Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
  • D06P1/221—Reducing systems; Reducing catalysts
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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  • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/18—Arsenic, antimony or bismuth
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/24—Chromium, molybdenum or tungsten
  • B01J23/28—Molybdenum
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
  • B01J23/42—Platinum
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/72—Copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/74—Iron group metals
  • B01J23/75—Cobalt
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/74—Iron group metals
  • B01J23/755—Nickel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/24—Nitrogen compounds
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/24—Nitrogen compounds
  • B01J27/26—Cyanides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
  • B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
  • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/16—Reducing
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B35/00—Boron; Compounds thereof
  • C01B35/02—Boron; Borides
  • C01B35/026—Higher boron hydrides, i.e. containing at least three boron atoms
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
  • C07C241/02—Preparation of hydrazines
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
  • C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
  • C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
  • C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B43/00—Preparation of azo dyes from other azo compounds
  • C09B43/08—Preparation of azo dyes from other azo compounds by reduction
  • C09B43/10—Preparation of azo dyes from other azo compounds by reduction with formation of a new azo or an azoxy bridge
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/60—Reduction reactions, e.g. hydrogenation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/60—Reduction reactions, e.g. hydrogenation
  • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations

Definitions

• alkali-metal borohydrides can be employed as reducing agents.
• this method has the disadvantage that in most of the technically valuable cases, reduction proceeds too slowly.
• Inorganic compounds which are components of an inorganic redox system the potential of which lies between 0 and l.5 volts at a pH value between 8 and l5.
• the rate of reduction is often favorably influenced by addition to the above catalysts or catalyst mixtures of compounds of tetra-valent sulfur, such as, e.g., sodium bisulfite or sodium sulfite, or compounds which can form the sulfite or bisulfite ion by the action of water, such as e.g. sulfur dioxide, the metabisulfites or the dithit nates and dithionites.
• compounds of tetra-valent sulfur such as, e.g., sodium bisulfite or sodium sulfite
• compounds which can form the sulfite or bisulfite ion by the action of water such as e.g. sulfur dioxide, the metabisulfites or the dithit nates and dithionites.
• metal sols mentioned under (a) are metal sols of tin, arsenic, copper, molybdenum, nickel, cobalt, or platinum.
• the preparation of metal sols wherein the metal is present in the colloidal state may proceed according to known methods, e.g., by reduction of soluble metal compounds, but it has been shown that frequently, e.g., for copper, nickel or tin, the activity of such metal sols is superior when they are obtained by reduction of a soluble metal complex compound. It is advisable to add protective colloids, e.g., glue, to the metal sols, in order to attain greater stability of such sols.
• protective colloids e.g., glue
• the metal sols employed according to the invention may still contain impurities, such as, e.g., hydrides, oxides, or borides.
• Examples of the metal complex compounds mentioned under (b) are the complex compounds of the metals copper, cobalt, nickel, antimony, molybdenum, tin, or chro- United States Patent 0 Friedrich Schubert,
• the complex forming components may be, e.g., glycol, ethanolamine, ethylenediamine, p-diketones, a-hydroxycarboxylic acids, or similar compounds.
• ammonia, hydroxyl (OH-) ions, and halogen ions may also be employed for complex formation.
• OH- hydroxyl
• halogen ions may also be employed for complex formation.
• the preparation of these metal complex compounds may be carried out according to known methods, e.g., by reaction of a metal salt with the complex forming agent, e.g., ethylene diamine.
• a metal salt e.g., ethylene diamine.
• the complex forming agent e.g., ethylene diamine.
• Examples of the inorganic compounds mentioned under (c) are, e.g., the complex alkali-metal cyanides of bivalent nickel, cobalt, chromium, or manganese, or alkali stannite +OH-ions, or alkali stannate.
• the compound employed according to the invention is added in its reduced form (cyanocobaltate (ll), for example) or in its oxidized form (cyanocobaltate (III), for example).
• Examples of the organic compounds mentioned under (d) are the anthraquinones and their substitution products, such as, e.g., anthraquinone-Z-sulfonic acid, l-aminoanthraquinone-8-sulfonic acid, l-amino-4-bromo-anthraquinone-2-sulfonic acid, 4-amino-anthraquinone-6-sulfonic acid, N,N dihydro anthraquinone-azine-3,3'-disulfonic acid, naphthol, indigo-trisulfonic acid or di[anthraquinonyl-( l ]-amine.
