KR100592111B1 - Method for preparing quaternary imidazolium salt using liquid phase process - Google Patents

Abstract

The present invention relates to a method for producing a quaternary imidazolium salt used in an electrolyte for an electrochemical system, such as an electrolyte of an energy storage device, such as an electric double layer capacitor, an aluminum, tantalum liquid electrolytic capacitor, and a secondary battery, and various sensors. Reacting a class imidazolium salt with an alkyl bromide; Purifying the product by filtering the reaction solution under reduced pressure; Anion exchange reaction of the obtained product, quaternary imidazolium bromide with a strong acid; Purification or recrystallization extraction method using an organic solvent consists of removing the metal bromide. Development of quaternization reaction process by liquid phase reaction instead of gas phase reaction improves instability of working condition, difficulty of controlling working condition, high cost and high risk of manufacturing equipment, and uses chloride compound for gas phase reaction. Excluding the use of toxic chlorine compounds due to the human body, there is an effect of providing a method for preparing a quaternary imidazolium salt having various anions by various anion exchange reactions with high conductivity.

Capacitor, Electrolyte, Non-Aqueous Electrolyte, Electric Double Layer Capacitor (EDLC), Secondary Battery, Sensor

Description

Preparation method of quaternary imidazolium salt using liquid phase process {Preparation of quaternary imidazolium salts by liquid phase process}             

1 is a flowchart illustrating a process for preparing a quaternary imidazolium salt and a non-aqueous electrolyte using the same according to the present invention.

Figure 2 shows the non-conductivity of the non-aqueous electrolyte using a class 4 imidazolium salt EMIBF ₆ , EMIPF ₆ and EMIClO ₄ with temperature.

Figure 3 shows the non-conductivity of the non-aqueous electrolyte using the quaternary imidazolium salt EDMIBF ₆ , EDMIPF ₆ and EDMIClO ₄ with temperature.

Figure 4 shows the non-conductivity according to the concentration of the non-aqueous electrolyte using the class 4 imidazolium salt EMIBF ₆ , EMIPF ₆ and EMIClO ₄ .

Figure 5 shows the non-conductivity according to the concentration of the non-aqueous electrolyte using the quaternary imidazolium salt EDMIBF ₆ , EDMIPF ₆ and EDMIClO ₄ .

FIG. 6 shows a measurement value of CV (Ptentiostat / Galvanostat 273A, EG & G) in a voltage range of −2 V to 2 V by fabricating a half cell using EMIPF ₆ as an electrolyte.

The present invention relates to a method for producing a quaternary imidazolium salt used in an electrochemical system such as an electric double layer capacitor, an aluminum and tantalum liquid electrolytic capacitor, a secondary battery, and various sensors. stable quaternary as a resonance structure by using a liquid phase process to overcome the problem and using an alkyl bromide imidazolium cation and the conductivity is high anion having a (BF _{4 ^{-, etc., PF 6 -, ClO 4 -}} -, CF 3 SO 3) A method for synthesizing quaternary imidazolium salts at low cost, safely and efficiently.

In general, the electrolyte of a capacitor has changed from an aqueous system to a non-aqueous system. Aqueous electrolyte has the advantages of low self-resistance of electrolyte, little effect on internal resistance of the device, no need to completely block moisture in the air, eco-friendliness and low cost, while decomposition voltage It is low (1.23V), difficult to use in the range of water coagulation / boiling point, and strong corrosion resistance of acidic or alkaline aqueous solution, which has many limitations in selecting other materials. In order to solve these problems, interest in non-aqueous electrolytes has begun.

Non-aqueous electrolytes are electrochemically more stable than aqueous electrolytes and can store large amounts of energy. In particular, organic electrolytes are frequently used because there should be no change in physical properties at high temperature.Aceto is mainly used as a solute using tertiary substances such as triethylamine or quaternary ammonium salts such as Et ₄ NBF ₄ as a solute. And those dissolved in nitrile (ACN), gamma butyrolactin (GBL), propylene carbonate (PC), or ethylene carbonate (EC). Currently, quaternary ammonium salts are mostly used as electrolytes for electric double layer capacitors (EDLC).

However, with the miniaturization of electronic components, there is a need for an electrolyte containing a new quaternary salt having a wide operating voltage range. In particular, quaternary imidazolium salts have a resonance structure (between two nitrogen atoms and carbon atoms) than quaternary ammonium salts and phosphates commonly used in electrolytes such as electric double layer capacitors, aluminum and tantalum liquid electrolytic capacitors, secondary batteries, and various sensors. The double bond of is moved thermally) and increases the ion dissociation degree, thereby having high conductivity and electrochemically stable, and when used as an electrolyte, it has a wide operating voltage range. In addition, it is an ionic liquid that can react without other solvents and is an environmentally friendly material that is completely dissolved in water.

