SE201210C1 - - Google Patents

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SE201210C1
SE201210C1 SE201210DA SE201210C1 SE 201210 C1 SE201210 C1 SE 201210C1 SE 201210D A SE201210D A SE 201210DA SE 201210 C1 SE201210 C1 SE 201210C1
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water
crystal phase
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KLASS INTERNATIONELLSVENSK C09 b22 b:1 PATENT- OCH REGISTRERINGSVERKET Ans. 1139/1961 inkoin den 3/2 1961 utlagd den /2/4 196 FARBWERKE HOECHST AG VORMALS MEISTER LUCIUS & BRVNING, FRANKFURT A.M., FORBUNDSREPUBLIKEN TYSKLAND Satt att framstalla linjart kinakridon av y-kristallfas Tillagg till 178 491 UppDirutare: 0 Fuchs och A Kirsch Prioritet begdrd Iran den 6 februari 1960 (Forbandsrepubliken Tgskland) Foremal for patentet 178 491 är ett salt att framsatlla linjart kinakridon av y-kristallfas, vilket bestar dari, att man varmer vattenhaltiga pastor av finfordelat rakinakridon med sadana organiska foreningar, som vid 100200° C aro bestandiga och flytande, vilkas kokpunkt vid normaltryck ligger over 100° C och som i kyla eller i det angivna temperaturomradet ha en loslighet for vatten av minst 5 viktprocent, till temperaturer av 100-200° C under samtidigt avlagsnande av vattnet. Den erhallna produkten lampar sig utmarkt val for fargning av lacker och plastiska massor. CLASS INTERNATIONAL SWEDISH C09 b22 b: 1 PATENT AND REGISTRATION AGENCY Ans. 1139/1961 inkoin den 3/2 1961 utlagd den / 2/4 196 FARBWERKE HOECHST AG VORMALS MEISTER LUCIUS & BRVNING, FRANKFURT AM, FEDERAL REPUBLICEN GERMANY Set to produce linear kinacridon of y-crystal phase Additions to Kir A: Additions to 178 A1 Priority given to Iran on 6 February 1960 (Federal Republic of Germany) Form of patent 178 491 is a salt to produce linear y-crystal phase kinacridone, which consists in heating aqueous pastes of finely divided rachinacridone with such organic compounds as at 100200 ° C. aro resistant and liquid, whose boiling point at normal pressure is above 100 ° C and which in the cold or in the specified temperature range have a solubility for water of at least 5% by weight, to temperatures of 100-200 ° C while simultaneously removing the water. The product obtained is an excellent choice for coloring varnishes and plastic masses.

Vid den fortsatta utvecklingen av denna uppfinningstanke har det nu visat sig, att man aven kan omvandla rakinakridon till dess ykristallf as, cm man. varmer vattenhaltiga pastor av finfordelat rakinakridon med sadana organiska foreningar, som aro flytande vid rumstemperatur eller under reaktionsbetingelserna och som ha en loslighet for vatten av minst 5 viktprocent, och som ej utgora kolvaten eller deras nitro- eller halogenderivat, till temperaturer av c:a 80-200° C, foretradesvis c:a 100-180° C. Som organiska foreningar, vilka i kyla eller vid reaktionstemperaturen aro losliga i vatten, ifragakomma exempelvis foljande: metanol, etanol, propanol, butanol, glykol, glycerol, metylglykol, etyldiglykol, aceton, clioxan, dimetylformamid, Nmetylacetamid, butyrolakton, attiksyra, propionsyra, bensoesyra, p-toluensulfonsyra, p toluensulf amid, fenol, trietanolamin, anilin, kinolin, pyridin, N-metylpyrrolidon, metyletylketon eller tetrametylensulfon. In the further development of this inventive concept, it has now been found that rakinacridone can also be converted to its ykry crystalline phase. warms aqueous pastes of finely divided rakinacridone with such organic compounds, which are liquid at room temperature or under the reaction conditions and which have a solubility in water of at least 5% by weight, and which do not constitute the hydrocarbons or their nitro or halogen derivatives, at temperatures of about 80 -200 ° C, preferably about 100-180 ° C. As organic compounds which are soluble in water in the cold or at the reaction temperature, there may be used, for example, the following: methanol, ethanol, propanol, butanol, glycol, glycerol, methylglycol, ethyl diglycol, acetone, clioxane, dimethylformamide, N-methylacetamide, butyrolactone, attic acid, propionic acid, benzoic acid, p-toluenesulfonic acid, p-toluenesulphamide, phenol, triethanolamine, aniline, quinoline, pyridine, N-methylpyrrolidone, methylethylketulone or tetramethylketol.

