EP3415662A1 - Verfahren zur herstellung einer ionischen flüssigkeit - Google Patents

Verfahren zur herstellung einer ionischen flüssigkeit Download PDF

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EP3415662A1
EP3415662A1 EP17176456.6A EP17176456A EP3415662A1 EP 3415662 A1 EP3415662 A1 EP 3415662A1 EP 17176456 A EP17176456 A EP 17176456A EP 3415662 A1 EP3415662 A1 EP 3415662A1
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chloride
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EP3415662B1 (de
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Xochitl Dominguez Benetton
Omar Martinez Mora
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Vito NV
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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
    • 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
    • C25B3/05—Heterocyclic compounds
    • 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
    • C25B3/09—Nitrogen containing compounds

Definitions

  • the present invention relates to a method for the electrochemical production of an aprotic ionic liquid of a cation and a halide based anion X - , according to the preamble of the first claim.
  • Ionic liquids are generally composed of a bulky, asymmetric organic cation and an anion, often of inorganic nature (1).
  • ionic liquids are organic salts with a melting point of below 100 °C, most of them being liquid at ambient temperature.
  • ionic liquids have aroused broad research and industrial interest because of their outstanding physicochemical properties, such as their extremely low vapor pressure, their high thermal stability and good solvation ability, which make them suitable candidates for a wide range of applications (2).
  • properties of ionic liquids such as melting point, viscosity, density, and hydrophobicity can be modified by changing the structure of the cation, the anion, or both.
  • ionic liquids that suit requirements imposed by a particular process in which their use is envisaged (3).
  • the use of ionic liquids has been explored in many fields of chemistry, for example, their use as solvents or catalysts in synthesis processes (4), in extraction processes (5), as media for CO 2 capture (6), as stationary phase in gas chromatography (7) or as supporting electrolyte in electrochemistry (8).
  • the synthesis of ionic liquids typically comprises a first step wherein the desired cation is formed, followed by an anion exchange, if necessary.
  • the following classical synthesis routes may be distinguished in general:
  • Ionic liquids have also been synthesized using non-conventional and greener methods, e.g. methods using microwaves or ultrasound irradiation (11, 12).
  • Microwave-assisted synthesis of ionic liquids has provided a higher energy efficiency than conventional heating, however consecutive microwave irradiation, may render heat control rather difficult because of the nonvolatile nature of Ionic liquids (13).
  • Ultrasound reactions also provide a few advantages, the main one being the use of non-hazardous acoustic radiation as an energy source. Yet, the main disadvantage is the non-homogeneous distribution of energy which hinders the industrial feasibility of the method as reactors need to be modified for upscaling (14).
  • the present invention therefore seeks to provide a method for producing ionic liquids, which is not compromised by the safety issues of the prior art electrochemical production methods.
  • the method of this invention has been found suitable for producing ionic liquids from a compound or a reactant selected from the group of compounds represented by the formula (1) above. These reactants proved to be extremely suitable precursors for the intended ionic liquid reaction products as the risk that they give rise to the formation of unwanted side products is minimal.
  • the reaction product is an ionic liquid which comprises the halide based anion and a cation which is obtained by electrochemical oxidation of the compound of formula (1) above.
  • a halide salt in particular a chloride salt is used as anion source as an alternative to the perchlorates known from prior art synthesis methods for ionic liquids.
  • the halide salt acts both as anion source in the electrochemical reaction for the anion of the envisaged ionic liquid reaction end product, and as supporting electrolyte in the electrochemical process.
  • chlorides have been so far overlooked for the electrosynthesis of ionic liquids, the main reason being that they are regarded as more electrochemically active than the organic cation precursors under the typical ionic liquid electrochemical synthesis conditions, and therefore prone to yield a negative impact on the overall ionic liquid synthesis selectivity and efficiency or to even impede the desired reaction.
  • the inventors have observed that although the halide ion, in particular the chloride anion, is not electrochemically inert at the electrochemical potential at which the reactant is oxidized, the risk to oxidation of the halide anion may nevertheless be reduced to a minimum.
  • the reactant is capable of counteracting or even inhibiting oxidation of the halide anion, in particular the chloride anion.