Representative synthesis of conventional quaternary ammonium salts, there is basically a method for synthesizing quaternary ammonium salts through quaternization and anion exchange reaction in the gas phase (AB McEwen et al. J. Electrochem. Soc., 146, 1687 -1695 (1999)) The quaternization reaction is a method of reacting a tertiary ammonium with an alkyl halide. In this reaction, the alkyl halide is used as a quaternizing agent and the reaction mechanism is shown in the following formula (1).

_{R 3 N + R'X → R 3} R'N + X - (X: halogen) (1)

In this reaction, R ₃ N tertiary ammonium is used as silver X and Cl ⁻ , and quaternization proceeds by gas phase reaction. When the quaternization reaction is completed, anion exchange reaction is performed for Cl ⁻ ions, and the reaction formula is shown in Equation (2).

_{^{R 3 R'N + X - + H}} + A - ⇔ R 3 R'N + A - + HX (A -: anions substituted) (2)

When H ⁺ A ^- is a strong acid, the equilibrium proceeds to the right according to the above equation, so that the stronger the acid, the easier anion substitution reaction occurs. On the other hand, when a weak acid such as an organic acid is used, it is difficult to perform an anion substitution reaction, and thus there is a disadvantage in that the reaction must be advanced at high temperature and high pressure.

In the present invention, it was intended to produce a quaternary imidazolium salt by applying the above reaction process. However, the existing manufacturing process as described above is made in the gas (gas state) using chloride. In general, the gas phase process has been recognized to be superior in terms of yield of the product than the liquid phase process, but the gas phase reaction is difficult to control the reaction rate because the reaction takes place in the gas state, causing considerable difficulty in controlling and controlling the pressure of the gas Due to the difficulty in controlling and controlling the temperature and pressure in the actual gaseous state, the yield is significantly reduced in the mass production process. In addition, the chlorine gas generated during the reaction is a very toxic gas, so it is very disadvantageous environmentally, and also has a critical defect that is very difficult to handle. In addition, the gas state has a fatal disadvantage that the safety is greatly reduced because it always involves the problem of pressure. In addition, these problems require mechanical equipment in terms of temperature, pressure, and environment, which leads to a complicated process and consequently a sharp increase in production costs.

The present invention is to overcome the problems of the prior art by developing a quaternization reaction process using the liquid phase reaction of bromide instead of the reaction process of the gas phase reaction of the conventional chloride to maintain a high yield at the same level as the gaseous phase while increasing the stability The objective was achieved by providing a method for producing a fourth-class imidazolium salt, which greatly reduces manufacturing cost and productivity by simplifying process configuration and production equipment.

The present invention relates to a method for preparing a quaternary imidazolium salt by a liquid phase process using bromide.

The method for preparing a quaternary imidazolium salt of the present invention comprises the steps of: a) reacting a tertiary imidazolium salt with an alkyl bromide; b) purifying the product by filtering the reaction solution under reduced pressure; c) for the product obtained quaternary imidazolium bromide, _{^{BF 4 -, PF 6 -,}} ClO 4 -, CF 3 SO 3 -, AsF 6 -, (CF 3 SO 2) 2 N -, SbF 6 -, C comprising any one of the anion exchange reaction with a strong acid containing eumyionreul of _{^{4 F 9 SO 3 - -,}} BEt 4; d) removing the metal bromide by the purification or recrystallization extraction method using an organic solvent, characterized in that the liquid phase process. However, a process of adding an organic solvent according to imidazolium bromide as a product at the time of the reaction of step a) or after the reduced pressure filtration of b) after the reaction may be added.

Referring to the production method of the quaternary imidazolium salt of the present invention in detail.

As a starting material, tertiary imidazolium salts such as 1-methylimidazole and 1,2-dimethylimidazole are used. Alkyl bromide such as bromomethane is used as a quaternizing agent, and sodium tetrafluoroborate, potassium hexafluorophosphate, sodium perchlorate and Strong acids such as potassium trifluoromethanesulfonate are used. Metal bromide, a byproduct of the anion exchange reaction, is removed using an organic solvent or by recrystallization extraction.

