JP5088918B2 - Ionic liquid and method for producing the same, and electrolytic capacitor including the ionic liquid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ion liquid capable of widely being used as a material for various kinds of electric devices and a solvent for various kinds of reactions and to provide a method for producing the ion liquid and to provide an electrolytic capacitor containing the ion liquid. <P>SOLUTION: The present invention relates to the ion liquid composed of a cationic component and an anionic component and connecting two fluorine atoms to either one carbon atom forming the cationic component. The cationic component comprises, preferably, an atomic group selected from a group consisting of a difluoroalkyl group, a difluorocycloalkyl group and difluorobenzyl group. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to an ionic liquid that can be preferably applied to electric device materials, various reaction solvents, and the like, a method for producing the same, and an electrolytic capacitor including the ionic liquid.

Ionic liquids, and generally, such as imidazo Liu arm cation, a suitable anion ^{_{(e.g., Br -, Cl -, RSO}} 4 -, BF 4 -, PF 6 -, (CF 3 SO 2) 2 N - etc. (however, R is a combination with any monovalent organic group)) and exhibits high ionic conductivity and excellent thermal stability, so it can be applied to electrolytes for batteries and capacitors, solvents for various chemical reactions, etc. Has been extensively studied. An ionic liquid having an ether group as a cation is known as a reaction solvent for enzyme reaction, and an ionic liquid having a wide potential window in an electric device material.

  Patent Document 1 proposes an ionic liquid composed of a quaternary salt containing nitrogen or phosphorus and having a melting point of 50 ° C. or lower, particularly an ionic liquid composed of a quaternary salt containing an ether group.

  However, the ionic liquid obtained by the above-described technique may not be sufficient in the characteristics as an electrolytic solution or a reaction solvent, and there are still problems in the characteristics.

  In Patent Document 2, 1-ethyl-3-methylimidazolium having a relatively low melting point and 1- (2,2,2-trifluoroethyl) -3-methylimidazolium having strong Lewis acidity are used as a cation component. An ionic liquid containing as has been proposed.

However, in the above technique, there is a practical problem that it is necessary to use a combination of at least two kinds of cation components, and it cannot be said that the glass transition temperature is sufficiently low. Furthermore, the viscosity, electrical conductivity, etc. The basic characteristics as an ionic liquid may not be obtained sufficiently.
International Application Publication No. 2002/076924 Pamphlet JP 2003-62467 A

  In view of the above situation, the present invention provides a low viscosity, low glass transition temperature ionic liquid that can be widely used as various electrical device materials and various reaction solvents, and a method for producing the same, particularly a difluoroalkyl group, difluorocyclohexane. An object of the present invention is to provide an ionic liquid having a group selected from the group consisting of an alkyl group and a difluorobenzyl group, and a method for producing the ionic liquid. Another object of the present invention is to provide an electrolytic capacitor containing the ionic liquid and having particularly excellent low temperature characteristics.

  The present invention relates to an ionic liquid in which two fluorine atoms are bonded to one carbon atom, and in particular, an ionic liquid to which a group selected from the group consisting of a difluoroalkyl group, a difluorocycloalkyl group and a difluorobenzyl group is added. About. It is known that the difluoromethylene group is stable and exhibits a function equivalent to an ether functional group in vivo due to the strong electronegativity of fluorine.

  The present invention relates to an ionic liquid comprising a cation component and an anion component, wherein two fluorine atoms are bonded to any one carbon atom forming the cation component.

  In the present invention, the cation component preferably contains an atomic group selected from the group consisting of a difluoroalkyl group, a difluorocycloalkyl group, and a difluorobenzyl group.

  In the present invention, the cation component is represented by the following formula (1),

(In the formula (1), m and n are each independently 0 or a positive integer. X and Y are each independently a divalent group comprising an aliphatic hydrocarbon group and an alicyclic carbonization. (Including one or more selected from the group consisting of a hydrogen group, an aromatic hydrocarbon group, a carbonyl group, an ester group, an ether group, an acyl group, an imino group, a carboxyl group, and an amino group)
Or the following formula (2),

(In the formula (2), a is a positive integer or 0, and b is a positive integer. X is a divalent group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic group. (Including one or more selected from the group consisting of a hydrocarbon group, a carbonyl group, an ester group, an ether group, an acyl group, an imino group, a carboxyl group, and an amino group.)
It is preferable to contain the chemical structure shown by these.

  In the present invention, the cation component preferably has a structure in which two fluorine atoms are bonded to the carbon atom at the terminal 2-position of the alkyl group.

  In the present invention, the cationic component is represented by the following formula (3),

(In formula (3), X is a divalent group, and is an aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, carbonyl group, ester group, ether group, acyl group, imino group. , A group containing one or more selected from the group consisting of a carboxyl group and an amino group.)
It is preferable to contain the chemical structure shown by these.

