EP0308838B1 - Procédé de production d'acides fluorés et leurs dérivés - Google Patents

Procédé de production d'acides fluorés et leurs dérivés Download PDF

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Publication number
EP0308838B1
EP0308838B1 EP88115288A EP88115288A EP0308838B1 EP 0308838 B1 EP0308838 B1 EP 0308838B1 EP 88115288 A EP88115288 A EP 88115288A EP 88115288 A EP88115288 A EP 88115288A EP 0308838 B1 EP0308838 B1 EP 0308838B1
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Prior art keywords
electrolysis
acid
carried out
cell
fluorine
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EP0308838A1 (fr
Inventor
Steffen Dr. Dapperheld
Rudolf Dr. Heumüller
Manfred Wildt
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/27—Halogenation
    • C25B3/28—Fluorination

Definitions

  • the invention relates to an electrochemical process for the production of fluorinated acrylic acids and their derivatives by selective dehalogenation of halogen-containing fluoropropionic acids and their derivatives.
  • Acrylic acid and methacrylic acid derivatives have a very wide range of applications as organic intermediates. They allow access to a large number of useful compounds, but they are particularly suitable for the production of plastics.
  • Halogenated and deuterated acrylic and methacrylic acid derivatives have been of particular interest for some time, since such substances are suitable for the production of special plastics with special properties.
  • ⁇ -Haloacrylic acid ester used for the production of radiation-sensitive protective layers in resist technology.
  • ⁇ -fluoroacrylic acid esters are suitable, for example, for the production of plastic glasses for aviation technology and are also suitable starting materials for polymer optical fibers, with deuterated derivatives being of particular interest owing to their better optical properties.
  • halogenated fluorine-containing acrylic acid derivatives can be prepared by dehalogenation of correspondingly halogenated fluoropropionic acid derivatives.
  • the most common methods of eliminating two vicinal halogen atoms in halogen propionic acids to form a double bond use metals as dehalogenating agents, with zinc, which is used in various forms and activities, being of the greatest importance. Frequently, however, the reactions with zinc are so slow that one is forced to work in higher boiling solvents such as dimethylformamide or in diphenyl ether in the presence of thiourea.
  • An additional disadvantage, especially for technical implementation, is that the use of metals as a dehalogenating reagent inevitably involves the accumulation of metal salts.
  • Electrochemical dehalogenation is one way of avoiding the formation of metal salts during dehalogenation.
  • the previous efforts to simultaneously electrochemically split off two vicinal halogen atoms from halogenated propionic acids have mainly been of an analytical nature and have been carried out, for example, using polarographic or cyclic voltammetric methods on mercury electrodes or glassy carbon electrodes (J. Am. Chem. Soc. 80 , 5402 (1959); J. Chem. Research (M) 1983, 2401).
  • M J. Chem. Research
  • the object was therefore to provide a technically feasible and economical process according to which halogen atoms can be split off from fluorine-containing halogen propionic acids or their derivatives by electrochemical means to form fluorine-containing acrylic acids without losses due to polymerization or saturation of the acrylic acid double bond and without so that a forced attack of metal halides is associated.
  • this object can be achieved by electrochemical dehalogenation under galvanostatic conditions in water, optionally in the presence of an auxiliary solvent and / or a salt a metal with a hydrogen overvoltage of more than 0.25V is carried out.
  • Perhalogenated propionic acids such as 2,3-dichloro-2,3,3-trifluoropropionic acid, 2,3-dibromo-2,3,3-trifluoropropionic acid, 2-bromo-3-chloro-2,3,3-trifluoropropionic acid, 3-bromo -2-chloro-2,3,3-trifluoropropionic acid, 2,3,3-trichloro-2,3-difluoropropionic acid, 2,2,3-trichloro-3,3-difluoropropionic acid and 2,3,3,3-tetrachloro -2-fluoropropionic acid, preferably 2,3-dibromo-2,3,3-trifluoropropionic acid, 2,3,3-trichloro-2,3-difluoropropionic acid and 2,3,3,3-tetrachloro-2-fluoropropionic acid, preferably 2,3-dibromo-2,3,3-trifluoropropi
  • the method according to the invention is carried out in divided or undivided cells.
  • the common diaphragms made of polymers, preferably perfluorinated polymers, or other organic or inorganic materials, such as glass or ceramics, but preferably ion exchange membranes, are used to divide the cells into anode and cathode spaces.
  • Preferred ion exchange membranes are cation exchange membranes from polymers, preferably perfluorinated polymers with carboxyl and / or sulfonic acid groups. The use of stable anion exchange membranes is also possible.
  • the electrolysis can be carried out in all customary electrolysis cells, for example in beaker or plate and frame cells or cells with fixed bed or fluidized bed electrodes. Both the monopolar and the bipolar switching of the electrodes can be used.
  • a method of operation in divided electrolysis cells with discontinuous execution of the cathode reaction and continuous operation of the anode reaction is particularly expedient.
  • the electrolysis can be carried out on all cathodes stable in the electrolyte.
  • Materials with a medium to high hydrogen overvoltage such as Pb, Cd, Zn, carbon, Cu, Sn, Zr and mercury compounds such as copper amalgam, lead malgam etc. are particularly suitable, but also alloys such as e.g. Lead-tin or zinc-cadmium.