In the case of 1-methylimidazole, 1-methylimidazole and alkyl bromide are mixed in a molar ratio of 1: 0.5 to 10, placed in a reactor, and reacted with stirring to facilitate a reaction. At this time, if the product is filtered under reduced pressure using an organic solvent, the product is also filtered. Therefore, the organic solvent is not used. Since this reaction is exothermic, the temperature in the reactor rises to over 100 ° C. In this case, it should be noted that since the boiling point of one of the reactants, bromomethane, is low, a cooling trap device is necessary to prevent the loss of the reactants in the exothermic reaction. Upon completion of the reaction, the product is placed in a hot dryer and vaporized to remove unreacted material.

    In the case of 1,2-dimethylimidazole, the reaction proceeds similarly to the case of 1-methylimidazole. 1,2-dimethylimidazole, bromomethane, and an organic solvent are suitably mixed and reacted in a molar ratio of 1: 0.5 to 10: 0.5 to 10. It is also possible to add an organic solvent after the reaction and before filtration under reduced pressure. In this case, unlike 1-methylimidazole, the use of an organic solvent is intended to facilitate separation since the product is obtained in the form of a solid powder when 1,2-dimethylimidazole is used.

Organic solvents that can be used include acetonitrile, ethanol, methanol, N-methylpyrrolidone (NMP), acetone, ethylene glycol (EG), gamma butyrolactin (GBL) and propylene carbonate (PC), dimethylformamide (DMF) And so on. After completion of the reaction, the product dissolved in the previously used organic solvent was purified and then filtered under reduced pressure to remove the unreacted product, followed by quaternization of 3-ethyl 1,2-dimethylimidazolium bromide. ) Can be obtained.

Sodium tetrafluoroborate, tetrafluoroborate, potassium hexafluorophosphate, sodium perchlorate, etc. are completely dissolved in distilled water for the anion exchange reaction, and the solution is a solution in which quaternary imidazolium bromide is completely dissolved in distilled water. And anion exchange reaction proceeds. Since this reaction is a metathesis reaction, when the reaction is completed, a quaternary imidazolium salt and metal bromide can be obtained as an aqueous solution. Since the desired substance is a quaternary imidazolium salt, a process for removing metal bromide is required. The process for removing metal bromide is as follows. Distilled water was removed by distillation under reduced pressure in an aqueous solution in which both the reactants and the product were dissolved. , Dissolved in an organic solvent such as propylene carbonate (PC) and filtered under reduced pressure to remove the metal bromide. Thereafter, the product is obtained by removing the used organic solvent through vacuum distillation.

In carrying out the anion exchange reaction after the quaternization reaction, a strong acid was used to smoothly move the equilibrium shift in the right direction during the anion exchange reaction as in Equation (2). In selecting an anion, the process was configured to allow the use of ions having various conductivity. The anions usable in the present invention are as follows and their conductivity depends on the size of each anion. The conductivity of these anions is as follows.

_{^{BF 4 -> PF 6 -,}} ClO 4 -> CF 3 SO 3 -, AsF 6 -, (CF 3 SO 2) 2 N -> SbF 6 -> C 4 F 9 SO 3 -> BEt 4 -

The mechanism of quaternization reaction according to the present invention is as follows.

The mechanism of anion exchange reaction according to the present invention is as follows.

Hereinafter, one specific configuration of the present invention will be described in detail by way of examples, but the scope of the present invention is not limited only to these embodiments.

Example 1 Preparation of Imidazolium Bromide

1-Methylimidazole and bromomethane were added to a reactor equipped with cold traps at molar ratios of 1: 0.5, 1: 1 and 1: 1.5, and stirred with a stirrer (rpm 100-400) until the reaction was completed. Reacted for 24 hours. After the reaction was completed, the reaction product was placed in a dryer to remove the unreacted product by evaporation at 80 ℃ to give 1-ethyl, 3-methylimidazolium bromide. The highest yield was also obtained at 85% at a molar ratio of 1: 1.5.

1,2-dimethylimidazole, bromomethane, and acetone as solvents are placed in a reactor equipped with cold traps at a molar ratio of 1: 0.5: 1, 1: 1: 1, 1: 1.5: 1, and reacted with stirring. After completion of the reaction, the unreacted material that is insoluble in acetone is removed by filtration under reduced pressure to recover white powdery 1-ethyl-2,3-dimethylimidazolium bromide. When the reaction was carried out in a molar ratio of 1: 1: 1, the highest yield was obtained at 87%.