• substitution products such as, e.g., anthraquinone-Z-sulfonic acid, l-aminoanthraquinone-8-sulfonic acid, l-amino-4-bromo-anthraquinone-2-sulf
• boron compounds employed according to the invention use is made, e.g., of alkali-metal borohydrides or borazanes or their dehydrogenation products such as the borazenes or borazines or their derivatives substituted by organic residues, e.g., alkyl or alltoxy groups, or compounds of the formula:
• mixtures of such boron compounds may also be employed.
• the activity of the catalyst mixtures is in many cases essentially higher than was to be expected by addition of their individual activities, so that there exists a synergistic effect.
• the described catalysts exhibit a particularly good activity for quite specific compounds which are to be reduced.
• This selectivity can in many cases be suspended or extended by combination with an- 3 other catalyst, whereby a good properties of the catalysts is obtained.
• the salt of anthraquinone-Z-monosulfonic acid already acts at room temperature to accelerate strongly the rate of reduction of quite specific vat dyestuffs.
• the salt of l-aminc-4-bromo-anthraquinonc-2-sulfonic acid causes acceleration of the reduction rate only at relatively much higher temperatures.
• a combination of these two compounds causes a strong acceleration of the reduction rate for organic compounds already at room temperature, whereby selectivity can no longer be observed.
• the catalysts or catalyst mixtures may be employed in amounts of 1-20%, preferably of 5-l0%, referred to the employed boron compounds, particularly to alkali-metal borohydrides. In some cases, it may be desirable to use still different proportions. Preliminary experiments can readily establish which catalyst combination will prove the most favorable in any individual case.
• the employed catalyst combinations act with particular advantage when they are added to the dye baths during dyeing with vat dyestuffs with the aid of boron compounds as reducing agents. However, the catalyst combinations may combination of the desired of the activity of the catalyst, a 10 g. piece of cotton fabric pen ions and left there at 60 C. for 1 hour, whilst the pieces of fabric are turned in the suspensions from time to time.
• the pieces of fabric are taken out, oxidized in a 0.5% solution of sodium perboratc, subsequently boiled for 20 minutes in a 0.5% soap solution, then washed and dried. About 1700% more of the dyestutI is adsorbed by the piece of fabric treated with the catalyst than by the piece of fabric treated with the catalyst-free suspension.
• the copper sol serving as catalyst was prepared as follows: 20 g. CuS0 .5H O are dissolved in 750 ml. H O, treated with 200 ml. .5% pearl glue solution, and subsequently reduced with 1 g. KBH, in ml. H 0.
• a further possibility for the preparation of a copper sol, for instance from ammoniacal solution is as follows: 20 g. CuS0 .5H,O are dissolved in 500 ml. 11,0 and treated with sufficient NH; solution just to redissolve the precipitate which separates at first. Then, 200 ml. of a 5% pearl glue solution are added, it is diluted to 950 ml. with water, and subsequently reduced with 1 g. KBH in ml. H30.
• Example I 200 ml. of a suspension containing the following compounds per liter:
• the catalyst mdrrd RK volume 1' 358m Do. and the dyestuff are replaced by the catalysts and the lngidklrquoise blue np sg fl, Do. dygstutfisl statedbtin thie f cl lkllowing table, th? tgesults :hert'e g 5% fifii.
• Period oi steaming for fixing equal amounts (Schultz oi dyestufl. Adsorhcd dyostur'l Catalyst Dyestuil' Fnrbstotitnhollen," amount alter equal 7th ed.) Steaming pcnods with Cu-S l o i a] Ind.- cllow GK Vol. I No. l 220 90 120 At 120 sec., 667 more. m-soifif iffli ui ImL-iil'own Vol. 11 No. 11227.- 90 240 At90see.,33% more. Ni-Sol (ammoniacal) Ind-brown Vol. I, No. 1,227 0 240 At 90 sec., 66% more. (lo-Sol Ind.-yellow3GFN ctzllraugfndrixkmdled. 45 120 At60sec., 25% more.
• Example 3 An ammoniacal Cu sol prepared as described in Exam- (a) 20 m1 of a solution containing: ple 1 rs dried by a spray drier m an atmosphere of nrtro- 40 gen. 200 ml. of a suspension containing the following potassfum dwhmmale 50 constituents per litre: potz'lsslum tomhydrlde --mg-- Cu colloid as catalyst (containing 0.05 g.
• a second piece of fabric is treated under the same conditions with a suspension having the above stated composition but containing 1 g. of sodium carbonate per liter and no catalyst.
• the sample for comparison is also oxidized and after-treated as described above. Essentially more dyestuif is fixed on the piece of fabric treated with the suspension containing the catalyst than on the piece of fabric treated with the catalyst-free suspension.
