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  • 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
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  • C25B3/23—Oxidation
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  • 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
  • C25B3/01—Products
  • C25B3/07—Oxygen containing compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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  • C07C69/96—Esters of carbonic or haloformic acids
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  • 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
  • C25B11/042—Electrodes formed of a single material
  • C25B11/043—Carbon, e.g. diamond or graphene
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  • 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
  • C25B11/061—Metal or alloy
• • 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
  • C25B3/01—Products
  • C25B3/03—Acyclic or carbocyclic hydrocarbons
• • 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
  • C25B3/26—Reduction of carbon dioxide

Definitions

• the invention relates to an electrochemical process for the preparation of arylalkyl carbonates and diaryl carbonates.
• the invention is based on electrochemical processes known per se for the preparation of diaryl carbonates.
• Arylalkyl carbonates and diaryl carbonates are important precursors in the production of polycarbonates.
• 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.
• the preparation of diaryl carbonates can also be carried out via an oxidative carbonylation.
• phenol is reacted directly with carbon monoxide as the carbonylating reagent (Journal of Molecular Catalysis A: Chemical, 1999, 139, 109-119).
• the oxidative carbonylation of phenol is also known as the electrochemical variant described in J. Phys. Chem. C, 2012, 116, 10607-10616, ACS Catal., 2013, 3, 389-392 and Res. Chem. Intermed., 2015, 41, 9497-9508.
• the necessity of using expensive palladium-based catalysts of great disadvantage In the chemical as well as the electrochemical oxidative carbonylation for the preparation of diaryl carbonates, the necessity of using expensive palladium-based catalysts of great disadvantage.
• the oxidative carbonylation for the preparation of diaryl carbonates has hitherto not been applied industrially.
• carbon dioxide is available as a waste product in many chemical processes and can therefore be regarded as a sustainable raw material. It is also advantageous that carbon dioxide is easier to handle as non-combustible gas than carbon monoxide.
• the use of expensive palladium-based catalysts is disadvantageous, especially if the palladium is present as a homogeneous catalyst and has to be separated from the product.
• the use of carbon dioxide as a precursor is preferable to the use of carbon monoxide.
• the object of the present invention is to develop a process in which, inter alia, carbon dioxide is used as a precursor for the preparation of arylalkyl carbonates and diaryl carbonates. In particular, not so many synthesis steps should be required here as in the prior art.
• a special object of the invention is to provide an alternative electrochemical process for
• Carbon dioxide is used as a precursor.
• the object is achieved in that an aromatic compound is reacted with a carbonate directly anodically optionally in the presence of an apro tic solvent.
• the carbonate used can be prepared directly from carbon dioxide in a preliminary stage.
• the invention relates to a process for the electrochemical preparation of arylalkylcarbonates and diarylcarbonates, characterized in that compounds of the formula (1)
• radical R 1 is an alkyl radical, preferably a radical from the series: C 1 -C 6 -alkyl, particularly preferably methyl, ethyl or tert-butyl, or cycloalkyl, preferably cyclohexyl, or an aryl radical, preferably tert-butylphenyl, cumylphenyl, naphthyl or phenyl, particularly preferably a phenyl radical and the radicals R -, R.
• C 1 -C 6 -alkyl particularly preferably methyl, ethyl or tert-butyl, or cycloalkyl, preferably cyclohexyl
• an aryl radical preferably tert-butylphenyl, cumylphenyl, naphthyl or phenyl, particularly preferably a phenyl radical and the radicals R -, R.
• R4 independently of one another denote hydrogen or an alkyl radical, preferably a radical from the series: G- to Ce-alkyl, isopropyl or tert-butyl or cycloalkyl, particularly preferably cyclohexyl, or with an aromatic compound of the formula (3) or with an aromatic compound of the formula (4) in the presence of one or more solvents, in particular aprotic solvent mittein implemented.
