WO2003027048A2 - Dehydration of fluorinated organic compounds - Google Patents

Dehydration of fluorinated organic compounds Download PDF

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Publication number
WO2003027048A2
WO2003027048A2 PCT/EP2002/010331 EP0210331W WO03027048A2 WO 2003027048 A2 WO2003027048 A2 WO 2003027048A2 EP 0210331 W EP0210331 W EP 0210331W WO 03027048 A2 WO03027048 A2 WO 03027048A2
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Prior art keywords
water
fluorinated
organic compounds
fluorinated organic
esters
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PCT/EP2002/010331
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German (de)
French (fr)
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WO2003027048A3 (en
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Max Braun
Helmut Bormann
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Solvay Fluor Und Derivate Gmbh
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Priority to AU2002338700A priority Critical patent/AU2002338700A1/en
Publication of WO2003027048A2 publication Critical patent/WO2003027048A2/en
Publication of WO2003027048A3 publication Critical patent/WO2003027048A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives

Definitions

  • the invention relates to a process for the production of dehydrated fluorinated organic compounds from water-containing fluorinated organic compounds.
  • Fluorinated organic compounds are known to be used for many purposes, for example as a solvent, as a reaction component or as a cleaning agent.
  • the presence of quantities of water which negatively influence the intended use is undesirable.
  • fluorinated organic compounds often contain water in such undesirable amounts, for example because water was used in their production or purification, because water of reaction is produced during their production (for example in the case of condensation reactions) or because the compounds have been used for dewatering and themselves loaded with water.
  • An example of the presence of water of reaction in fluorinated organic compounds is the preparation of aminohalogen crotonates, which are described in German Offenlegungsschrift DE 198 49 918 A1 and EP-A-0 808 826 (corresponding US patents: US Pat. No.
  • ⁇ -ketocarboxylic acid esters are reacted with ammonia, amines or acid adducts of ammonia or amines with elimination of water.
  • the water of reaction can be separated off in a known manner using drying agents such as sodium sulfate. Since two phases form, it can also be removed by phase separation.
  • drying agents such as sodium sulfate. Since two phases form, it can also be removed by phase separation.
  • Another possibility of water separation is that inert gas is already reacted by the reactants during the reaction. tion mixture conducts or the water is distilled off aceotropically with the addition of an entrainer.
  • the object of the present invention is to provide a simplified process for the production of dehydrated fluorinated organic compounds by separating water from water-containing fluorinated organic compounds. This object is achieved by the method according to the invention.
  • the process according to the invention for the production of dehydrated fluorinated organic compounds by separating the water from water-containing fluorinated organic compounds provides that the water-containing fluorinated organic compounds are contacted with pervaporation membranes, water is separated off and the dewatered fluorinated organic compounds are obtained.
  • the process can be carried out batchwise or continuously.
  • the method is carried out continuously, particularly in those cases in which the loading of the compound to be treated with water increases with a continuous period of time. This is the case, for example, with condensation reactions in which there are equilibrium reactions, e.g. B. in the production of esters from carboxylic acids and alcohols.
  • the continuous procedure is also useful if a reaction constantly produces water which has undesirable or harmful effects on the yield, purity, reaction rate or other parameters. This is the case in the production of amino halogen crotonates already mentioned, where it has been found that the yield and purity can be increased if the reaction water is separated off during the reaction.
  • Another case in which the continuous procedure is recommended is the use of fluorinated organic compounds as drainage agents, for example for drying surface-treated metals. That for Organic agents used for drying, which is constantly loaded with water, can advantageously be continuously dewatered.
  • dewater compounds which have a water content in the range from 0.1% by weight to 50% by weight. You can also first carry out a rough separation of the water by phase separation and then further reduce the remaining water content using the membrane technology.
  • the water content can be reduced to the desired maximum content by single or multiple treatment with the pervaporation membrane or membranes.
