KR100768528B1 - The manufacturing method of ionic liquids having highpurity - Google Patents

Abstract

A method for preparing an ionic liquid having high purity is provided to improve yield, to minimize the remaining of unreacted materials and to inhibit use of a solvent. A method for preparing an ionic liquid comprises the steps of dissolving 0.8-1.2 mol of an alkyl halide and 0.8-1.2 mol of pyrimidine or an alkyl imidazole in a first solvent to react it at a temperature of 0-200 deg.C and under a pressure of 1-12 bar for 4-24 hours, and removing the first solvent under the reduced pressure of 0-760 mmHg to prepare a cation compound; and dissolving 0.8-1.2 mol of the cation compound and 0.8-1.2 mol of an anion compound in a second solvent to react it at a temperature of -10 to 100 deg.C, and distilling it under the reduced pressure to remove the second solvent.

Description

High purity ionic liquid manufacturing method {THE MANUFACTURING METHOD OF IONIC LIQUIDS HAVING HIGHPURITY}

The present invention is the first reaction step of preparing a cationic compound by removing the solvent by dissolving the alkyl halide, pyridine or alkyl imidazole in a solvent to react to produce a high-purity ionic liquid (pressure liquid) and ,

The cationic compound and the anion compound are dissolved in a solvent and reacted, followed by a secondary reaction step of preparing an ionic liquid by removing the solvent by vacuum distillation to prepare an ionic liquid having high purity capable of efficiently producing an ionic liquid. It is about a method.

Ionic liquids have recently been studied in Korea as active materials for many applications such as environmentally friendly clean solvents, secondary battery electrolytes, and electrically conductive materials.

The general characteristics of ionic liquids are organic cations and organic / inorganic anions. They are liquid at room temperature or below 100 ℃, have high heat resistance, non-flammable and very low solubility in water unlike general ionic materials. It is a material with high solubility in organic solvents. In addition, the movement of the electrons is active and the conductivity is very excellent.

Although the field of application of ionic liquids is not very active in Korea, the application is in progress in various industries overseas.

In particular, US patent US 2005/0205468 A1 was applied for the purification of impurities from natural gas and US 2006/0135839 A1 was used as a catalyst in the alkylation process of olefins. As another example, US 6673737 B2 shows applications as catalysts for various chemical reactions, Chem. Commun. 2972 (2002) describes an application as a dye-sensitized solar cell in Electrochem. Commun 5, 1016 (2003) shows application as a secondary battery electrolyte.

Some applications are also applied as patents in Korea, but the development of the application is insignificant.

Despite the application of these ionic liquids, a small number of companies synthesize them and use them in Korea.

Briefly referring to the method for preparing the ionic liquid in Japanese Patent 2005-232077, the reaction was induced by stirring for 8 hours at 80 ° C. or more using pyridine and acetnatrile as a solvent using alkyl halide as a first reaction. The solvent and the unreacted raw materials were removed through reduced pressure, and the residue was dried again under reduced pressure. Activated carbon was used for purification. The primary reactant was added to pure water and filtered after stirring for 1 hour or more with activated carbon. The alkyl pyridinium halide synthesized as described above is reacted with an organic or inorganic ionic substance in an aqueous solution in a secondary reaction, extracted with ethyl acetate, washed twice with pure water, and ethyl acetate is removed under reduced pressure to prepare an ionic liquid. Doing.

In addition, US Patent US 2006/0135839 A1 introduces a process for removing unreacted raw materials through a reduced pressure by reacting at a high temperature (140 ° C.) for 12 hours or more without using an organic solvent in a secondary reaction. Hot acetone was used to obtain pure material.

As an example of the two patents mentioned, the first reaction uses an excess of a substance and decompresses it in order to remove it, which can have a significant effect on yield. In the second reaction, it is difficult to increase the yield by extraction of the organic solvent. Even if the organic solvent is removed under reduced pressure, a small amount of the organic solvent is contained in the ionic liquid unless there is a special device, which greatly affects the physical properties of the ionic liquid. I had a problem.

In the present invention, in order to solve the above problems in order to efficiently produce the ionic liquid, in the reaction of the alkyl halide and pyridine or alkyl imidazole in the first reaction induces an improvement in yield and minimizes the remaining of unreacted substances It is an object of the present invention to provide a method for producing an ionic liquid which suppresses the use of the solvent and increases the yield by removing the organic solvent in the water washing method after the reaction in the secondary reaction and proceeding with water washing.

It aims to produce a high yield of ionic liquid through a two-step reaction and purification process.

In order to achieve the above object, in the present invention, 0.8 to 1.2 mole of alkyl halide and 0.8 to 1.2 mole of pyridine or alkyl imidazole are dissolved in a primary solvent and 4 to 12 bar at a temperature of 0 to 200 ° C. After reacting for 24 hours and carried out under reduced pressure at 0 ~ 760mmHg to remove the primary solvent to prepare a cationic compound (S1); And,

The secondary reaction for preparing the ionic liquid by dissolving the cationic compound 0.8 ~ 1.2 mole and the anionic compound 0.8 ~ 1.2mole in a secondary solvent to react at -10 ~ 100 ℃ and then removing the secondary solvent by vacuum distillation A high purity ionic liquid production method consisting of the step (S2); the main configuration.

Hereinafter, the above configuration will be described in more detail.

In the first reaction, alkyl pyridinium halides or alkyl imidazolininium halides are prepared using alkyl halides, pyridine and alkyl imidazoles as raw materials.

