CH467841A - Process for the production of basic dyes - Google Patents

Description

  

  Process for the preparation of basic dyes The invention relates to a process for the preparation of basic dyes of the formula
EMI0001.0005
    wherein the radicals R1 are identical or different, optionally substituted alkyl radicals, or two or three of the radicals R1 either together with the quaternized nitrogen atom or together with y, R7,

      the N atom bonded to R7 and the quaternized N atom form a saturated or unsaturated heterocyclic ring system, and in which R7 is optionally substituted alkyl, R9 is halogen, R11 -CO-alkyl, R12 and R13 is halogen, R18 is hydrogen, halogen or alkyl ,

      y denotes an optionally substituted alkylene radical, X o denotes an anion and n denotes one of the numbers 1 or 2, characterized in that 1 mol of a diazo compound is obtained from an amine of the formula
EMI0001.0037
    with 1 mole of a compound of the formula
EMI0001.0039
    clutch.

        Particularly valuable dyes are those of the formula
EMI0002.0001
    wherein R9 and R13 Cl or Br, R11 -COCH3, R18 H, Cl, Br or methyl, preferably H or methyl, R7 methyl, ethyl.

       Propyl or butyl, y is -C2H4 or -CH2 - CH-CH3 and A is one of the following radicals
EMI0002.0018
    where D is an optionally substituted alkyl radical, preferably a methyl or ethyl radical.



  In general, substituted or unsubstituted alkyl radicals are the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl or hexyl radicals or then the hydroxyethyl, cyanoethyl, chloromethyl or chloroethyl radicals.



  Further preferred dyes are those of the formula
EMI0002.0039
         where R3 and Rie are Cl or B.r, R11 is -CO-CH3, R18 is H, Cl, Br or methyl, preferably H or methyl, R7 is methyl, ethyl, propyl or butyl, y is -CH4- or -CHrrCH-CH3,

   and A stands for one of the following residues
EMI0002.0057
  
EMI0002.0058
    where D is an optionally substituted alkyl radical, preferably a methyl or ethyl radical.



  Important dyes are also those of the formula
EMI0002.0064
    where D is an optionally substituted alkyl radical, preferably a methyl, ethyl, propyl, butyl, amyl, hexyl, hydroxyethyl, chloroethyl or chloromethyl radical.



  Anion X is understood to mean both organic and organic ions, such as. B. methyl sulfate, sulfate, disulfate, perchlorate, chloride, bromide, iodide, phosphate, phosphorus molybdate, phosphotungsten molybdate, benzenesulfonate, 4-chlorobenzenesulfonate, oxalate, maleic acid, acetate, propionate -,

          Methanesulfonate, chlorine acetate, benzoate or complex anions such as. B. that of zinc chloride double salts.



  The azo coupling is carried out in a weakly alkaline to acidic, optionally buffered, aqueous or organic or aqueous-organic medium.



  The dyes obtained can, for. B. by Fil trieTen, optionally after evaporation or precipitation, isolated.



  The new dyes are preferably used for dyeing, padding or printing fibers, threads or textiles made therefrom which consist of or contain acrylonitrile polymers or acrylonitrile polymers.



  Acrylonitrile polymers are to be understood as meaning, in particular, polymers with more than 80% acrylonitrile; Acrylonitrile copolymers are generally copolymers of 80-95% acrylonitrile and 5-20% vinyl acetate, vinyl pyridine, vinyl chloride, vinylidene chloride and also acrylic acid, acrylic acid esters, methacrylic acid,

          Methacrylic acid esters, etc.



  These fibers can be dyed in a mixture with others. Strong, level dyeings with good lightfastness and good all-round fastness properties are obtained, particularly good washing, welding, subliming, pleating, decaturing, ironing, rubbing, carbonizing, water, sea water, dry cleaning,

          Over-dyeing and solvent fastness. They also have good pH stability, good drawability, good resistance to boiling, e.g.