  • the method according to the invention is suitable for use on any water-containing fluorinated organic compounds. Dehydrated by fluorine and optionally other substituents such as chlorine, esters, carboxylic acids, carboxylic acid derivatives, keto esters, thioesters, amides are preferred.
  • the process according to the invention for dewatering is very particularly preferably used in the course of the production of fluorinated esters by condensation reactions and also aldol reactions.
  • the process according to the invention is very particularly preferably applied to esters which iron carboxylic acids having 2 to 15 carbon atoms (including the carbon atom of the carboxy group).
  • the method according to the invention for water separation is used in the production of A inohalogencrotonatucunen as disclosed in the aforementioned German patent application and the European patent application or the cited US patents. It is a manufacturing process a 3-amino-4, 4,4-trihalogencrotonate compound of the formula (I)
  • X represents fluorine or chlorine
  • A represents 0, S or NR 5
  • B represents R 6 , OR 6 , SR 6 or NR 3 R 4 ;
  • R, R 1 , R 2 , R 3 , R 4 , R 5 and R ⁇ each independently of one another for H, (Cl-C6) alkyl, (C2-C6) alkenyl, (C2-C6) alkynyl, phenyl or Phenyl (C1-C6) alkyl; or for (C1-C6) alkyl, (C2-C6) alkenyl, (C2-C6) alkynyl, phenyl or phenyl (C1-C6) alkyl, substituted with one or more groups independently selected from halogen, CN, NO 2 ; (Cl-C6) alkyl, (C2-C6) alkenyl, (C2-C6) alkynyl, phenyl, phenyl (C2-C6) alkyl, (Cl-C6) alkoxy, (C2-C6) alkenyloxy and phenoxy; or R 1 and R 2 , and R 3 and R 4 can each independently be linked to the nitrogen to which they
  • CX 3 is preferably CF 3 , CF 2 C1 or CHF.
  • R 1 and R 2 are the same or different and are preferably Cl-C3-alkyl.
  • A is preferably 0 or S, in particular O.
  • R is preferably H or C1-C3-alkyl.
  • B is preferably OR 6 or SR 6 .
  • R 3 , R 4 and R 5 are preferably H or Cl-C3-alkyl.
  • R6 is preferably Cl-C3-alkyl and can if desired, be substituted by 1 or more fluorine atoms.
  • a preferred embodiment provides for the application to the preparation of carboxylic acid esters of the general formula (I) R 7 -C (0) -OR 8 by reacting corresponding carboxylic acids with corresponding alcohols with elimination of water.
  • R 7 is preferably a Cl-C3 alkyl group which is substituted by at least 1 fluorine atom.
  • Preferred examples of R 7 are CF 3 , CHF 2 , CF 2 C1, C 2 F 5 and C 3 F 7 .
  • R 8 is preferably a Cl-C4-alkyl group, which can also be substituted, for example by halogen atoms such as fluorine.
  • CH 3 , C 2 H 5 , C 3 H 7 and CF 3 CH 2 are preferred for R 8 .
  • Pervaporation membranes are known to the person skilled in the art. They are also commercially available. For example, composite polymer membranes and silicate membrane systems can be used. These membranes are available from Sulzer Che tech GmbH, Neuenmün, Germany. The person skilled in the art can find information on such membranes in the publication by Nick Wynn in Sulzer technical review 3/2000, pages 10 to 12. Further information can be found in the Internet documents at the Internet addresses htt: // www. sulzerchemtech. com / 1l_pervaporation.htm, http: // www. ecn.nl/news/sulzer2.html and http: // www. ecn.nl/news/sulzerl.html.
  • the process according to the invention allows the simple and energy-saving removal of water from water-containing fluorinated organic compounds.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a method for dehydrating fluorinated compounds, for example esters that have been substituted by fluorine (and optionally chlorine or other substituents). According to said method, the compounds containing water are dehydrated using pervaporation membranes. The method is, for example, suitable for the isolation of reaction water.