• Example 5 25 ml. of a solution containing 10 mg of. potassium boranate and 5 mg. of methyl orange in a test tube are placed in a beaker with boiling water. After 20 minutes, the solution has hardly decolorised, i.e. less than 10% of the methyl orange has been reduced.
• the skeins are taken out, oxidized in a 05% solution of sodium perborate, then boiled for 20 minutes in a 0.5% soap solution, washed, and dried. Over 10,000% more of the dyestutf are fixed 0n the skein treated with the catalyst than there is on the skein treated with the catalyst-free suspension.
• Example 6(a) is then carried out with this suspension.
• the suspension containing the catalyst 2000% more dyestufi are fixed on the fiber than by use of the catalyst-free suspension.
• Example 7 200 ml. of a suspension containing the following compounds per liter:
• Catalyst solution (containing 0.1 g. CoCl +5 ml.
• KBH4 g are first heated to 45 C., then 3.5 ml. of sodium hydroxide solution (38 B.) are added, it is heated further to 60 C., and then the dyeing process described in Example 6(a) is carried out.
• the suspension containing the catalyst 1500% more of the dyestutf are fixed on the fiber than by use of the catalyst-free suspensron.
• Example 8 A suspension containing mg. of potassium boranate, 5 mg. of Indanthrene brilliant green. B (Schultz Farbstofftabellen, 7th edition, volume I, No. .1269) or 5 mg. of Indanthrene orange RRTS (Schultz FFarbstoiftabellen, 7th edition, volume II, page 131) and 20mg. of sodium hydroxide in ml. of water is placed in a test tube into a beaker with boiling water. It was then ohserved which percentage portion of the dyestufi had bethe suspension complete or nearly comp elfiwyatting had already taken place for both dyestuffs within a short time. The following combinations were employed as catalysts:
• Sorbitol Aminoacctlc acid Diacetyldioxime. Ethylenediamine lyrog lo Ethylenc-his-(iininooctic acid).
• Diacetyldioxime Ethylenediamine Sorbitol Cu-complex with p ethylene iminebiguanidene (ci. DBP 954,686).
• Example 9 200 ml. of a suspension containing per litre:
• Indanthrene scarlet R Schotz Farbstofitabellen, 7th edition, volume ll, page 132
• the pieces of fabric are taken out, oxidised in a 0.5% solution of sodium perborate, boiled for 20 minutes in a 0.5% soap solution, then washed and dried.
• Dyeing is then carried out by the method described under (a). In this case, however, between the oxidising and soap bath, the piece of fabric was introduced into a 1% solution of acetic acid at C. for 5 minutes. 400% more of the dyestufi was fixed on the fabric treated with the suspension containing the catalyst.
• dyeings are obtained whereby the piece of fabric treated with the suspension containing the catalyst contains about 900% more dyestutf than the piece of fabric treated with the catalyst-free suspension.
• Example 10 Indanthrene navy blue TRF --g-.. 8 RBI-I g 6 Na CO; g 20 and are subsequently squeezed uniformly between 2 roll:
• Sodlum-diplienylaminei-sult'onate 7 (2) For equal periods 01' steaming lasting for 120 sec- 0.25 N(2'-hydroxyphenyl)-2-hydroxy-naphthoquinoneonds, the amount of dycstutf fixed on the piece of fabric (LU- 4 6 i 0.25 2-cliloro-3-amino-napiithoqulnone-(1,4) 2 treated with the suspension containing the catalyst s more than the amount of dyestuflf on the piece of fabric 30 N *Plmwqulmne (114) 3 treated with the catalyst-free suspension.
• Example 12 70 0.25 (1,1')-dianthrimide-(4,4)-diaulphonic acid 7 0.25 l-benzoyiamiuo-anthraqulnone-b-aulphouic acid 7 A suspenslon comalmng 5 of potassumf hora-Date 0.25 Sodium-l-nitroanthraquinone-Z-carboxylate 5 5 mg. of Indanthrene orange RRTS (Schultz FaibStOlf- 0.25 Potassium-1-bromo-anthraqulnone-B-sulphonate 5.5 tabeucn," 7th cdltlon, Volume II, page 131) and 300 mg.
• Example 14 is stirred into an aqueous vat dye suspension which contains l5 g./litre of Indanthrene red F 3 B (German patent specification 825,111, Example 4).
• a cotton web is foularded and steamed by a continuous process using this bath at 25 C. and an apparatus described by F. Weiss in Die Kiipenfarbstoflfe, 1953, page 201.
• the amount of liquid remaining on the fabric comprises about 70% of the weight of the fabric.
• the speed of passing the goods amounts to 60 m./min., the stay in the steaming apparatus about seconds.