In the present invention, the cationic component, ammonium and derivatives thereof, imidazo Liu arm and its derivatives, pyridinium and its derivatives, pyrrolidinium and its derivatives, pyrrolinium and derivatives thereof, pyrazinium and its derivatives, pyrimidinium and its derivatives, triazonium and derivatives, Triazinium and its derivatives, triazine derivative cations, quinolinium and its derivatives, isoquinolinium and its derivatives, indolinium and its derivatives, quinoxalinium and its derivatives, piperazinium and its derivatives, oxazolinium and its derivatives, thiazolinium and its derivatives, morpholinium and its derivatives Derivatives, piperazine and its derivatives, sulfonium and its derivatives, phosphoniu And it is preferred that the derivative is one or more selected from the group consisting of.

In the present invention, the anionic component is preferably an atomic group containing fluorine.
In the present invention, the ratio of the number of hydrogen atoms nH to the number of fluorine atoms nF in the anion component is preferably nH: nF = 0: 100 to 60:40.

  In the present invention, the anion component is represented by the following formula (4),

(In Formula (4), x is an integer of 1-20, and y is an integer of 0-5.)
Formula (5),

(In Formula (5), z is an integer of 1-20, and y is an integer of 0-5.)
Formula (6),

(In Formula (6), x is an integer of 1-20, and y is an integer of 0-5.)
And formula (7),

(In Formula (7), z is an integer of 1-20 and y is an integer of 0-5.)
One or more chemical structures selected from the group consisting of chemical structures represented by

In the ionic liquid of the present invention, the anion component is bis (trifluoromethylsulfonyl) imide anion atomic group, CHF ₂ —CF ₂ —CH ₂ OSO ₃ ^— atomic group, CHF ₂ — (CF ₂ ) ₃ —CH ₂ OSO. ₃ ^- _{atomic, CF 3 - (CF 2)} 2 -CH 2 OSO 3 - _{atomic, CF 3 - (CF 2)} 6 -CH 2 OSO 3 - _{atomic, CHF 2 -CF 2 -CH 2 SO} 3 - _{atomic, CHF 2 - (CF 2)} 3 -CH 2 SO 3 - _{atomic, CF 3 - (CF 2)} 2 -CH 2 SO 3 - _{atomic, CF 3 - (CF 2)} 6 -CH 2 SO 3 ^- atomic, _{and, CF 3 - (CF 2)} 3 - (CH 2) 2 SO 3 - may comprise one or more atomic groups selected from the group consisting of atomic.

In the ionic liquid of the present invention, the anionic component, R _B -SO _V ^- atomic (where, v is an integer from 2 to 4, R _B is 1-50 aromatic compound carbon atoms or aliphatic compound Are preferably included.

In the ionic liquid of the present invention, the anion component can preferably contain a carboxy anion (—COO ⁻ ).

  The ionic liquid of the present invention preferably has the following formula (8),

The structure shown in FIG.
The ionic liquid of the present invention preferably has the following formula (9),

The structure shown in FIG.
The ionic liquid of the present invention preferably has the following formula (10),

The structure shown in FIG.
The ionic liquid of the present invention preferably has the following formula (11),

The structure shown in FIG.
The ionic liquid of the present invention preferably has the following formula (12),

The structure shown in FIG.
The present invention is also a production method for obtaining the ionic liquid as described above, and in the production of a cation component, fluorine that only fluorinates the ketone group of a halogenated keto hydrocarbon or a derivative thereof using a fluorinating reagent. The present invention relates to a method for producing an ionic liquid characterized by comprising a crystallization step.

  In the method for producing an ionic liquid of the present invention, the halogenated keto hydrocarbon is a halogenated-2-ketoalkane, and in the fluorination step, a ketone group at the terminal 2-position of the halogenated-2-ketoalkane using a fluorinating reagent is used. Only the reaction of fluorinating can be conducted.

  In the method for producing an ionic liquid of the present invention, the halogenated keto hydrocarbon derivative is a halogenated-2-keto hydrocarbon derivative. In the fluorination step, the halogenated-2-keto hydrocarbon is used using a fluorinating reagent It is possible to go through a reaction in which only the ketone group at the terminal 2-position of the derivative is fluorinated.

  The present invention also relates to an electrolytic capacitor comprising the ionic liquid described above or an ionic liquid obtained by the above-described method for producing an ionic liquid.

  The present invention includes a cation component having a structure in which two fluorine atoms are bonded to one carbon atom, particularly a cation component having a group selected from the group consisting of a difluoroalkyl group, a difluorocycloalkyl group and a difluorobenzyl group. An ionic liquid and a method for producing the same are provided. The ionic liquid has a low viscosity and glass transition temperature, and can be widely used as various electric device materials, various lubricating oils, various heat exchange media, and various reaction solvents. Particularly, since the ionic liquid of the present invention has a low glass transition temperature, when the ionic liquid is used in an electrolytic capacitor, good low temperature characteristics are imparted.