  • any oxidation of the halide anion that might occur has a negligible or even no effect on the electrochemical conversion of the reactant. In other words, it has been found that any oxidation of the halide anion that might possibly occur does not seem to hamper the electrochemical conversion of the reactant.
  • Halide ionic liquids in particular chloride based ionic liquids present the additional advantage that they are compliant for conversion into other ionic liquids wherein the halide anion, in particular the chloride anion, may be exchanged for another anion, thereby showing a higher versatility in electrosynthesis of ionic liquids.
  • the toxicity of halide ionic liquids, in particular the toxicity of chloride based ionic liquids to humans is substantially lower or even negligible in comparison to ionic liquids derived from perchlorates.
  • halide salts, in particular chloride salts arise as an extremely suitable alternative to perchlorates.
  • the skilled person will be capable of selecting the nature of the halide salt taking into account its electrochemical stability window, so that its electrochemical stability window falls within the electrochemical potential at which the method of this invention is carried out.
  • Electrosynthesis has proven to be an environmentally-friendly method for diverse organic syntheses (non-ionic liquid cases mostly), because the electrons active in the electrochemical synthesis process permit to dispense with the use of hazardous redox agents. Moreover, the electrons active in the electrochemical synthesis process can be obtained from renewable energy sources. Additionally, high efficiency and selectivity can be achieved by controlling the current or the potential of the reaction, which is typically carried out at room temperature and atmospheric pressure.
  • the reaction mixture may contain the halide salt in a slight molar excess with respect to the reactant.
  • a slight excess is meant a molar excess of maximum 10%, preferably maximum 7.5 %, more preferably maximum 5%.
  • the reactant is present in the reaction mixture in a high concentration.
  • a high concentration is meant that the reaction mixture contains the halide salt in a high concentration, i.e. in a concentration which is such that the molar ratio of the concentration of the reactant with respect to the halide salt varies between 0.9 and 1.5, preferably between 0.9 and stoichiometric.
  • the halide salt is a salt selected from the group of M 2+ X 2 , M 3+ X 3 or a halide salt of an organic aprotic cation, wherein M 2+ and M 3+ are respectively divalent and trivalent metal cations, wherein the halide X is preferably chloride.
  • M 2+ and M 3+ respectively represent divalent and trivalent metal cations, for example Fe 3+ or Ni 2+ or Co 2+ .
  • the halogen salt is an organic ammonium halide, preferably an organic ammonium chloride, preferably an alkylammonium chloride.
  • ammonium chlorides examples include trimethylammonium chlorides (Me 3 RNCl), wherein the additional alkyl group R on the N is a C1-C18 alkyl groups, tetraalkylammonium chlorides (R 4 NCl) which may be symmetric, in particular ammonium chlorides containing C 1 -C 12 alkyl groups, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, choline chloride, benzalkonium chloride. It shall however be clear to the skilled person that many other ammonium halides, in particular many other ammonium chlorides exist, which may be suitably be used in the method of the present invention.
  • Suitable reactants for use with the present invention include di-amines which respond to the formula: R 1 R 2 -N-(CR) n -N-R 3 R 4 (2) wherein
  • R, R 1 , R 2 ,R 3 , R 4 may be substituted with one or more substituents selected from the group of a -OH, - OR, -COOH, -COOR moiety.
  • di-amines suitable for use with the present invention include di-amines selected from the group of an N,N'-dialkylethylenediamine and an N,N'-dialkylpropanediamine, preferably a 1,3-dialkylethylenediamine and a 1,3-dialkylpropanediamine.
  • the reactant is selected from the group of N, N'-diethylethylenediamine, N,N'-dipropylethylenediamine, N,N'-di-tert-butylethylenediamine and N,N'-dimethylpropanediamine, N,N'-di-ethylpropanediamine, N.N'-dipropylpropanediamine , N,N'-di-tert-butylethylenediamine or derivatives of the afore-mentioned compounds.
  • N-substituted diamines or N, N' di-substituted diamines exist and that many other diamines may be used in the present invention.
  • symmetric di-substituted N, N'-diamines will usually give rise to symmetric substituted ionic reaction products
  • asymmetric di-substituted N, N'-diamines will usually give rise to asymmetric substituted ionic reaction products.
