EP3649277A1 - Procédé électrochimique de production de carbonates d'arylalkyle ou de carbonates de diaryle - Google Patents

Procédé électrochimique de production de carbonates d'arylalkyle ou de carbonates de diaryle

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Publication number
EP3649277A1
EP3649277A1 EP18735288.5A EP18735288A EP3649277A1 EP 3649277 A1 EP3649277 A1 EP 3649277A1 EP 18735288 A EP18735288 A EP 18735288A EP 3649277 A1 EP3649277 A1 EP 3649277A1
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EP
European Patent Office
Prior art keywords
electrocatalyst
range
gas diffusion
gold
radical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP18735288.5A
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German (de)
English (en)
Inventor
Vinh Trieu
Stefanie Eiden
Dana KAUBITZSCH
Jimena RUESTA ALVAREZ
Marc KOPER
Marta FIGUEIREDO
Jan HEIJL
Niklas Meine
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Intellectual Property GmbH and Co KG
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Covestro Deutschland AG
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Filing date
Publication date
Application filed by Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP3649277A1 publication Critical patent/EP3649277A1/fr
Withdrawn legal-status Critical Current

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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
    • C25B3/23—Oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/01—Preparation of esters of carbonic or haloformic acids from carbon monoxide and oxygen
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C25B11/032—Gas diffusion electrodes
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/065—Carbon
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • 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
    • C25B3/29—Coupling reactions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Definitions

  • the invention relates to an electrochemical process for the preparation of arylalkyl carbonates or diaryl carbonates.
  • Arylalkyl carbonates and diaryl carbonates form important precursors in the preparation of
  • diaryl carbonates used in the melt transesterification process for aromatic polycarbonates, e.g. through the interfacial process is described in principle in the literature, see e.g. in Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964), p. 50/51.
  • the diaryl carbonate is prepared by reacting phenol with a carbonyl dihalide (e.g., phosgene) prepared from carbon monoxide.
  • a carbonyl dihalide e.g., phosgene
  • diaryl carbonates can also be carried out via an oxidative carbonylation.
  • Phenol is reacted directly with carbon monoxide as the carbonylating reagent, e.g. described in Journal of Molecular Catalysis A: Chemical, 1999, 139, 109-119.
  • the choice of catalyst appears to be limited to palladium-based materials only. No example of the reaction of the oxidative carbonylation of phenol which could be successfully carried out without a palladium-based catalyst has been found in the prior art.
  • the preparation of arylalkyl carbonates can also be carried out via an oxidative carbonylation using a palladium-based catalyst described in Green. Chem., 2013, 15, 1146-1149.
  • a palladium-based catalyst described in Green. Chem., 2013, 15, 1146-1149.
  • formic acid methyl ester by means of a Alkalimethanolats activated and disproportionated in an equilibrium reaction to carbon monoxide and methanol.
  • the subsequent carbonylation with phenol takes place on a homogeneous catalyst-cocatalyst system consisting of a Pd (II) salt (eg PdBr 2 , Pd (OAc) 2 ) and Mn (acac) 3 at elevated pressure.
  • Pd (II) salt eg PdBr 2 , Pd (OAc) 2
  • Mn (acac) 3 at elevated pressure.
  • carbon dioxide is an inert molecule. So it takes an energy input to convert carbon dioxide into a higher quality chemical. In order to produce a product with a low carbon dioxide footprint, the generation of the supplied energy should in turn be associated with as little carbon dioxide emissions as possible. For example, electric power obtained from renewable energy sources is suitable for this purpose.
  • the process described above has several disadvantages. Thus, numerous synthesis steps are required, which make the process consuming.
  • ethylene oxide is used, the use of which requires special safety measures with increased expenditure. Due to the low equilibrium constant of the transesterification reaction to dimethyl carbonate is a large
  • WO 2011/024327 A1 also describes the preparation of diaryl carbonates via homogeneous catalysis with palladium. This application focuses on making the reaction as efficient as possible and describes exclusively the use of a gold electrode as a discharge or reoxidation, which converts the catalytically inactive Pd ° back into the catalytically active homogeneously dissolved Pd 2+ .
