EP0000505A1 - Metal complexes, process for their preparation and their application as pigments - Google Patents

Metal complexes, process for their preparation and their application as pigments Download PDF

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Publication number
EP0000505A1
EP0000505A1 EP78100373A EP78100373A EP0000505A1 EP 0000505 A1 EP0000505 A1 EP 0000505A1 EP 78100373 A EP78100373 A EP 78100373A EP 78100373 A EP78100373 A EP 78100373A EP 0000505 A1 EP0000505 A1 EP 0000505A1
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European Patent Office
Prior art keywords
metal complexes
substituted
benzene
parts
formula
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EP78100373A
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German (de)
French (fr)
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EP0000505B1 (en
Inventor
Horst Dr. Tappe
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Sanofi Aventis Deutschland GmbH
Cassella Farbwerke Mainkur AG
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Cassella AG
Cassella Farbwerke Mainkur AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/69—Two or more oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • 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
    • C09B55/00—Azomethine dyes
    • C09B55/002—Monoazomethine dyes
    • C09B55/003—Monoazomethine dyes with the -C=N- group attached to an heteroring

Definitions

  • the invention relates to valuable metal complexes of the formula where X for and the benzene or naphthalene nucleus formed by X with the rest of the molecule also by one or two substituents from the series methyl, methoxy, chlorine, bromine, trifluoromethyl, nitro, cyano, CONR 1 R 2 or COOR 3 , where R 1 and R 2 represents hydrogen or alkyl having 1 to 4 carbon atoms and R 3 represents alkyl having 1 to 4 carbon atoms, which may be substituted, and Me represents a nickel, copper, zinc or cobalt atom.
  • the invention further relates to the use of the metal complexes as pigments and for pigmenting lacquers, high-molecular plastic compositions and printing pastes.
  • Metal complexes of the formula II the benzene nucleus I can also be substituted as stated above, in particular simply in the para position to the oxygen, that is to say the 4 position, are of particular interest.
  • the new metal complexes can be prepared by mam 3-formyl-4-methyl-2,6-dihydroxy-pyridine or an alkali or alkaline earth salt thereof with an ortho-aminohydroxy compound of the formula III wherein X has the meaning given above and a benzene or naphthalene nucleus, as indicated above, can be substituted, reacted according to methods known per se and the resulting condensation product metallized according to a method known per se.
  • ortho-aminohydroxy compounds are suitable as starting products: ortho-aminophenol, 2-amino-4- (or 3- or 5- or 6-) nitrophenol, 2-amino-4- (or 3- or 5- or 6-) chloro-phenol, 2-amino-4- (or 3- or 5- or 6-) bromo-phenol, 2-amino-4- (or 3- or 5- or 6-) cyano-phenol, 2-amino- 4- (or 3- or 5- or 6-) methoxycarbonyl phenol, 2-amino-4- (or 3- or 5- or 6-) ethoxycarbonyl phenol, 2-amino-4- (or 3-) butoxycarbonyl -phenol, 2-amino-4- (or 5-) trifluoromethyl-phenol, 2-amino-4- (or 5 -) - carbonamido-phenol, 2-amino-4- (or 5-) dimethylcarbonamidophenol, 2 -Amino-4- (or 5-) ethylcarbonamido-phenol, 2-amino-1-nap
  • the compounds of the formula III are mostly known or can easily be synthesized by the methods known for the preparation of ertho-aminohydroxy compounds.
  • the 3-formyl-4-methyl-2,6-dihydroxy-pyridine and its alkali or alkaline earth salts are new. It can be easily prepared as described in the examples below.
  • the sodium and potassium salts are particularly suitable.
  • Other tautomeric forms of the metal complexes of the general formula I are also conceivable.
  • the present invention encompasses any of the possible tautomeric forms.
  • the reaction of the 3-formyl-4-methyl-2,6-dihydroxy-pyridine or the corresponding alkali or alkaline earth metal salt with the ortho-amino-hydroxy compound is carried out in suitable organic solvents, for example alcohols with 1 to 5 C- Atoms, glycol ethers. such as. Ethylene glycol dimethyl ether, glacial acetic acid, aprotic solvents. like z, ld. Toluene, carbon tetrachloride, 1,4-dioxane, tetrahydrofuran and the like, especially dipolar aprotic. Solvents, e.g.
  • the azomethine formed in this reaction can be metallized without isolation, but isolation of the azomethine before the metallization is also possible. However, it is generally sufficient to metallize the azomethine in a suitable solvent without isolation.
  • the metal-free azomethine in the solvent or solvent mixture used for the azomethine condensation is mixed with a metal salt, preferably an acetate, e.g. Copper II acetate, among the same
  • Conditions implemented in the production of azomethine It may be useful to keep the pH of the solution between 5 and 6, which e.g. can be done by successively adding sodium acetate solution.
  • the metal-free azomethines are yellow-orange to brown products, while the metal-containing new metal complexes are usually yellowish green to olive green and are only slightly or very slightly soluble in the usual solvents.
  • the new metal complexes are therefore suitable as strong-color, solution-resistant and temperature-resistant, but especially excellent light and weather-resistant pigments for the production of printing inks, for coloring plastics in bulk and as spinning dyes and in particular for the production of lacquers and paints. Due to the good fastness properties, the pigments are particularly interesting in the form of their metallic paints (aluminum paints) for high-quality exterior (car) paints.
  • the metal-free and metal-containing azomethines have a free position in the pyridine nucleus to which diazo components can still be coupled. This makes it possible to produce valuable metal-free and metal-containing azomethines which still contain an azo group.
  • the product is filtered off hot and washed with 1200 parts of 80 ° C hot water and dried at 40 ° C in a vacuum. 44 parts of the azomethine-copper complex of the formula are obtained.
  • the olive-green pigment obtained can be processed in the customary manner to give a printing ink which gives strong-color prints with excellent lightfastness.
  • An automotive baking varnish produced in the usual manner using the pigment obtained showed very good light fastness, weather fastness and over-spray fastness after baking.
  • the conversion of the potassium or sodium salt into the metal-free compound takes place in such a way that 19.1 parts of the product obtained in 200 parts of a mixture of 160 parts len acetic acid and 40 parts of water are suspended and the reaction mixture is concentrated in vacuo to 50 parts. After the concentrated solution has been left to stand, the metal-free compound crystallizes out. By redissolving and recrystallizing from a mixture of 160 parts of ethanol and 40 parts of water, the pure 3-formyl-4-methyl-2,6-di-hydroxypyridine with a melting point of 180 to 182 ° C. is obtained.
  • 4.5 g of the metal complex obtained according to Example 1 are shaken with 25.5 g of a rub-on lacquer consisting of a 20% solution of alkyd resin lacquer in xylene on the vibratory ball mill for 45 minutes, with 60 g clear lacquer consisting of 52.5 g a 70% alkyd resin solution in xylod, 35 g of a 55% melamine resin solution in butanol, 2.5 g of bunyl glycol, 5 g of butanol and 5 g of mineral spirits. You get a clear yellowish-green full tone detail. the ned emn aluminum sheet is injected and 30 minutes at burns a yellowish-green color of Einwsodiseiom fastness to overcoating and excellent light and weather fastness results.
  • a rub-on lacquer consisting of a 20% solution of alkyd resin lacquer in xylene on the vibratory ball mill for 45 minutes
  • 60 g clear lacquer consisting of 5
  • a mixture of 62.5 ml of glass beads, 3 mm in diameter, 4.5 g of the metal complex obtained according to Example 2 and 25.2 g of acrylic grinding varnish 25% is shaken in a sealed plastic cup of 125 ml for 30 minutes on the paint shaker. 60.3 g of a 48% acrylic melamine resin clear lacquer are then mixed in and the glass balls are then removed by sieving.
  • the 5% full-tone paint produced in this way with respect to the organic pigment is coated with an acrylic melamine resin paint containing 3% aluminum pigment in a weight ratio of 3: 5 mixed.
  • a mixture of 62.5 ml glass beads, 3 mm in diameter, 3.8 g of metal complexes according to Example 1 and 27.4 g of 25% alkyd rubbing lacquer is shaken in a sealed plastic cup of 125 ml for 60 minutes on the paint shaker. Then 44.8 g of a 56% alkyd-melamine resin clear lacquer are mixed in and then the glass balls are removed by sieving.
  • the full-tone color lacquer produced in this way, containing 5 percent by weight of pigment, is applied to a white card with a black horizontal stripe in a wet film thickness of 75 ⁇ m by means of a hand coater. After flashing off, bake in the drying cabinet at 140 ° C for 30 minutes. The result is a strong yellow-green coating with excellent fastness properties.
  • This whitening is applied with the help of a hand coater in a wet film thickness of 75 .mu.m to a white hardness and the spread is baked in the drying cabinet at 140 ° C. for 30 minutes.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Pyridine Compounds (AREA)