Man forfar lampligen sa, att det fuktiga rakinakridonet blandas med den organiska foreningen och blandningen darefter varmes under omroring. Efter verkstalld omvandling isoleras reaktionsprodukten och torkas efter avlagsnandet av den for omvandlingen anvanda organiska foreningen genom tvattning med vatten, metanol eller en utspadd mineralsyra. Den f6r omvandlingen gynnsamma temperaturen är beroende av det anvanda rakinakridonet och av den organiska foreningen och ligger vid c:a 100-180° C. I de fall dar man arbetar Over reaktionsblandningens kokpunkt foretages omvandlingen i en omroringsbar tryekbehallare. Ay praktiska skill anvandas for omvandlingen foretradesvis sadana organiska fOreningar, som utgora tekniska storprodukter och som lata sig v1 regenereras ur de vattenhaltiga blandningarna. It is conveniently said that the moist rakina acridone is mixed with the organic compound and the mixture is then heated with stirring. After the transformation has taken place, the reaction product is isolated and dried after the removal of the organic compound used for the transformation by washing with water, methanol or a dilute mineral acid. The temperature favorable for the conversion depends on the rakinacridone used and on the organic compound and is at about 100-180 ° C. In cases where the boiling point of the reaction mixture is worked, the conversion is carried out in a stirring pressure vessel. For practical purposes, organic compounds are preferably used for the conversion which constitute major technical products and which can be regenerated from the aqueous mixtures.

Rakinakridoner, som 5.ro lampliga for en omvandling till y-fasen enligt forfarandet enligt uppfinningen kunna exempelvis erhallas genom kondensation am 2,5-dianilino-tereftalsyra med polyfosforsyra, vattenfritt flourvate, aluminiumklorid eller titantetraklorid i triklorbensen eller i en natriumklorid-aluminiumklorid-smalta och efterfoljande hydrolys av de erhallna reaktionsprodukterna. Torkat linj art kinakridon, som icke an lampligt for 2201 2 en omvandling, kan genom omlosning t. ex. ur koncentrerad svavelsyra eller polyfosforsyra och efterfoljande hydrolys Ater overforas till den omvandlingsbara formen och genom forfarandet enligt uppfinningen omvandlas till y-fasen. Rakinacridones which are suitable for a conversion to the γ-phase according to the process of the invention can be obtained, for example, by condensation of 2,5-dianilino-terephthalic acid with polyphosphoric acid, anhydrous fluorvate, aluminum chloride or titanium tetrachloride in trichlorobenzene or in a sodium chloride-aluminum chloride-narrow and subsequent hydrolysis of the obtained reaction products. Dried line art kinacridon, which is not suitable for 2201 2 a conversion, can by translocation e.g. from concentrated sulfuric acid or polyphosphoric acid and subsequent hydrolysis Ater is transferred to the convertible form and by the process according to the invention is converted to the γ-phase.

Det enligt det angivna forfarandet erhallna rOda pigmentet med stick i Matt utgor y-fasen av linjart kinakridon. Det utmarker sig f6r framstaende akthetsegenskaper, men framforallt for en mycket god kornmjukhet. Den sistnamnda egenskapen har speciellt fordelaktig inverkan vid fargning av mjukningsmedelshaltig polyvinylklorid, eftersom man harvid endast med mycket kornmjuka produkter kan uppna fargningar utan fargprickar. Produkten är utmarkt val lampad for fargning av lacker och plastiska massor, for framstallning av tryck- och malningsfarger, samt for alla Ovriga anvandningsomraden for organiska pigment. The red pigment obtained by sticking in Matt according to the specified procedure constitutes the y-phase of linear kinacridone. It is distinguished by excellent care properties, but above all for a very good grain softness. The latter property has a particularly advantageous effect when dyeing plasticizer-containing polyvinyl chloride, since dyeing can only be achieved with color-grained products without color dots. The product is an excellent choice for coloring paints and plastics, for the production of printing and grinding paints, and for all other areas of application for organic pigments.