  • the actual catalyst is here, as already described above, the homogeneous Pd 2+ .
  • JP H673582 describes heterogeneous electrocatalysis on a palladium electrode, but only dialkyl carbonates are prepared.
  • Comparative Example 6 shows, using such an electrode, the formation of a diaryl carbonate and also an arylalkyl carbonate could not be detected.
  • US 2003/070910 Al only describes the preparation of dialkyl carbonates.
  • WO2014 / 046796 A2 describes, inter alia, the preparation of (phosgene) COCl 2 as a starting material for carbonyls with electrochemical conversion of CO 2 to CO and of a hydrogen halide or halogen salt into a halogen. This is not an in-situ production of CO from CO 2 in the preparation of diaryl or arylalkyl, since initially phosgene is formed, which is then converted to the carbonates.
  • the present invention has for its object to provide an electrochemical process for the preparation of arylalkyl or diaryl carbonates, in which electricity can be used as an energy source, with fewer reaction steps than in the prior art and a heterogeneous catalyst can be used as an electrocatalyst, the is not palladium-based, and its catalytic activity is not limited to the particle size range ⁇ 2 nm.
  • the object is achieved by a process for the electrochemical preparation of arylalkyl or diaryl carbonates, which is characterized in that a compound of formula where the radical R 1 is an alkyl radical, preferably a radical from the series: C 1 - to C 6 -alkyl, preferably methyl, or ethyl, isopropyl or tert-butyl, or cycloalkyl, preferably cyclohexyl, with a compound of the formula ( 2) R 2 -OH where the radical R 2 is an aryl radical, preferably tert-butylphenyl, cumylphenyl, naphthyl or phenyl, particularly preferably a phenyl radical, is reacted anodically with CO at an electrode with gold as the electrocatalyst.
  • the electrocatalyst is heterogeneous and preferably free of palladium.
  • the electrochemical preparation of arylalkyl or diaryl carbonates in particular of methyl phenyl carbonate (MPC) or diphenyl carbonate (DPC), allows.
  • MPC methyl phenyl carbonate
  • DPC diphenyl carbonate
  • the used heterogeneous electrocatalyst based on gold in turn allows in a wide range of particle sizes easy reuse, since complex separation processes of catalytically active metal complexes can be omitted.
  • By eliminating the size limitation of the electrocatalyst on the Range ⁇ 2 nm results in greater freedom in the design of the electrodes. Also can be increased by a larger particle size of the electrocatalyst its long-term stability.
  • the process according to the invention uses compounds of the formula (1) and (2).
  • Preferred starting compounds of the formula (1) are those selected from the series:
  • Particularly preferred starting compounds of the formula (2) are those from the series:
  • reaction equation of the process according to the invention for the electrochemical preparation of aryl carbonates is shown by the example of the reaction of ⁇ and shown schematically:
  • the formation of arylalkyl carbonates or diaryl carbonates results from a series of coupled reaction steps.
  • the dimethyl carbonate forms anodically from the methanol used:
  • the dimethyl carbonate formed can be transesterified with phenol to methylphenyl carbonate:
  • methylphenyl carbonate can be transesterified in a further step to diphenyl carbonate:
  • reaction sequence comprising
  • dimethyl carbonate was initially charged in the electrolyte and the reaction was observed upon addition of phenol with electrochemical activation.
  • This potentiostatically conducted experiment was performed in a 3 electrode assembly at room temperature.
  • a platinum wire was used as the counter electrode, and a commercially available Ag / AgCl electrode was used as a reference.
  • the working electrode a sheet of gold plate, was previously polished with an aluminum suspension, with MiliQ water (18.4 ohms) and treated for 5 min in an ultrasonic bath.