• Suitable counterions to the anions of the formula (1) are typically cationic quaternary ammonium compounds, in particular T etraalky lammon ium, preferably T etrabuty lammonium.
• a preferred process is therefore characterized in that the compounds of the formula (1) are used as salts with cationic quaternary ammonium compounds, in particular tetraalkylammonium, preferably tetrabutylammonium, as counterions.
• Preferred starting compounds of the formula (1) are those selected from the series:
• Another object of the invention is the use of available from the new process arylalkyl or diaryl carbonates for the production of polycarbonates.
• reaction equation of the new electrochemical manufacturing process is the example of
• the hydrogen evolution from acidic solution serves:
• the new anodic electrochemical reaction is preferably carried out at a current density in the range of 0.5 to 100 mA / cm 2 and at a temperature in the range of 10 to 80 ° C.
• Commercially available boron-doped diamond electrodes which are connected as the anode, can preferably be used to carry out the novel process.
• the advantage of the boron-doped diamond electrode is that it is chemically very stable under anodic conditions, and in particular is very resistant to radical intermediates in the electrochemical reaction.
• Diamond electrodes, which are in principle particularly suitable for the new method are characterized in that an electrically conductive diamond layer, which may be boron-doped, is applied to a suitable electrically conductive carrier material.
• HFCVD hot filament chemical vapor deposition
• the boron doping is based on low concentrations of diboranes, trimethylborane, boron trioxide or borates [L. Pan and D. Kanja, Diamond: Electronic Properties and Applications, Kl uvver Academic Publishers: Boston, 1995]. It is also common to pass an additional hydrogen gas stream through a methanol / boron trioxide solution (with a defined C / B ratio)
• the anodic reaction is carried out on a boron-doped diamond electrode as an anode, in which the boron-doped diamond layer is applied to different base materials.
• a boron-doped diamond electrode as an anode, in which the boron-doped diamond layer is applied to different base materials.
• preference is given to using titanium, silicon or whether as carrier material for the diamond layer.
• Particularly preferred carrier material is silicon.
• Other carrier materials on which the diamond layer adheres and forms a dense layer can in principle be used.
• the electrically conductive support for producing the boron-doped diamond layer may basically be a mesh, fleece, foam, woven fabric, braid or expanded metal.
• a carrier in the form of an expanded metal is used.
• the carrier may be single-layered or multi-layered.
• a multilayer carrier may be constructed of two or more superposed nets, nonwovens, foams, woven, braided or expanded metals.
• the nets, nonwovens, foams, woven fabrics, braids or expanded metals can be different. They may, for example, be different thicknesses or different porosity or have a different mesh size.
• Two or more nets, nonwovens, foams, woven fabrics, braids or expanded metals may be joined together, for example, by sintering or welding.
• a boron-doped diamond electrode is used, which is constructed on a support based on at least one material selected from the following series: tantalum, silicon and niobium, preferably silicon.
• a further preferred embodiment of the novel process is characterized in that the compounds of the formula wherein the radical R i is an alkyl radical, preferably a radical from the series: O to Ce- alkyl, or cycloalkyl, preferably cyclohexyl, or an aryl radical, preferably tert-butylphenyl, cumylphenyl, naphthyl or phenyl, starting from the corresponding alcohol RiOH be generated by a reaction upstream of the anodic reaction with carbon dioxide at a cathode electrochemically.
• the radical R i is an alkyl radical, preferably a radical from the series: O to Ce- alkyl, or cycloalkyl, preferably cyclohexyl, or an aryl radical, preferably tert-butylphenyl, cumylphenyl, naphthyl or phenyl, starting from the corresponding alcohol RiOH be generated by a reaction upstream of the anodic reaction with carbon dioxide
• the preferred alcohol RiOH is an alcohol from the series: methanol, ethanol, n-propanol, n-butanol, tert-butanol, n-pentanol, n-hexanol, cyclohexanol, tert-butylphenol, cumylphenol, naphthol or Phenol used.