Abstract

1. Metal complex compounds of the formula I see diagramm : EP0000505,P9,F2 wherein X stands for see diagramm : EP0000505,P9,F3 see diagramm : EP0000505,P9,F4 see diagramm : EP0000505,P9,F5 or see diagramm : EP0000505,P9,F6 and the benzene or naphthalene ring formed by X and the remaining portion of the molecule may also be substituted with one or two substituents of the methyl, methoxy, chloro, bromo, trifluoromethyl, nitro, cyano, -CONR1 R2 or -COOR3 series, R1 and R2 standing for hydrogen or alkyl with 1 to 4 carbon atoms and R3 for alkyl with 1 to 4 carbon atoms, and Me denotes a nickel, copper, zinc or cobalt atom.

Description

Die Erfindung betrifft wertvolle Metallkomplexe der Formel

Figure imgb0001
worin X für
Figure imgb0002
steht und der durch X mit dem übrigen Teil des Moleküls gebildete Benzol- oder Naphthalinkern auch durch ein oder zwei Substituenten aus der Reihe Methyl, Methoxy, Chlor, Brom, Trifluormethyl, Nitro, Cyan, CONR1R2 oder COOR3, wobei R1 und R2 für Wasserstoff oder Alkyl mit 1 bis 4 C-Atomen und R3 für Alkyl mit 1 bis 4 C-Atomen stehen, substituiert sein kann, und Me ein Nickel-, Kupfer-, Zinkoder Kobaltatom bedeutet. Die Erfindung betrifft ferner die Verwendung der Metallkomplexe als Pigmente und zur Pigmentierung von Lacken, hochmolekularen plastischen Massen und Druckpasten.The invention relates to valuable metal complexes of the formula
Figure imgb0001
 where X for
Figure imgb0002
 and the benzene or naphthalene nucleus formed by X with the rest of the molecule also by one or two substituents from the series methyl, methoxy, chlorine, bromine, trifluoromethyl, nitro, cyano, CONR 1 R 2 or COOR 3 , where R 1 and R 2 represents hydrogen or alkyl having 1 to 4 carbon atoms and R 3 represents alkyl having 1 to 4 carbon atoms, which may be substituted, and Me represents a nickel, copper, zinc or cobalt atom. The invention further relates to the use of the metal complexes as pigments and for pigmenting lacquers, high-molecular plastic compositions and printing pastes.