The alkyl halide is 1-ethyl chloride, 1-butyl chloride, 1-hexyl chloride, 1-octyl chloride, 1-decyl chloride, 1-dodecyl chloride, 1-tetradecyl chloride, 1-hexadecyl chloride, 1-octa Decyl chloride, 1-ethyl bromide, 1-butyl bromide, 1-hexyl bromide, 1-octyl bromide, 1-decyl bromide, 1-dodecyl bromide, 1-tetradecyl bromide, 1-hexadecyl bromide, 1-octadecyl Bromide, 1-ethyl iodide, 1-butyl iodide, 1-hexyl iodide, 1-octyl iodide, 1-decyl iodide, 1-dodecyl iodide, 1-tetradecyl i Odide, 1-hexadecyl iodide, 1-octadecyl iodide, 1-ethyl fluoride, 1-butyl fluoride, 1-hexyl fluoride, 1-octyl fluoride, 1-decyl fluoride, 1 -Dodecyl fluoride, 1-tet Decyl fluoride, and a 1-hexadecyl fluoride, 1-octadecyl fluoride any one kind or not less than 2 kinds selected from.

The alkyl halide uses 0.8 to 1.2 mole, and when used at 0.8 mole or less, economic efficiency is lost in the reaction yield, and when used at 1.2 mole or more, an additional process time is added to remove unreacted reactants. It is preferable to use 0.8 to 1.2 mole.

The alkyl imidazole is characterized in that 1-methyl imidazole or 1-ethyl imidazole.

The alkyl imidazole is 0.8 ~ 1.0mole is used, when using less than 0.8mole is economical in the reaction yield, when using more than 1.0mole process time is added to the removal of unreacted reactants It is preferable to use 0.8 ~ 1.0 mole because it occurs.

The primary solvent is a solvent, ethanol, isopropyl alcohol, butanol, acetone, methyl ethyl ketone, diethyl ether, ethyl acetate, chloroform, is characterized in that any one or two or more selected from methyl chloride.

Reaction conditions in the first reaction step is to maintain 1 ~ 12 bar at atmospheric pressure or pressurized conditions, having a reaction time of 4 to 24 hours at a reaction temperature of 1 ~ 200 ℃,

When the pressurization condition is 1bar or less, the reactivity rapidly decreases and the reaction time is long due to the azeotropy of the solvent and the alkyl halide, and when it is 12bar or more, it is difficult to manufacture the equipment of a general reactor, so additional equipment is required. It is preferable to maintain the ˜12 bar, preferably 1 to 6 bar, more preferably 1 to 3 bar.

When the reaction temperature is 0 ℃ or less, the reaction rate is slowed and the reaction time is long, and when the reaction temperature is 200 ℃ or more, the reaction rate is lowered above the boiling point of the solvent and some raw materials, it is preferable to maintain 0 ~ 200 ℃, Preferably it is 50-150 degreeC, More preferably, it is good to maintain 80-140 degreeC.

When the reaction time is 4 hours or less, the reaction yield is low, and when the reaction time is 24 hours or more, since the reaction yield is not further enhanced, it is preferable to maintain 4 to 24 hours, preferably 10 to 18. It is preferable to maintain the time, more preferably 10 to 16 hours.

Concentration conditions for obtaining the first reactant are carried out under reduced pressure to remove the solvent. Condensation conditions are carried out at 0 to 760 mmHg as the concentration conditions. If additional equipment is required and the atmospheric pressure is 760 mmHg or more, the remaining amount of the solvent remains, so it is preferable to maintain 0 to 760 mmHg, preferably 0 to 500 mmHg, more preferably 0 to 200 mmHg. Good to do.