  • the electrode potential was controlled with a potentiostat ER466 from E-DAQ.
  • the electrolytic solution was purged with Ar oxygen-free for 10 min before the experiment, then the electrolytic solution was saturated with CO and maintained during the experiment by further CO supply.
  • Carbon cycle is called. Carbon dioxide is available as a waste product in many chemical processes and can thus be used as a sustainable raw material. It is also advantageous that carbon dioxide as a non-combustible gas is easy to handle.
  • the method according to the advantageous embodiment described above is thus characterized by particular sustainability. This is preferably an in-situ generation of the carbon dioxide.
  • the CO thus obtained is preferably reacted directly in the process according to the invention for the electrochemical preparation of arylalkyl carbonates or diaryl carbonates in the anodic reaction on the electrocatalyst gold.
  • the reaction for the cathodic formation of carbon monoxide can basically be carried out in an analogous manner as described by way of example in Bull, Chem. Soc. Jpn, 1987, 60, 2517-2522. be described described.
  • a solution of TEAP tetraethylammonium perchlorate (0.1 mol / L) in acetonitrile is saturated with CO 2 .
  • the system is sealed gas-tight and the saturated electrolyte is circulated at a rate of 1 mL / min.
  • the CO 2 is cathodically reacted at a copper, indium, silver, palladium or gold electrode at an electrode potential of -2.6 V (versus one Ag / AgCl / (0.01 mol / L LiCl + 0.1 mol / L TEAP / CH 3 CN) - electrode as reference).
  • a charge of 100 C. flows.
  • the anodic electrochemical reaction at a current density in the range of 0.1 to 5000 mA / cm 2 , preferably 0.1 to 500 mA / cm 2 , more preferably 0.1 to 100 mA / cm 2 and most preferably 0.2 to 50 mA / cm 2 .
  • methanol is used as the alcohol of formula (1) or a mixture of the alcohol of formula (1) with other solvents, in particular a solvent selected from acetonitrile, propylene carbonate, dimethylformamide, dimethylsulfoxide, 1, 2-dimethoxyethane , Dichloromethane or N-methyl-2-pyrrolidone.
  • solvents selected from acetonitrile, propylene carbonate, dimethylformamide, dimethylsulfoxide, 1, 2-dimethoxyethane , Dichloromethane or N-methyl-2-pyrrolidone.
  • the upstream cathodic reaction takes place in particular in acetonitrile as solvent, but can also be carried out in other aprotic solvents such as propylene carbonate, dimethylformamide, dimethyl sulfoxide, 1, 2-dimethoxyethane or N-methyl-2-pyrrolidone, or else in water.
  • lithium chloride lithium bromide, lithium perchlorate, sodium perchlorate, lithium bis (trifluoromethylsulfonyl) imide, sodium phenolate, lithium phenolate, according to a further embodiment of the method according to the invention
  • Tetrabutylammonium chloride preferably lithium perchlorate, or imidazolium, ammonium, phosphonium or pyridinium-based ionic liquids, preferably 1-ethyl-3-methylimidazolium tetrafluoroborate, are used.
  • the ionic liquids comprise cations as imidazolium, ammonium, phosphonium or pyridinium.
  • the anodic electrochemical reaction at a temperature in the range of 10 to 250 ° C, in particular in the range of 20 to 100 ° C and particularly preferably in the range of room temperature are performed.
  • the reaction can be carried out at atmospheric pressure or elevated pressure, in particular at up to 1 bar overpressure.
  • elevated pressure can be achieved at the electrode higher local concentrations and thus better productivity.
  • gas diffusion electrodes it is possible with preference to use gas diffusion electrodes.
  • the reaction for cathodic formation of carbon monoxide may be performed on a gas diffusion electrode.
  • anodic reaction for the formation of arylalkyl carbonates or diaryl carbonates the use of a gas diffusion electrode is advantageous.