Metallkomplexe der Formel II

Figure imgb0003
wobei der Benzolkern I auch noch wie vorstehend angegeben, insbesondere einfach in para-Stellung zum Sauerstoff, d.h.in 4-Stellung, substituiert sein kann, sind von besonderem Interesse.Metal complexes of the formula II
Figure imgb0003
 the benzene nucleus I can also be substituted as stated above, in particular simply in the para position to the oxygen, that is to say the 4 position, are of particular interest.

Die neuen Metallkomplexe können dadurch hergestellt werden, daß mam 3-Formyl-4-methyl-2,6-dihydroxy-pyridin bzw. ein Alkali- oder Erdalkalisalz davon mit einer ortho-Aminohydroxyverbindung der Formel III

Figure imgb0004
worin X die oben genannte Bedeutung besitzt und ein Benzol-oder Naphthalinkern, wie vorstehend angegeben, substituiert sein kann, nach an sich bekannten Methoden umsetzt und das entstehende Kondensationsprodukt nach einer an sich bekannten Methode metallisiert.The new metal complexes can be prepared by mam 3-formyl-4-methyl-2,6-dihydroxy-pyridine or an alkali or alkaline earth salt thereof with an ortho-aminohydroxy compound of the formula III
Figure imgb0004
 wherein X has the meaning given above and a benzene or naphthalene nucleus, as indicated above, can be substituted, reacted according to methods known per se and the resulting condensation product metallized according to a method known per se.

Als Ausgangsprodukte sind z.B. folgende ortho-Aminohydroxyverbindungen geeignet: ortho-Aminophenol, 2-Amino-4-(oder 3- oder 5- oder 6-)nitrophenol, 2-Amino-4-(oder 3- oder 5-oder 6-)chloro-phenol, 2-Amino-4-(oder 3- oder 5- oder 6-) bromo-phenol, 2-Amino-4-(oder 3- oder 5- oder 6-)cyano- phenol, 2-Amino-4-(oder 3- oder 5- oder 6-)methoxycarbonyl- phenol, 2-Amino-4-(oder 3- oder 5- oder 6-)äthoxycarbonyl- phenol, 2-Amino-4-(oder 3-)butoxycarbonyl-phenol, 2-Amino-4-(oder 5-)trifluormethyl-phenol, 2-Amino-4-(oder 5-)-carbonamido-phenol, 2-Amino-4-(oder 5-)dimethylcarbonamido- phenol, 2-Amino-4-(oder 5-)äthylcarbonamido-phenol,2-Amino-1-naphthol, l-Amino-2-naphthol, 2-Amino-3-naphthol, 2-Amino-4-(oder 5- oder 7-)chloro-1=naphthol, L-Amino-4-(oder 5-, 6- oder 7-)chloro-2-naphthol, 1-Amino-3-(oder 4- oder 8-) nitro-2-naphthol.The following ortho-aminohydroxy compounds are suitable as starting products: ortho-aminophenol, 2-amino-4- (or 3- or 5- or 6-) nitrophenol, 2-amino-4- (or 3- or 5- or 6-) chloro-phenol, 2-amino-4- (or 3- or 5- or 6-) bromo-phenol, 2-amino-4- (or 3- or 5- or 6-) cyano-phenol, 2-amino- 4- (or 3- or 5- or 6-) methoxycarbonyl phenol, 2-amino-4- (or 3- or 5- or 6-) ethoxycarbonyl phenol, 2-amino-4- (or 3-) butoxycarbonyl -phenol, 2-amino-4- (or 5-) trifluoromethyl-phenol, 2-amino-4- (or 5 -) - carbonamido-phenol, 2-amino-4- (or 5-) dimethylcarbonamidophenol, 2 -Amino-4- (or 5-) ethylcarbonamido-phenol, 2-amino-1-naphthol, l-amino-2-naphthol, 2-amino-3-naphthol, 2-amino-4- (or 5- or 7 -) chloro-1 = naphthol, L-amino-4- (or 5-, 6- or 7-) chloro-2-naphthol, 1-amino-3- (or 4- or 8-) nitro-2-naphthol .

