DD145021A3 - METHOD FOR PRODUCING NEW SIZIUM ORGANIC AZOFINS - Google Patents

Abstract

Silicon-containing azo dyes of the general formula X, -Si-Z-, CH-, CHo-NH-Ar- [IM = N-Ar]

Description

~ λ ~ 204 59

Process for the preparation of new azo-organics: azo dyes

The invention relates to silicon-containing azo dyes _? the polymer for the dyeing of organic compounds _s can be used before zugsv / else organosiloxanes or polyorganosiloxanes ^ so · as of inorganic materials. These azo dyes are at the same time also reactive dye: for synthetic or natural fibers of plant or animal origin ₀ The dyes can be incorporated into the polymer molecule with homopolar binding or "correspond" to the fibers applied without additional fixing »there is still the possibility -silicon-containing coupling component on to apply the surface to be dyed and then the azo dye by reaction

with an aromatic diazonium salt solution »

Charakteris tik he d known tech ^

The preparation of azo dyes based on Triliiethylsilyl anilin en by reacting these biliziumverbindungen with diazotized aromatic amines was from

- 2- fe »»

BONJOUE (Dissertation 1970, ETH Zurich) and HASHIMOTO (Xakugaln'Zasshi 80 (1960), 1399-1404). These azo dyes do not have sufficient adhesion to the substrate ₉ to be dyed because they contain only inactive methyl groups on the Si atom and therefore they did not acquire any technical significance,

Silicon-containing azo dyes with hydrolysiertaren, adhesion-promoting groups are z * B _{o β} been described in US Patents 2,925,313, 2,927,839, 2,931,693, 2934 · 459. "2955898, 2955899 and 2963 3S3 As Starting components were arylamino- or aminoarylalkylalkoxysilanes used dyeings with these azo dyes are characterized on glass fibers, natural fibers such as "wool, silk, cotton and synthetic fibers by good adhesion and durability." Of disadvantage, however, their mostly strong alkaline character and the complex and complicated production the silicon-containing amino-Ausgangsverb indung _β

In the US-PS 3 888 891, 3 888 89% 3963744 and 3981 include _e a * describes azo dyes having a tris (trimethylsilyl) Siloxyalkylaminorest contain "These dyestuffs are characterized by a certain degree of compatibility with certain polyorganosiloxanes comprising _However, your inactive siloxy moiety prevents sufficient adhesion and does not cause durable dyeings even of glass fibers, natural and synthetic organic fibers with them. are achievable. The coloring components can not be realized with these dyes by means of 'homopolar bonding in the polymer molecule or on the fiber *

Object of the invention

The aim of the invention is to find hitherto unknown silicon-containing azo dyes, in a simple manner from readily available starting materials in good yields

ßijg w

are producible ¹ ,. The coloring components should be able to be anchored to or in the polymeric structures with homopolar bonding. In addition, these dyes should at least meet the technological requirements for silicone products, stain polymeric substances permanently, and employ reactive dyes

It has been found that silicon-containing _s azo dyes of the general formula

X ₀ ~ Si-Z- ¹ CH - ² CH ₀ - KH'- Ar - / IT = H ~ Ar7 "

ö. j ( c. * ~ """Il

polymeric materials, in particular silicone products can stain permanently and the silicone products made and known high requirements in terms of silicone-specific properties, such as erfüllen _{β ε ε} temperature resistance meet 5 In the general formula X = X = the same or different hydrolyzable groups - or a siloxane .

Z = divalent alkyl radical having 2 to 10 C atoms, which may also be interrupted by oxygen atoms,

1 p

may contain cyclic moieties wherein C and C may form part of a cycloalkyl ring, R = monovalent organic radical _s Ar = substituted or unsubstituted aryl radical, as integers of. 1 to 3",

η = nipder « ³ ^ up ze Za tiJ.