• reaction for the cathodic formation of a monoalkyl carbonate can in principle be carried out in an analogous manner as described by way of example in Tetrahedron Letters, 1997, p. 20 3565-3568, the addition of an alkylating reagent described therein being omitted:
• the cathode reaction to form a monoalkyl carbonate is basically described in Novel Trends in Electroorganic Synthesis, 3rd, Kurashiki, Japan, Sept. 24-27, 1997 (1998), 193-196.
• the upstream cathodic reaction takes place in particular in acetonitrile as solvent, but can also be carried out in other aprotic solvents such as DMF, DMSO, 1,2-dimethoxyethane or N-methyl-2-pyrrolidone.
• the upstream cathodic reaction can be carried out in particular at a current density in the range of 2 to 100 mA'cm 2 and a temperature in the range of 10 to 80 ° C.
• the invention also provides the use of the arylalkyl carbonates and diaryl carbonates obtained from the process according to the invention for the preparation of polycarbonates by the melt transesterification process.
• the transesterification reaction can be described by way of example according to the following equation:
• preferred further starting materials and process variants of the melt transesterification process known per se for the production of polycarbonates are mentioned which can be used for the reaction of the arylalkyl carbonates and diaryl carbonates obtainable from the process according to the invention.
• arylalkyl carbonates a basically known conversion to a diaryl carbonate is carried out before the melt transesterification process. This is described by way of example in EP2650278 or EP1837328.
• EP 2650278 describes a process for the preparation of diaryl carbonates for the production of polycarbonate, wherein an arylalkyl carbonate is prepared as an intermediate.
• a variant of the process according to the invention provides a direct access to arylalkyl carbonates, which can be used according to the process described in EP 2650278 for the preparation of diaryl carbonates.
• a disproportionation reaction takes place in which dialkyl carbonates and diaryl carbonates are formed.
• the resulting dialkyl can be reacted with the appropriate aryl alcohol again in arylalkyl carbonate, wherein alkyl alcohols are released.
• Such processes are known to the person skilled in the art and are described in detail, for example, in EP1837328.
• Chain terminators and branching agents are known from the literature. Some are described for example in DE-A 38 33 953.
• Preferred chain terminators are phenol or alkylphenols, in particular phenol, p-tert-butylphenol, isooctylphenol, cumylphenol, their chlorocarbonic acid esters or acid chlorides of monocarboxylic acids or mixtures of these chain terminators.
• Preferred chain terminators are phenol, cumyl-phenol, isooctylphenol, para-tert-butylphenol.
• branching compounds are aromatic or aliphatic compounds having more than three, preferably three or four hydroxy groups.
• Particularly suitable examples with three or more than three phenolic hydroxyl groups are phloroglucinol, 4,6-dimethy1-2,4,6-tri- (4-hydroxyphenyl) -heptene-2, 4,6-dimethyl-2,4,6-tri - (4-hydroxyphenyl) heptane, 1, 3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, tri- (4-hydroxyphenyl) -phenyl - methane, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenyl-isopropyl) -phenol, tetra- (4- hydroxyphenyl) methane.
• branching agents examples include 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
• Particularly preferred branching agents are 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydro-indole and 1,1,1-tri (4-hydroxyphenyl) -ethane.
• the optionally used branching agents in a concentration of 0.05 to 2 mol%, based on the bisphenols used, can be used together with the bisphenols. It must be ensured that the reaction components for the transesterification, the bisphenols and the diaryl carbonates, are free of alkali and alkaline earth ions, with amounts of less than 0.1 ppm of alkali and alkaline earth metal ions can be tolerated. Such pure bisphenols or diaryl carbonates are obtainable by recrystallizing, washing or distilling the bisphenols or diaryl carbonates. In the downstream transesterification process, the content of alkali metal and alkaline earth metal ions in both the bisphenol and the diaryl carbonate should be ⁇ 0.1 ppm.