  • the use of carbon cathodes is preferred, especially for electrolysis in acidic electrolytes, since some of the electrode materials listed above, e.g. Zn, Sn, Cd and Pb, can suffer corrosion.
  • all possible carbon electrode materials come into question as carbon cathodes, e.g. Electrode graphites, impregnated graphite materials, carbon felts and also glassy carbon.
  • All materials on which the known anode reactions take place can be used as the anode material.
  • Examples are lead, lead oxide on lead or other carriers, platinum or with noble metal oxides, eg platinum oxide, doped titanium dioxide on titanium or other materials for the development of oxygen from dilute sulfuric acid or carbon or titanium dioxide doped with noble metal oxides on titanium or other materials for the development of chlorine from aqueous alkali metal chloride or aqueous or alcoholic hydrogen chloride Solutions.
  • Preferred anolyte liquids are aqueous mineral acids or solutions of their salts, such as, for example, dilute sulfuric acid, concentrated hydrochloric acid, sodium sulfate or sodium chloride solutions and solutions of hydrogen chloride in alcohol.
  • the electrolyte in the undivided cell or the catholyte in the divided cell contains 0 to 100% water and 100 to 0% of one or more organic solvents.
  • suitable solvents are: Short-chain, aliphatic alcohols such as methanol, ethanol, propanol or butanol, diols such as ethylene glycol, propanediol but also polyethylene glycols and their ethers, ethers such as tetrahydrofuran, dioxane, amides such as N, N-dimethylformamide, hexamethylphosphoric triamide, N-methyl-2-pyrrolidone, Nitriles such as acetonitrile, propionitrile, ketones such as acetone, and other solvents such as dimethyl sulfoxide and sulfolane.
  • suitable solvents are: Short-chain, aliphatic alcohols such as methanol, ethanol, propanol or butanol, diols such as ethylene glycol, propanediol but also polyethylene glycols and their ethers, ethers such as tetrahydrofuran, dioxane, amides such
  • the electrolyte can also consist of water and a water-insoluble organic solvent such as t-butyl methyl ether or methylene chloride in conjunction with a phase transfer catalyst.
  • a water-insoluble organic solvent such as t-butyl methyl ether or methylene chloride in conjunction with a phase transfer catalyst.
  • inorganic or organic acids can be added to the catholyte in the divided cell or to the electrolyte in the undivided cell, preferably Acids such as hydrochloric, boric, phosphoric, sulfuric or tetrafluoroboric acid and / or formic, acetic or citric acid and / or their salts.
  • organic bases may also be necessary to set the pH value which is favorable for the electrolysis and / or have a favorable influence on the course of the electrolysis.
  • Suitable are primary, secondary or tertiary C2-C12 alkyl or cycloalkylamines, aromatic or aliphatic-aromatic amines or their salts, inorganic bases such as alkali or alkaline earth metal hydroxides such as Li, Na, K, Cs, Mg, Ca, Ba hydroxide, quaternary ammonium salts, with anions such as fluorides, chlorides, bromides, iodides, acetates, sulfates, hydrogen sulfates, tetrafluoroborates, phosphates or hydroxides, and with cations such as C1-C12-tetraalkylammonium, C1-C12 -Trialkylarylammonium or C1-C12-trialkylalkylarylammonium, but also anionic or
  • compounds can be added to the electrolyte which are oxidized at a more negative potential than the released halogen ions in order to avoid the formation of the free halogen.
  • the salts of oxalic acid, methoxyacetic acid, glyoxylic acid, formic acid and / or hydrochloric acid are suitable.
  • the electrolyte in the undivided cell or the catholyte in the divided cell can be salts of Metals with a hydrogen overvoltage of at least 0.25 V (based on a current density of 300 mA / cm2) and / or dehalogenating properties can be added.
  • the most suitable salts are the soluble salts of Cu, Ag, Au, Zn, Cd, Hg, Sn, Pb, Tl, Ti, Zr, Bi, V, Ta, Cr or Ni, preferably the soluble Pb, Zn, Cd, Ag and Cr salts.
  • the preferred anions of these salts are Cl ⁇ , SO4 ⁇ , NO3 ⁇ , and CH3COO ⁇ .
  • the salts can be added directly to the electrolysis solution or, e.g. by adding oxides, carbonates etc. - in some cases also the metals themselves (if soluble) - in the solution.
  • Electrolysis is carried out at a current density of 1 to 600 mA / cm2, preferably at 10 to 500 mA / cm2, without potential control.
  • the electrolysis temperature is in the range from -10 ° C to the boiling point of the electrolyte liquid, preferably from 10 ° to 90 ° C, in particular from 15 ° to 80 ° C.
  • the electrolysis product is worked up in a known manner, e.g. by extracting or distilling off the solvent.
  • the compounds added to the catholyte can thus be returned to the process.
  • Electrolysis cell 1
  • Anolyte dilute aqueous sulfuric acid or methanolic hydrochloric acid
  • Cation exchange membrane single-layer membrane made from a copolymer of a perfluorosulfonylethoxy vinyl ether and tetrafluoroethylene Mass transfer: by magnetic stirrer
  • Electrolytic cell 2
  • Jacketed glass pot circulation cell with a volume of 450 cm3 Anode: platinum mesh, graphite or lead plate (20 cm2) Cathode area: 12 cm2 Electrode distance: 1 cm Anolyte: dilute aqueous sulfuric acid or methanolic hydrochloric acid Cation exchange membrane as in electrolysis cell 1 Current density: 83 mA / cm2 Terminal voltage: 5 V
  • Electrolysis cell 1
  • Electrolysis cell 1
  • CCl3-CFCl-COOH 0.428 g
  • CCl2 CF-COOH 0.206 g
  • CHCl CF-COOH 0.204 g