The cationic compounds obtained under the above reaction conditions are pyridine series, 1-ethyl pyridinium chloride, 1-butyl pyridinium chloride, 1-hexyl pyridinium chloride, 1-octyl pyridinium chloride, 1-decyl pyridininib Chloride, 1-dodecyl pyridininib chloride, 1-tetradecyl pyridininib chloride, 1-hexadecyl pyridininib chloride, 1-octadecyl pyridininib chloride, 1-ethyl pyridinium bromide, 1-butyl pyridine Dinitin bromide, 1-hexyl pyridinium bromide, 1-octyl pyridinium bromide, 1-decyl pyridinium bromide, 1-dodecyl pyridinium bromide, 1-tetradecyl pyridinium bromide, 1-hexadecyl Pyridinium bromide, 1-octadecyl pyridinium bromide, 1-ethyl pyridinium iodide, 1-butyl pyridinium iodide, 1-hexyl pyridine Dinitin iodide, 1-octyl pyridinium iodide, 1-decyl pyridinium iodide, 1-dodecyl pyridinium iodide, 1-tetradecyl pyridinium iodide, 1- Hexadecyl pyridinium iodide, 1-octadecyl pyridinium iodide, 1-ethyl pyridinium fluoride, 1-butyl pyridinium fluoride, 1-hexyl pyridinium fluoride, 1-octyl Pyridinium fluoride, 1-decyl pyridinium fluoride, 1-dodecyl pyridinium fluoride, 1-tetradecyl pyridinium fluoride, 1-hexadecyl pyridinium fluoride, 1-octadecyl pyridine Dinitin fluoride and the like are prepared, and the 1-methyl imidazole series includes 1-ethyl 3-methyl imidazolininium chloride, 1-butyl 3-methyl imidazolininibium chloride, 1-hexyl 3-methyl imidazolininib Chloride, 1-octyl 3-methyl imidazolininisot chlora Id, 1-decyl 3-methyl imidazolininib chloride, 1-dodecyl 3-methyl imidazolininib chloride, 1-tetradecyl 3-methyl imidazolininib chloride, 1-hexadecyl 3-methyl imidazoli Niche chloride, 1-octadecyl 3-methyl imidazolininib chloride, 1-ethyl 3-methyl imidazolininib bromide, 1-butyl 3-methyl imidazolininib bromide, 1-hexyl 3-methyl imidazolininib Bromide, 1-octyl 3-methyl imidazolininib bromide, 1-decyl 3-methyl imidazolininib bromide, 1-dodecyl 3-methyl imidazolininib bromide, 1-tetradecyl 3-methyl imidazolininib Bromide, 1-hexadecyl 3-methyl imidazolininib bromide, 1-octadecyl 3-methyl imidazolininib bromide, 1-ethyl 3-methyl imidazolininib iodide, 1-butyl 3-methyl imida Jolininib Iodide, 1-hexyl 3-methyl imid Jolininib iodide, 1-octyl 3-methyl imidazolininib iodide, 1-decyl 3-methyl imidazolininib iodide, 1-dodecyl 3-methyl imidazolininib iodide, 1 -Tetradecyl 3-methyl imidazolininib iodide, 1-hexadecyl 3-methyl imidazolininib iodide, 1-octadecyl 3-methyl imidazolininib iodide, 1-ethyl 3-methyl Imidazolininibfloride, 1-butyl 3-methyl imidazolininib fluoride, 1-hexyl 3-methyl imidazolininib fluoride, 1-octyl 3-methyl imidazolininib fluoride, 1-decyl 3 -Methyl imidazolininium fluoride, 1-dodecyl 3-methyl imidazolininib fluoride, 1-tetradecyl 3-methyl imidazolininib fluoride, 1-hexadecyl 3-methyl imidazolininib fluoride , 1-octadecyl 3-methyl imidazolininium fluoride, etc. are prepared, and 1-ethyl imidazole type Thermally, 1-ethyl 3-ethyl imidazolininib chloride, 1-butyl 3-ethyl imidazolininib chloride, 1-hexyl 3-ethyl imidazolininib chloride, 1-octyl 3-ethyl imidazolininib chloride, 1-decyl 3-ethyl imidazolininib chloride, 1-dodecyl 3-ethyl imidazolininib chloride, 1-tetradecyl 3-ethyl imidazolininib chloride, 1-hexadecyl 3-ethyl imidazolininib chloride , 1-octadecyl 3-ethyl imidazolininib chloride, 1-ethyl 3-ethyl imidazolininib bromide, 1-butyl 3-ethyl imidazolininib bromide, 1-hexyl 3-ethyl imidazolininib bromide, 1-octyl 3-ethyl imidazolininib bromide, 1-decyl 3-ethyl imidazolininib bromide, 1-dodecyl 3-ethyl imidazolininib bromide, 1-tetradecyl 3-ethyl imidazolininib bromide, 1-hexadecyl 3-ethyl imidazolini 윰 bromide, 1-octadecyl 3-ethylimidazolininib bromide, 1-ethyl 3-ethyl imidazolininib iodide, 1-butyl 3-ethyl imidazolininib iodide, 1-hexyl 3-ethyl Imidazolininib iodide, 1-octyl 3-ethyl imidazolininib iodide, 1-decyl 3-ethyl imidazolininib iodide, 1-dodecyl 3-ethyl imidazolininib iodide , 1-tetradecyl 3-ethyl imidazolininib iodide, 1-hexadecyl 3-ethyl imidazolininib iodide, 1-octadecyl 3-ethyl imidazolininib iodide, 1-ethyl 3 -Ethyl imidazolininibfloride, 1-butyl 3-ethyl imidazolininib fluoride, 1-hexyl 3-ethyl imidazolininib fluoride, 1-octyl 3-ethyl imidazolininib fluoride, 1- Decyl 3-ethyl imidazolininib fluoride, 1-dodecyl 3-ethyl imidazolininib fluoride, 1-te It is characterized in that it is any one selected from Radecyl 3-ethyl imidazolininium fluoride, 1-hexadecyl 3-ethyl imidazolininib fluoride, and 1-octadecyl 3-ethyl imidazolininib fluoride. .

The reactants reacting secondary with the product of the first reaction are inorganic / organic anion compounds, the anion compounds being lithium trifluoro methane sulfonate, lithium bis (trifluoro methane sulfonyl) imide, lithium chloro oxide, sodium Trifluoro methane sulfonate, sodium bis (trifluoro methane sulfonyl) imide, and sodium chloro oxide.

The cationic compound is used at 1.0 to 1.1 mole, and when used at 1.0 or less, the reaction yield is reduced, and when used at 1.1 mole or more, it is difficult to recover unreacted material after the reaction and remains as impurities because it is 1.0. It is preferable to use at 1.1 mole.

The anionic compound is used at 0.8 ~ 1.0 mole, the reaction yield is lowered when using less than 0.8 mole, and when using more than 1.0 mole unreacted substances remain as impurities, further post-treatment measures are required It is recommended to use 0.8 ~ 1.0 mole.

The secondary solvent used in the secondary reaction is water at atmospheric pressure, and the auxiliary solvent is selected from chloroform, methylene chloride, ethyl ether, ethyl acetate, carbon tetrachloride, ligroin, petroleum ether, butanol, hexanol It is an organic solvent which mixed 1 type or 2 or more types.

In the secondary reaction, the reaction temperature is -10 to 100 ° C., when the reaction temperature is -10 ° C. or lower, the fluidity of the reactants is lost, and when the temperature is 100 ° C. or higher, the boiling point of the solvent and the auxiliary solvent is greater than that, thus requiring additional equipment for work. It is good to maintain 10-100 degreeC, Preferably 0-50 degreeC is good, More preferably, it is good to carry out at 0-40 degreeC.