Description

Entwässerung fluorierter organischer Verbindungen Drainage of fluorinated organic compounds
BesehreibungBesehreibung
Die Erfindung bezieht sich auf ein Verfahren zur Herstellung von entwässerten fluorierten organischen Verbindungen aus wasserhaltigen fluorierten organischen Verbindungen.The invention relates to a process for the production of dehydrated fluorinated organic compounds from water-containing fluorinated organic compounds.
Fluorierte organische Verbindungen werden bekanntermaßen für viele Zwecke eingesetzt, beispielsweise als Lösungsmittel, als Reaktionskomponente oder als Reinigungsmittel. Die Anwesenheit von den Anwendungszweck negativ beeinflussenden Mengen an Wasser ist dabei unerwünscht. Oftmals enthalten fluorierte organische Verbindungen aber Wasser in solch unerwünschten Mengen, beispielsweise weil Wasser bei ihrer Herstellung oder Reinigung verwendet wurde, weil bei ihrer Herstellung Reaktionswasser entsteht (z. B. bei Kondensations- reaktionen) oder weil die Verbindungen zur Entwässerung verwendet worden sind und sich dabei mit Wasser beladen haben. Ein Beispiel für die Anwesenheit von Reaktionswasser in fluorierten organischen Verbindungen stellt die Herstellung von Aminohalogencrotonaten dar, die in der deutschen Offenle- gungsschrift DE 198 49 918 AI und der EP-A-0 808 826 (entsprechende US-Patente: US-A 5,777,154 und 5,910,602) beschrieben wird. Dabei werden ß-Ketocarbonsäureester mit Ammoniak, Aminen oder Säureaddukten von Ammoniak bzw. Aminen unter Wasserabspaltung umgesetzt. Das Reaktionswasser kann nach beendeter Reaktion in bekannter Weise über Trockenmitteln wie Natriumsulfat abgetrennt werden. Da sich zwei Phasen bilden, kann es auch durch Phasentrennung entfernt werden. Eine andere Möglichkeit der Wasserabtrennung sieht vor, daß man bereits während der Reaktion Inertgas durch die Reak- tionsmischung leitet oder das Wasser unter Zusatz eines Schleppmittels aceotrop abdestilliert.Fluorinated organic compounds are known to be used for many purposes, for example as a solvent, as a reaction component or as a cleaning agent. The presence of quantities of water which negatively influence the intended use is undesirable. However, fluorinated organic compounds often contain water in such undesirable amounts, for example because water was used in their production or purification, because water of reaction is produced during their production (for example in the case of condensation reactions) or because the compounds have been used for dewatering and themselves loaded with water. An example of the presence of water of reaction in fluorinated organic compounds is the preparation of aminohalogen crotonates, which are described in German Offenlegungsschrift DE 198 49 918 A1 and EP-A-0 808 826 (corresponding US patents: US Pat. No. 5,777,154 and 5,910,602). Here, β-ketocarboxylic acid esters are reacted with ammonia, amines or acid adducts of ammonia or amines with elimination of water. After the reaction has ended, the water of reaction can be separated off in a known manner using drying agents such as sodium sulfate. Since two phases form, it can also be removed by phase separation. Another possibility of water separation is that inert gas is already reacted by the reactants during the reaction. tion mixture conducts or the water is distilled off aceotropically with the addition of an entrainer.
Aufgabe der vorliegenden Erfindung ist es, ein vereinfachtes Verfahren zur Herstellung von entwässerten fluorierten organischen Verbindungen durch Abtrennung von Wasser aus wasserhaltigen fluorierten organischen Verbindungen anzugeben. Diese Aufgabe wird durch das erfindungsgemäße Verfahren gelöst.The object of the present invention is to provide a simplified process for the production of dehydrated fluorinated organic compounds by separating water from water-containing fluorinated organic compounds. This object is achieved by the method according to the invention.