   B. in water, at different pH values; they also reserve wool and other natural or synthetic polyamide fibers excellently. The dyes generally have good compatibility with salts; In addition, some of the dyes of the formula (I) are particularly soluble in water or organic solvents.



  The dyes are also suitable for dyeing or printing polyester or polyolefin fibers modified by acid groups.



  Dyeing is usually done in an aqueous, neutral or acidic medium at boiling temperature under atmospheric pressure or in a closed vessel at elevated temperature under elevated pressure. Commercially available retarders do not interfere, but are not required. The dyes are also suitable for coloring acrylonitrile polymerisation products and other, optionally dissolved plastics in bulk in light and wet-fast shades,

   for dyeing oils or lacquers or for dyeing cotton, especially tannin cotton, cellulose, regenerated cellulose and paper in every manufacturing stage. It has been shown that mixtures of two or more dyes of the formula (I) can also advantageously be used.



  In the following examples, the parts are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius.



  <I> Example 1 </I> 28 parts of 1-amino-4-acetyl-2,6-dibromobenzo: l are diazotized in the usual way with nitrosylsulfuric acid and at 0 with 24.5 parts (N-ethyl-N phenyl ) - aminoethyl trimethylammonium chloride of the formula
EMI0003.0077
         dissolved in 400 parts of water, coupled.

   It is neutralized with sodium hydroxide solution, 300 parts of 25% sodium chloride solution are added, the mixture is filtered and dried. An orange powder results.



  <I> Example 2 </I> 20 parts of 1-amino-4-acetyl-2,6-dichlorobenzene who diazotized in the usual way using nitrosylsulfuric acid and at 0 with 27.5 parts (N ethyl-N-phenyl) aminoethyl pyridinium chloride, dissolved in 400 parts of water, coupled.



  After salting out with sodium chloride, filtration and drying, an orange-colored powder is obtained which, on polyacrylonitrile fibers, gives reddish-tinged yellow colorations with excellent properties.

      The required (N-ethyl-N-phenyl) -aminoethyl pyridine chloride is obtained by reacting N-'A' ethyl-N-chloroethyl aminobenzene with the equivalent amount of pyridine in an alcoholic or aqueous medium at 80 to 90 .



  <I> Dyeing Example A </I> 20 parts of the dye obtained according to Example 1 are first intimately mixed with 80 parts of dextrin in a ball mill for 48 hours.



  Then 1 part of the preparation obtained in this way is made into a paste with 1 part of 40% acetic acid, 400 parts of distilled water of 60 are poured over the pulp while shaking constantly and the whole thing is briefly boiled. It is diluted again with 7600 parts of distilled water, 2 parts of glacial acetic acid are added and, at 60, 100 parts of Dralon (registered trademark) are added to the dyebath.

   The material was pretreated for 10 to 15 minutes at 60 in a bath of 8,000 parts water and 2 parts glacial acetic acid. It is now heated to 100 within 30 minutes, boiled for 1 hour and rinsed. A level orange dyeing of excellent light fastness and very good wet fastness properties is obtained.



  <I> Dyeing example B </I> (Foulard dyeing) 50 grams / liter of dye are used to produce the padding paste (corresponding to the dyeing preparation made with dextrin in dyeing example A)

    3 grams / liter of sodium alginate 5 grams / liter of concentrated acetic acid 20 grams / liter of Glauber's salt polyacrylonitrile fibers are padded cold on a 2- or 3-roll pad by the usual methods. The squeeze effect is 80%.

   After a short intermediate drying at 90 in the stenter, hot flue or with the help of an infrared heater, the nozzle fixture is fixed with dry air at 170-190 for 1-3 minutes, then rinsed, soaped and rinsed again.