In the reaction process of the secondary reaction, a cationic compound and an anionic compound are dissolved in a solvent, respectively, and then a homogeneous phase reaction is performed. When water is used as the solvent, the reactants appear in water due to the nature of the ionic liquid. In this case, to improve phase separation with water, an auxiliary solvent is added and used. The co-solvent uses an organic solvent having a weak polarity that can be separated from water well and uses the co-solvent described above.

The organic layer separated from the aqueous layer is distilled under reduced pressure to remove the solvent, thereby removing the organic solvent from the ionic liquid. At this time, if the removal of the organic solvent is not complete, it will affect the non-volatile, inert properties, etc. of the ionic liquid and must be removed completely. The solvent removal step is vacuum vacuum distillation, and the reduced pressure is carried out at 0 ~ 200 ℃, the vacuum pressure is carried out at 0 ~ 760 mmHg.

When the decompression temperature is 0 ° C. or less, it is difficult to remove the auxiliary solvent, and when the temperature is 200 ° C. or higher, the removal of the solvent is easy, but discoloration of the product due to unreacted material is caused, so it is preferable to maintain 0 to 200 ° C., preferably It is good to maintain 20-100 degreeC, More preferably, keep it at 30-100 degreeC.

When the vacuum pressure is 0 mmHg or less, the removal of the auxiliary solvent proceeds easily, but an expensive additional facility is required for manufacturing, and economical consideration should be taken into account. When the vacuum pressure is more than 760 mmHg, the removal time is long and the removal of the solvent and auxiliary solvent is It is preferable to maintain 0 to 760 mmHg because it is difficult, preferably 0 to 500 mmHg, and more preferably 0 to 100 mmHg.

The ionic liquid obtained in the secondary reaction is a pyridine substance, such as 1-ethyl pyridinine trifluoro methane sulfonate, 1-butyl pyridinine trifluoro methane sulfonate, 1-hexyl pyridinine trifluoro methane sulfo Nate, 1-octyl pyridinium trifluoro methane sulfonate, 1-decyl pyridinium trifluoro methane sulfonate, 1-dodecyl pyridinium trifluoro methane sulfonate, 1-tetradecyl pyridinium tri Pyridinium trifluoro methane sulfonate series consisting of fluoromethane sulfonate, 1-hexadecyl pyridininitri trifluoro methane sulfonate, 1-octadecyl pyridininitri trifluoro methane sulfonate,

1-ethyl pyridinium bis (trifluoro methane sulfonyl) imide, 1-butyl pyridinium bis (trifluoro methane sulfonyl) imide, 1-hexyl pyridinium bis (trifluoro methane sulfonyl ) Imide, 1-octyl pyridinium bis (trifluoro methane sulfonyl) imide, 1-decyl pyridinium bis (trifluoro methane sulfonyl) imide, 1-dodecyl pyridinium bis (tri Fluoro methane sulfonyl) imide, 1-tetradecyl pyridinium bis (trifluoro methane sulfonyl) imide, 1-hexadecyl pyridinium bis (trifluoro methane sulfonyl) imide, 1-octa A bis (trifluoro methane sulfonyl) imide series consisting of decyl pyridinium bis (trifluoro methane sulfonyl) imide,

1-ethyl pyridinium chloro oxide, 1-butyl pyridinium chloro oxide, 1-hexyl pyridinium chloro oxide, 1-octyl pyridinium chloro oxide, 1-decyl pyridinium chloro oxide, 1-dodecyl pyridine A chloro oxide series consisting of diniq chloro oxide, 1-tetradecyl pyridinini chloro oxide, 1-hexadecyl pyridinini chloro oxide, 1-octadecyl pyridinini chloro oxide,

1-ethyl 3-methyl imidazolininib trifluoro methane sulfonate, 1-butyl 3-methyl imidazolininib trifluoro methane sulfonate, 1-hexyl 3-methyl imidazoli as 1-methyl imidazole material Nitrile trifluoro methane sulfonate, 1-octyl 3-methyl imidazolininiche trifluoro methane sulfonate, 1-decyl 3-methyl imidazolininib trifluoro methane sulfonate, 1-dodecyl 3-methyl imid Dazolininib trifluoro methane sulfonate, 1-tetradecyl 3-methyl imidazolininib trifluoro methane sulfonate, 1-hexadecyl 3-methyl imidazolininib trifluoro methane sulfonate, 1-octadecyl A trifluoro methane sulfonate family consisting of 3-methyl imidazolininib trifluoro methane sulfonate,

1-ethyl 3-methyl imidazolininib bis (trifluoro methane sulfonyl) imide, 1-butyl 3-methyl imidazolininib bis (trifluoro methane sulfonyl) imide, 1-hexyl 3-methyl Imidazolininib bis (trifluoro methane sulfonyl) imide, 1-octyl 3-methyl imidazolininib bis (trifluoro methane sulfonyl) imide, 1-decyl 3-methyl imidazolininib trifluor Rho methane sulfonate, 1-dodecyl 3-methyl imidazolininib bis (trifluoro methane sulfonyl) imide, 1-tetradecyl 3-methyl imidazolininib bis (trifluoro methane sulfonyl) imide Bis (tri) consisting of 1-hexadecyl 3-methyl imidazolininib bis (trifluoro methane sulfonyl) imide, 1-octadecyl 3-methyl imidazolininib bis (trifluoro methane sulfonyl) imide Fluoromethane sulfonyl) imide series,

1-Ethyl 3-methyl imidazolininiche chloro oxide, 1-butyl 3-methyl imidazoline niche chloro oxide, 1-hexyl 3-methyl imidazolininiche chloro oxide, 1-octyl 3-methyl imidazolininiche chloro Oxide, 1-decyl 3-methyl imidazolininib chloro oxide, 1-dodecyl 3-methyl imidazolininib chloro oxide, 1-tetradecyl 3-methyl imidazolininib chloro oxide, 1-hexadecyl 3-methyl A chloro oxide series consisting of imidazolininiche chloro oxide, 1-octadecyl 3-methyl imidazolininiche chloro oxide is prepared, and 1-ethyl imidazoline is also prepared in the same series as 1-methyl imidazoline.