Das erfindungsgemäße Verfahren zur Herstellung von entwässerten fluorierten organischen Verbindungen durch Abtrennung des Wassers aus wasserhaltigen fluorierten organischen Verbindungen sieht vor, daß man die wasserhaltigen fluorierten organischen Verbindungen mit Pervaporationsmembranen kontaktiert, dabei Wasser abtrennt und die entwässerten fluorierten organischen Verbindungen gewinnt.The process according to the invention for the production of dehydrated fluorinated organic compounds by separating the water from water-containing fluorinated organic compounds provides that the water-containing fluorinated organic compounds are contacted with pervaporation membranes, water is separated off and the dewatered fluorinated organic compounds are obtained.
Das Verfahren kann batchweise oder kontinuierlich durchgeführt werden. Das Verfahren wird besonders in jenen Fällen kontinuierlich durchgeführt, in welchen sich die Beladung der zu behandelnden Verbindung mit Wasser mit fortlaufender Zeitdauer erhöht. Dies ist beispielsweise bei Kondensationsreaktionen der Fall, in welchen Gleichgewichtsreaktionen vorliegen, z. B. bei der Herstellung von Estern aus Carbonsäuren und Alkoholen. Die kontinuierliche Verfahrensweise ist auch nützlich, wenn bei einer Reaktion ständig Wasser anfällt, welches unerwünschte oder schädliche Einflüsse auf Ausbeute, Reinheit, Reaktionsgeschwindigkeit oder andere Parameter ausübt. Dies ist bei der schon erwähnten Herstellung von A ino- halogencrotonaten der Fall, wo festgestellt wurde, daß Ausbeute und Reinheit erhöht werden können, wenn das Reaktions- wasser schon während der Umsetzung abgetrennt wird. Ein weiterer Fall, bei welchem sich die kontinuierliche Verfahrensweise empfiehlt, ist die Verwendung von fluorierten organischen Verbindungen als Entwässerungsmittel, beispielsweise zur Trocknung von oberflächenbehandelten Metallen. Das zur Trocknung verwendete organische Mittel, das ja ständig mit Wasser beladen wird, kann vorteilhaft kontinuierlich entwässert werden.The process can be carried out batchwise or continuously. The method is carried out continuously, particularly in those cases in which the loading of the compound to be treated with water increases with a continuous period of time. This is the case, for example, with condensation reactions in which there are equilibrium reactions, e.g. B. in the production of esters from carboxylic acids and alcohols. The continuous procedure is also useful if a reaction constantly produces water which has undesirable or harmful effects on the yield, purity, reaction rate or other parameters. This is the case in the production of amino halogen crotonates already mentioned, where it has been found that the yield and purity can be increased if the reaction water is separated off during the reaction. Another case in which the continuous procedure is recommended is the use of fluorinated organic compounds as drainage agents, for example for drying surface-treated metals. That for Organic agents used for drying, which is constantly loaded with water, can advantageously be continuously dewatered.
Man kann Verbindungen entwässern, die einen Wassergehalt im Bereich von 0,1 Gew.-% bis 50 Gew.-% aufweisen. Eventuell kann man auch zuerst eine grobe Abtrennung des Wassers durch Phasenabtrennung durchführen und dann den verbleibenden Wassergehalt durch die Membrantechnologie weiter verringern.It is possible to dewater compounds which have a water content in the range from 0.1% by weight to 50% by weight. You can also first carry out a rough separation of the water by phase separation and then further reduce the remaining water content using the membrane technology.
Man kann den Wassergehalt durch ein- oder mehrfache Behandlung mit der oder den Pervaporationsmembranen auf den gewünschten Maximalgehalt verringern.The water content can be reduced to the desired maximum content by single or multiple treatment with the pervaporation membrane or membranes.