Further, "these azo dyes are due to their hydrolyzable groups at the Si atom as reactive dyes usable" The coloring components can be incorporated or homöopo- 'lax bonds in a Polymerrnolekül bound to a polymeric structure, which for high color fastness, such as z * B _ö Light = · »and migration fastness Prerequisite is" Synaereseerscheinungen in Silicones do not occur "

The preparation of the new, silicon-containing azo dyes is very simple and by reacting silanes or siloxanes of the general formula X ₀ - Si-Z- ¹ CH - ² CH ₀ - NH - Ar

^E 3-a ^0H

with diazotized aromatic amines (Diaz oniums al ζ en) of the general formula

N * ~ Ar

easy to implement "Since the silicon-containing starting compounds for virtually all diazotizable aromatic amines can be coupling partners, many variants of these new silicon-containing azo dyes result"

As diazotizable aromatic amines can be used for example:

Aminobenzenes 1-Amino-4-nitrobenzene, 1-Amino-2,4-dinitrobenzene 1-Amino-2-chlorobenzene, 1-Amino-4-chlorobenzene oil, 1-Amino-2-dichlorobenzene, 4-Acetylamino-1 aminöbenzol, 4-benzoylamino ~ 1 ~ aminobenzene, i-aminobenzene-3-sulfohsäure, 1-aminobenzene-4 ~ sulfonic acid, i-amino-2-methylbenzene, 1-amino-3- ^m sthylbenzol, i-amino-4-methylbenzene , i-amino-2,4-dimethylbenzene 1-amino-2,5-dimethylbenzene, 1-amino-4-phenylbenzene, 4-amino-1 _s 1 ^f -asobenzene, 2-aminonaphthol, i-aminonaphthol-5-sulfonic acid , 1-aminonaphthol-7-sulfonic acid, 2-aminonaphthol-6-sulfonic acid, 1-amino-hydroxy-4-nitrobenzene, etc. »

The diazotization of the diazotizable aromatic amines can be carried out with conventional, known diazotization methods. Since it makes sense in the case of silicon compounds having hydrolyzable groups to couple in organic solvents in order to protect the hydrolyzable groups.

• Λ ⁷ · & la i ¹ ?

should already done the diazotization of the diazotizable aromatic compounds in non-aqueous media, "Suitable solvents may be cited% for example, alcohols, acetone, formic _acid-acetic or propionic 'acid and dimethylformamide AUOH" Di coupling is advantageously also equal in the einenij Solvents are suitable for this purpose in groups which are expediently in a strongly acidic medium. "The mostly firmly separating azo dye is sucked off and can _? if necessary, also by recrystallization. be further cleaned®

The preparation of the silicon-containing starting compounds can be easily by reacting silanes or siloxanes of the general formula

X _n - Si - Z - ¹ CH - ² GH ₀

with arylamines of the general formula

H ₂ N - Ar ".

The reaction takes place almost quantitatively and is completed after a few hours. To improve the solubility of some arylamines, the reaction should be carried out expediently in solvents. Suitable solvents are: B «» alkanol acetone «. Carboxylic acid alkyl ester, benzene, toluene u _e a <> No addition of catalysts is required, After removal of unreacted starting materials, and any solvent, 2 _S B, by vacuum distillation, the reaction product as a coupling partner for diazotized aromatic compounds (diazonium salts) is ready for use

The. However, new novel azo dyes according to the invention can also be prepared on the product, provided that the material to be dyed has previously been impregnated with the silicon starting compounds containing hydrolyzable groups ». The impregnation may be, _e B _e effected by dipping and subsequent drying, "The azo dye is then formed by treatment with the diazotized aromatic amines (diazonium salt)" This variant has the advantage that this aqueous diazonium salt solutions can be used, which in particular for the Dyeing of natural and synthetic fibers such as wool, silk, cotton, regenerated fibers, polyamide, polyester etc. is very favorable. "Between home dyeing and substrate, the homeo-polar bonds necessary for high fastnesses can be reliably realized.