Hereinafter, the above-described configuration will be described in more detail with reference to the following examples.

Example 1

After mixing 148.5 g of isopropyl alcohol with 228.5 g (2.9 mole) of 1-chlorohexane of 98% purity and 350 g (2.9 mole) of reagent grade pyridine, the mixture was introduced into a 1 liter pressurized reactor and the reaction temperature was increased to 135 ° C. It was controlled to maintain and stirred using a magnetic stirrer and the total reaction time was 10 hours. At this time, the pressure inside the reactor is generated by the natural vapor pressure of 0.5 bar is maintained continuously during the reaction. The reaction was terminated based on the total amine number and the reaction was terminated when the total amine value was 5.0 mg KOH / g or less. Concentration of the reaction was carried out using a rotary evaporator to remove the unreacted raw material and isopropyl alcohol to give 517.2 g of 1-hexyl pyridinium chloride as a yellow viscous liquid.

Dissolve 199.7 g (1.0 mole) of hexyl pyridinium chloride and 287.1 g (1.0 mole) of lithium bis (trifluoromethane sulfonyl) imide prepared in the first reaction in 100 g of water, and then 1000 ml two-neck round flask. After filling with an aqueous solution of hexyl pyridinium chloride, an aqueous solution of lithium bis (trifluoromethane sulfonyl) imide was added to a stirring solution of hexyl pyridinium chloride at room temperature. The reaction proceeded with a slight exotherm and the reaction was terminated at the point where the exotherm was terminated and transferred to the separation tank and left to stand. Phase separation proceeds with ionic liquid and water within 5 minutes, ionic liquid in the lower part, water in the upper part, and only the lower liquid is separated to remove the small amount of water present in the reactant through the first vacuum distillation. Lithium chloride, a secondary reactant dissolved in, is produced as a solid in the reactant. Lithium chloride mixed with the reactant as a solid was removed by filtration to obtain 408.5 g (91.9%) of pure hexyl pyridinium bis (trifluoro methyl sulfonyl) imide.

Example 2

In the first reaction, 268.45 g (2.9 mole) of 1-chlorobutane with a purity of 98% or more and 144.6 g of isopropyl alcohol were prepared in the same manner as in Example 1 with 350 g (2.9 mole) of reagent grade pyridine. Dissolve 171.7 g (1.0 mole) of 1-butyl pyridinium chloride and 287.1 g (1.0 mole) of lithium bis (trifluoromethane sulfonyl) imide in 100 g of water, respectively, and then hexyl pyridi in a 1000 ml two-necked round flask. After filling with niobium chloride aqueous solution, an aqueous lithium bis (trifluoromethane sulfonyl) imide solution was added to a stirring aqueous solution of hexyl pyridinium chloride at room temperature. The reaction proceeds with a slight exotherm and 50 ml of a solvent chloroform which is not mixed with water at the point of exotherm was added, stirred for 30 minutes, and then transferred to a separation tank to stand still. Phase separation is carried out within 5 minutes of the ionic liquid chloroform solution and water, and the ionic liquid chloroform solution is disposed at the lower part, and water is present at the upper part. Only the lower liquid is separated and washed twice with 200 ml of water. The separated ionic liquid solution was subjected to primary vacuum distillation to remove chloroform and a small amount of water present in the reaction product to obtain 383.1 g (yield 92%) of pure butyl pyridinium bis (trifluoro methyl sulfonyl) imide. Could.

Example 3

199.7 g (1.0 mole) of hexyl pyridinium chloride prepared in Example 1 and 156 g (1.0 mole) of lithium trifluoromethane sulfonate were dissolved in 100 g of water, respectively, and then hexyl pyridinidi chloride in a 1000 ml two-necked round flask. After the aqueous solution was filled, an aqueous lithium trifluoro methane sulfonate solution was added to a stirring aqueous solution of hexyl pyridinium chloride at room temperature. The reaction proceeded with a slight exotherm and the reaction was terminated at the point where the exotherm was terminated and transferred to the separation tank and left to stand. Phase separation proceeds with ionic liquid and water within 5 minutes, ionic liquid in the lower part, water in the upper part, and only the lower liquid is separated to remove the small amount of water present in the reactant through the first vacuum distillation and Lithium chloride, a secondary reactant dissolved in, is produced as a solid in the reactant. Lithium chloride mixed with reactants as a solid was removed by filtration to obtain 275.7 g (88% yield) of pure hexyl pyridinium trifluoro methane sulfonate.