Prinzipiell eignet sich das erfindungsgemäße Verfahren zur Anwendung auf beliebige wasserhaltige fluorierte organische Verbindungen. Bevorzugt entwässert man durch Fluor und gegebenenfalls andere Substituenten wie Chlor substituierte Ester, Carbonsäuren, Carbonsäurederivate, Ketoester, Thio- ester, Amide.In principle, the method according to the invention is suitable for use on any water-containing fluorinated organic compounds. Dehydrated by fluorine and optionally other substituents such as chlorine, esters, carboxylic acids, carboxylic acid derivatives, keto esters, thioesters, amides are preferred.
Ganz besonders bevorzugt wendet man das erfindungsgemäße Verfahren zur Entwässerung im Rahmen der Herstellung fluorierter Ester durch Kondensationsreaktionen und auch Aldol- reaktionen an.The process according to the invention for dewatering is very particularly preferably used in the course of the production of fluorinated esters by condensation reactions and also aldol reactions.
Ganz besonders bevorzugt wendet man das erfindungsgemäße Verfahren auf Ester an, die Carbonsäuren mit 2 bis 15 Kohlenstoffatomen (inklusive des Kohlenstoffato s der Carboxy- gruppe) auf eisen.The process according to the invention is very particularly preferably applied to esters which iron carboxylic acids having 2 to 15 carbon atoms (including the carbon atom of the carboxy group).
Gemäß einer Ausführungsform wendet man das erfindungsgemäße Verfahren zur Wasserabtrennung bei der Herstellung von A inohalogencrotonatverbindungen an, wie sie in der vorgenannten deutschen Offenlegungsschrift und der europäischen Patentanmeldung bzw. den zitierten US-Patenten offenbart sind. Es handelt sich dabei um ein Verfahren zur Herstellung einer 3-Amino-4, 4,4-trihalogencrotonat-Verbindung der Formel (I)According to one embodiment, the method according to the invention for water separation is used in the production of A inohalogencrotonatverbindungen as disclosed in the aforementioned German patent application and the European patent application or the cited US patents. It is a manufacturing process a 3-amino-4, 4,4-trihalogencrotonate compound of the formula (I)
X3C-C(NR1R2) = C(R)-C(A)BX 3 CC (NR 1 R 2 ) = C (R) -C (A) B
wobeiin which
X für Fluor oder Chlor steht; A für 0, S oder NR5 steht; B für R6, OR6, SR6 oder NR3R4 steht;X represents fluorine or chlorine; A represents 0, S or NR 5 ; B represents R 6 , OR 6 , SR 6 or NR 3 R 4 ;
R, R1, R2, R3, R4, R5 und Rδ jeweils unabhängig voneinander für H, (Cl-C6)Alkyl, (C2-C6)Alkenyl, (C2-C6)Alkinyl, Phe- nyl oder Phenyl (C1-C6) alkyl; oder für (C1-C6)Alkyl, (C2-C6)Alkenyl, (C2-C6)Alkinyl, Phenyl oder Phenyl (C1-C6) alkyl, substituiert mit einer oder mehreren Gruppen unabhängig voneinander ausgewählt aus Halogen, CN, N02; (Cl-C6)Alkyl, (C2-C6)Alkenyl, (C2-C6)Alkinyl, Phenyl, Phenyl (C2-C6) alkyl, (Cl-C6)Alkoxy, (C2-C6)Alkenyloxy und Phenoxy stehen; oder R1 und R2, und R3 und R4 jeweils unabhängig voneinander mit dem Stickstoff, an den sie gebunden sind, verbunden sein können, so daß sie einen fünf, sechs- oder siebengliedrigen heterozyklischen Ring bilden; oder, wenn A für NR5 steht und B für OR6 oder SR6 steht, R5 und R6 mit der A=C-B-Gruppe, an die sie gebunden sind, verbunden sein können, so daß sie einen fünf-, sechs- oder siebengliedrigen heterozyklischen Ring