Example 2 Anion Exchange Reaction of Imidazolium Bromide

1: 1.0, 1: 1.2, 1: 1,4, 1: 1.6, 1 with 1-ethyl, 3-methylimidazolium bromide and sodium tetrafluoroborate, potassium fluorophosphate and sodium perchlorate for the anion exchange reaction The reaction was carried out at 20, 40, 60 and 100 ° C. at molar ratios of: 1.8 and 1: 2.0. After dissolving 1-ethyl, 3-methylimidazolium bromide and the material for the anion exchange reaction in distilled water, the sodium tetrafluoroborate solution, potassium fluorophosphate solution, and sodium perchlorate solution were respectively stirred at room temperature. The reaction was advanced while slowly adding methylimidazolium bromide solution. In order to remove the side reactions, the aqueous solution in which the reactants and the products are present was distilled under reduced pressure to remove distilled water, and acetone was added to dissolve the quaternary imidazolium salt and insoluble sodium bromide and potassium bromide were removed by filtration under reduced pressure. Subsequently, acetonitrile was also removed by distillation under reduced pressure, and according to each anion, 1-ethyl, 3-methylimidazolium tetrafluoroborate (EMIBF ₄ ), 1-ethyl, 3-methylimidazolium hexafluorophosphate (EMIPF ₆ ) and 1-ethyl, 3-methylimidazolium perchlorate (EMIClO ₄ ) were obtained. EMIBF ₄ , EMIPF ₆ and EMIClO ₄ yielded higher yields as the molar ratio and reaction temperature were increased.

In addition, 1-ethyl, 2,3-dimethylimidazolium bromide was reacted with sodium tetrafluoroborate, potassium fluorophosphate and sodium perchlorate in a 1: 1.0, 1: 1.2, 1: 1,4, 1 for anion exchange reaction. Reaction was carried out in the same manner as 1-ethyl, 2methylimidazolium bromide at 20, 40, 60 and 100 ° C. in a molar ratio of: 1.6, 1: 1.8 and 1: 2.0, and purified using DMF. -Ethyl, 2,3-dimethylimidazolium tetrafluoroborate (EDMIBF ₄ ), 1-ethyl, 2,3-dimethylimidazolium hexafluorophosphate (EDMIPF ₆ ), 1-ethyl, 2,3-dimethyl Imidazolium perchlorate (EDMIClO ₄ ) was obtained. The yield of EDMIBF ₄ , EDMIPF ₆ and EDMIClO ₄ increased as the molar ratio and reaction temperature increased, but there was no significant difference in the yield of more than 80% from the molar ratio of 1: 1.8 and above 60 ℃.

Example 3 Non-conductivity According to Temperature of Non-aqueous Electrolyte

The non-conductive conductivity of non-aqueous electrolyte containing 1M of EMIBF ₄ , EMIPF ₆ and EMIClO ₄ in propylene carbonate (PC) was measured by Conductivity Meters CDM210, meterLab. . Conductivity of the electrolyte containing the EMIBF ₄ is increased from 11.97mS / cm to 31.9mS / cm, the conductivity of the electrolyte containing EMIPF ₆ is increased from 12.56mS / cm to 38.41mS / cm, an electrolyte containing EMIClO ₄ The non-conductivity of increased from 8.89mS / cm to 29.98mS / cm. As the molar concentration increased over all temperature ranges, the non-conductivity also increased. It can be seen that it has high thermal stability because it shows high non-conductivity up to 90 ℃.

The non-conductive conductivity of the non-aqueous electrolyte containing 1M concentration of EDMIBF ₄ , EDMIPF ₆ and EDMIClO ₄ in propylene carbonate (PC) was measured by Conductivity Meters CDM210, meterLab. . The conductivity of the electrolyte containing EDMIBF ₄ increased from 12.46mS / cm to 33.80mS / cm, the conductivity of the electrolyte containing EDMIPF ₆ increased from 11.99mS / cm to 34.20mS / cm, and the electrolyte containing EDMIClO ₄ The non-conductivity of increased from 9.25mS / cm to 30.90mS / cm. As the molar concentration increased over all temperature ranges, the non-conductivity also increased. It can be seen that it has high thermal stability because it shows high non-conductivity up to 90 ℃.