Exempel 1. 100 viktdelar 2,5-dianilino-tereftalsyra kondenseras till linjart kinakridon genom varmning vid 120-130° C i c:a 500 viktdelar polyfosforsyra med en P-halt av c:a 82-84 %. Smaltan hydrolyseras. Den erMina produkten avsuges och tvattas med vatten. For att avlagsna sura bestandsdelar kan man urkoka filterMerstoden med utspatt alkali, eventuellt under tillsattning av etylalkohol. Produkten avsuges darefter pa nytt och tvattas med vatten till neutral reaktion. Example 1. 100 parts by weight of 2,5-dianilino-terephthalic acid are condensed to linear quinacridone by heating at 120-130 ° C in about 500 parts by weight of polyphosphoric acid with a P content of about 82-84%. The melt is hydrolyzed. The erMina product is sucked off and washed with water. To remove acidic constituents, the filter Merstoden can be boiled with dilute alkali, possibly with the addition of ethyl alcohol. The product is then filtered off with suction again and washed with water until neutral.

Det pa della satt erhallna fuktiga rakinakridonet varmes 3 timmar vid 120-150° C med 400 viktdelar 95-proc. etylalkohol i en tryckbehallare. Efter avkylningen avsuges, tvattas med vatten och torkas. Man erhaller ett r6tt pigment med stick i Matt, som efter röntgenanalys utgor y-fasen av linj art kinakridon. Det utmarker sig for sin kornmjukhet och en hog genomsynlighet. The partially obtained moist rakina acridone is heated for 3 hours at 120-150 ° C with 400 parts by weight of 95%. ethyl alcohol in a pressure vessel. After cooling, aspirate, wash with water and dry. A red pigment is obtained with a stick in Matt, which after X-ray analysis constitutes the y-phase of line art kinacridone. It stands out for its grain softness and high transparency.

Exempel 2. 225 viktdelar av det enligt uppgifterna i exempel 1 erhallna fuktiga c:a 20- proc. rakinakridonet omrores i en tryckbehallare 3 timmar vid 130-1° C med 135 viktdelar anilin, kinolin eller pyridin. Reaktionsblandningen surgores med utspadd mineralsyra, pigmentet avsuges, tvattas med vatten till neutral reaktion och torkas. Man erhaller det linjara kinakridonet i dess y-kristallfas. Example 2. 225 parts by weight of the moist 20% obtained according to the information in Example 1. the rakinacridone is stirred in a pressure vessel for 3 hours at 130-1 ° C with 135 parts by weight of aniline, quinoline or pyridine. The reaction mixture is acidified with dilute mineral acid, the pigment is filtered off with suction, washed with water until neutral and dried. The linear quinacridone is obtained in its γ-crystal phase.

Exempel 3. 225 viktdelar av det enligt uppgifterna i exempel 1 erhallna c:a 20-proc. fuktiga rakinakridonet omrores i en tryckbehallare 15 timmar vid 90-100° C i 350 viktdelar etylalkohol. Efter avkylningen avsuges reaktionsprodukten, tvattas med vatten och torkas. Den utgor y-kristallfasen av linjart kinakridon och Tamper sig utmarkt val som fargamne far fargning av lacker och plastiska massor. Example 3. 225 parts by weight of the approx. 20% obtained according to the information in Example 1. The moist rakinacridone is stirred in a pressure vessel for 15 hours at 90-100 ° C in 350 parts by weight of ethyl alcohol. After cooling, the reaction product is filtered off with suction, washed with water and dried. It constitutes the y-crystal phase of linear kinacridone and Tamper is an excellent choice as a dye for dyeing lacquers and plastic masses.

I foljande tabell anges ytterligare for omvandling av rakinakridonet lampliga organiska foreningar och reaktionsbetingelserna, varvid i vane fall y-kristallfasen erhalles. The following table further lists suitable organic compounds for the conversion of the rakinacridone and the reaction conditions, whereby in the usual case the γ-crystal phase is obtained.