Die Verbindungen der Formel III sind zumeist bekannt bzw. können leicht nach den für die Herstellung von ertho-Aminohydroxyverbindungen bekannten Methoden synthetisiert werden. Das 3-Formyl-4-methyl-2,6-dihydroxy-pyridin und seine Alkali- oder Erdalkalisalze sind neu. Es kann leicht, wie in den nachfolgenden Beispielen beschrieben, hergestellt werden. Von dem 3-Formyl-4-methyl-2,6-dihydroxy-pyridin sind auch andere tautomere Formen, z.B. das 2-Hydroxy-3-formyl-4-methylpyridon-(6), denkbar. Von seinen Salzen simd besonders das Natrium- und Kaliumsalz geeignet. Auch von den Metallkomplexen der allgemeinen Formel I sind noch andere tautomere Formen denkbar. Selbstverständlich wird von der vorliegenden Erfindung jede der möglichen tautomeren Formen umfaßt. Die Umsetzung des 3-Formyl-4-methyl-2,6-dihy- droxy-pyridins oder des entsprechenden Alkali- oder Erdalkalisalzes mit der ortho-Amino-hydroxy-Verbindung wird in geeigneten organischen Lösungsmitteln, beispielsweise Alkoholen mit 1 bis 5 C-Atomen, Glykoläthern. wie z.B. Athylenglykoldimetliyläther, Eisessig, aprotischen Lösungsmitteln. wie z,ld. Toluol, Tetrachlorkohlenstoff, 1,4-Dioxan, Tetrahydrofuran und dergleichen, insbesondere dipolar aprotischen. Lösemitteln, wie z.B. Dimethylformamid, Dimethylsulfoxid, N-Xethylpyrolidon, Tetramethylensulfon und dergleichen oder Wasser oder Gemischen davon, zweckmäßigerweise unter einer Atmosphäre eines Inertgases,wie Stickstoff, bei erhöhten Temperaturen durchgeführt. Als Reaktionstemperaturen können Temperaturen von 60°C bis zur Rückflußtemperatur des Lösungsmittels in Betracht kommen. Die bevorzugten Reaktionstemperaturen betragen von 80 bis 120°C. Die Umsetzung ist normalerweise innerhalb von 2 bis 8 Stunden beendet. Das bei dieser Umsetzung entstandene Azomethin kann ohne Isolierung metallisiert werden, aber auch eine Isolierung des Azomethins vor der Metallisierung ist möglich. Es genügt jedoch im allgemeinen, das Azomethin ohne Isolierung in einem geeigneten Lösungsmittel zu metallisieren. Zu diesem Zweck wird das metallfreie Azomethin in dem zur Azomethinkondensation benutzten Lösungsmittel oder Lösungsmittelgemisch mit einem Metallsalz, vorzugsweise einem Acetat, z.B. Kupfer-II-acetat, unter den gleichenThe compounds of the formula III are mostly known or can easily be synthesized by the methods known for the preparation of ertho-aminohydroxy compounds. The 3-formyl-4-methyl-2,6-dihydroxy-pyridine and its alkali or alkaline earth salts are new. It can be easily prepared as described in the examples below. Other tautomeric forms of the 3-formyl-4-methyl-2,6-dihydroxy-pyridine, e.g. the 2-hydroxy-3-formyl-4-methylpyridone- (6), conceivable. Of its salts, the sodium and potassium salts are particularly suitable. Other tautomeric forms of the metal complexes of the general formula I are also conceivable. Of course, the present invention encompasses any of the possible tautomeric forms. The reaction of the 3-formyl-4-methyl-2,6-dihydroxy-pyridine or the corresponding alkali or alkaline earth metal salt with the ortho-amino-hydroxy compound is carried out in suitable organic solvents, for example alcohols with 1 to 5 C- Atoms, glycol ethers. such as. Ethylene glycol dimethyl ether, glacial acetic acid, aprotic solvents. like z, ld. Toluene, carbon tetrachloride, 1,4-dioxane, tetrahydrofuran and the like, especially dipolar aprotic. Solvents, e.g. Dimethylformamide, dimethyl sulfoxide, N-xethylpyrolidone, tetramethylene sulfone and the like or water or mixtures thereof, conveniently carried out under an atmosphere of an inert gas such as nitrogen at elevated temperatures. Temperatures from 60 ° C. to the reflux temperature of the solvent can be considered as reaction temperatures. The preferred reaction temperatures are from 80 to 120 ° C. The reaction is usually complete within 2 to 8 hours. The azomethine formed in this reaction can be metallized without isolation, but isolation of the azomethine before the metallization is also possible. However, it is generally sufficient to metallize the azomethine in a suitable solvent without isolation. For this purpose, the metal-free azomethine in the solvent or solvent mixture used for the azomethine condensation is mixed with a metal salt, preferably an acetate, e.g. Copper II acetate, among the same

Bedingungen wie bei der Azomethinherstellung umgesetzt. Dabei kann es.zweckmäßig sein, den pH-Wert der Lösung zwischen 5 und 6 zu halten, was z.B. durch sukzessive Zugabe von Natriumacetatlösung erfolgen kann.Conditions implemented in the production of azomethine. It may be useful to keep the pH of the solution between 5 and 6, which e.g. can be done by successively adding sodium acetate solution.

Die metallfreien Azomethine sind gelborgangefarbene bis braune Produkte, während die metallhaltigen neuen Metallkomplexe normalerweise gelbstichig-grün bis olivgrün und in den üblichen Lösungsmitteln nur schwer bis sehr schwer löslich sind. Die neuen Metallkomplexe eignen sich daher als farbstarke lösungs- und temperaturbeständige, besonders aber hervorragend licht- und wetterechte Pigmente zur Herstellung von Druckfarben, zum Färben von Kunststoffen in der Masse und als Spinnfarbstoffe und insbesondere zur Herstellung von Lacken und Anstrichstoffen. Aufgrund der guten Echtheiten sind die Pigmente besonders auch in Form ihrer Metallic-Lacke (Aluminium-Lacke) für hochwertige Außen-(Auto-)lacke interessant.The metal-free azomethines are yellow-orange to brown products, while the metal-containing new metal complexes are usually yellowish green to olive green and are only slightly or very slightly soluble in the usual solvents. The new metal complexes are therefore suitable as strong-color, solution-resistant and temperature-resistant, but especially excellent light and weather-resistant pigments for the production of printing inks, for coloring plastics in bulk and as spinning dyes and in particular for the production of lacquers and paints. Due to the good fastness properties, the pigments are particularly interesting in the form of their metallic paints (aluminum paints) for high-quality exterior (car) paints.

Die metallfreien und metallhaltigen Azomethine weisen im Pyridinkern eine freie Stellung auf, an die noch Diazokomponenten angekuppelt werden können. So ist es möglich, wertvolle metallfreie und metallhaltige Azomethine herzustellen, die noch eine Azogruppe enthalten.The metal-free and metal-containing azomethines have a free position in the pyridine nucleus to which diazo components can still be coupled. This makes it possible to produce valuable metal-free and metal-containing azomethines which still contain an azo group.

Wenn nichts anderes angegeben ist, sind in den nachfolgenden Beispielen Teile in Gewichtsteilen und Temperaturen in Grad Celcius angegeben.Unless otherwise indicated, parts in parts by weight and temperatures in degrees Celsius are given in the examples below.