Example 4 Non-conductivity According to Salt Concentration of Non-aqueous Electrolyte

The non-conductivity of the non-aqueous electrolyte containing EMIBF ₄ , EMIPF ₆ and EMIClO ₄ in propylene carbonate (PC) was measured according to the concentration of the electrolyte and is shown in FIG. 4. Dilution was performed based on 2M electrolyte, and the temperature was lowered to 20 ° C after complete dissolution at 60 ° C. Dilution was performed from the concentration at which no precipitation occurred at 20 ° C, the concentration was adjusted, and the non-conductivity was measured. In all cases, there was no change in non-conductivity above 1.6M. Conductivity of the electrolyte containing the EMIBF ₄ is increased from 4.12mS / cm to 14.1mS / cm, the conductivity of the electrolyte containing EMIPF ₆ is increased from 4.45mS / cm to 14.3mS / cm, an electrolyte containing EMIClO ₄ The specific conductivity of was increased from 4.13mS / cm to 12.15.mS/cm. At low concentrations, the non-conductivity increases rapidly as the molar concentration increases.

The non-conductive conductivity of the non-aqueous electrolyte containing EDMIBF ₄ , EDMIPF ₆ and EDMIClO ₄ in propylene carbonate (PC) was measured according to the concentration of the electrolyte and is shown in FIG. 5. Dilution was performed based on 2M electrolyte, and the temperature was lowered to 20 ° C after complete dissolution at 60 ° C. Dilution was performed from the concentration at which no precipitation occurred at 20 ° C, the concentration was adjusted, and the non-conductivity was measured. In all cases, there was no change in non-conductivity above 1.6M. The conductivity of the electrolyte containing EDMIBF ₄ increased from 5.65 mS / cm to 13.75 mS / cm, and the conductivity of the electrolyte containing EDMIPF ₆ increased from 5.24 mS / cm to 13.62 mS / cm, and the electrolyte containing EMIClO ₄ The non-conductivity of increased from 4.45mS / cm to 13.48mS / cm. At low concentrations, the non-conductivity increases rapidly as the molar concentration increases.

Example 5 CV measurement of half cell using EMIPF ₆ as electrolyte

A half cell using EMIPF ₆ as an electrolyte was prepared, and CV (Ptentiostat / Galvanostat 273A, EG & G) was measured in a voltage range of -2V to 2V. Platinum (Pt) was used as a counter electrode and an SCE saturated calomel electrode (sat'd KCl) was used as a reference electrode. As the working electrode, BP20 (specific surface area 2000 m ² / g, Kuraray. Co. Ltd) was used by coating the aluminum electrode using a binder.

As a result, it has a current range in the range of -7.4mA to 7.8mA and shows a nearly uniform value in the measured voltage range.

In the method for preparing a quaternary imidazolium salt used in electrolytes of energy storage devices such as electric double layer capacitors, aluminum, tantalum liquid electrolytic capacitors, secondary batteries, and electrolytes for electrochemical systems such as various sensors, Development of liquid phase reaction process using bromide compounds and their continuous manufacturing process instead of quaternization reaction through gas phase reaction improves the stability of the reaction while maintaining high final yield and simplifies the production process by facilitating the reaction control. To increase. It also reduces manufacturing costs by simplifying the construction of equipment and reducing safety equipment. In addition, by developing various anion exchange reaction process with high conductivity, various quaternary imidazolium salts are synthesized to prepare electrolyte salts for various electrochemical systems.

Claims (5)

a) reacting a tertiary imidazolium salt with an alkyl bromide; b) purifying the product by filtering the reaction solution under reduced pressure; c) for the product obtained quaternary imidazolium bromide, _{^{BF 4 -, PF 6 -,}} ClO 4 -, CF 3 SO 3 -, AsF 6 -, (CF 3 SO 2) 2 N -, SbF 6 -, C comprising any one of the anion exchange reaction with a strong acid containing eumyionreul of _{^{4 F 9 SO 3 - -,}} BEt 4; And d) a quaternary imidazolium salt prepared by a liquid phase process comprising removing metal bromide by a purification or recrystallization extraction method using an organic solvent. The non-aqueous electrolyte according to claim 1, wherein the product is purified by adding an organic solvent during the reaction of step a) or before the reduced pressure filtration of step c) after step a). The method of claim 1 or claim 2, wherein the organic solvent is ethanol, methanol, propanol, NMP, acetone, acetonitrile, ethylene glycol (EG), gamma butyrolactone (GBL), propylene carbonate (PC), dimethylformamide Non-aqueous electrolyte, characterized in that one organic solvent selected from the group consisting of (DMF). 3. A non-aqueous electrolyte according to claim 1 or 2, wherein the strong acid is sodium tetrafluoroborate, potassium hexafluorophosphate, sodium perchlorate or potassium trifluoromethanesulfonate. delete

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