bilden; oder, wenn A für NR5 steht und B für NR3R4 steht, R3 oder R4 und R5 mit der A=C-B-Gruppe, an die sie gebunden sind, verbunden sein können, so daß sie einen fünf-, sechs- oder siebengliedrigen heterozyklischen Ring bilden, aus Ammoniak oder den entsprechenden Aminen sowie der entsprechenden ß-Keto- carbonsäureverbindung. CX3 ist bevorzugt CF3, CF2C1 oder CHF . R1 und R2 sind gleich oder verschieden und bedeuten bevorzugt Cl-C3-Alkyl. A ist bevorzugt 0 oder S, insbesondere O. R ist bevorzugt H oder C1-C3-Alkyl. B ist bevorzugt OR6 oder SR6. R3, R4 und R5 sind bevorzugt H oder Cl-C3-Alkyl. R6 ist bevorzugt Cl-C3-Alkyl und kann ge- wünschtenfalls durch 1 oder mehrere Fluoratome substituiert sein.R, R 1 , R 2 , R 3 , R 4 , R 5 and R δ each independently of one another for H, (Cl-C6) alkyl, (C2-C6) alkenyl, (C2-C6) alkynyl, phenyl or Phenyl (C1-C6) alkyl; or for (C1-C6) alkyl, (C2-C6) alkenyl, (C2-C6) alkynyl, phenyl or phenyl (C1-C6) alkyl, substituted with one or more groups independently selected from halogen, CN, NO 2 ; (Cl-C6) alkyl, (C2-C6) alkenyl, (C2-C6) alkynyl, phenyl, phenyl (C2-C6) alkyl, (Cl-C6) alkoxy, (C2-C6) alkenyloxy and phenoxy; or R 1 and R 2 , and R 3 and R 4 can each independently be linked to the nitrogen to which they are attached so that they form a five, six or seven membered heterocyclic ring; or, if A is NR 5 and B is OR 6 or SR 6 , R 5 and R 6 can be linked to the A = CB group to which they are attached so that they form a five-, six- or form a seven-membered heterocyclic ring; or, if A is NR 5 and B is NR 3 R 4 , R 3 or R 4 and R 5 can be linked to the A = CB group to which they are attached so that they form a five-, form a six- or seven-membered heterocyclic ring from ammonia or the corresponding amines and the corresponding β-ketocarboxylic acid compound. CX 3 is preferably CF 3 , CF 2 C1 or CHF. R 1 and R 2 are the same or different and are preferably Cl-C3-alkyl. A is preferably 0 or S, in particular O. R is preferably H or C1-C3-alkyl. B is preferably OR 6 or SR 6 . R 3 , R 4 and R 5 are preferably H or Cl-C3-alkyl. R6 is preferably Cl-C3-alkyl and can if desired, be substituted by 1 or more fluorine atoms.
Eine bevorzugte Ausführungsform sieht die Anwendung auf die Herstellung von Carbonsäureestern der allgemeinen Formel (I) R7-C(0)-OR8 durch Umsetzung von entsprechenden Carbonsäuren mit entsprechenden Alkoholen unter Wasserabspaltung vor. R7 ist vorzugsweise eine Cl-C3-Alkylgruppe, die durch mindestens 1 Fluoratom substituiert ist. Bevorzugte Beispiele für R7 sind CF3, CHF2, CF2C1, C2F5 und C3F7. R8 ist bevorzugt eine Cl-C4-Alkylgruppe, die auch substituiert sein kann, beispielsweise durch Halogenatome wie Fluor. Bevorzugte für R8 sind CH3, C2H5, C3H7 und CF3CH2.A preferred embodiment provides for the application to the preparation of carboxylic acid esters of the general formula (I) R 7 -C (0) -OR 8 by reacting corresponding carboxylic acids with corresponding alcohols with elimination of water. R 7 is preferably a Cl-C3 alkyl group which is substituted by at least 1 fluorine atom. Preferred examples of R 7 are CF 3 , CHF 2 , CF 2 C1, C 2 F 5 and C 3 F 7 . R 8 is preferably a Cl-C4-alkyl group, which can also be substituted, for example by halogen atoms such as fluorine. CH 3 , C 2 H 5 , C 3 H 7 and CF 3 CH 2 are preferred for R 8 .