  In the present invention, the present invention has been completed by focusing on and synthesizing an ionic liquid containing a cation component having a structure in which two fluorine atoms are bonded to one carbon atom, particularly a cation component having a difluoroalkyl group. Conventionally, an ionic liquid containing a cation component having a fluoroalkyl group substituted with two or more fluorine atoms has been synthesized, but an ion containing a cation component having a structure in which two fluorine atoms are bonded to one carbon atom. There has been no known liquid, particularly an ionic liquid containing a cation component characterized by having a difluoromethyleneated alkyl group at one site.

<Ionic liquid>
“Ionic liquid” corresponds to the Japanese translation of “Ionic liquid”. It is a generic name for ammonium salts, sulfonium salts, phosphonium salts, and the like that are liquid at room temperature, and conventionally called by various Japanese names such as “ionic liquid”, “ionic liquid”, “room temperature molten salt”, and the like. Adopted by the Ionic Liquid Research Society, which was established in 2004, and was named “Ionic Liquid” in accordance with the Ministry of Education, Culture, Sports, Science and Technology's Scientific Research Subsidy and “Science of Ionic Liquid”.

<Cation component of ionic liquid>
The cation component of the ionic liquid according to the present invention is not particularly limited as long as it contains two fluorine atoms at one position of the main chain or side chain, that is, two fluorine atoms bonded to one carbon atom. . Since the cation component has a structure in which two fluorine atoms are bonded to one atom, an ionic liquid having a low viscosity, a low glass transition temperature, and a high electrical conductivity can be obtained. Two or more structures in which two fluorine atoms are bonded to one carbon atom may be formed in the cation component, but an ionic liquid with low viscosity, low glass transition temperature and excellent electrical conductivity can be easily obtained. Therefore, it is preferable that only one of the structures is formed in the cation component.

  The cation component in the present invention preferably contains an atomic group composed of a hydrocarbon group in that it can easily obtain a hydrophobic, that is, water-insoluble ionic liquid, and particularly includes a difluoroalkyl group and a difluorocycloalkyl group. And an atomic group selected from the group consisting of a difluorobenzyl group. Among these, from the viewpoint of low viscosity and glass transition temperature, a cation component containing an atomic group selected from the group consisting of a difluoroaliphatic alkyl group and a difluorocycloalkyl group is preferably used, and particularly includes a difluoroaliphatic alkyl group. A cationic component is preferably used. When the cationic component contains a difluoroaliphatic alkyl group, both a low viscosity of, for example, 3 poise or less and a low glass transition temperature of, for example, -80 ° C or less can be easily realized.

  In addition, the cation component in the present invention may include a structure in which hydrogen of a hydrocarbon group is substituted with, for example, a carboxyl group or an amino group.

  The cation component in the ionic liquid of the present invention has the following formula (1),

(In the formula (1), m and n are each independently 0 or a positive integer. X and Y are each independently a divalent group comprising an aliphatic hydrocarbon group and an alicyclic carbonization. A group containing one or more selected from the group consisting of a hydrogen group, an aromatic hydrocarbon group, a carbonyl group, an ester group, an ether group, an acyl group, an imino group, a carboxyl group, and an amino group)
Or the following formula (2),

(In the formula (2), a is a positive integer or 0, and b is a positive integer. X is a divalent group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic group. (Including one or more selected from the group consisting of a hydrocarbon group, a carbonyl group, an ester group, an ether group, an acyl group, an imino group, a carboxyl group, and an amino group.)
It is preferable to contain the chemical structure shown by these. When the cationic component has the chemical structure represented by the formula (1) or (2), it is advantageous in that an ionic liquid having a low viscosity and a low glass transition temperature can be easily obtained. Here, X and Y in the formula (1) may be different groups or the same kind of group, and can be particularly a divalent organic group.

  When the cationic component contains a hydrocarbon group, it is advantageous in that the glass transition temperature and viscosity can be easily adjusted according to the application by controlling the structure of the hydrocarbon group. When the cation component in the present invention includes the structure represented by formula (1) or formula (2), it is preferable that at least one of X and Y in the formula is a hydrocarbon group, and at least any of X and Y Is particularly preferably an aliphatic hydrocarbon group.

  The values of m and n in formula (1) and the values of a and b in formula (2) depend on the use of the ionic liquid, and the ionic liquid is stable in the liquid state near the temperature during use, particularly near room temperature. Are preferably designed to be present in In the structure represented by Formula (1) or Formula (2), the carbon number is 2 or more, but the carbon number is preferably designed to be 3 or more in that the temperature at which the ionic liquid is gasified can be further increased. In view of the fact that the glass transition temperature can be further lowered, it can be preferably designed to be 15 or less and further 10 or less.

  Examples of the position of the carbon atom to which the fluorine atom is bonded include the carbon atom at the terminal position 2 of the cation component and the carbon atom at the terminal position 3 or more.