Example 4

199.7 g (1.0 mole) of hexyl pyridinium chloride prepared in Example 1 and 106.4 g (1.0 mole) of lithium perchlorite were dissolved in 100 g of water, respectively, and a 1000 ml two-necked round flask was charged with an aqueous solution of hexyl pyridinium chloride. At room temperature, a lithium perchlorite aqueous solution was added to a stirring hexyl pyridinium chloride aqueous solution. The reaction proceeded with a slight exotherm and the reaction was terminated at the point where the exotherm was terminated and transferred to the separation tank and left to stand. Phase separation proceeds with ionic liquid and water within 5 minutes, ionic liquid in the lower part, water in the upper part, and only the lower liquid is separated to remove the small amount of water present in the reactant through the first vacuum distillation and Lithium chloride, a secondary reactant dissolved in, is produced as a solid in the reactant. Lithium chloride mixed with the reactant as a solid was removed by filtration to obtain 275.7 g (88% yield) of pure hexyl pyridinium trifluoro methane sulfonate.

Example 5

92.57 g (1 mole) of 1-chlorobutane with a purity of 98% or more and 174 g of ethyl alcohol are mixed with a reagent grade 1-methyl imidazole 82.1 (1 mole) solvent, and then introduced into a 1 liter pressurized reactor, followed by reaction temperature of 135 ℃ was controlled to maintain and stirred using a magnetic stirrer and the total reaction time was carried out for 11 hours. At this time, the pressure inside the reactor is generated by the natural vapor pressure of 0.5 bar is maintained continuously during the reaction. The reaction was terminated based on the total amine number and the reaction was terminated when the total amine value was 85 mg KOH / g or less. Concentration of the reaction was carried out using a rotary evaporator to remove the unreacted raw material and ethyl alcohol to give 167.4 g (yield 95.9%) of 1-butyl 3-methyl imidazolininib chloride as a yellow viscous liquid.

148.7 g (0.85 mole) of 1-butyl 3-methyl imidazolininium chloride prepared in the first reaction was dissolved in 140 g of water, and charged into a 1000 ml two-neck round flask, followed by lithium bis (trifluoro methane sulfonyl). 244 g (0.85 mole) of imide was added to the aqueous solution of 1-butyl 3-methyl imidazolineinium chloride in powder form. Thereafter, the conditions were the same as those of Example 1, where 386.7 g (yield 98%) of pure 1-butyl 3-methyl imidazoliny cos (trifluoromethyl sulfonyl) imide was obtained.

Example 6

Hexyl pyridinium perflorite was prepared using lithium perchlorite under the same conditions as the first reactant prepared in Example 3.

Example 7

1-Butyl 3-methyl imidazoliny coen perchlorite was prepared using lithium perchlorite under the same conditions as the primary reactant prepared in Example 5.

As described above, the method for preparing the ionic liquid according to the present invention induces an improvement in yield in the reaction of the alkyl halide with pyridine or alkyl imidazole in the first reaction and minimizes the residual of unreacted material. How to do it,

In the secondary reaction, the organic solvent is removed from the water washing method after the reaction, and the water washing process is performed to suppress the use of the solvent and to increase the yield.

Claims (9)