Pervaporationsmembranen sind dem Fachmann bekannt. Sie sind auch im Handel erhältlich. Brauchbar sind beispielsweise Kompositpolymermembranen und Silikatmembransysteme. Diese Membranen sind von der Firma Sulzer Che tech GmbH, Neuenkirchen, Deutschland, erhältlich. Informationen über solche Membranen findet der Fachmann in der Publikation von Nick Wynn in Sulzer technical review 3/2000, Seiten 10 bis 12. Weitere Informationen finden sich in den Internet-Dokumenten unter den Internet-Adressen htt : //www. sulzerchemtech. com/1l_pervaporation.htm, http: //www. ecn.nl/news/sulzer2.html und http: //www. ecn.nl/news/sulzerl.html.Pervaporation membranes are known to the person skilled in the art. They are also commercially available. For example, composite polymer membranes and silicate membrane systems can be used. These membranes are available from Sulzer Che tech GmbH, Neuenkirchen, Germany. The person skilled in the art can find information on such membranes in the publication by Nick Wynn in Sulzer technical review 3/2000, pages 10 to 12. Further information can be found in the Internet documents at the Internet addresses htt: // www. sulzerchemtech. com / 1l_pervaporation.htm, http: // www. ecn.nl/news/sulzer2.html and http: // www. ecn.nl/news/sulzerl.html.
Ob eine von ihm ausgewählte Membran für ein bestimmtes Trennverfahren brauchbar ist, insbesondere bezüglich der Stabilität gegenüber der fluorierten organischen Verbindung, kann der Fachmann anhand ganz einfacher Maßnahmen erkennen. Er kontaktiert das Material mit der organischen Verbindung, beispielsweise über einen Zeitraum von einigen Tagen. Danach kann er bereits erkennen, ob das ausgewählte Material die geeignete Stabilität besitzt. Ob die Membran sich zur Abtrennung von Wasser aus der ausgewählten wasserhaltigen organi- sehen Verbindung eignet, testet er einfach, indem er die Membran anwendet.The person skilled in the art can see from very simple measures whether a membrane selected by him can be used for a specific separation process, in particular with regard to the stability to the fluorinated organic compound. He contacts the material with the organic compound, for example over a period of a few days. Then he can already see whether the selected material has the appropriate stability. Whether the membrane is suitable for separating water from the selected water-containing organic see connection, he simply tests by using the membrane.
Das Verfahren der Pervaporation ist seit wenigstens 25 Jahren bekannt, siehe das Stichwort "Pervaporation" in Römpp's Chemie-Lexikon, 8. Auflage (1985), Seite 3070. Auch das Problem der Wasserabtrennung aus fluorierten organischen Verbindungen ist lange bekannt, siehe z. B. die obenerwähnte deutsche bzw. europäische Patentanmeldung. Gleichwohl ist erstmals mit der vorliegenden Erfindung eine Verknüpfung des Problems mit der erfindungsgemäßen Lösung vorgenommen worden.The method of pervaporation has been known for at least 25 years, see the keyword "pervaporation" in Römpp's Chemie-Lexikon, 8th edition (1985), page 3070. The problem of water separation from fluorinated organic compounds has also been known for a long time. B. the above-mentioned German or European patent application. Nevertheless, the present invention has for the first time linked the problem with the solution according to the invention.