• the web passes as usual a roller vat system for rinsing, oxidising, and soaping. A bright blue red dyeing is obtained.
• Indanthrene scarlet R (Schultz Farbstofftabellen," 7th edition, volume II, page 132) Indanthrene blue 5 G (Schultz Farbstoiftabellen, 7th
• Example 15 In an apparatus such as is mentioned by F. Weiss in Die Kiipenfarbstofie, 1953, page 218, a cotton yarn cheese is dyed at a ratio of goods weight to bath weight of 1:10 in such a manner that a dyestufl suspension containing per litre of liquor 3 g. Indanthrene blue 5 G (Schultz Farbstofitabellen, 7th edition, volume I, No. 1238) which is divided as finely as possible is circulated 15 at 25' C. Then, there is added, at the rate of 2 g./l., a mixture consisting of:
• Example 16 A piece of cotton fabric is soaked in a suspension containing per litre 20 g. of Indanthrene brilliant green FFB (Schultz Farbstofitabellen," 7th edition, volume II, page 128), 6 g. of potassium boranate, and 22 g. of sodium carbonate which is thereupon squeezed uniformly between two rolls until the amount of liquid remaining on the fabric comprises about 85% of the net weight of the fabric; it is subsequently exposed for 1 minute to saturated steam at normal pressure, and then oxidised in a 0.5% solution of sodium perborate and thereafter boiled for 20 minutes in a 0.5% soap solution. A green dyeing is obtained.
• Indanthrene brilliant green FFB Schotz Farbstofitabellen
• the dyeing becomes deeper. If, for example, 2 g./l., of sodium anthraquinone-Z-sulphonate are added to the suspension, the dyeing is 80% deeper than that without catalyst; or if 2 g./l., of K [Co- (CN)s] are added as catalyst, the dyeing is 200% deeper.
• the catalyst activity is essentially more intense, when both catalysts are added simultaneously and in equal parts, and in fact half the amounts stated above so that the suspension again contains a total of 2 g./l. of catalysts.
• the dyeing is now 400% deeper than that from the suspension without the catalyst.
• Example 17 25 ml. of a suspension containing 5 mg. of Indanthrene yellow GK (Schultz Farbstofitabellen, 7th edition, volume I, No. 1241), 5mg. of potassium boranate, 300 mg. of sodium hydroxide, and one of the following catalyst combinations, are placed in a test tube into a beaker with boiling water, and it is observed after what time and to what extent vatting takes place.
• the catalyst combinations employed are: (a) 0.1 ml. of a copper sol containing 0.5 mg. of copper, and 0.25 mg. of sodium anthraquinone-Z-sulphonate; (b) 0.1 ml. of a copper sol containing 0.5 mg. of copper, and 0.05 mg. of 1,2-diamino-anthraquinone-3-sulphonic acid.
• the copper sol serving as catalyst is prepared by dissolving 20 of CuSO -5H,O in 500 ml. of water, and treating with sufficient conc. ammonium hydroxide solution just to redissolve the precipitate which separates at first. Then, 200 ml. of a 5% solution of pearl glue are added, the mixture made up with water to 950 ml., and the copper salt is subsequently reduced with 1 g. potassium boranate in 50 ml. of water.
• Example 18 g. of copper sulphate, 2 g. of aminoacetic acid, and 4 g. of sodium hydroxide, (b) 0.25 mg. of sodium anthraquinone-2-sulphonate, and (c) 0.05 mg. of quinizarine, are placed in a test tube into a beaker with boiling water, and it is observed after what time and to which extent vatting takes place. After 4 minutes, 50% of the dyestuif have been vatted.
• Example 19 25 ml. of solution containing 10 mg. of potassium boranate or 6.8 mg. of sodium boranate, and 5 mg. of methyl orange are placed in a test tube into a beaker with boiling water. After 15 minutes, the solution has not decolorized, i.e. less than 5% of the methyl orange have been reduced.
• Example 20 131 20.5 g. of sodium carbonate, and 7.5 g. of diborazyl or 11.3 g. of isopropylborazane, which is thereupon squeezed uniformly between two rolls until the amount of liquid remaining on the fabric comprises about of the net weight of the fabric. Subsequently, it is exposed to saturated steam at normal pressure. Thereupon, it is oxidized in a 0.5% solution of sodium perborate and boiled for 20 minutes in a 0.5% soap solution, washed, and dried. An orange dyeing is obtained.
• vat dyestuffs e.g. Indanthrene brilliant green FFB (Schultz Farbstofitabellen," 7th edition, volume H, page 128).
