DK143400B - METHOD FOR PREPARING 2,2, 3,3! -TETRACARBOXYDIPHENYLETHERDIAN HYDRIDE - Google Patents

METHOD FOR PREPARING 2,2, 3,3! -TETRACARBOXYDIPHENYLETHERDIAN HYDRIDE Download PDF

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DK143400B
DK143400B DK332774A DK332774A DK143400B DK 143400 B DK143400 B DK 143400B DK 332774 A DK332774 A DK 332774A DK 332774 A DK332774 A DK 332774A DK 143400 B DK143400 B DK 143400B
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ether
dianhydride
anhydride
mixture
organic solvent
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DK332774A
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DK143400C (en
DK332774A (en
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A S Hay
T Takekoshi
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Gen Electric
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/54Preparation of carboxylic acid anhydrides
    • C07C51/567Preparation of carboxylic acid anhydrides by reactions not involving carboxylic acid anhydride groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Furan Compounds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Description

143400143400

Den foreliggende opfindelse angår en særlig fremgangsmåde til fremstilling af 2,2',3,3'-tetracarboxydiphenyletherdianhydrid.The present invention relates to a particular process for the preparation of 2,2 ', 3,3'-tetracarboxydiphenyl ether dianhydride.

Forud for den foreliggende opfindelse er natriumnitrit blevet anvendt til at omdanne p-nitrobenzønitril til det tilsvarende diphenyletherdinitril som beskrevet i beskrivelsen til tysk patent nr. 2.037.781. Reaktionen gennemføres i et dipolært aprot opløsningsmiddel, såsom N-methylpyrroiidon, og der anvendes mere end 1 mol ækvivalent natriumnitrit. Stærkt reaktive forbindelse, såsom nitro-phthalsyreanhydrider, kan ikke anvendes under sådanne reaktionsbetingelser til gennemførelse af en kondensation til det tilsvarende diphenyletherdianhydrid, uden at der sker uønskede sidereaktioner.Prior to the present invention, sodium nitrite has been used to convert p-nitrobenzonitrile to the corresponding diphenyl ether dinitrile as described in the specification of German Patent No. 2,037,781. The reaction is carried out in a dipolar aprotic solvent such as N-methylpyrroiidone and more than 1 mole equivalent of sodium nitrite is used. Highly reactive compounds such as nitrophthalic anhydrides cannot be used under such reaction conditions to effect a condensation to the corresponding diphenyl ether dianhydride without undesirable side reactions.

Den foreliggende opfindelse er baseret på den erkendelse, at 3-nitrophthalsyreanhydrid kan omdannes til Z/Z'^S'-tetracarboxy-diphenyletherdianhydrid med formlen: a) ^o|)—° (o|> o=c c=o o=c ooThe present invention is based on the realization that 3-nitrophthalic anhydride can be converted to Z / Z 'S-tetracarboxy-diphenyl ether dianhydride of the formula: a)

\ / V\ / V

o 0 ved at gennemføre kondensation af 3-nitrophthalsyreanhydrid i nærværelse af katalytiske mængder af et nitritsalt:o 0 by conducting condensation of 3-nitrophthalic anhydride in the presence of catalytic amounts of a nitrite salt:

/~~\ MNO/ ~~ \ MNO

(O)- N°2 - --»· formel (I) o=c c=o(O) - N ° 2 - - »· formula (I) o = c c = o

VV

under smeltebetingelser eller i nærværelse af et inaktivt organisk opløsningsmiddel, hvor M er et alkalimetal. Det har overraskende vist sig, at 4-nitrophthalsyreanhydrid under tilsvarende reaktionsbetingelser tilvejebragte mindre end 5% udbytte af det tilsvarende diphenyl-ethertetracarboxydianhydrid.under melting conditions or in the presence of an inert organic solvent where M is an alkali metal. Surprisingly, it has been found that under similar reaction conditions, 4-nitrophthalic anhydride provided less than 5% yield of the corresponding diphenyl-ether-tetracarboxylic anhydride.