Beispiel 1example 1

21,1 g 2-Hydroxy-3-formyl-4-methylpyridon-(6) als Kaliumsalz werden zusammen mit 14,9 g 4-Chlor-2-aminophenol in 300 ml Eisessig suspendiert und unter Stickstoffatmosphäre 3 Stunden zum Sieden erhitzt (ca. 118°C). Dann werden 10 g Kupfer-II-acetat, gelöst in 300 ml Dimethylformamid, zugegeben, und es wird eine Stunde bei 140°C gehalten. Nach Abkühlen wird abgesaugt, mit Methanol und Wasser gewaschen und getrocknet. Man erhält 33,5 g eines gelbstichig-grünen Metallkomplexes der Formel

Figure imgb0005
der bei seiner Verwendung als Pigmente, z.B. in Metallic-(Aliminium)-Autolacken, hervorragende Licht- und Wetterechtheiten zeigt.21.1 g of 2-hydroxy-3-formyl-4-methylpyridone- (6) as the potassium salt are suspended together with 14.9 g of 4-chloro-2-aminophenol in 300 ml of glacial acetic acid and heated to boiling under a nitrogen atmosphere for 3 hours (approx . 118 ° C). Then 10 g of copper (II) acetate, dissolved in 300 ml of dimethylformamide, are added and the mixture is kept at 140 ° C. for one hour. After cooling, the product is filtered off with suction, washed with methanol and water and dried. 33.5 g of a yellowish-green metal complex of the formula are obtained
Figure imgb0005
 which shows excellent light and weather fastness when used as pigments, e.g. in metallic (aluminum) car paints.

Beispiel 2Example 2

1200 Teile Wasser werden unter Einleiten von Stickstoff zum Sieden erhitzt und unter Stickstoffeinleitung auf 20°C abgekühlt. Dann gibt man 57,3 Teile 2-Hydroxy-3-formyl-4-methylpyridon-(6) und 34,5 Teile o-Aminophenol zu; erhitzt 4 Stunden am Rückfluß, saugt heiß ab und wäscht mit 1000 Teilen 80°C heißem Wasser. Die erhaltene gelbe Paste des Azomethins gibt man in 6000 Teile Wasser, fügt 60 Teile Kupfer-II-acetat zu und erhitzt 3 1/2 Stunden am Rüekxluß, wobei man durch sukzessive Zugabe von 1100 Teilen 10%iger Natrium-acetat-Lösung den pH-Wert zwischen 5 und 6 hält. Am Ende der Reaktion beträgt der pH-Wert 5,4. Das Produkt wird heiß abgesaugt und mit 1200 Teilen 80°C heißem Wasser gewaschen und bei 40°C im Vakuum getrocknet. Man erhält 44 Teile des Azomethin-Kupfer-Komplexes der Formel

Figure imgb0006
Das erhaltene olivgrüne Pigment kann in üblicher Weise zu einer Druckfarbe verarbeitet werden, die farbstarke Drucke von hervorragender Lichtechtheit liefert.1200 parts of water are heated to the boil while introducing nitrogen and cooled to 20 ° C. while introducing nitrogen. Then 57.3 parts of 2-hydroxy-3-formyl-4-methylpyridone- (6) and 34.5 parts of o-aminophenol are added; heated to reflux for 4 hours, suction filtered hot and washed with 1000 parts of 80 ° C hot water. The yellow paste of the azomethine obtained is added to 6000 parts of water, 60 parts of copper (II) acetate are added and the mixture is heated at the back for 3 1/2 hours, the pH being increased by successively adding 1100 parts of 10% sodium acetate solution -Value between 5 and 6 holds. At the end of the reaction the pH is 5.4. The product is filtered off hot and washed with 1200 parts of 80 ° C hot water and dried at 40 ° C in a vacuum. 44 parts of the azomethine-copper complex of the formula are obtained
Figure imgb0006
 The olive-green pigment obtained can be processed in the customary manner to give a printing ink which gives strong-color prints with excellent lightfastness.

Ein unter Verwendung des erhaltenenPigments in üblicher Weise hergestellter Autoeinbrennlack zeigte nach dem Einbrennen sehr gute Lichtechtheit, Wetterechtheit und Überspritzechtheit.An automotive baking varnish produced in the usual manner using the pigment obtained showed very good light fastness, weather fastness and over-spray fastness after baking.

Ähnlich wie im vorstehenden Beispiel 2 wurden die in den nachfolgenden Tabellen angegebenen Metallkomplexe hergestellt:

Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
 Similar to Example 2 above, the metal complexes listed in the tables below were prepared:
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011

Das in den vorstehenden Beispielen als Ausgangsprodukt benutzte 6-Hydroxy-3-formyl-4-methylpyridon- (6) bzw. sein Natriumsalz kann, ausgehend vom 4-Methyl-2,6-dihydroxypyridin, folgendermaßen hergestellt werden:

  • 125 Teile 4-Methyl-2,6-dihydroxypyridin in 400 Teilen
Starting from 4-methyl-2,6-dihydroxypyridine, the 6-hydroxy-3-formyl-4-methylpyridone (6) or its sodium salt used as the starting product in the above examples can be prepared as follows:
  • 125 parts of 4-methyl-2,6-dihydroxypyridine in 400 parts

Äthanol werden mit 80 Teilen Natriumacetat, gelöst in 100 Teilen Wasser, und 148 Teilen Chloral in 400 Teilen Wasser zusammengegeben und das Gemisch 8 Stunden bei 20°C gerührt, anschließend läßt man weitere 48 Stunden bei Zimmertemperatur stehen, saugt dann das ausgefallene Produkt ab, wäscht den Rückstand mit Wasser und trocknet bei 30°C im Vakuum. Man erhält so 218 Teile (=80% d.Th.) 3-(β,β,β-Trichlor-α-hydroxy)-äthyl-4-methyl-2,6-dihydroxypyridin, das nach Umkristallisation aus Essigsäureäthylester einen Schmelzpunkt von 1950C besitzt.