  • Mono substituted N-alkylethylenediamine and N-alkylpropanediamine and their derivates will usually give asymetric substituted ionic reaction products.
  • Suitable reactants for use with the present invention also include phosphines which respond to the formula (3): Wherein R 1 , R 2 ,R 3 , may be the same or different and may, independently of each other be H, a straight chain or a branched saturated alkyl group, a cyclic alkyl group or an aromatic hydrocarbon moiety.
  • a trialkylphosphine is used, which may be symmetric, i.e. with R 1 , R 2 ,R 3 , being the same, or asymmetric with one or more of R 1 , R 2 ,R 3 , being different from the others.
  • R 1 , R 2 , R 3 will contain between 1-20 carbon atoms, more preferably between 1 and 12 carbon atoms
  • R 1 , R 2 ,R 3 may be substituted with one or more substituents selected from the group of a -OH, -OR, -COOH, -COOR moiety.
  • the phosphine reactants described above may be converted into phosphonium based ionic liquids.
  • Table 1 and 2 below provides some examples of reactants and the reaction products that may be produced therefrom using the method of this invention. It shall be clear to the skilled person that the use of other reactants will give rise to the formation of other reaction products.
  • Table 1 General structure of the compounds that could be synthesized using the proposed method.
  • Starting Material Product N,N'-Dialkylethylenediamines 1,3-Dialkylimidazolinium salts N,N'-Dialkylpropanediamines 1,3-Dialkyl-1,4,5,6-tetrahydropyrimidin-3-ium salts
  • Trialkylphosphines Hexaalkyldiphosphonium salts *Where R might be any alkyl radical Table 2. Examples of reactants and reaction products that can be produced therefrom using the method of this invention Starting Material Product N,N'-Dialkylethylenediamines 1,3-Dialkylimidazolinium salts N,N'-Dialkylpropanediamines 1,3-Dialkyl-1
  • n is the number of electrons involved in the process
  • F Faraday's constant (96485 C mol -1 )
  • V is the volume of the working solution (L)
  • C is the concentration of electroactive species in the solution (g L -1 )
  • M is the molecular mass of the electroactive species (g mol -1 ).
  • n is known to the skilled person, for example where the reactant is a di-amine, n will usually be at least 3, where the reactant is a phosphine, n will usually be 2.
  • the reaction mixture may further contain a proton scavenger or the reaction mixture is subjected to proton scavenging.
  • Protons released in the course of the oxidation of the reactant may lead to the formation of non-electroactive protonated species and risk to reduce the yield of the desired end product.
  • the presence of a weak Bronsted base capable of acting as a proton acceptor or a proton scavenger, permits to minimize the risk to the occurrence of this step.
  • a weak Bronsted base is understood to refer to a compound having a pKb which is below the pKb of the reactant.
  • a weak Bronsted base is understood to refer to a compound having a pKb of at least 2.5.
  • the pKb will not be more than 4, preferably not more 3.5.
  • the concentration of the proton scavenger in the reaction mixture is not critical to the invention. However if a maximum yield and selectivity towards the desired end product is envisaged, the proton scavenger will be present in an equimolar concentration to the reactant or a concentration which is maximum 10 % below or maximum 10 % higher than an equimolar amount.
  • an organic amine or a mixture of two or more organic amines in particular a monoamine or a mixture of two or more thereof, more preferably an aliphatic amine, a cyclic amine and an aromatic amine, more in particular an alkyl amine, which may be represented by the formula R-NH 2 (4)
  • R is H or a C 1 -C 10 alkyl group, preferably a C 4 -C 8 alkyl group.
  • R may be branched, but preferably is a R straight chain alkyl group. Usually R will not contain further substituents, but this is not imperative.
  • Suitable proton scavengers include tert-butylamine, triethylamine, pyridine.
  • n-hexylamine has been found to be particularly suitable for use with the present invention as it is oxidized at an electrochemical potential which is sufficiently higher than the electrochemical potential at which the reactant is oxidized.
  • the skilled person will take care to employ a proton scavenger which is electrochemically stable at the electrochemical potential at which the reaction is carried out.