  The cation component can preferably include a structure in which two fluorine atoms are bonded to the carbon atom at the terminal 2-position of the alkyl group or a group having a structure in which at least one of hydrogen of the alkyl group is substituted. In addition, an ionic liquid having a low glass transition temperature can be easily obtained. In particular, a structure in which two fluorine atoms are bonded to the carbon atom at the terminal 2-position of the alkyl group, that is, a difluoromethylene structure in which the terminal is a methyl group can be preferably included in the cation component. This structure can be considered as a structure having two fluorine substituents at the terminal 2-position of the alkyl group.

  Moreover, in this invention, a cation component is following formula (3),

(In formula (3), X is a divalent group, and is an aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, carbonyl group, ester group, ether group, acyl group, imino group. , A group containing one or more selected from the group consisting of a carboxyl group and an amino group.)
It is preferable to contain the chemical structure shown by these. This is advantageous in that an ionic liquid having a low viscosity and glass transition temperature can be obtained more easily. X can in particular be a divalent organic group.

  The cation component in the ionic liquid of the present invention preferably contains quaternized nitrogen. This is advantageous in that a stable ionic liquid having a wide potential window can be easily obtained.

Cation component in the ionic liquid of the present invention, ammonium and derivatives thereof, imidazo Liu arm and its derivatives, pyridinium and its derivatives, pyrrolidinium and its derivatives, pyrrolinium and derivatives thereof, pyrazinium and its derivatives, pyrimidinium and its derivatives, triazonium and derivatives , Triazinium and its derivatives, triazine derivative cations, quinolinium and its derivatives, isoquinolinium and its derivatives, indolinium and its derivatives, quinoxalinium and its derivatives, piperazinium and its derivatives, oxazolinium and its derivatives, thiazolinium and its derivatives, morpholinium and its Derivatives thereof, piperazine and derivatives thereof, sulfonium and derivatives thereof, Honiumu and derivatives thereof, preferably contains at least one member selected from the group consisting of. Among them, imidazo Liu arm and its derivatives, ammonium and derivatives or pyridinium and its derivatives, being more preferred. Here, the derivative means that at least one hydrogen atom that can be substituted in the basic compound is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a carboxyl group, an ester group, an ether. A compound substituted with a substituent such as a group, acyl group or amino group.

<Anionic component of ionic liquid>
The anion component used in the present invention is not particularly limited, but an anion which is an atomic group containing fluorine can be preferably used in that an ionic liquid having good electrical conductivity and a wide potential window can be obtained.

  In the present invention, the ratio of the number of hydrogen atoms nH to the number of fluorine atoms nF in the anion component is preferably nH: nF = 0: 100 to 60:40. That is, the ratio of the number of fluorine atoms nF to the total number of hydrogen atoms nH and fluorine atoms nF is preferably 40% or more. When the ratio is 40% or more, it is advantageous in that it has hydrophobicity, better electrical conductivity, and a wider potential window.

  In the present invention, the anion component is represented by the following formula (4),

(In Formula (4), x is an integer of 1-20, and y is an integer of 0-5.)
Formula (5),

(In Formula (5), z is an integer of 1-20, and y is an integer of 0-5.)
Formula (6),

(In Formula (6), x is an integer of 1-20, and y is an integer of 0-5.)
And formula (7),

(In Formula (7), z is an integer of 1-20 and y is an integer of 0-5.)
It is preferable to include one or more chemical structures selected from the group consisting of chemical structures represented by: When the anion component contains at least one of the structures represented by the above formulas (4) to (7), it is advantageous in that an ionic liquid having a higher electric conductivity and a wider potential window can be obtained.

Preferred examples of the anion component, R _B -SO _V ^- atomic (where, v is an integer from 2 to 4, R _B is 1-50 aromatic compound or aliphatic compound carbon atoms) An anionic component containing can be illustrated. An anionic component containing the above atomic group is advantageous in terms of electrical conductivity and potential window. Here, the aromatic compound or the aliphatic compound may have a branch or a substituent, and may contain one or more fluorine atoms.

Among them, R ₁ —SO ₂ —atomic group (where R ₁ is an aromatic compound or aliphatic compound having 1 to 50 carbon atoms, may have a branch or a substituent, An anionic component having 1 or more) may be preferably exemplified.

Further, examples of preferable anion components include bis (trifluoromethylsulfonyl) imide anion (TFSI) atomic group, CHF ₂ —CF ₂ —CH ₂ OSO ₃ ^— atomic group, CHF ₂ — (CF ₂ ) ₃ —CH _2. OSO ₃ ^- _{atomic, CF 3 - (CF 2)} 2 -CH 2 OSO 3 - _{atomic, CF 3 - (CF 2)} 6 -CH 2 OSO 3 - _{atomic, CHF 2 -CF 2 -CH 2 SO} 3 ^- _{atomic, CHF 2 - (CF 2)} 3 -CH 2 SO 3 - _{atomic, CF 3 - (CF 2)} 2 -CH 2 SO 3 - _{atomic, CF 3 - (CF 2)} 6 -CH 2 SO ₃ ^- atomic, _{and, CF 3 - (CF 2)} 3 - (CH 2) 2 SO 3 - , such as one or more atomic groups selected from the group consisting of atomic can be exemplified, and these are electrically conductive It can be preferably used in terms of degree and potential window.