• Example 22 borazane, and 0.25 mg. of K [Ni(CN) are placed in 1 a test tube into a beaker with boiling water. After 4 /2 minutes, the solution has become decolorized corresponding to complete reduction of the methyl orange.
• dimethyl borazane is replaced by 12.5 mg. of diborazyl, 50% of the methyl orange are reduced after 10 minutes.
• Example 23 A solution containing 20 g. of nitrosodimethyl amine, 80 ml. of water, 5 ml. of a 45% sodium hydroxide solution and 5.15 g. of sodium boranate are heated at 100 C. under reflux for about 5 hours. Subsequently to the reaction mixture there are added 150 ml. of a 45% sodium hydroxide solution and the mixture is then subjected to a steam distillation. The distillate obtained is boiled with diluted sulfuric acid, and upon addition of sodiumbicarbonate there is analyzed by an iodometrical analysis the content of the asymmetrical dimethyl hydrazine. The content is about 0.4% of the theoretical.
• Example 24 25 ml. of a solution containing 10 mg. of ammonium sulfate and 5 mg. of Sirius light orange 3 GLD are reacted with 5 mg. of potassium boranate and 3.5 mg. of sodium boranate and it is observed after What time the dyestuff is decolorized, that means reduced. After a period of 600 seconds decolorizing takes place only to less than 5%. If to the reaction mixture there are added 0.01 ml. of an ammoniacal cuprous sol containing 0.05 mg. of copper, the reaction mixture is completely decolorized within 90 seconds.
• Example 25 10 g. of a cotton fabric are dyed at 85 C. for 20 minutes from a solution containing 2 g. of Sirius light orange 3 GLD and 10 g. per liter of sodium sulfate. The dyeing is rinsed and dried. A small piece of this dyed cotton fabric is completely soaked with a solution containing per liter 10 g. of sodium carbonate, 20 g. of potassium boranate and 1.25 g. of sodium hydroxide. Thereafter the cotton fabric is treated for 60 seconds in a stream of steam and is then rinsed with a 1% acetic acid solution, then 5 minutes treated with water and subsequently dried. The dyeing on the cotton fabric is now bleached to less than 10%. Its color is brownish-red.
• potassium boranate there can be used also as reduction agent N-methyl borazane or N-trimethyl borazane in a solution containing ammonium sulfate.
• Example 26 A mixture consisting of 24 g. of nitrobenzene, 7.5 g. of sodium boranate and 5 ml. of a 45 sodium hydroxide solution is heated to 160 for 2 hours. The reaction product is subjected to a steam distillation. Thereby 65% of the nitrobenzene are recovered. Azoxybenzene is obtained with a yield of 15% of the theoretical besides small amounts of azo benzene.
• catalyst 1 g. of K,[Ni(CN) or 0.5 g. of the sodium salt of anthiaquinonc-Z-sulfonic acid there is obtained azo benzene besides a small amount of azoxybenzol. Yield in the case of the K [Ni(CN) 70% and in the case of the anthraquinone sulfonic acid 42% referred to the reacted nitrobenzene.
• Example 27 A cotton fabric is soaked in a suspension containing per liter 33 g. of Indanthrene orange RRTS (Schultz Farbstoiftabellen, 7th edition, volume II, page 131,
• the cotton fabric is squeezed uniformly between 2 rolls until the amount of liquid remaining on the fabric comprises about 85% of the net weight of the fabric. Thereafter it is exposed to saturated steam at normal pressure for 2 minutes. Thereupon it is oxidized in a 0.5% solution of sodium perborate and boiled in a 0.5% soap solution, washed and dried. An orange dyeing is obtained.
• a process for the reduction of a vat dyestuff with 5 an alkali-metal borohydride the improvement which consists in carrying out the reduction in the presence of a catalytic proportion of a catalyst composition of the group consisting of a (a) aqueous colloidal sols of a metal of the group consisting of tin, arsenic, copper, molybdenum, nickel, cobalt, and platinum, and
• a process as defined in claim 1 in which the catalyst composition is an alkali-metal salt of the divalent tetracyanonickel(ll)ous acid [H Ni(CN) 4.
• a process as defined in claim 1 in which the catalyst composition is an alkali-metal salt of the trivalent tetracyanon-ickel(ll)ic acid [H Ni(CN) 5.
• a process as defined in claim 1 in which the catalyst composition is an alkali-metal salt of the tetravalent hexacyanocobalt(ll)ous acid [H Co(CN) 6.
• the catalyst composition is an alkali-metal salt of the trivalent hexacyanocoba.lt(IlI)ic acid

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• 1958
  • 1958-09-27 CH CH6443258A patent/CH383935A/de unknown
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