• the transesterification reaction of the bisphenol and the diaryl carbonate in the melt is preferably carried out in two stages.
• the melting of the bisphenol and the diaryl carbonate takes place at temperatures of 80-250 ° C., preferably 100-230 ° C., more preferably 120-190 ° C. under normal pressure in 0-5 hours, preferably 0.25-3 Hours instead.
• the catalyst After addition of the catalyst by applying vacuum (up to 2 mm Hg) and increasing the temperature (up to 260 ° C) by distilling off the monophenol, the oligocarbonate from the bisphenol and the diaryl carbonate is prepared.
• the oligocarbonate thus prepared has an average molecular weight Mw (determined by measuring the relative solution viscosity in dichloromethane or in mixtures of identical amounts by weight of phenol / o-dichlorobenzene, calibrated by light scattering) in the range from 2000 to 18,000, preferably from 4,000 to 15,000 This process recovers the majority of monophenol (80%) from the process.
• the polycarbonate is produced in the polycondensation by further increasing the temperature to 250-320 ° C, preferably 270-295 ° C and a pressure of ⁇ 2 mm Hg. In this case, the remainder of monophenols is recovered.
• Suitable catalysts in the context of the melt transesterification process are all inorganic or organic basic compounds, for example lithium, sodium, potassium, cesium, calcium, barium, magnesium, hydroxides, carbonates, halides, phenolates, diphenolates, fluorides, acetates, phosphates, hydrogen phosphates, boronates, nitrogen and phosphorus bases such as, for example, tetramethylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium fluoride, tetramethylammonium tetraphenylboranate, tetraphenylphosphonium fluoride, Tetraphenylphosphonium tetraphenylboranate, dimethyldiphenylammonium hydroxide, tetraethylammonium hydroxide, DHU.
• inorganic or organic basic compounds for example lithium, sodium, potassium, cesium, calcium, barium, magnesium, hydroxides, carbonates, hal
• the catalysts can also be used in combination (two or more) with each other.
• alkali / alkaline earth metal catalysts When using alkali / alkaline earth metal catalysts, it may be advantageous to add the alkali / alkaline earth metal catalysts at a later time (e.g., after the oligocarbonate synthesis in the second stage polycondensation).
• the addition of the alkali / alkaline earth metal catalyst may e.g. as a solid or as a solution in water, phenol, oligocarbonate or polycarbonate.
• the reaction of the bisphenol and the diaryl carbonate with the polycarbonate can be carried out batchwise or preferably continuously in the melt transesterification process, for example in stirred vessels, thin-layer evaporators, falling-film evaporators, stirred tank cascades, extruders, kneaders, simple disk reactors and high-pressure disk reactors and heat exchangers.
• the aromatic polycarbonates obtainable from the melt transesterification process should in particular have average weight molecular weights Mw of 18,000 to 80,000, preferably 19,000 to 50,000, determined by measuring the rel. Solution viscosity in dichloromethane or in mixtures of equal amounts by weight of phenol / o-dichlorobenzene, calibrated by light scattering.
• the crude monophenols which are isolated in the transesterification process can be synthesized, inter alia, with diaryl carbonates, bisphenol, salicylic acid, isopropenylphenol, phenoxybenzoic acid phenylester, Xanthone, the hydroxymonoaryl carbonate be contaminated.
• the cleaning can be done by the usual cleaning method, ie z. B. distillation or recrystallization.
• the purity of the monophenols is then> 99%, preferably> 99.8%, particularly preferably> 99.95%.