The anion component preferably contains a carboxy anion (—COO ⁻ ). In this case, an advantage is obtained that it can be produced at a low cost and relatively easily.

  Although the preferable structure which can be contained in the anion component was described above, of course, the anion component which can be contained in the ionic liquid of the present invention is not limited to these examples.

  As the most typical ionic liquid of the present invention, for example, the following formulas (8) to (12),

An ionic liquid having the structure shown in FIG.
<Potential window>
The ionic liquid is also characterized by being electrochemically stable and having a wide potential region (that is, a potential window) where the ionic liquid itself does not undergo oxidation or reductive decomposition. In general, the stability to oxidation depends on the anionic species, while the stability to reduction depends on the cationic species. The potential window of the ionic liquid of the present invention can be, for example, in the range of −1.5 V to +1.5 V, more preferably in the range of −2.0 V to +2.0 V.

<Viscosity>
The ionic liquid according to the present invention is advantageous in that the viscosity is low because two fluorine atoms are bonded to any one carbon atom forming the cation component. The viscosity of the ionic liquid of the present invention can be, for example, in the range of 0.01 to 100 poise (that is, 0.001 to 10 Pa · s). When the viscosity is 100 poise or less, and further 50 poise or less, it is convenient to use the ionic liquid as an electric device material or a reaction solvent.

  In the present invention, the viscosity can be measured by the following method. That is, using a E-type viscometer (for example, Toki Sangyo, TV-22), it is possible to employ the measurement result of the viscosity 3 minutes after the start of rotation measured at 25 ° C.

<Glass transition temperature>
The ionic liquid according to the present invention is also advantageous in that it has a low glass transition temperature because two fluorine atoms are bonded to any one carbon atom forming the cation component. The glass transition temperature of the ionic liquid of the present invention can be set in the range of −150 to + 50 ° C., for example. When the glass transition temperature is 50 ° C. or lower, and further 20 ° C. or lower, the ionic liquid can maintain a liquid state in the vicinity of the use temperature in various applications. For example, the ionic liquid is used as an electrolytic solution of an electrolytic capacitor Is preferable in that good low temperature characteristics are imparted.

  The glass transition temperature can be measured, for example, using a DSC (Differential Scanning Calorimeter), with a temperature increase rate and a temperature decrease rate of about 10 ° C./min.

<Electrical conductivity>
The ionic liquid according to the present invention is also advantageous in that a desired degree of electrical conductivity can be secured while having a low glass transition temperature and a low viscosity. The electrical conductivity of the ionic liquid of the present invention can be in the range of, for example, 0.1 to 50 mS / cm. When the electrical conductivity is 0.1 mS / cm or more, and further 2.0 mS / cm or more, the ionic liquid can be preferably used as an electrolytic solution.

<Moisture content>
The ionic liquid is essentially composed only of a salt composed of a cation component and an anion component, and ideally, other components such as water are not mixed in the ionic liquid. Some moisture may be mixed during use. In the ionic liquid according to the present invention, since the cation component has a structure in which two fluorine atoms are bonded to one carbon atom, for example, compared with an ionic liquid containing a cation component having a perfluorinated structure. It is more hydrophobic and tends to be less likely to contain moisture. Thereby, good electrical conductivity can be maintained for a long time.

  In the ionic liquid according to the present invention, for example, the water content measured by a coulometric titration method at 25 ° C. is preferably 1000 ppm or less. When the water content is 1000 ppm or less, the electrical conductivity is maintained well for a long period.

<Method for producing cationic component>
The ionic liquid according to the present invention has two fluorine atoms, for example, by a fluorination reaction in which only a ketone group of a halogenated keto hydrocarbon or a derivative thereof is selectively substituted with a fluorine group using a fluorinating reagent. It can be manufactured by a manufacturing method including a fluorination step for forming a structure bonded to a carbon atom.

  Typically, a corresponding difluorohalogenated hydrocarbon or derivative thereof is obtained by reacting a halogenated keto hydrocarbon or derivative thereof with a fluorinating reagent in a solvent under an inert gas atmosphere such as argon or nitrogen. be able to.

  As the halogenated keto hydrocarbon, a halogenated keto aliphatic hydrocarbon, a halogenated keto alicyclic hydrocarbon, a halogenated keto aromatic hydrocarbon, or a derivative thereof can be used. For example, halogenated-2-keto hydrocarbons or derivatives thereof, and further halogenated-2-keto aliphatic hydrocarbons or derivatives thereof are preferably used in that they easily provide an ionic liquid having a low glass transition temperature and a low viscosity. . Furthermore, a halogenated-2-ketoalkane can be preferably exemplified.