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Automation & Control Theory (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (9)

  1. Procédé pour préparer des composés fluorés répondant à la formule I
    Figure imgb0010
     dans laquelle
    R¹   représente un atome de fluor, un radical méthyle ou un radical deutérométhyle,
    R² et R³   représentent chacun, indépendamment l'un de l'autre, un atome de fluor, de chlore, de brome, d'iode, d'hydrogène ou de deutérium, et
    R⁴   représente un radical cyano ou un radical
    Figure imgb0011
     dont le symbole R⁵ représente -OH, -OD, -OMe (Me désignant un ion de métal alcalin, de métal alcalino-terreux ou NH₄⁺), un alcoxy en C₁-C₁₂, ou un radical -NR⁶R⁷ dans lequel R⁶ et R⁷ représentent chacun, indépendamment l'un de l'autre, H, D, un alkyle en C₁-C₁₂ ou un phényle,
    par réduction électrolytique, procédé caractérisé en ce qu'on soumet à une électrolyse des composés fluorés répondant à la formule II :
    Figure imgb0012
     dans laquelle R¹, R², R³ et R⁴ ont les significations qui leur ont été données ci-dessus et R⁸ et R⁹ représentent chacun, indépendamment l'un de l'autre, un atome de chlore, de brome ou d'iode,
    dans une cellule non compartimentée ou dans une cellule compartimentée, dans un liquide d'électrolyse constitué - à chaque fois par rapport à la quantité totale de l'électrolyte dans la cellule non compartimentée ou du catholyte dans la cellule compartimentée -
    de 0 à 100 % en poids d'eau
    de 100 à 0 % en poids d'un ou de plusieurs solvants organiques
    de 0 à 10 % en poids d'un sel d'un métal ayant une surtension d'hydrogène d'au moins 0,25 V (pour une densité de courant de 300 mA/cm²) et/ou des propriétés déshalogénantes,
    à une température comprise entre -10 °C et la température d'ébullition du liquide d'électrolyse et galvanostatiquement, avec une densité de courant de 1 à 600 mA/cm², la cathode étant constituée de plomb, de cadmium, de zinc, de cuivre, d'étain, de zirconium ou de carbone.
  2. Procédé selon la revendication 1 caractérisé en ce qu'on effectue l'hydrolyse à un pH compris entre 0 et 11 dans l'électrolyte de la cellule non compartimentée ou dans le catholyte de la cellule compartimentée.
  3. Procédé selon la revendication 1 caractérisé en ce qu'on soumet à une électrolyse :
    l'acide dibromo-2,3 trifluoro-2,3,3 propionique,
    l'acide trichloro-2,3,3 difluoro-2,3 propionique,
    l'acide tétrachloro-2,3,3,3 fluoro-2 propionique,
    l'acide dibromo-2,3 difluoro-2,3 propionique ou
    l'acide dibromo-2,3 fluoro-2 propionique,
    ou leurs dérivés.
  4. Procédé selon la revendication 1 caractérisé en ce qu'on effectue l'hydrolyse à une température de 10 à 90 °C.
  5. Procédé selon la revendication 1 caractérisé en ce qu'on effectue l'hydrolyse avec une densité de courant de 10 à 500 mA/cm².
  6. Procédé selon la revendication 1 caractérisé en ce qu'on effectue l'hydrolyse dans une cellule compartimentée avec réaction discontinue à la cathode et réaction continue à l'anode.
  7. Procédé selon la revendication 1 caractérisé en ce qu'on effectue l'hydrolyse dans une cellule non compartimentée.
  8. Procédé selon la revendication 1 caractérisé en ce qu'on effectue l'hydrolyse en utilisant une cathode en carbone.
  9. Procédé selon la revendication 1 caractérisé en ce qu'un sel soluble de cuivre, d'argent, d'or, de zinc, de cadmium, de mercure, d'étain, de plomb, de thallium, de titane, de zirconium, de bismuth, de vanadium, de tantale, de chrome, de cérium, de cobalt ou de nickel est présent en une concentration d'environ 10⁻⁵ à 10 % en poids par rapport à la quantité totale de l'électrolyte ou du catholyte.
EP88115288A 1987-09-23 1988-09-17 Procédé de production d'acides fluorés et leurs dérivés Expired - Lifetime EP0308838B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88115288T ATE72269T1 (de) 1987-09-23 1988-09-17 Verfahren zur herstellung von fluorierten acrylsaeuren und ihren derivaten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873731914 DE3731914A1 (de) 1987-09-23 1987-09-23 Verfahren zur herstellung von fluorierten acrylsaeuren und ihren derivaten
DE3731914 1987-09-23