• GC Gas chromatographic analyzes
• GC-2010 Gas chromatographic analyzes
• the interaction of the sample with the stationary phase takes place in a quartz capillary column ZB-5MSi from Phenomenex, USA (length: 30 m, internal diameter: 0.25 mm, film thickness of the covalently bonded stationary phase: 0.25 ⁇ m, precaution column: 5 m, Carrier gas: hydrogen; Injector temperature: 250 ° C; Detector temperature: 310 ° C; Program: "hard” method: 50 ° C start temperature for 1 min, heating rate: 15 ° C / min, 290 ° C final temperature for 8 min)
• Gas chromatographic mass spectra (GCMS) were recorded using the gas chromatograph GC-2010 combined with the mass detector GCMS-QP2010 from Shimadzu, Japan, on a ZB-5MSi quartz capillary column from Phenomenex, USA (length: 30 m, inner diameter: 0 , 25 mm; film thickness of
• the NMR spectroscopic investigations were carried out on multicore resonance spectrometers of the type AV 11 400 from Bmker, Analytical Measurement Technology, Düsseldorf. The solvents used are indicated in each case. All ⁇ and i3 C spectra were calibrated according to the residual content of non-deuterated solvent according to the NMR Solvent Data Chart from Cambridge Isotopes Laboratories, USA. The assignment of the ⁇ and 13 C signals was carried out if necessary with the aid of HH-COZY. HC-HSQ and H, C-HMBC spectra. The chemical shifts are given as ⁇ values in ppm. The evaluation of the NMR spectra was carried out with the program MestReNova (Version: vl O.0.1-14719).
• the electrolysis is carried out galvanostatically with a current density of 2.0 mA / cm 2 and a charge amount of 3.5 F at room temperature (20 ° C) and atmospheric pressure (1 atm). After the end of the electrolysis, the cell contents are separated in a separatory funnel between 50 ml of water and 50 ml of ethyl acetate. The organic phase is washed twice with 50 ml of water, dried with sodium sulfate and the solvent removed under reduced pressure on a rotary evaporator.
• the crude product obtained was purified by preparative HPLC on a C18 column (KNAUER Scientific Equipment GmbH, Germany, Eurospher II, pore size: 100 ⁇ , particle size: 5 ⁇ m, length: 250 mm, diameter: 30 mm).
• Method: Flow 20 ml / min, eluent is acetonitrile (A) and water 95% / acetonitrile 5% / phosphoric acid (1 ml to 1000 ml) (B), 0-40 min 15% A + 85% B, 40-120 min 100% A.
• the cell contents are separated in a separatory funnel between 50 ml of water and 50 ml of ethyl acetate.
• the organic phase is washed once with 50 ml of water, dried with magnesium sulfate and the solvent removed under reduced pressure on a rotary evaporator fer.
• the crude product obtained was purified with a Kugelrohr still (BÜCHI Laboratory GmbH, Essen, Germany).
• Teflon 1.0 mmol of mesitylene are with 3.5 mmol of tetrabutyl ammoniumethylcarbonat dissolved in 5 ml of acetonitrile, and a boron-doped diamond electrode (DIACHEM ®, 15 micron diamond film on silicon substrate, CONDIAS ( .mbH, Itzehoe, Germany) anodically reacted with a platinum cathode, the electrode spacing is 0.5 cm, and the electrolysis is carried out galvanostatically with a current density of 2.0 mA / cm 2 and a charge of 2 F at room temperature ( 20 ° C) and atmospheric pressure (1 atm.) The reaction mixture was analyzed by GC-MS.
• the electrolysis is carried out galvanostatically with a current density of 2.0 mA / 'cm 2 and a charge amount of 4.5 F at room temperature (20 ° C) and atmospheric pressure (1 atm).
• the analysis of the reaction mixture was carried out by means of G-MS.
• the electrolysis is carried out galvanostatically with a current density of 2.0 mA / cm 2 and a charge amount of 4.5 F at room temperature (20 ° C) and atmospheric pressure (1 atm).
• the analysis of the reaction mixture was carried out by GC-MS.
• the electrolysis is carried out galvanostatically with a current density of 2.0 mA / cm 2 and a charge amount of 4.5 F at room temperature (20 ° C) and atmospheric pressure (1 atm).
• the analysis of the reaction mixture was carried out by GC-MS.

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