Fremgangsmåden ifølge opfindelsen er således ejendommelig ved, at 3-nitrophthalsyreanhydrid under smeltebetingelser eller i nærværelse af op til 20 vægtprocent af et inaktivt organisk opløs-ningsmiddel opvarmes ved temperaturer mellem 210°C og 260°C i nærværelse af fra 0,1 til 10 vægtprocent af et nitritsalt af et alkalimetalsalt.Thus, the process of the invention is characterized in that, under melting conditions or in the presence of up to 20% by weight of an inert organic solvent, 3-nitrophthalic anhydride is heated at temperatures between 210 ° C and 260 ° C in the presence of 0.1 to 10% by weight. of an nitrite salt of an alkali metal salt.

2 1434002 143400

Alkalimetalnitritter, såsom nitritter af natrium, kalium, rubidium og cesium, anvendes som nævnt som katalysatorer.Alkali metal nitrites, such as nitrites of sodium, potassium, rubidium and cesium, are used as catalysts as mentioned.

Ved den praktiske gennemførelse af fremgangsmåden ifølge den foreliggende opfindelse opvarmes 3-nitrophthalsyreanhydrid i nærværelse af nitritsaltet, hvorved der fremkommer et produkt, som fortrinsvis omkrystalliseres i et egnet organisk opløsningsmiddel.In the practical practice of the process of the present invention, 3-nitrophthalic anhydride is heated in the presence of the nitrite salt to give a product which is preferably recrystallized in a suitable organic solvent.

Seiv om tilsætningsrækkefølgen for de forskellige bestanddele ikke er kritisk, foretrækkes det at sætte nitritsaltkatalysatoren til 3-nitrophthalsyreanhydridet i form af nævnte smelte eller i blanding med det inaktive organiske opløsningsmiddel. Egnede organiske opløsningsmidler er f.eks. nitrobenzen, chlorerede benzener og andre aromatiske opløsningsmidler. En mængde organisk opløsningsmiddel pi op til 20 vægtprocent af blandingen af 3-nitrophthalsyreanhydrid og organisk opløsningsmiddel kan som nævnt anvendes. His større mængder af organisk opløsningsmiddel benyttes, formindskes reaktionshastigheden mærkbart, og udbyttet af dianhydrid påvirkes i uheldig retning.Although the order of addition of the various constituents is not critical, it is preferred to add the nitrite salt catalyst to the 3-nitrophthalic anhydride in the form of said melt or in admixture with the inactive organic solvent. Suitable organic solvents are e.g. nitrobenzene, chlorinated benzenes and other aromatic solvents. An amount of organic solvent in up to 20% by weight of the mixture of 3-nitrophthalic anhydride and organic solvent can be used, as mentioned. His larger amounts of organic solvent are used, the reaction rate is markedly decreased and the yield of dianhydride is adversely affected.

Nitritsaltet anvendes som nævnt i en mængde på fra 0,1 til 10 vægtprocent af 3-nitrophthalsyreanhydridet eller blandingen af dette og det organiske opløsningsmiddel.As mentioned, the nitrite salt is used in an amount of from 0.1 to 10% by weight of the 3-nitrophthalic anhydride or mixture thereof and the organic solvent.