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S e c tio n s e p e s 1 e

Example _r ._J "

18.6 parts by weight of aniline were mixed with 56 parts by weight of 3-glycidoxypropyltriethoxysilane. "Thereafter, the mixture was boiled for 6 hours and then" at a pressure of 1 Torr, unreacted starting materials were distilled off. A yield of 87 % of aniline was obtained of ethylpropyltriethoxysilane obtained in a 5% strength ethanol solution of anilinopropanoloxy

10% propyltriethoxysilane were dipped % Thermisch.ent smoothened glass fabric, cotton fibers, wool, polyamide fibers, polyacrylonitrile fibers and polyesters. Fibers * After printing the fibers and drying (ca * 60 mi] at temperatures around 20 ⁰ C) the thus treated Faseien were treated with solutions of diazotized arylamines As arylamines aniline and · 2,4 ~ dinitraniline were selected which in the usual way with UaKfOp / HCl bzv / _o liitrosylschweielsäure had been diazotized. In the ice-water highly diluted diazonium salt-impregnated Anilinopropanoloxypropyltriäthoxysilan fibers, and the glass cloth were dipped _o The coupling was carried 'instantly, so that the materials after 5 to 10 see the Diazonj

 Ν - "

The mixture was then rinsed in water until it did not stain. Yellow was obtained with phenyldiazonium chloride and violet dyeings with 2 × 4-dinitrophenyldiazonium sulfate

Bed sm. el_2

4-9 g of 2 parts by weight of β-3 _s ^-1 l of β-epoxycyclohexylethyltrimethoxysilane in 50 ml of methanol were mixed with 28.8 parts by weight of β-naphthylamine and heated to boiling for about 8 hours. Subsequently, the solvent was distilled off and then under vacuum unreacted Bpoxycyclohexyläthyltrimethoxysilan Only 3 parts by mass of the ¹ SiIans could be isolated from the reaction mixture,

In the usual way 27.6 parts by mass of 4-nitraniline were diazotized. 39.2 parts by weight of the above reaction product were initially introduced into the diazonium salt solution. The immediately appearing coloration indicated the proceeding coupling. The crystalline product was then filtered off with suction for a further 30 minutes and washed several times with methanol.

1 g of the yellow-red azo dye was mixed with 80 g of a 70 follow xylene solution of a three-dimensionally networked Met hylphenyl silicone resin "In one form, then the silicone resin reading was pre-dried at 80 G and then cured for three hours at 250 ⁰ G ca" A transparent, preserved yellow-red colored silicone resin body «

Claims (1)

IP O 09 Β, / 204 590 -S- 2 Invention claim to processes for the preparation of novel silicon-containing azo dyes for dyeing polymeric organic or inorganic compounds and natural and synthetic tischer fibers ^ characterized _s that silanes or siloxanes of the general formula X _n - Si - Z - ¹ CH - CH ² ₀ - HH - Αία, d E ₀ OH
j * - <a with aryldiazonium compounds of the general formula H * - Ar converted to azo dyes of the general formula X-Si-Z-¹CH -²CH₀ -HH-Ar- / "K =TS- Ar 7 "a,et --η. ^R 3 ~ a ^0H wherein the coloring component is bonded to the Si atom by means of homopolar bonds and are: X = same or different hydrolyzable groups or a siloxane residue, Z = divalent alkyl radical having 2 to 10 C atoms, which also interrupted by oxygen atoms'in and / or •1 may contain alicyclic parts and C as well C can form part of a cycloalkyl ring, R = monovalent organic radical, Ar = substituted or unsubstituted aryl radical, j a = integers from I. to 3 and η ~ lower integer, 'O ', η fj Π. O £ <'"C ^! - WP C 09 B / 204 590 2β method according to 'point. 1, characterized in that the silane or siloxane contains alkanol groups, 3e procedure according to point. 1, characterized ₉ that the silane or siloxane containing Cycloalkanolgruppen 4 »Process according to items 1 to 3, characterized in that the reaction takes place in the presence of natural or synthetic fibers and the reactive dyes formed are formed immediately on the fiber, 5 * Procedure according to points 1 to 3? characterized in that natural or synthetic fibers impregnated with the corresponding silanes or siloxanes are reacted with the azo compounds. ? 1 ΛPR 1 q P. MaRS -5- R