  • a gas diffusion electrode is used for the anodic reaction, wherein the gas diffusion electrode comprises at least one planar, electrically conductive carrier and a gas diffusion layer and applied electrocatalyst deposited on the carrier,
  • gas diffusion layer comprises a mixture of an electrocatalyst and a hydrophobic polymer
  • the electrocatalyst in the form of gold powder and / or in the form of gold particles supported on a carbon support is present, wherein the carbon support is selected from
  • Activated carbon, carbon black, graphite, graphene or carbon nanotubes, especially carbon black is present, and
  • hydrophobic polymer is a fluorine-substituted polymer, more preferably polytetrafluoroethylene (PTFE).
  • PTFE polytetrafluoroethylene
  • Gas diffusion electrodes are electrodes in which the three states of matter - solid, liquid and gaseous - are in contact with each other and the solid, electron-conducting catalyst catalyzes an electrochemical reaction between the liquid and the gaseous phase.
  • the carbon support in turn may contain activated carbon, carbon black such as Ketjenblack EC-300j or EC 600 JD, graphite, graphene or carbon nanotubes, especially Ketjenblack.
  • the gas diffusion electrode which is characterized in that the gold particles with an average particle diameter (dso measured by laser diffraction) in the range of 1 to 100 ⁇ preferably in the range of 2 to 90 ⁇ present and / or that the mean particle diameter of Carbon-supported gold particles in the range of 2 nm to 100 ⁇ , preferably in the range of 2 nm to 1 ⁇ .
  • the proportion of electrocatalyst in the form of powder is from 80 to 97% by weight, preferably 90 to 95% by weight, based on the total weight of electrocatalyst and hydrophobic polymer, or that the proportion of electrocatalyst in the form of particles on a carbon support of 40 to 60 wt .-%, based on the total weight of electrocatalyst and hydrophobic polymer.
  • electrocatalyst and hydrophobic polymer are applied and compressed in powder form on the carrier and form the gas diffusion layer.
  • the gas diffusion electrode based on gold powder as the electrocatalyst has a total loading of catalytically active component in a range from 5 mg / cm 2 to 300 mg / cm 2 , preferably from 10 mg / cm 2 to 250 mg / cm 2 , and / or that the
  • Gas diffusion electrode based on carbon-supported gold particles has a total loading of catalytically active component in a range of 0.5 mg / cm 2 to 20 mg / cm 2 , preferably from 1 mg / cm 2 to 5 mg / cm 2 .
  • the carrier of the gas diffusion electrode may contain nickel, gold, or silver or a combination of nickel with gold or silver.
  • the carrier may be in the form of a net, woven fabric, knitted fabric, knitted fabric, fleece, expanded metal or foam, preferably a woven fabric, particularly preferably a net.
  • the gas diffusion electrode can be produced by applying the catalyst / powder mixture directly to a carrier.
  • the powder mixture is produced in a particularly preferred embodiment by mixing the catalyst powder and the binder and optionally other components.
  • the mixing is preferably done in a mixing device which mixes rapidly rotating mixing elements, e.g. Have flywheel.
  • the mixing elements rotate preferably at a speed of 10 to 30 m / s or at a speed of 4000 to 8000 U / min. After mixing, the
  • Powder mixture preferably sieved.
  • the sieving is preferably carried out with a sieve device, which with networks o-the like. equipped, whose mesh size 0.04 to 2 mm.
  • the temperature during the mixing process is preferably 35 to 80 ° C.
  • a coolant for example liquid nitrogen or other inert heat-absorbing substances.
  • Another way of Temperature control may be accomplished by interrupting mixing to allow the powder mixture to cool or by selecting suitable mixing units or changing the fill in the mixer.
  • the application of the powder mixture to the electrically conductive carrier takes place, for example, by scattering.
  • the spreading of the powder mixture onto the carrier can e.g. done by a sieve.
  • a frame-shaped template is placed on the carrier, wherein the template is preferably selected so that it just covers the carrier.