Udvindingen af dianhydridet kan ske ved hjælp af i og for sig kendt teknik, såsom ved omkrystallisering af det rå produkt med et organiske opløsningsmiddel. En foretrukken metode til rensning af dianhydridet består i at opløse den rå reaktionsblanding ved stuetemperatur i et vandigt alkalihydroxid. Opløsningen kan fortyndes yderligere med vand og ekstraheres med diethylether. Den vandige fase kan gøres sur med en mineralsyre, såsom saltsyre, og yderligere ekstraheres med ether. Etheren kan derefter fjernes og resten opløses i kogende eddikesyreanhydrid, og eddikesyreanhydridet kan afdrives i vakuum til opnåelse af renset dianhydrid. Det ved fremgangsmåden ifølge opfindelsen fremstillede anhydrid kan f.eks. anvendes i forbindelse med organiske diaminer til fremstilling af polyetherimider. Endvidere kan 2,2',3,3'-tetracarboxydiphenyletherdianhydrid anvendes som hærder for epoxyharpikser.The dianhydride can be recovered by prior art, such as by recrystallizing the crude product with an organic solvent. A preferred method of purifying the dianhydride is to dissolve the crude reaction mixture at room temperature in an aqueous alkali hydroxide. The solution can be further diluted with water and extracted with diethyl ether. The aqueous phase can be acidified with a mineral acid such as hydrochloric acid and further extracted with ether. The ether can then be removed and the residue dissolved in boiling acetic anhydride and the acetic anhydride can be stripped in vacuo to give purified dianhydride. The anhydride prepared by the process according to the invention may e.g. is used in conjunction with organic diamines for the production of polyetherimides. Furthermore, 2,2 ', 3,3'-tetracarboxydiphenyl ether dianhydride can be used as a curing agent for epoxy resins.

Opfindelsen vil i det følgende blive belyst nærmere ved følgende eksempler. Alle dele er vægtdele.The invention will now be described in more detail by the following examples. All parts are parts by weight.

3 Μ340Ω EKSEMPEL 1 3-nitrophthaisyreanbydrfd blev opvarmet til en temperatur mellem 230°C og 240°C. En katalytisk mængde natriumnitrit blev sat til 3-nitrophthalsyreanhydridet svarende til ca. 0,5 vægtprocent baseret pi den resulterende blanding. Blandingen blev omrørt i et vakuum pi 90 tor ved en temperatur på omkring 230°C i ca. 40 minutter. Blandingen fik derefter lov til at afkøle, omkrystaliiseredes derefter i eddikesyreanhydrid. Der opnåedes lysbrune krystaller, der blev yderligere om krysta I liseret i ortho-dichlorbenzen til opnåelse af gule nåle. Et 28%-udbytte af produktet blev opnået med et smeltepunkt på 247-249°C. Udfra fremstillingsmetodén og produktets IR, NMR og massespektra blev produktet identificeret som Z^'^S'-tetracarboxydi-phenyletherdianhydrid.3 Μ340Ω EXAMPLE 1 The 3-nitrophthalic acid supply was heated to a temperature between 230 ° C and 240 ° C. A catalytic amount of sodium nitrite was added to the 3-nitrophthalic anhydride corresponding to ca. 0.5% by weight based on the resulting mixture. The mixture was stirred in a vacuum of 90 tor at a temperature of about 230 ° C for about 30 hours. 40 minutes. The mixture was then allowed to cool, then recrystallized from acetic anhydride. Light brown crystals were obtained, which were further crystallized in ortho-dichlorobenzene to obtain yellow needles. A 28% yield of the product was obtained with a melting point of 247-249 ° C. From the method of preparation and the IR, NMR and mass spectra of the product, the product was identified as Z ^ ^S tet tetracarboxydiphenyl ether dianhydride.

EKSEMPEL 2 0,3 dele natriumnitrit blev sat til en blanding af 9,86 dele 3-nitrophthalsyreanhydrid og ca. 2,25 dele 1,2,4-trichlorbenzen, opvarmet til 230°C. Reaktionsblandingen blev holdt ved 230-235°C i 50 minutter, i hvilket tidsrum der udviklede sig brun nitrogenoxidgas.EXAMPLE 2 0.3 parts sodium nitrite was added to a mixture of 9.86 parts 3-nitrophthalic anhydride and ca. 2.25 parts 1,2,4-trichlorobenzene, heated to 230 ° C. The reaction mixture was maintained at 230-235 ° C for 50 minutes, during which time brown nitric oxide gas developed.