  A conventionally well-known thing can be suitably selected as a solvent and a fluorination reagent. Examples of the fluorinating reagent include N-fluoro-5- (trifluoromethyl) pyridinium-2-sulfonate, S- (trifluoromethyl) dibenzothiophenium-3-sulfonate, N, N′-difluoro-2, 2'-bipyridinium-bis (tetrafluoroborate), 1,1,2,3,3,3-hexafluoro-1-diethylamino-propane, bis (2-methoxyethyl) aminosulfur trifluoride, triethylamino-trishydro A fluorinating reagent such as fluoride can be preferably used. For the fluorination reaction of the present invention, bis (2-methoxyethyl) aminosulfur trifluoride is preferably used from the viewpoint of reaction recovery rate and reaction selectivity.

  As the solvent, for example, polar solvents such as ketones, chlorinated alkanes, ethers and amine solvents are preferably used. Chlorination of methylene chloride, etc., especially from the point of solubility of halogenated keto hydrocarbons or their derivatives and fluorinating reagents, recovery rate of reaction products, difluorohalogenated hydrocarbons or their derivatives, and reaction selectivity Alkanes are preferred.

  It is obvious from the knowledge of organic synthetic chemists that recovery of difluorohalogenated hydrocarbons or derivatives thereof obtained by fluorination reaction is not particularly difficult. For example, the reaction product was dropped into water. Thereafter, it can be appropriately recovered by a method such as extraction and purification. Subsequently, the obtained difluorohalogenated hydrocarbon or derivative thereof is reacted with, for example, a compound containing quaternized nitrogen to form a halogenated salt containing quaternized nitrogen, and further, the anion of the ionic liquid of the present invention As a salt containing an anion as a component, for example, a lithium compound or the like is used, and a target ionic liquid can be obtained by performing salt exchange.

  The details of the method for preparing the ionic liquid can be in accordance with a conventional method for synthesizing the ionic liquid described in, for example, International Application Publication No. 2005/012599.

  The present invention also relates to an electrolytic capacitor containing the ionic liquid described above. The ionic liquid according to the present invention is preferably applied to an electrolytic solution in an electric device such as a battery or a capacitor or a reaction solvent in various chemical reactions. Since the ionic liquid according to the present invention has a low glass transition temperature, for example, when it is used as an electrolytic solution of an electrolytic capacitor, an advantage of improving low temperature characteristics such as improvement of driving voltage in a low temperature region can be obtained.

[Example]
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

<Evaluation method>
Characteristics of the ionic liquids obtained in Examples and Comparative Examples described later were evaluated by the following methods.

(Potential window measurement)
A measurement sample consisting of 20 ml of the ionic liquid obtained in Examples and Comparative Examples was placed in a 30 ml capacity beaker, and a working electrode, a counter electrode, and a reference electrode were arranged. A platinum plate of φ1 mm × 5 mm was used as the working electrode, a platinum plate of 10 mm × 10 mm × 0.1 mm was used as the counter electrode, and an Ag / Ag ⁺ electrode (RE-5 electrode manufactured by BAES) was used as the reference electrode. Subsequently, the potential was scanned from 0 V to the plus side at a scanning speed of 10 mV / sec, and measurement was performed until a current of 20 mA / cm ² flowed, and the plus-side potential window was measured. The negative potential window is measured after the positive measurement is completed, the measurement sample is replaced, and the same procedure as the measurement of the positive potential window described above is used, and the scanning speed is 10 mV / sec. The voltage was scanned until the current of 20 mA / cm ² flowed. The measurement of the potential window was performed using an electrochemical analyzer (1255B manufactured by Solartron).

(viscosity)
Using an E-type viscometer (Toki Sangyo, TV-22), the measurement result of the viscosity of the ionic liquid 3 minutes after the start of rotation at 25 ° C. was determined as the viscosity (unit: poise).

(Hydrophilic, hydrophobic)
10 g of the ionic liquids obtained in Examples and Comparative Examples were mixed with 20 g of pure water at 25 ° C. and allowed to stand at 25 ° C. for 12 hours, and then phase-separated from water to make the ionic liquid separated into two phases hydrophobic. The ionic liquid that was evaluated and remained mixed with pure water was evaluated as hydrophilic.

(Electrical conductivity)
Using a “solartron 1255B impedance analyzer” manufactured by Toyo Technica, the measurement result of the electrical conductivity at 25 ° C. was evaluated as the electrical conductivity (unit: mS / cm) of the ionic liquid.

(amount of water)
Using a trace moisture measuring device “CA-100” manufactured by Mitsubishi Chemical, the moisture content measurement result at 25 ° C. in a nitrogen atmosphere was evaluated as the moisture content (unit: ppm) in the ionic liquid.