Figure imgb0012
272,5 Teile 3-(β,β,β-Trichlor-α-hydroxy)äthyl-4-methyl-2,6-dihydroxypyridin werden in 3000 Teile Äthanol eingetragen und mit einer Lösung von 500 Teilen Kaliumhydroxid in 400 Teilen Wasser und 1700 Teilen Äthanol versetzt. Das Reaktionsgemisch wird 30 Minuten am Rückfluß unter Rühren am Sieden gehalten, dann auf 20°C abgekühlt. Das hierbei ausgeschiedene Produkt wird abgesaugt, mit 200 Teilen Äthanol gewaschen und getrocknet. Das so erhaltene Rohprodukt kann durch Waschen bis zur neutralen Reaktion mit verdünnter Essigsäure von anhaftender überschüssiger Kalilauge befreit werden. Man erhält so 94 Teile des Kalium-3-formyl-4-methyl-2,6-dihydroxypyridins (= 49% d.Th.) , das nach Umkristallisation aus Wasser einen Schmelzpunkt von über 350°C besitzt.
Figure imgb0013
Verwendet man anstelle von Kaliumhydroxid Natriumhydroxid, so erhält man das entsprechende Natriumsalz.Ethanol is combined with 80 parts of sodium acetate, dissolved in 100 parts of water, and 148 parts of chloral in 400 parts of water and the mixture is stirred for 8 hours at 20 ° C., then left to stand at room temperature for a further 48 hours, then the precipitated product is filtered off with suction. washes the residue with water and dries at 30 ° C in a vacuum. This gives 218 parts (= 80% of theory) of 3- (β, β, β-trichloro-α-hydroxy) ethyl-4-methyl-2,6-dihydroxypyridine which, after recrystallization from ethyl acetate, has a melting point of 195 0 C.
Figure imgb0012
 272.5 parts of 3- (β, β, β-trichloro-α-hydroxy) ethyl-4-methyl-2,6-dihydroxypyridine are introduced into 3000 parts of ethanol and with a solution of 500 parts of potassium hydroxide in 400 parts of water and 1700 Parts of ethanol are added. The reaction mixture is refluxed with stirring for 30 minutes, then cooled to 20 ° C. The product which separates out is filtered off with suction, washed with 200 parts of ethanol and dried. The crude product thus obtained can be freed from adhering excess potassium hydroxide solution until the reaction with neutral acetic acid is neutral. This gives 94 parts of potassium 3-formyl-4-methyl-2,6-dihydroxypyridine (= 49% of theory) which, after recrystallization from water, has a melting point of above 350 ° C.
Figure imgb0013
 If sodium hydroxide is used instead of potassium hydroxide, the corresponding sodium salt is obtained.

Die Überführung des Kalium- oder Natriumsalzes in die Metallfreie Verbindung geschieht in der Weise, daß 19,1 Teile des erhaltenen Produkts in 200 Teilen eines Gemischs aus 160 Teilen Essigsäure und 40 Teilen Wasser suspendiert werden und das Reaktionsgemisch im Vakuum auf 50 Teile eingeengt wird. Nach Stehenlassen der eingeengten Lösung kristallisiert die metallfreie Verbindung aus. Durch Umlösen und Umkristallisieren aus einem Gemisch aus 160 Teilen Äthanol und 40 Teilen Wasser erhält man das reine 3-Formyl-4-methyl-2,6-di- hydroxypyridin vom Schmelzpunkt 180 bis 182°C.The conversion of the potassium or sodium salt into the metal-free compound takes place in such a way that 19.1 parts of the product obtained in 200 parts of a mixture of 160 parts len acetic acid and 40 parts of water are suspended and the reaction mixture is concentrated in vacuo to 50 parts. After the concentrated solution has been left to stand, the metal-free compound crystallizes out. By redissolving and recrystallizing from a mixture of 160 parts of ethanol and 40 parts of water, the pure 3-formyl-4-methyl-2,6-di-hydroxypyridine with a melting point of 180 to 182 ° C. is obtained.

Figure imgb0014
Figure imgb0014

Beispiel 3Example 3

4,5 g des nach Beispiel 1 erhaltenen Metallkomplexes werden mit 25,5 g eines Anreibelacks, bestehend aus ciner 20 %igen Lösung von Alkydharzlack in Xylol auf der Vibrasionskugel- mühle 45 Minuten geschüttelt, mit 60 g Klarlack, bestehend aus 52,5 g einer 70 %igen Alkydharzlösung in Xylod, 35 g einer 55 %igen Melaminharzlösung in Butanol, 2,5 g Bunylglykol, 5 g Butanol und 5 g Lackbenzin verseszt. Man embält so einen klaren gelbstichig-grünen Volltondeek. der ned emn Aluminiumblech gespritzt und 30 Minuten bei

Figure imgb0015
brannt eine gelbstichig-grüne Färbung von einwsodiseiom Überlackierechtheit und ausgezeichneter Licht- und Wetterechtheit ergibt.4.5 g of the metal complex obtained according to Example 1 are shaken with 25.5 g of a rub-on lacquer consisting of a 20% solution of alkyd resin lacquer in xylene on the vibratory ball mill for 45 minutes, with 60 g clear lacquer consisting of 52.5 g a 70% alkyd resin solution in xylod, 35 g of a 55% melamine resin solution in butanol, 2.5 g of bunyl glycol, 5 g of butanol and 5 g of mineral spirits. You get a clear yellowish-green full tone detail. the ned emn aluminum sheet is injected and 30 minutes at
Figure imgb0015
burns a yellowish-green color of Einwsodiseiom fastness to overcoating and excellent light and weather fastness results.