After dissolving 0.8 ~ 1.2 mole of alkyl halide and 0.8 ~ 1.2 mole of pyridine or alkyl imidazole in primary solvent, reacting at 1 ~ 12 bar, 0 ~ 200 ℃ for 4 ~ 24 hours, and decompressing at 0 ~ 760mmHg By removing the primary solvent to prepare a cationic compound the first reaction step (S1); And, The secondary reaction for preparing the ionic liquid by dissolving the cationic compound 0.8 ~ 1.2 mole and the anionic compound 0.8 ~ 1.2mole in a secondary solvent to react at -10 ~ 100 ℃ and then removing the secondary solvent by vacuum distillation Step (S2); high purity ionic liquid production method characterized in that consisting of. The alkyl halide of claim 1, wherein the alkyl halide is 1-ethyl chloride, 1-butyl chloride, 1-hexyl chloride, 1-octyl chloride, 1-decyl chloride, 1-dodecyl chloride, 1-tetradecyl chloride, 1-hexadecyl Chloride, 1-octadecyl chloride, 1-ethyl bromide, 1-butyl bromide, 1-hexyl bromide, 1-octyl bromide, 1-decyl bromide, 1-dodecyl bromide, 1-tetradecyl bromide, 1-hexadecyl bromide , 1-octadecyl bromide, 1-ethyl iodide, 1-butyl iodide, 1-hexyl iodide, 1-octyl iodide, 1-decyl iodide, 1-dodecyl iodide, 1-tetradecyl iodide, 1-hexadecyl iodide, 1-octadecyl iodide, 1-ethyl fluoride, 1-butyl fluoride, 1-hexyl fluoride, 1-octyl fluoride, 1- Decyl Floride, 1-Dodecyl Flora De, 1-tetradecyl fluoride, 1-hexadecyl fluoride, 1-octadecyl fluoride either alone or in combination of two method for producing an ionic liquid of high purity, characterized in that mixing of two or more selected from. The method of claim 1 wherein the alkyl imidazole is 1-methyl imidazole or 1-ethyl imidazole. The method of claim 1, wherein the primary solvent is any one selected from solvents, ethanol, isopropyl alcohol, butanol, acetone, methyl ethyl ketone, diethyl ether, ethyl acetate, chloroform, methyl chloride, or a mixture of two or more thereof. A high purity ionic liquid production method characterized by the above-mentioned. The method of claim 1, wherein the secondary solvent is water and any one or two selected from chloroform, methylene chloride, ethyl ether, ethyl acetate, carbon tetrachloride, ligroin, petroleum ether, butanol, hexanol as an auxiliary solvent A high purity ionic liquid production method characterized by the above mixture. The compound according to claim 1, wherein the cationic compound is 1-ethyl pyridinium chloride, 1-butyl pyridinium chloride, 1-hexyl pyridinium chloride, 1-octyl pyridinium chloride, 1-decyl pyridinium chloride, 1 -Dodecyl pyridinium chloride, 1-tetradecyl pyridininib chloride, 1-hexadecyl pyridininib chloride, 1-octadecyl pyridininib chloride, 1-ethyl pyridinib bromide, 1-butyl pyridinib bromide , 1-hexyl pyridinium bromide, 1-octyl pyridinium bromide, 1-decyl pyridinium bromide, 1-dodecyl pyridinium bromide, 1-tetradecyl pyridinium bromide, 1-hexadecyl pyridininib Bromide, 1-octadecyl pyridinium bromide, 1-ethyl pyridinium iodide, 1-butyl pyridinium iodide, 1-hexyl pyridinium iodide, 1-octyl pyridine Dinitin iodide, 1-decyl pyridinium iodide, 1-dodecyl pyridinium iodide, 1-tetradecyl pyridininib iodide, 1-hexadecyl pyridininib iodide, 1 Octadecyl pyridinium iodide, 1-ethyl pyridinium fluoride, 1-butyl pyridinium fluoride, 1-hexyl pyridinium fluoride, 1-octyl pyridinium fluoride, 1-decyl pyridine Dinitin fluoride, 1-dodecyl pyridinium fluoride, 1-tetradecyl pyridinium fluoride, 1-hexadecyl pyridinium fluoride, 1-octadecyl pyridinium fluoride, and the like. Methyl imidazole series include 1-ethyl 3-methyl imidazolininib chloride, 1-butyl 3-methyl imidazolininib chloride, 1-hexyl 3-methyl imidazolininib chloride, 1-octyl 3-methyl imida Jolininib chloride, 1-decyl 3-methyl imidazolini 윰 chloride, 1-dodecyl 3-methyl imidazolininib chloride, 1-tetradecyl 3-methyl imidazolininib chloride, 1-hexadecyl 3-methyl imidazolininib chloride, 1-octadecyl 3-methyl imid Dazolininib chloride, 1-ethyl 3-methyl imidazolininib bromide, 1-butyl 3-methyl imidazolininib bromide, 1-hexyl 3-methyl imidazolininib bromide, 1-octyl 3-methyl imidazoli Nichem bromide, 1-decyl 3-methyl imidazolininib bromide, 1-dodecyl 3-methyl imidazolininib bromide, 1-tetradecyl 3-methyl imidazolininib bromide, 1-hexadecyl 3-methyl imida Jolininib bromide, 1-octadecyl 3-methyl imidazolininib bromide, 1-ethyl 3-methyl imidazolininib iodide, 1-butyl 3-methyl imidazolininib iodide, 1-hexyl 3- Methyl imidazolininib iodide, 1-octyl 3 -Methyl imidazolininib iodide, 1-decyl 3-methyl imidazolininib iodide, 1-dodecyl 3-methyl imidazolininib iodide, 1-tetradecyl 3-methyl imidazolininib Iodide, 1-hexadecyl 3-methyl imidazolininib iodide, 1-octadecyl 3-methyl imidazolininib iodide, 1-ethyl 3-methyl imidazolininib fluoride, 1-butyl 3-methyl imidazolininibfloride, 1-hexyl 3-methyl imidazolininib fluoride, 1-octyl 3-methyl imidazolininib fluoride, 1-decyl 3-methyl imidazolininib fluoride, 1 -Dodecyl 3-methyl imidazolininib fluoride, 1-tetradecyl 3-methyl imidazolininib fluoride, 1-hexadecyl 3-methyl imidazolininib fluoride, 1-octadecyl 3-methyl imida Jolininib fluoride and the like are prepared as the 1-ethyl imidazole series 1-ethyl 3-ethyl imidazoli 윰 Chloride, 1-butyl 3-ethyl imidazolininib chloride, 1-hexyl 3-ethyl imidazolininib chloride, 1-octyl 3-ethyl imidazolininib chloride, 1-decyl 3-ethyl imidazolininib Chloride, 1-dodecyl 3-ethyl imidazolininib chloride, 1-tetradecyl 3-ethyl imidazolininib chloride, 1-hexadecyl 3-ethyl