(Glass-transition temperature)
Using a DSC (Differential Scanning Calorimeter) “DSC-50” manufactured by Shimadzu Corporation, the temperature increase rate and the temperature decrease rate were set to 10 ° C./min, the temperature was increased from −120 ° C. to 100 ° C., and from 100 ° C. to −120 The temperature was lowered to ° C., the temperature was raised for the second time from −120 ° C. to 100 ° C., and the glass transition temperature (unit: ° C.) was measured from the peak at the time of the second temperature rise.

(Gasification behavior)
Using a TGA (thermogravimetric measuring device) “TGA-50” manufactured by Shimadzu Corporation, the temperature was raised from 25 ° C. to 500 ° C. at a temperature rising rate of 5 ° C./min, and the TGA spectrum of the ionic liquid 1 was measured.

<Example 1>
(1) Synthesis of 4-bromobutan-2-one In an argon atmosphere, aluminum chloride (4.00 g, 30.0 mmol) and dichloromethane (30 ml) were placed in an eggplant flask, cooled to −50 ° C., and then 3-bromopropionyl. Chloride (5.14 g, 30.0 mmol) was added and stirred for 30 minutes. The temperature was raised to −30 ° C., and after 2 hours, trimethylaluminum (1.4M in n-hexane, 8.70 ml) was added dropwise, and the temperature was slowly returned from −30 ° C. to room temperature over 5 hours. After cooling to 0 ° C. and adding water to stop the reaction, extraction with dichloromethane was performed three times. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo using an evaporator. Purification by silica gel flash column chromatography (hexane: ethyl acetate = 6: 1 to 0: 1) gave 4-bromobutan-2-one (3.54 g, 23.4 mmol) in a yield of 78%. The structure of the product was confirmed by NMR and IR. The results are shown below. The Rf value of the product measured from the development position of thin layer chromatography is
Rf = 0.36 (hexane / ethyl acetate = 4/1)
Met.

[NMR spectral data]
¹ HNMR (400 MHz, ppm, CDCl ₃ , J = Hz) δ = 2.20 (3H, s), 3.05 (2H, t, J = 6.3), 3.55 (2H, t, J = 6.3).
¹³ C NMR (100 MHz, ppm, CDCl ₃ ) δ = 25.31, 30.23, 45.94, 205.38.
[IR spectrum data]
IR (neat, cm ⁻¹ ) 2978, 2916, 1717, 1366, 1335, 1267, 1159, 1007, 549.

(2) Synthesis of 1-bromo-3,3-difluorobutane In an argon atmosphere, a bromo (2 ml) solution of 4-bromobutan-2-one (1.51 g, 10 mmol) in a dichloromethane (5.0 ml) solution in an eggplant flask. -Methoxyethyl) aminosulfur trifluoride (manufactured by Aldrich) (3.76 g, 17 mmol) in dichloromethane (2.0 ml) was added dropwise at room temperature. Subsequently, ethanol (5.0 ml) was added to the mixture and stirred at room temperature for 5 days. The progress of the reaction was monitored by gas chromatography, and when the peak of the raw material ketone disappeared and converted to a difluoromethylene, the reaction was stopped by adding water after cooling to 0 ° C., followed by extraction with dichloromethane. After the organic layer was washed with water three times, the organic layer was dried over anhydrous MgSO ₄ and then filtered to obtain a solution containing 1-bromo-3,3-difluorobutane.
GC (100 ° C, no temperature rise)
1-bromo-3,3-difluorobutane ... 1.84 min.
4-Bromobutan-2-one ... 2.34 min.
(CH ₃ OCH ₂ CH ₂ ) ₂ NSF ₃ ... 2.98 min.
(3) Synthesis of ethyl- (3,3-difluorobutyl) dimethylammonium bromide Under an argon atmosphere, the solution containing 1-bromo-3,3-difluorobutane obtained above was placed in an eggplant flask, and dimethylethylamine ( 0.73 g, 10 mmol) was added, and the mixture was heated to reflux at 60 ° C. for 2 days. The reaction solution is allowed to cool to room temperature, washed with a hexane-ethyl acetate (4: 1) mixed solution, concentrated under reduced pressure using an evaporator, and lyophilized to obtain a brown muddy substance, which is an ethyl bromide salt, ethyl- (3,3-Difluorobutyl) dimethylammonium bromide (2.54 g) was obtained. Since hexane and ethyl acetate could not be completely removed, no yield was determined. The structure of the product was confirmed by NMR and IR. The results are shown below.

[NMR spectral data]
¹ HNMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ = 1.48 (3H, t, J = 7.3), 1.78 (3H, t, J = 18.8), 2.60− 2.78 (2H, m), 3.46 (2H, t, J = 7.8), 3.53 (6H, s), 3.85 (2H, q, J = 7.3).
¹³ C NMR (126 MHz, ppm, CDCl ₃ , J = Hz) δ = 7.92, 23.41 (t, J _CF = 29.8), 30.93 (t, J _CF = 25.0), 48. 04, 50.16, 57.76, 122.02 (t, J _CF = 240.0).
¹⁹ FNMR (470 MHz, ppm, CDCl ₃ , J = Hz) δ = 70.91 (sex, J _FF = 17.3).
[IR spectrum data]
IR (neat, cm ⁻¹ ) 3018, 1628, 1466, 1398, 1350, 1238, 1020, 961, 916, 868, 804.