  • the skilled person will take care to select a proton scavenger which is oxidized at an electrochemical potential sufficiently above the electrochemical potential at which the reactant is oxidized. From figure S1, it can be observed that the electrochemical potential at which hexylamine is oxidized is 1.35 V vs SCE (Fig. S1 has been extracted from electronic supplementary information (ESI)).
  • proton scavenging may also be achieved by cathodic deprotonation.
  • the amount of proton scavenger contained in the reaction mixture may vary within some ranges. However, in order to achieve optimal results, the amount of proton scavenger is at least equimolar to the amount of reactant and halogen salt contained in the reaction mixture.
  • the reaction mixture is substantially water-free, which means that it contains less than 100.00 ppm of water.
  • Minimizing the water content may be achieved by subjecting the halide salt to drying in advance of supplying it to the reaction mixture. Minimizing the water content may further involve subjecting one or more of the other components of the reaction mixture, including the reactant, the proton scavenger and the solvent to drying before supplying them to the reaction mixture.
  • the method of this invention may further be preferred to carry out the method of this invention in an inert atmosphere, i.e. in He, Ar, Ne or under N 2 gas atmosphere, to minimize the risk that oxygen would interfere in the anodic oxidation.
  • an inert atmosphere i.e. in He, Ar, Ne or under N 2 gas atmosphere.
  • the oxygen concentration in the reaction mixture is less than 1000 ppm, preferably less than 100 ppm.
  • the process of the present invention is generally carried out in a liquid phase, which contains the reactants in a solution in an aprotic solvent, preferably an organic aprotic solvent.
  • an aprotic solvent preferably an organic aprotic solvent.
  • the solvent will be chosen such that the reactant and other compounds that interact in the method of this invention, show a sufficient solubility in or miscibility with the solvent.
  • the aprotic solvent is preferably selected such that it does not react at or within the electrochemical potential window used to carry out the method of this invention.
  • suitable solvents are known to the skilled person, and include a.o. dimethylformamide (DMF), dimethylsulfoxide (DMSO), acetonitrile, etc.
  • the reaction mixture of the present invention contains a supporting electrolyte.
  • the supporting electrolyte may contain other compounds. These compounds shall however be selected such that they do not adversely affect the yield and selectivity of the present invention.
  • the risk to the formation of by-products due to undesired conversion, for example oxidation, of other compounds than the reactant may be minimized by selecting an appropriate temperature window for carrying out the method. Therefore, the method of this invention is preferably carried out at a constant temperature between10 °C and 75 °C, preferably between 10 °C and 60 °C, more preferably between 15 °C and 60°C or between 15 °C and 50°C, most preferably between 15 °C and 45 °C.
  • the risk of unwanted oxidation of the proton scavenger may be reduced to a minimum, and volatility of the solvent and/or reactants used does not play a major role.
  • the method of this invention is carried out at an electrochemical potential of between 0.5-1.25 V, preferably between 0.74 and 1.1 V.
  • N,N'-di-tert-butylethylenediamine (DTDA) (Alfa Aesar, 98%), n-hexylamine (HexA) (Alfa Aesar, 99%), cobalt (II) chloride hexahydrate (CoCl 2 ⁇ 6H 2 O) (Alfa Aesar, 98%), tetrabutylammonium chloride (TBAC) (Sigma-Aldrich, ⁇ 97%), tetrabutylammonium hexafluorophosphate (TBAPF 6 ) (Sigma-Aldrich, ⁇ 99%) and anhydrous dimethylformamide (DMF) (Sigma-Aldrich, 99.8%) were used as purchased without further purification.
  • DTDA N,N'-di-tert-butylethylenediamine
  • HexA Alfa Aesar, 99%
  • Cyclic voltammetry (CV) and bulk potentiostatic electrolysis were performed using a multi-potentiostat (VSP Bio-Logic).
  • VSP Bio-Logic multi-potentiostat
  • a three-electrode borosilicate glass conical cell 80 mL, Bio-Logic, which allows temperature control and gas purging, was employed.