Beispiel 4Example 4

Eine Mischung von 62,5 ml Glasperlen, 3 mm Durchmesser, 4,5 g des nach Beispiel 2 erhaltenen Metallkomplexes und 25,2 g Acryl-Anreibelack 25%ig wird in einem verschlossenen Plastikbecher von 125 ml Inhalt 30 Minuten auf dem Paintshaker geschüttelt. Anschließend werden 60,3 g eines 48%igen Acryl-Melaminharz-Klarlacks zugemischt und sodann die Glaskugeln durch Sieben entfernt.A mixture of 62.5 ml of glass beads, 3 mm in diameter, 4.5 g of the metal complex obtained according to Example 2 and 25.2 g of acrylic grinding varnish 25% is shaken in a sealed plastic cup of 125 ml for 30 minutes on the paint shaker. 60.3 g of a 48% acrylic melamine resin clear lacquer are then mixed in and the glass balls are then removed by sieving.

Der so hergestellte in bezug auf das organische Pigment 5%ige Volltonlack wird mit einem 3 % Aluminium-Pigment enthaltenden Acryl-Melaminharzlack im Gewichtsverhältnis 3 : 5 vermischt.The 5% full-tone paint produced in this way with respect to the organic pigment is coated with an acrylic melamine resin paint containing 3% aluminum pigment in a weight ratio of 3: 5 mixed.

Anschließend wird mit Xylol, Butanol und Solvesso 100, ein aus mehreren Aromaten bestehendes Lösemittelgemisch,(l : 2,3 : 3,3) auf Spritzviskosität 4" (Viskospatel) eingestellt und dieser Metalleffektlack auf ein mit einem Washprimer und einem Einbrennweißlack wie üblich grundiertes Blech mit der Spritzpistole (Düse 1,5 mm Durchmesser, Spritzdruck 4 bar) in 6 waagerechten Gängen aufgebracht.Subsequently, with xylene, butanol and Solvesso 100, a solvent mixture consisting of several aromatics, (1: 2.3: 3.3) the spray viscosity is set to 4 "(visco spatula) and this metallic effect paint is primed with a wash primer and a baking white paint as usual Sheet with the spray gun (nozzle 1.5 mm diameter, spray pressure 4 bar) applied in 6 horizontal passages.

Nach dem Ablüften wird,30 Minuten bei 140°C im Trockenschrank eingebrannt. Die Echtheiten der Lackierung, insbesondere die Licht- und Wetterechtheiten, sind hervorragend.After flashing off, baked in the drying cabinet at 140 ° C for 30 minutes. The fastness of the paint, especially the light and weather fastness, are excellent.

Beispiel 5Example 5

Eine Mischung von 62,5 ml Glasperlen, 3 mm Durchmesser, 3,8 g Metallkomplexe nach Beispiel 1 und 27,4 g Alkyd-Anreibelack 25%ig wird in einem verschlossenen Plastikbecher von 125 ml Inhalt 60 Minuten auf dem Paintshaker geschüttelt. Anschließend werden 44,8 g eines 56 %igen Alkyd-Melaminharz-Klarlacks zugemischt und sodann die Glaskugeln durch Sieben entfernt. Der so hergestellte 5 Gewichtsprozente Pigment enthaltende Vollton-Farblack wird mittels eines Handcoaters in einer Naßfilmstärke von75/um auf ein weißes Kärtchen mit schwarzem Querstreifen aufgezogen. Nach dem Ablüften wird '30 Minuten bei 140°C im Trockenschrank eingebrannt. Es resultiert ein farbstarker gelbstichig-grüner Überzug mit hervorragenden Echtheiten.A mixture of 62.5 ml glass beads, 3 mm in diameter, 3.8 g of metal complexes according to Example 1 and 27.4 g of 25% alkyd rubbing lacquer is shaken in a sealed plastic cup of 125 ml for 60 minutes on the paint shaker. Then 44.8 g of a 56% alkyd-melamine resin clear lacquer are mixed in and then the glass balls are removed by sieving. The full-tone color lacquer produced in this way, containing 5 percent by weight of pigment, is applied to a white card with a black horizontal stripe in a wet film thickness of 75 μm by means of a hand coater. After flashing off, bake in the drying cabinet at 140 ° C for 30 minutes. The result is a strong yellow-green coating with excellent fastness properties.

Beispiel 6Example 6

2 Gewichtsteile eines 5 Gewichtsprozente Pigment enthaltenden, durch 60 Minuten langes Anreiben auf dem Paintshaker gemäß Beispiel 5 hergestellten Alkyd-Melaminharz-Einbrennlacks werden mit 2,5 Gewichtsteilen eines Einbrennweißlacks vermischt, der ebenfalls auf Alkyd-Melaminharz-Basis 20 Gewichtsprozente Ti02 enthält.2 parts by weight of an alkyd-melamine resin baking varnish containing 5 parts by weight of pigment and prepared by rubbing for 60 minutes on the paint shaker according to Example 5 are mixed with 2.5 parts by weight of a baking white varnish which also contains 20% by weight of TiO 2 on an alkyd-melamine resin basis.

Diese Weißaufhellung wird mit Hilfe eines Handcoaters in einer Naßfilmstärke von 75 um auf ein weißes Härtchen aufgezogen und der Aufstrich nach dem Ablüften 30 Minuten bei 140°C im Trockenschrank eingebrannt.This whitening is applied with the help of a hand coater in a wet film thickness of 75 .mu.m to a white hardness and the spread is baked in the drying cabinet at 140 ° C. for 30 minutes.

