C N = N - <#NI Orange C2H4NH, CN CH, Cl (, --- # CH, 10 C # N = NN Yellowish orange I C2H4NH, "CDN / CzHs . . 11 N- C - @@ N = N NI Orange ji \ C2H4NH, Cl CH3 Example dye hue of the dye on polyaeryl nitrile fiber '- N 12. @ N = N - @@@ N Yellowish orange C, H @ NH2 C -N CH3 N -C 13 N = N @ - N CH 3 strongly yellowish orange C2 H, N Hz CN 14 N - C 1 / \ N = N- <P-N ' C2 H5 orange C2H4NH CH3 Cl CH, N -C I. 15 <- j- N = N-1 - \ - NH - C2 HIN H # C H3 very strong yellowish orange I. CN CH3 N = C C2 H5 16 N = N N \ strongly yellowish orange C2H @ NH-CH3 C = NC H3 C1 17 N - CI @ N = NN / H brick red. - \ D- \ C 2 H NHCH 4 3 CN CH3 / CH3 18 HZ N O2.13 N = NN \ Orange C2H4NH2 / Cz H5 19 H2 N 02 SN = NJ @ - N reddish orange `C2H4NH2 CH, CH, 5 20 'j N 02 S - -1 - \ - N = N N C2 H the same C H3 @. - I C2H4NHz CH, Hue of Example dye staining on l'oly- acrylnite CH2 CH-OH @ I strong 21 I33 CN - (C H2) 3 -NH - OC - N = N - @@ - N - C H2 red-tinged violet g H0 H 22 `H3C-N- (CH2) 3-NH- OC - <: D -N = NC C-CH3 1I 1I H HO-C N N yellow 0 i 23 H3C-N- (CH2) 3-NH-OC- <D- N = NC C-CH3 l1 l1 H HO-C N N Grünstichi I yellow S 02

Claims (1)

PATENT CLAIM: Further development of the process for coloring polymers or copolymers of acrylonitrile or asymmetric dicyanethylene with Azo dyes according to patent application F 19188 IVc / 8me, characterized in that sulfonic acid and carboxylic acid group-free monoazo dyes are used which have at least contain a non-aromatically bound primary or secondary amino group.