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EP0308838A1 EP0308838A1 (fr) 1989-03-29
EP0308838B1 true EP0308838B1 (fr) 1992-01-29

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US (1) US5114546A (fr)
EP (1) EP0308838B1 (fr)
JP (1) JPH01108389A (fr)
KR (1) KR890005302A (fr)
CN (1) CN1021977C (fr)
AT (1) ATE72269T1 (fr)
AU (1) AU623865B2 (fr)
DE (2) DE3731914A1 (fr)
ES (1) ES2030129T3 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4029068A1 (de) * 1990-09-13 1992-03-19 Hoechst Ag Verfahren zur herstellung von halogenierten acrylsaeuren
US5729645A (en) * 1996-08-13 1998-03-17 The Trustees Of The University Of Pennsylvania Graded index optical fibers
DE102004023041B4 (de) * 2004-05-06 2012-02-16 Eastman Kodak Co. Verfahren zur Ausrichtung von Farbauszügen eines Druckbildes auf einem Bedruckstoff
CN101717949B (zh) * 2009-11-17 2011-06-29 华东师范大学 一种对乙烯基苯乙酸的制备方法
CN103819332A (zh) * 2014-02-20 2014-05-28 常州市正锋光电新材料有限公司 三氯丙烯酸的制备方法
CN104557512B (zh) * 2015-01-06 2016-05-11 山西大学 一种3-(溴代苯基)-2,2’-二氟丙酸的制备方法
RU2686408C1 (ru) * 2018-06-20 2019-04-25 Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук Способ электролитического получения алюминия
CN110438523B (zh) * 2019-09-05 2021-12-03 南京大学 一种以重水为氘源的无催化剂电化学氘代方法
WO2024030044A1 (fr) * 2022-08-02 2024-02-08 Владислав Владимирович ФУРСЕНКО Procédé de production d'aluminium par électrolyse d'une solution d'alumine dans de la cryolite

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1498456A (en) * 1975-12-17 1978-01-18 Ici Ltd Electrochemical process for the preparation of dihaloalkenes
JPS53132504A (en) * 1977-04-26 1978-11-18 Central Glass Co Ltd Dehalogenation of halogenated hydrocarbons
DE3607446A1 (de) * 1986-03-07 1987-09-10 Hoechst Ag Verfahren zur enthalogenierung von chlor- und von bromessigsaeuren
DE3718726A1 (de) * 1987-06-04 1988-12-22 Hoechst Ag Verfahren zur herstellung fluorierter vinylether

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CN1032199A (zh) 1989-04-05
US5114546A (en) 1992-05-19
ES2030129T3 (es) 1992-10-16
DE3868204D1 (de) 1992-03-12
JPH01108389A (ja) 1989-04-25
ATE72269T1 (de) 1992-02-15
AU2272688A (en) 1989-03-23
AU623865B2 (en) 1992-05-28
EP0308838A1 (fr) 1989-03-29
DE3731914A1 (de) 1989-04-06
CN1021977C (zh) 1993-09-01
KR890005302A (ko) 1989-05-13

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