Das erfindungsgemäße Verfahren gestattet die einfache und energiesparende Abtrennung von Wasser aus wasserhaltigen fluorierten organischen Verbindungen. The process according to the invention allows the simple and energy-saving removal of water from water-containing fluorinated organic compounds.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von entwässerten fluorierten organischen Verbindungen durch Entwässerung von wasserhaltigen fluorierten organischen Verbindungen, wobei man die wasserhaltigen fluorierten organischen Verbindungen mit einer oder mehreren Pervaporationsmembranen kontaktiert, dabei Wasser abtrennt und die entwässerten fluorierten organischen Verbindungen gewinnt.1. Process for the production of dehydrated fluorinated organic compounds by dehydrating water-containing fluorinated organic compounds, wherein the water-containing fluorinated organic compounds are contacted with one or more pervaporation membranes, water is separated off and the dewatered fluorinated organic compounds are obtained.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man fluorierte Ester, fluorierte Carbonsäuren, fluorierte Carbonsäurederivate, fluorierte Ketone und Thioketone, fluorierte Ketoester, fluorierte Amide und generell in Kondensationsreaktionen entwässert.2. The method according to claim 1, characterized in that dehydrated fluorinated esters, fluorinated carboxylic acids, fluorinated carboxylic acid derivatives, fluorinated ketones and thioketones, fluorinated keto esters, fluorinated amides and generally in condensation reactions.
3. Verfahren nach Anspruch 1 oder 2 , dadurch gekennzeichnet, daß man die Wasserabtrennung bei einer Temperatur im Bereich oberhalb des Festpunktes der zur entwässernden Verbindung bis zur thermischen Stabilitätsgrenze der Membran bevorzugt aber im Bereich des Siedepunktes von Wasser (in Abhängigkeit des herrschenden Druckes) durchführt.3. The method according to claim 1 or 2, characterized in that one carries out the water separation at a temperature in the range above the fixed point of the compound to be dewatered up to the thermal stability limit of the membrane but preferably in the range of the boiling point of water (depending on the prevailing pressure) ,
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das abzutrennende Wasser Reaktionswasser ist, vorzugsweise Reaktionswasser, das bei Umsetzungen fluorierter organischer Verbindungen entstanden ist.4. The method according to claim 1, characterized in that the water to be separated is water of reaction, preferably water of reaction which has arisen during reactions of fluorinated organic compounds.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Wasser bei der Veresterung von fluorierten Carbonsäuren mit Alkoholen oder bei der Herstellung von Aminohälogen- crotonaten durch Umsetzung eines Amins oder eines Säureadduk- tes des Amins mit ß-Ketocarbonsäureestern freigesetzt wird. 5. The method according to claim 1, characterized in that the water is released in the esterification of fluorinated carboxylic acids with alcohols or in the production of aminohalogen crotonates by reacting an amine or an acid adduct of the amine with β-ketocarboxylic acid esters.
PCT/EP2002/010331 2001-09-21 2002-09-14 Dehydration of fluorinated organic compounds WO2003027048A2 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5108549A (en) * 1989-02-25 1992-04-28 Gkss-Forschungszentrum Geesthacht Gmbh Method of separating and recovering components of mixtures via pervaporization
EP0516029A1 (en) * 1991-05-28 1992-12-02 Daikin Industries, Limited A method of desiccating articles
DE19849918A1 (en) * 1997-11-07 1999-05-20 Solvay Fluor & Derivate Production of lower alkyl 3-amino-4-halo-crotonate derivatives useful as intermediates e.g. for uracil herbicides
EP0992476A2 (en) * 1999-04-07 2000-04-12 Daikin Industries, Limited Method for recovering fluoroalcohol

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5108549A (en) * 1989-02-25 1992-04-28 Gkss-Forschungszentrum Geesthacht Gmbh Method of separating and recovering components of mixtures via pervaporization
EP0516029A1 (en) * 1991-05-28 1992-12-02 Daikin Industries, Limited A method of desiccating articles
DE19849918A1 (en) * 1997-11-07 1999-05-20 Solvay Fluor & Derivate Production of lower alkyl 3-amino-4-halo-crotonate derivatives useful as intermediates e.g. for uracil herbicides
EP0992476A2 (en) * 1999-04-07 2000-04-12 Daikin Industries, Limited Method for recovering fluoroalcohol

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