imidazolininib chloride, 1-octadecyl 3-ethyl imida Jolininib chloride, 1-ethyl 3-ethyl imidazolininib bromide, 1-butyl 3-ethyl imidazolininib bromide, 1-hexyl 3-ethyl imidazolininib bromide, 1-octyl 3-ethyl imidazolininib Bromide, 1-decyl 3-ethyl imidazolininib bromide, 1-dodecyl 3-ethyl imidazolininib bromide, 1-tetradecyl 3-ethyl imidazolininib bromide, 1-hexadecyl 3-ethyl imidazoli Nippon Bromide, 1-octadecyl 3-ethyl Imidazolininib bromide, 1-ethyl 3-ethyl imidazolininib iodide, 1-butyl 3-ethyl imidazolininib iodide, 1-hexyl 3-ethyl imidazolininib iodide, 1- Octyl 3-ethyl imidazolininib iodide, 1-decyl 3-ethyl imidazolininib iodide, 1-dodecyl 3-ethyl imidazolininib iodide, 1-tetradecyl 3-ethyl imida Jolininib iodide, 1-hexadecyl 3-ethyl imidazolininib iodide, 1-octadecyl 3-ethyl imidazolininib iodide, 1-ethyl 3-ethyl imidazolininib fluoride, 1 -Butyl 3-ethyl imidazolininib fluoride, 1-hexyl 3-ethyl imidazolininib fluoride, 1-octyl 3-ethyl imidazolininib fluoride, 1-decyl 3-ethyl imidazolininib fluoride , 1-dodecyl 3-ethyl imidazolininib fluoride, 1-tetradecyl 3-ethyl imidazolininib A method of producing an ionic liquid of high purity, characterized in that any one selected from among the group consisting of a lloride, 1-hexadecyl 3-ethyl imidazolininium fluoride and 1-octadecyl 3-ethyl imidazolininium fluoride. The method of claim 1 wherein the anionic compound is lithium trifluoro methane sulfonate, lithium bis (trifluoro methane sulfonyl) imide, lithium chloro oxide, sodium trifluoro methane sulfonate, sodium bis (trifluoro methane sulfonate) Ponyyl) Imid, sodium chloro oxide any one selected from high purity ionic liquid production method characterized in that. The method of claim 1, wherein the vacuum pressure is carried out at a reduced pressure temperature of 0 ~ 200 ℃ and the vacuum pressure is 0 ~ 760mmHg. 2. The ionic liquid according to claim 1, wherein the ionic liquid is a pyridine material as 1-ethyl pyridinium trifluoro methane sulfonate, 1-butyl pyridinium trifluoro methane sulfonate, 1-hexyl pyridinium trifluoro methane sulfo Nate, 1-octyl pyridinium trifluoro methane sulfonate, 1-decyl pyridinium trifluoro methane sulfonate, 1-dodecyl pyridinium trifluoro methane sulfonate, 1-tetradecyl pyridinium tri Pyridinium trifluoro methane sulfonate series consisting of fluoromethane sulfonate, 1-hexadecyl pyridininitri trifluoro methane sulfonate, 1-octadecyl pyridininitri trifluoro methane sulfonate, 1-ethyl pyridinium bis (trifluoro methane sulfonyl) imide, 1-butyl pyridinium bis (trifluoro methane sulfonyl) imide, 1-hexyl pyridinium bis (trifluoro methane sulfonyl ) Imide, 1-octyl pyridinium bis (trifluoro methane sulfonyl) imide, 1-decyl pyridinium bis (trifluoro methane sulfonyl) imide, 1-dodecyl pyridinium bis (tri Fluoro methane sulfonyl) imide, 1-tetradecyl pyridinium bis (trifluoro methane sulfonyl) imide, 1-hexadecyl pyridinium bis (trifluoro methane sulfonyl) imide, 1-octa A bis (trifluoro methane sulfonyl) imide series consisting of decyl pyridinium bis (trifluoro methane sulfonyl) imide, 1-ethyl pyridinium chloro oxide, 1-butyl pyridinium chloro oxide, 1-hexyl pyridinium chloro oxide, 1-octyl pyridinium chloro oxide, 1-decyl pyridinium chloro oxide, 1-dodecyl pyridine A chloro oxide series consisting of diniq chloro oxide, 1-tetradecyl pyridinini chloro oxide, 1-hexadecyl pyridinini chloro oxide, 1-octadecyl pyridinini chloro oxide, 1-ethyl 3-methyl imidazolininib trifluoro methane sulfonate, 1-butyl 3-methyl imidazolininib trifluoro methane sulfonate, 1-hexyl 3-methyl imidazoli as 1-methyl imidazole material Nitrile trifluoro methane sulfonate, 1-octyl 3-methyl imidazolininiche trifluoro methane sulfonate, 1-decyl 3-methyl imidazolininib trifluoro methane sulfonate, 1-dodecyl 3-methyl imid Dazolininib trifluoro methane sulfonate, 1-tetradecyl 3-methyl imidazolininib trifluoro methane sulfonate, 1-hexadecyl 3-methyl imidazolininib trifluoro methane sulfonate, 1-octadecyl A trifluoro methane sulfonate family consisting of 3-methyl imidazolininib trifluoro methane sulfonate, 1-ethyl 3-methyl imidazolininib bis (trifluoro methane sulfonyl) imide, 1-butyl 3-methyl imidazolininib bis (trifluoro methane sulfonyl) imide, 1-hexyl 3-methyl Imidazolininib bis (trifluoro methane sulfonyl) imide, 1-octyl 3-methyl imidazolininib bis (trifluoro methane sulfonyl) imide, 1-decyl 3-methyl imidazolininib trifluor Rho methane sulfonate, 1-dodecyl 3-methyl imidazolininib bis (trifluoro methane sulfonyl) imide, 1-tetradecyl 3-methyl imidazolininib bis (trifluoro methane sulfonyl) imide Bis (tri) consisting of 1-hexadecyl 3-methyl imidazolininib bis (trifluoro methane sulfonyl) imide, 1-octadecyl 3-methyl imidazolininib bis (trifluoro methane sulfonyl) imide Fluoromethane sulfonyl) imide series, 1-ethyl 3-methyl imidazolininiche chloro oxide, 1-butyl 3-methyl imidazolininiche chloro oxide, 1-hexyl 3-methyl imidazolininiche chloro oxide, 1-octyl 3-methyl imidazolininiche chloro Oxide, 1-decyl 3-methyl imidazolininib chloro oxide, 1-dodecyl 3-methyl imidazolininib chloro oxide, 1-tetradecyl 3-methyl imidazolininib chloro oxide, 1-hexadecyl 3-methyl A chloro oxide series consisting of imidazolininium chloro oxide, 1-octadecyl 3-methyl imidazolininium chloro oxide, A high purity ionic liquid production method, characterized in that any one selected from 1-ethyl imidazoline in the same series as 1-methyl imidazoline.