  • the template can also be chosen smaller than the surface of the carrier. In this case remains after sprinkling the powder mixture and the pressing with the carrier an uncoated edge of the carrier free of electrochemically active coating.
  • the thickness of the template can be selected according to the amount of powder mixture to be applied to the carrier.
  • the template is filled with the powder mixture. Excess powder can be removed by means of a scraper. Then the template is removed.
  • the powder mixture is pressed in a particularly preferred embodiment with the carrier.
  • the pressing can be done in particular by means of rollers.
  • a pair of rollers is used.
  • a roller on a substantially flat base wherein either the roller or the base is moved.
  • the pressing can be done by a ram.
  • the forces during pressing are in particular 0.01 to 7 kN / cm.
  • Another aspect relates to the use of arylalkyl or diaryl carbonates obtained from the process according to the invention for the production of polycarbonate, preferably by the melt transesterification process.
  • the transesterification reaction can be described by way of example according to the following equation:
  • GC Gas Chromatography
  • GC Gas chromatographic
  • Heating rate 15 ° C / min, 260 ° C final temperature for 8 min).
  • Spectrophotometers used. A CaF2 prism with an angle of 60 ° was used, with the spectrum consisting of the average of 100 interferograms with a resolution of 8 cm -1 and p-polarized light.
  • the spectra were obtained from a setup in which the electrode is pressed under controlled potential against the prism window.
  • As reference serves a spectrum, which at a
  • Electrolytic solution consisting of 0.1 mol / L of methanol, and 0.1 mol / L of phenol was purged with Ar oxygen-free for 10 min before the experiment, then the electrolyte solution was saturated with CO and maintained during the experiment by further CO supply ,
  • the gas diffusion electrode was produced by the dry process, wherein 93% by weight gold powder SPF 1775 from Ferro, 7% by weight PTFE from DYNEON TF2053 were mixed in an IKA mill AI 1 basic. Subsequently, the powder mixture was pressed with a roller press at a force of 0.5 kN / cm on a nickel carrier network. For an electrode of size 24 cm 2, 7.7 g of the powder mixture were needed.
  • the experiment was carried out in a commercially available Electrocell Model Micro Flow Cell volume (0.001 m 2 ) in a 2-electrode setup.
  • As the counter electrode an iridium MMO (iridium mixed metal oxide electrode, commercially available from Electrocell) was used.
  • the working electrode is a gas diffusion electrode prepared according to Example 2 consisting of a mixture of gold powder and PTFE rolled on a nickel support.
  • the electrolysis was carried out at 1.2 V for 1 h (current density at about 1 mA / cm 2 ). During this time, 40 mL of electrolyte was pumped in a circle at a rate of 2 mL / min.
  • the experiment was carried out in a commercially available Electrocell Model Micro Flow Cell volume (0.001 m 2 ) in a 2-electrode setup.
  • an Ir-MMO iridium mixed metal oxide electrode, commercially available from Electrocell
  • the working electrode is a gas diffusion electrode consisting of a mixture of gold powder and PTFE, which has been rolled on a substrate made of nickel.
  • the electrolysis was carried out at 1.2 V for 1 h (current density at about 1 mA / cm 2 ). During this time, 40 mL of electrolyte was pumped in a circle at a rate of 2 mL / min.
  • the gas diffusion electrode was produced by the dry process, wherein 93 wt .-% palladium powder M8039 from Ferro, 7 wt .-% PTFE from DYNEON TF2053 were mixed in an IKA mill Al l basic. Subsequently, the powder mixture was pressed with a roller press at a force of 0.29 kN / cm on a nickel carrier network. For a 32 cm 2 electrode, 4.3 g of the powder mixture was needed.
  • the experiment was carried out in a commercially available Electrocell Model Micro Flow Cell volume (0.001 m 2 ) from Electrocell in a 2-electrode run.
  • the experiment was carried out in a commercially available Electrocell Model Micro Flow Cell volume (0.001 m 2 ) from Electrocell in a 2-electrode run.