Rakinakridon fuktigt, ca 20-procentigt (viktdelar) Organisk forening Viktdelar Reaktionstid Temperatur (timmar)c 2Butanol 13 1 N-metylpyrrolidon 11 Metyl-etylketon 21 Tetrametylensulfon. 23 1 p-toluen-sulfonsyra 23 1 Exempel 4. 100 viktdelar dianilino-tereftalsyra hoprores 1 timme vid 125-130° C med 500 viktdelar polyfosforsyra med en P205-halt av minst 85 %. Smaltan vidarebearbetas till rakinakridon pa det i exempel 1 angivna sattet. Det fuktiga rakinakridonet varmes i en tryckbehallare nagra timmar vid 150° C med 240 viktdelar kinolin. Efter avkylningen hopror man med metanol eller utspadd mineralsyra, avsuger, uttvattar filteraterstoden väl med metanol eller vatten och torkar. Man erhaller pa. detta satt y-fasen av det linjara kinakridonet, varvid emellertid det erhMlna pigmentet skiljer sig frau den enligt exempel 1 erhallna produkten genom sin tydligt gulare fargton och sin avsevart stone tackkraft. Rakinacridone moist, about 20% (parts by weight) Organic compound Weight parts Reaction time Temperature (hours) c 2Butanol 13 1 N-methylpyrrolidone 11 Methyl ethyl ketone 21 Tetramethylene sulfone. 23 1 p-toluenesulfonic acid 23 1 Example 4. 100 parts by weight of dianilino-terephthalic acid are mixed for 1 hour at 125-130 ° C with 500 parts by weight of polyphosphoric acid with a P2 O5 content of at least 85%. The melt is further processed into raquinacridone in the manner set forth in Example 1. The moist rakina acridone is heated in a pressure vessel for several hours at 150 ° C with 240 parts by weight of quinoline. After cooling, it is mixed with methanol or diluted mineral acid, filtered off with suction, the filtrate residue is washed well with methanol or water and dried. Man erhaller pa. this set the y-phase of the linear quinacridone, however, the pigment obtained differs from the product obtained according to Example 1 by its distinctly yellower hue and its considerable stone gratitude.

Efterfoljande tabell beskriver ett antal ytterligare for rakinakridonets omvandling till y-kristallfas lampliga organiska foreningar samt reaktionsbetingelserna. The following table describes a number further for the conversion of the rakinacridone to γ-crystal phase suitable organic compounds as well as the reaction conditions.

RakinakridonOrganisk forening fuktigt, ca 20-procentigt (viktdelar) ViktdelarReaktionstid (timmar) Temperatnr c 2Metanol 270 6 1 Isopropanol 21 Isobutanol 21 201 23 2Glykol 11 Glycerol 22 1 Metylglykol 11 Etyldiglykol 24 1 Aceton 21 Dioxan 21 Dimetylformamid 90 1 N-metylacetamid 24 1 Butyrolakton 80 1 Attiksyra 21 Propionsyra 27 1 Trietanolamin 1 Fenol 21 Bensoesyra 11 p-toluensulfamid 11 Kinolin 90 1 180 Exempel 5. I en tryckbehallare varmes 140 viktdelar 2,5-dianilinotereftalsyra med 1000 viktdelar vattenfritt fluorvate 4-5 timmar under omroring vid 150° C. Den storsta delen av fluorvatesyran avdestilleras och aterstoden halles pa is. Overskottet av fluorvatesyran neutraliseras med natronlut, pigmentet avsuges darefter och tvattas med vatten till neutral reaktion. Det sá erhallna fuktiga rakinakridonet varmes i en tryckbehallare 5 Emmet. vid 130° C under omroring med 500 viktdelar isopropanol. Reaktionsprodukten upparbetas pa det i de fi3regaende exemplen beskrivna sattet. Man erhaller det linjara kinakridonet i dess y-kristallfas. RakinacridoneOrganic compound moist, about 20% (parts by weight) parts by weightReaction time (hours) Temperature no. C 2Methanol 270 6 1 Isopropanol 21 Isobutanol 21 201 23 2Glycol 11 Glycerol 22 1 Methylglycol 11 Ethyl diglycol 24 1 Acetone 21 Dioxane 21 Dimethylmethylformamide 90 80 1 Attic acid 21 Propionic acid 27 1 Triethanolamine 1 Phenol 21 Benzoic acid 11 p-toluenesulphamide 11 Quinoline 90 1 180 Example 5. In a pressure vessel, 140 parts by weight of 2,5-dianilinotherephthalic acid are heated with 1000 parts by weight of anhydrous fluorine 4-5 hours with stirring at 150 ° C Most of the fluorate acid is distilled off and the residue is kept on ice. The excess fluoric acid is neutralized with sodium hydroxide solution, the pigment is then filtered off with suction and washed with water until neutral. The resulting moist raquin chridon is heated in a pressure vessel 5 Emmet. at 130 ° C with stirring with 500 parts by weight of isopropanol. The reaction product is worked up in the manner described in the above examples. The linear quinacridone is obtained in its γ-crystal phase.