Ovennævnte reaktionsblanding fik derefter lov til at afkøle og blev opløst i ca. 100 dele af en 5% vandig natriumhydroxidopløsning. Opløsningen blev derefter fortyndet med yderligere 100 dele vand og ekstraheret med ether. Den vandige fase blev syrnet med et ringe overskud af koncentreret saltsyre, og den resulterende opløsning blev kontinuerligt ekstraheret med ether. Etherekstrakten blev inddampet i vakuum til opnåelse af en viskos olie, der krystalliserede ved henstand. Der opnåedes en 2,2',3,3'-tetracarboxylsyre af diphe-nylether med et smeltepunkt på 158-162°C.The above reaction mixture was then allowed to cool and dissolved in ca. 100 parts of a 5% aqueous sodium hydroxide solution. The solution was then diluted with an additional 100 parts of water and extracted with ether. The aqueous phase was acidified with a slight excess of concentrated hydrochloric acid and the resulting solution was continuously extracted with ether. The ether extract was evaporated in vacuo to give a viscous oil which crystallized on standing. A 2,2 ', 3,3'-tetracarboxylic acid of diphenyl ether having a melting point of 158-162 ° C was obtained.

Tetrasyren blev derefter opløst i 25 ml kogende eddikesyreanhydrid. Opløsningen blev inddampet i vakuum til tørhed til opnåelse af en rest krystallinsk materiale, der blev vasket med varm eddikesyre. Det lysegule produkt blev udvundet i et udbytte på ca. 45,1% og var ud fra fremstillingsmetoden E^'^S'-tetracarboxydiphenyletherdi-anhydrid.The tetracar acid was then dissolved in 25 ml of boiling acetic anhydride. The solution was evaporated in vacuo to dryness to give a residual crystalline material which was washed with hot acetic acid. The pale yellow product was recovered in a yield of ca. 45.1% and was based on the preparation method E ^'S S tetracarboxydiphenyl ether dihydride.

Ovennævnte dianhydrid blev indført i en epoxyharpiks afledt af diglycidyletheren af bisphenol-A i en koncentration på 45% dianhydrid baseret på blandingens vægt. Blandingen blev opvarmet til 160°C, og den resulterende harpiks størknede til et hårdt ikke-klæ-bende faststof.The above dianhydride was introduced into an epoxy resin derived from the diglycidyl ether of bisphenol-A at a concentration of 45% dianhydride based on the weight of the mixture. The mixture was heated to 160 ° C and the resulting resin solidified to a hard non-adhesive solid.

ifSIFS

DK332774A 1973-06-22 1974-06-20 METHOD FOR PREPARING 2,2 ', 3,3'-TETRACARBOXYDIPHENYLETHERDIAN HYDRIDE DK143400C (en)

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BR (1) BR7405070D0 (en)
DD (1) DD112430A5 (en)
DE (1) DE2416594C2 (en)
DK (1) DK143400C (en)
FR (1) FR2299331A1 (en)
GB (1) GB1467275A (en)
IT (1) IT1015232B (en)
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JPS58193198A (en) * 1982-05-07 1983-11-10 株式会社日立製作所 Exchanger for recording element of recording apparatus
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JPS6038795U (en) * 1983-08-23 1985-03-18 アルプス電気株式会社 X-Y plotter
US5185451A (en) * 1989-05-15 1993-02-09 Occidental Chemical Corporation Bis-imides of dioxydiphthalic acid
US5166404A (en) * 1989-05-15 1992-11-24 Occidental Chemical Corporation Dioxydiphthalic acid esters
CN108350148A (en) * 2015-03-19 2018-07-31 衡所华威电子有限公司 Use the epoxy molding compounds of anhydride hardener, preparation method and use

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IT1015232B (en) 1977-05-10
FR2299331A1 (en) 1976-08-27
SE412226B (en) 1980-02-25
SU561504A3 (en) 1977-06-05
DE2416594C2 (en) 1983-12-08
JPS5032143A (en) 1975-03-28
SE7408147L (en) 1974-12-23
FR2299331B1 (en) 1979-02-23
AU6775674A (en) 1975-10-16
DK143400C (en) 1981-12-21
DK332774A (en) 1975-03-17
JPS5850992B2 (en) 1983-11-14
BR7405070D0 (en) 1975-01-21
DE2416594A1 (en) 1975-01-16
GB1467275A (en) 1977-03-16
DD112430A5 (en) 1975-04-12

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