  • Gas diffusion electrode prepared according to Comparative Example 5 was anodically switched, as the counter electrode, an iridium-MMO electrode (iridium mixed metal oxide electrode, commercially available from Electrocell) was used.
  • the electrolysis was carried out at a current density of 0.2 mA / cm 2 for one hour.
  • the flow rate of CO was 0.5 L / h and the electrolyte (30 mL) was circulated at a flow rate of 2 mL min 1 .
  • Electrolytes were dissolved in CH 3 CN (200 mL) PhOH (14.11 g, 0.15 mol, 0.75 mol L 1 ) and LiCl (114.5 mg, 2.7 mmol, 0.014 mol L 1 ).

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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)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé de production électrochimique de carbonates de diaryle ou de carbonates d'arylalkyle. Le procédé est caractérisé en ce que des composés de la formule (1) R1-OH, le radical R1 étant un radical alkyle, de préférence un radical de la série : alkyle en C1 à C6, de préférence un méthyle ou éthyle, isopropyle ou tert-butyle, ou cycloalkyle, de préférence cyclohexyle, est mis à réagir avec un composé de la formule (2) R2-OH, R2 représentant un groupe aryle, de préférence un tert-butylphényle, cumylphényle, naphtyle ou phényle, de manière particulièrement préférée un radical phényle, au niveau d'une électrode en présence d'or utilisé comme électrocatalyseur hétérogène, la réaction se faisant anodiquement avec du CO, ainsi que leur utilisation dans la production de polycarbonates.
EP18735288.5A 2017-07-03 2018-06-29 Procédé électrochimique de production de carbonates d'arylalkyle ou de carbonates de diaryle Withdrawn EP3649277A1 (fr)

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EP17179362 2017-07-03
PCT/EP2018/067548 WO2019007828A1 (fr) 2017-07-03 2018-06-29 Procédé électrochimique de production de carbonates d'arylalkyle ou de carbonates de diaryle

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JPH043582A (ja) 1990-04-19 1992-01-08 Mitsubishi Electric Corp イメージ・スキャナ装置
JPH0673582A (ja) * 1992-08-27 1994-03-15 Daicel Chem Ind Ltd 炭酸ジエステルの製造方法および製造装置
DE19512618A1 (de) * 1995-04-05 1996-10-10 Bayer Ag Platinmetall enthaltende Träger-Katalysatoren und Verfahren zur Herstellung von Diarylcarbonaten
US6695963B2 (en) * 2001-07-05 2004-02-24 Asahi Kasei Kabushiki Kaisha Organic electrolysis reactor for performing an electrolytic oxidation reaction and method for producing a chemical compound by using the same
DE10148599A1 (de) 2001-10-02 2003-04-10 Bayer Ag Verfahren zur Herstellung von Gasdiffusionselektroden aus trockenen Pulvermischungen mittels Walzen
JPWO2011024327A1 (ja) * 2009-08-31 2013-01-24 三菱化学株式会社 炭酸ジエステルの製造方法
US9175135B2 (en) * 2010-03-30 2015-11-03 Bayer Materialscience Ag Process for preparing diaryl carbonates and polycarbonates
SG174714A1 (en) * 2010-03-30 2011-10-28 Bayer Materialscience Ag Process for preparing diaryl carbonates and polycarbonates
DE102010042937A1 (de) * 2010-10-08 2012-04-12 Bayer Materialscience Aktiengesellschaft Verfahren zur Herstellung von Diarylcarbonaten aus Dialkylcarbonaten
CN102586799A (zh) * 2011-01-04 2012-07-18 索尼公司 电解制备碳酸酯的方法
WO2014046797A2 (fr) 2012-09-19 2014-03-27 Liquid Light, Inc. Production électrochimique conjointe de produits chimiques au moyen d'un sel d'halogénure

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WO2019007828A1 (fr) 2019-01-10

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