I stallet for isopropanol kan man aven under samma betingelser anvanda metyletylketon eller N-metylpyrrolidon. Instead of isopropanol, methyl ethyl ketone or N-methylpyrrolidone can also be used under the same conditions.

Exempel 6. 200 viktdelar 2,5-dianilino-tereftalsyra kondenseras vid 180° C under omriiring till det linjara kinakridonet i en smalta av 1000 viktdelar aluminiumklorid och 280 viktdelar natriumklorid. Smaltan hydrolyseras med 5000 viktdelar is och 500 viktdelar 10-procentig saltsyra. Fargamnessuspensionen avsuges och tvattas neutral med vatten. Det pa detta satt erhallna fuktiga rakinakridonet varmes 5 timmar under onaroring vid 150180° C med 1200 viktdelar kinolin. Reaktionsblandningen upparbetas pa det i exempel 2 angivna sattet. Man erhaller det linjKra kinakridonet i dess y-kristallfas. Example 6. 200 parts by weight of 2,5-dianilino-terephthalic acid are condensed at 180 ° C with conversion to the linear quinacridone in a melt of 1000 parts by weight of aluminum chloride and 280 parts by weight of sodium chloride. The melt is hydrolyzed with 5000 parts by weight of ice and 500 parts by weight of 10% hydrochloric acid. The dye suspension is sucked off and washed neutral with water. The moist rakina acridone thus obtained is heated for 5 hours with stirring at 150180 ° C with 1200 parts by weight of quinoline. The reaction mixture is worked up in the manner set forth in Example 2. The linear kinacridone is obtained in its γ-crystal phase.

Exempel 7. 50 viktdelar torrt linjart kinakridon lOses under omroring i en timme vid 0° C 1 500 viktdelar koncentrerad svavelsyra. Man hydrolyserar den svavelsura losningen genom att halla den i 2500 viktdelar is. Det erhallna rakinakridonet avsuges och tvattas neutralt med vatten. Darefter varmer man den fuktiga filteraterstoden 5 timmar vid 150° C med 250 viktdelar etylalkohol. Efter avkylningen avsuges och torkas. Man erhaller pa detta Ott det linjara kinakridonet i dess y-kristallf as. Example 7. 50 parts by weight of dry linear quinacridone is dissolved with stirring for one hour at 0 ° C 1500 parts by weight of concentrated sulfuric acid. The sulfuric acid solution is hydrolyzed by pouring it into 2500 parts by weight of ice. The resulting rakinacridone is aspirated and washed neutral with water. The moist filter residue is then heated for 5 hours at 150 ° C with 250 parts by weight of ethyl alcohol. After cooling, aspirate and dry. This yields the linear kinacridone in its γ-crystal phase.

Claims (1)

1. Patentansprak: Modifikation av forfarandet att framstalla linj art kinakridona av y-kristallfas, vilket lam-par sig for fargning av lacker och plastiska massor samt for alla ovriga anvandningsomrb.den for organiska pigment, enligt det svenska patentet 178 491, kannetecknad darav, att man varmer vattenhaltiga pastor av finfordelat rakinakridon med sadana organiska foreningar, som aro flytande vid rumstemperatur eller under reaktionsbetingelserna och som ha en loslighet for vatten av minst 5 viktprocent, och som ej utgora kolvaten eller deras nitroeller halogenderivat, till temperaturer av 80200° C foretradesvis 100-180° C. Anforda publikationer: Patentskrifter [ran Frankrike 1. 189 154; Storbritannien 828 052, 851 976.Patent claim: Modification of the process for producing line art kinakridona of the y-crystal phase, which is suitable for dyeing lacquers and plastic pulps and for all other areas of application for organic pigments, according to Swedish patent 178 491, of which heating aqueous pastes of finely divided rachinacridone with such organic compounds, which are liquid at room temperature or under the reaction conditions and which have a solubility in water of at least 5% by weight, and which do not constitute the hydrocarbons or their nitroal halogen derivatives, are preferably 80200 ° C 100-180 ° C. Request publications: Patents [from France 1. 189 154; United Kingdom 828 052, 851 976.
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