Claims (11)

1. Metallkomplexe der Formel I
Figure imgb0016
worin X für
Figure imgb0017
steht und der durch X mit dem übrigen Teil des Moleküls gebildete Benzol- oder Naphthalinkern auch durch ein oder zwei Substituenten aus der Reihe Methyl, Methoxy, Chlor, Brom, Trifluormethyl, Nitro, Cyan, CONR R oder COOR3, wobei R1 und R2 für Wasserstoff oder Alkyl mit 1 bis 4 C-Atomen und R3 für Alkyl mit 1 bis 4 C-Atomen stehen, substituiert sein kann, und Me ein Nickel-, Kupfer-, Zink- oder Kobaltatom bedeutet.1. Metal complexes of the formula I.
Figure imgb0016
 where X for
Figure imgb0017
 and the benzene or naphthalene nucleus formed by X with the rest of the molecule also by one or two substituents from the series methyl, methoxy, chlorine, bromine, trifluoromethyl, nitro, cyano, CONR R or COOR 3 , where R 1 and R 2 represents hydrogen or alkyl having 1 to 4 carbon atoms and R 3 represents alkyl having 1 to 4 carbon atoms, may be substituted, and Me denotes a nickel, copper, zinc or cobalt atom. 2. Metallkomplexe der Formel II
Figure imgb0018
wobei der Benzolkern I wie in Anspruch 1 angegeben, substituiert sein kann.2. Metal complexes of the formula II
Figure imgb0018
 wherein the benzene nucleus I can be substituted as indicated in claim 1. 3. Metallkomplexe nach Anspruch 2, dadurch gekennzeichnet, daß der Benzolkern I unsubstituiert ist.3. Metal complexes according to claim 2, characterized in that the benzene nucleus I is unsubstituted. 4. Metallkomplexe nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß der Benzolkern I in 4-Stellung substituiert ist.4. Metal complexes according to claims 1 and 2, characterized in that the benzene nucleus I is substituted in the 4-position. 5. Metallkomplexe nach den Ansprüchen 1 bis 2 und 3, dadurch gekennzeichnet, daß der Benzolkern durch Chlor, Brom, Nitro oder Methoxycarbonyl substituiert ist.5. Metal complexes according to claims 1 to 2 and 3, characterized in that the benzene nucleus is substituted by chlorine, bromine, nitro or methoxycarbonyl. 6. Verwendung der Metallkomplexe nach den Ansprüchen 1 bis 5 als Pigmente.6. Use of the metal complexes according to claims 1 to 5 as pigments. 7. Verwendung der Metallkomplexe nach den Ansprüchen 1 bis 5 zum Pigmentieren von Lacken.7. Use of the metal complexes according to claims 1 to 5 for pigmenting paints. 8. Verfahren zur Herstellung der Metallkomplexe nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß 3-Formy-4-methyl-2,6-dihydroxy-pyridin oder eines'seiner Alkali-oder Erdalkalisalze mit einer ortho-Amino-hydroxy-verbindung der Formel
Figure imgb0019
worin X die in Anspruch 1 genannte Bedeutung besitzt und der durch X mit dem übrigen Teil des Moleküls gebildete Benzol-oder Naphthalinkern auch,wie in den Ansprüchen bis 5 angegeben, substituiert sein kann, umgesetzt und das entstandene Kondensationsprodukt metallisiert wird.8. Process for the preparation of the metal complexes according to Claims 1 to 5, characterized in that 3-formy-4-methyl-2,6-dihydroxy-pyridine or one of its alkali or alkaline earth metal salts with an ortho-amino-hydroxy compound of the formula
Figure imgb0019
 wherein X has the meaning given in claim 1 and the benzene or naphthalene nucleus formed by X with the rest of the molecule can also be substituted, as indicated in claims to 5, and the resulting condensation product is metallized. 9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß die Umsetzung und/oder Metallisierung in einem organischen Lösungsmittel oder Wasser bei Temperaturen von 60°C bis zur Rückflußtemperatur des Lösungsmittels durchgeführt wird.9. The method according to claim 8, characterized in that the reaction and / or metallization in an organic solvent or water is carried out at temperatures from 60 ° C to the reflux temperature of the solvent. 10. Verfahren nach den Ansprüchen 8 oder 9, dadurch gekennzeichnet, daß die Umsetzung und/oder Metallisierung unter Inertgasatmosphäre durchgeführt wird.10. The method according to claims 8 or 9, characterized in that the reaction and / or metallization is carried out under an inert gas atmosphere. 11. Verfahren nach den Ansprüchen 8 bis 10, dadurch gekennzeichnet, daß bei der Metallisierung ein pH-Wert zwischen ,5 und 6 eingehalten wird.11. The method according to claims 8 to 10, characterized in that a pH value between 5 and 6 is maintained during the metallization.
EP78100373A 1977-07-29 1978-07-12 Metal complexes, process for their preparation and their application as pigments Expired EP0000505B1 (en)

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US4494745A (en) * 1981-12-16 1985-01-22 The Ward Machinery Company Feeding apparatus for paperboard sheets
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DE2008938A1 (en) * 1970-02-26 1971-09-09 Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen Azomethine-metal complex pigment dyes
FR2163519A1 (en) * 1971-12-13 1973-07-27 Ciba Geigy Ag

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DE2008938A1 (en) * 1970-02-26 1971-09-09 Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen Azomethine-metal complex pigment dyes
FR2163519A1 (en) * 1971-12-13 1973-07-27 Ciba Geigy Ag

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DE3315596A1 (en) * 1983-04-29 1984-10-31 Basf Ag, 6700 Ludwigshafen Use of polyurethane prepolymers as flocculating agents

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