  • the products of the electrolysis reactions were evaluated using a high resolution mass spectrometer (Q Exactive Thermo Scientific) with positive electrospray ionization (HRMS-pESI) method with a resolution setting of 70000. Freshly electrolyzed samples were diluted, with methanol prior to direct infusion to the mass spectrometer.
  • the electrochemical behavior of DTDA in the presence of the chlorides salts in DMF was characterized using cyclic voltammetry. Given that during in the oxidation of DTDA protons are released into the medium, cyclic voltammetry experiments were also carried out in the presence of the mild base HexA, which was used as a proton scavenger. Through the cyclic voltammetry analysis, the working potentials for the electrolyses were fixed. As a point of reference, the cyclic voltammetry of DTDA 4 mM, with or without an equimolar amount of HexA, using TBAPF 6 0.1 M as supporting electrolyte was performed in DMF.
  • Oxidative electrolysis experiments were carried out following a modified method from the previously reported by Gallardo and Vila. Oxidative electrolysis experiments were carried in nitrogen gas atmosphere and at 25 °C, controlled potential electrolyses were performed in a DTDA 93 mM solution in DMF, containing HexA in an equimolar amount to DTDA and CoCl 2 or TBAC 0.1 M as supporting electrolyte and chloride source. The working electrode polarization potential was previously determined by CV analysis.
  • the peak at 0.93 V vs SCE is related to the monoelectronic oxidation of one of the secondary amino groups of DTDA followed by a deprotonation reaction, which occurs on the C a -H bond next to the amino group (Scheme 2) leading to the formation of the radical species [DTDA] ⁇ .
  • the proton released can react with a neutral molecule of DTDA, yielding a monoprotonated species ([DTDAH] + ) which is oxidized at 1.53 V vs SCE in a monoelectronic process to form the radical cation [DTDAH + ] ⁇ + .
  • Fig. 3 shows the CV of 0.1 M CoCl 2 in DMF at 100 mV s -1 .
  • the forward sweep (from 0.0 to 1.4 V vs SCE) displays an oxidation wave from 0.95 V to 1.4 V vs SCE, whereas in the corresponding reversal sweep, a reduction peak, approximately at 0.7 V vs SCE, is observed.
  • the CV of 0.1 M TBAC in DMF at 100 mV s -1 shows an oxidation current wave from 0.8 V to 1.5 V vs SCE in the forward sweep (from 0.0 to 1.6 V vs SCE) and a reduction peak at 0.4 V vs SCE in the reversal sweep.
  • This behavior is attributed to the oxidation of the Cl- anion (24).
  • the Cl- anion is oxidized in a process that involves a two-electron transfer from which two species may be generated, chlorine (Cl 2 ) and the trichloride anion (Cl 3 - ) (24, 25).
  • the reduction peak in the reversal sweep is in good agreement with the reduction of the Cl 2 formed (24).
  • the chloride salts here evaluated are not electrochemically inert at the potentials where DTDA is oxidized (about 1.0 V vs SCE, Fig. 2 ) as the electrochemical window of CoCl 2 0.1 M in DMF is from -1.0 V to 1.0 V vs SCE, whereas the anodic limit potential of the electrochemical window of TBAC 0.1 M in DMF is at 0.8 V vs SCE, in comparison with TBAPF 6 whose anodic limit potential is settled at 1.6 V (see Figs. S2-S4 in ESI).
  • the chosen potential was 1.03 V vs SCE for the electrolysis using CoCl 2 as supporting electrolyte which corresponds to the oxidation peak of DTDA 93 mM in the presence of HexA 93 mM and CoCl 2 in DMF at 10 mV s -1 (inset in Fig. 3 ).
  • the working potential for the experiments with TBAC was set at 1.1 V vs SCE.
  • the potential chosen was determined by the potential of the oxidation peak of DTDA 93 mM in DMF and TBAPF 6 0.1 M as supporting electrolyte (Fig. S5, ESI).

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WO2023090143A1 (ja) * 2021-11-16 2023-05-25 国立大学法人熊本大学 イオン液体やイオン液体原料を製造する方法、またその製造する装置

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WO2023090143A1 (ja) * 2021-11-16 2023-05-25 国立大学法人熊本大学 イオン液体やイオン液体原料を製造する方法、またその製造する装置

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