   An orange dyeing with excellent lightfastness properties is obtained.
EMI0003.0156
  
    <I> Coloring example </I> <SEP> C <SEP> (print)
<tb> A <SEP> print phase <SEP> consists of <SEP> consisting of <SEP> together <SEP>
<tb> 75 <SEP> parts <SEP> dye <SEP> (corresponding to <SEP> the <SEP> in the <SEP> dyeing example <SEP> A <SEP> made with <SEP> dextrin <SEP>
<tb> dye preparation)
<tb> 10 <SEP> parts <SEP> concentrated <SEP> acetic acid
<tb> 450 <SEP> parts <SEP> sodium alginate thickener
<tb> 25 <SEP> parts <SEP> of a <SEP> cationic <SEP> plasticizer,

   <SEP> to
<tb> Example <SEP> of a <SEP> condensation product
<tb> from <SEP> 1 <SEP> mol <SEP> stearic acid <SEP> and <SEP> 1 <SEP> mol <SEP> triethanolamine
<tb> 25 <SEP> Share <SEP> Glauber's salt
<tb> <U> 415 <SEP> Divide </U> <SEP> water
<tb> 1000 <SEP> parts of polyacrylonitrile fibers are printed using the customary hand printing process, the fiber material is then air-dried, steamed in a star steamer with juice for <B> 2040 </B> minutes, then rinsed, soaped and again flushed. An orange print with very good fastness properties is obtained.

        Other valuable dyes, as they can be obtained by the processes listed in Examples 1 and 2, are described in the table below. They correspond to the formula
EMI0004.0003
    where the symbols R9, R11, R12, R13, R16 and R13 have the meanings given in the table.



  The anions X E) listed in the description come into consideration: The symbols K1 to K13 listed in the table below stand for the following radicals:
EMI0004.0016
  
   
EMI0004.0017
  
          In the table, the remainder K can be replaced by any other remainder K in each individual case. Is z. If, for example, the remainder K1 is given in a table example, one of the symbols K2 to K13 can just as easily be used for this.

    
EMI0004.0023
  
     
EMI0005.0001
  
     
EMI0006.0001
  


 

Claims (1)

PATENT CLAIM Process for the production of basic colorants of the formula EMI0007.0005 wherein. the radicals R1 represent the same or different, optionally substituted alkyl radicals, or two or three of the radicals R1 either together with .dem quaternized nitrogen atom or together with y, R7, the N atom bonded to R7 and the quaternized N atom form a saturated or unsaturated heterocyclic ring system, and in which R7 is optionally substituted alkyl, Rg is halogen, R11 -CO-alkyl, R12 and R13 is halogen, R18 is hydrogen , Halogen or alkyl, y is an optionally substituted alkylene radical, X o is an anion and n is one of the numbers 1 or 2, characterized in that 1 mol of a diazo compound is obtained from an amine of the formula EMI0007.0041 with 1 mole of a compound of the formula EMI0007.0043 clutch. SUBCLAIMS 1. Process according to claim, characterized in that dyes of the formula EMI0007.0047 where Rg and R13 Cl or Br, Rll = CO-CH3, R18 H, Cl, Br or methyl, R7 methyl, ethyl, propyl or butyl, y is -C2H4 or -CH2-CH-CH3 and A is one of the radicals EMI0007.0064 stands, where <B> D </B> denotes an optionally substituted alkyl radical. 2. Process according to patent claim, characterized in that dyes of the formula EMI0008.0001 where Rs and R12 Cl or Br, Rii -CO-CH3, Ri $ H, Cl, Br or methyl, R7 methyl, ethyl, Propyl or butyl, y is -C_, H4- or -GH2-CH-CH3 and A is one of the radicals EMI0008.0019 stands, where D is an optionally substituted alkyl radical. 3. The method according to claim, characterized in that one dyes of the formula EMI0008.0026 where D is an optionally substituted alkyl radical. <I> Note from the </I> Federal <I> Office for Intellectual Property: </I> If parts of the description are inconsistent with the definition of the invention given in the claim, it should be remembered that according to Art. 51 of the Patent Act, the patent claim is authoritative for the material scope of the patent.