(4) Synthesis of ethyl (3,3-difluorobutyl) dimethylammonium = bis (trifluoromethanesulfonyl) imide In an eggplant flask under an argon atmosphere, ethyl bromide salt ethyl- (3,3-difluorobutyl) dimethylammonium = Bromide (1.00 g, 4.06 mmol) and LiTFSI (Lithium bis (trifluoromethanesulfonyl) imide) (Li (CF ₃ SO ₂ ) ₂ N) (1.23 g, 4.28 mmol) and dry -Acetone (4.0 ml) was added, and salt exchange was performed by stirring at room temperature for 24 hours. Subsequently, the resultant was concentrated under reduced pressure with an evaporator, washed with pure water, and then washed with a mixed solution of hexane-ethyl acetate (4: 1). This was diluted with dry-acetone (4.0 ml), activated carbon (0.5 g) was added, and the mixture was stirred at room temperature for 3 hours, filtered through celite, and then applied to an activated alumina (neutral type II) column five times with the acetone solution. The solution was concentrated under reduced pressure, and acetone was distilled off. It is dried by heating under vacuum at 50 ° C. for 24 hours, freeze-dried for 24 hours, and the following formula (8) as a yellow viscous liquid:

Ethyl (3,3-difluorobutyl) dimethylammonium bis (trifluoromethanesulfonyl), which is a salt of an ethyl (3,3-difluorobutyl) dimethylammonium cation and a TFSI (trifluoromethanesulfonylimide) anion ) Ionic liquid 1 consisting of imide (721 mg, 1.62 mmol) was obtained in a yield of 39%. The structure of the ionic liquid 1 was confirmed by NMR and IR. The results are shown below. Further, DSC measurement and TGA measurement of the ionic liquid 1 were performed under the measurement conditions described above.

[NMR spectral data]
¹ H-NMR (300 MHz, ppm, DMSO-d ₆ , J = Hz) σ = 1.25 (sextet, J = 9 Hz, 3H), 2.70 (triplet, J = 9 Hz, 3H), 3.10 ( singlet, 3H), 3.25 (quintet, J = 9 Hz, 2H), 3.42 (quintet, J = 9 Hz, 3H)
¹ HNMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ = 1.48 (3H, t, J = 7.3), 1.78 (3H, t, J = 18.8), 2.60− 2.78 (2H, m), 3.46 (2H, t, J = 7.8), 3.53 (6H, s), 3.85 (2H, q, J = 7.3).
¹³ C NMR (126 MHz, ppm, CDCl ₃ , J = Hz) δ = 7.92, 23.41 (t, J _CF = 29.8), 30.93 (t, J _CF = 25.0), 48. 04, 50.16, 57.76, 121.18 (q, J _CF = 320.5), 122.02 (t, J _CF = 240.0).
¹⁹ FNMR (470 MHz, ppm, CDCl ₃ , J = Hz) δ = 70.91 (dsex, J _FF = 328.3, 17.3), 82.72 (d, J _FF = 201.5).
[IR spectrum data]
IR (neat, cm ⁻¹ ) 2961, 2885, 1472, 1396, 1333, 1139, 1057, 899, 791, 619.

  FIG. 1 is a diagram showing an FT-IR chart of the ionic liquid 1 obtained in Example 1, FIG. 2 is a diagram showing a DSC chart of the ionic liquid 1 obtained in Example 1, and FIG. 2 is a diagram showing a TGA chart of the ionic liquid 1 obtained in Example 1. FIG. It was -78 degreeC when the glass transition temperature of the ionic liquid 1 was calculated | required by the peak analysis from the chart shown in FIG. Moreover, from the chart shown in FIG. 3, it was confirmed that the ionic liquid 1 was able to maintain the liquid state up to about 300 ° C.

<Example 2>
Ionic liquid 2 was synthesized by the following operation.

(1) Synthesis of methylcyclopentanol Under an argon atmosphere, cyclopentanone (2.10 g, 25.0 mmol) and tetrahydrofuran (25 ml) were placed in an eggplant flask, cooled to −78 ° C. and stirred for 15 minutes, Methyl lithium (1.4M in diethyl ether, 35.7 ml) was added dropwise and stirring was continued for 2 days at -78 ° C. After stopping the reaction by adding an aqueous ammonium chloride solution, extraction with diethyl ether was performed three times. The organic layer was dried over anhydrous magnesium sulfate, filtered, concentrated in water using an evaporator, and concentrated under reduced pressure. 1.98 g of a crude product of pentanol was obtained. This was used in the next reaction without purification.

(2) Synthesis of 6-bromohexane-2-one A crude product of 1-methylcyclopentanol (assuming 1.98 g, 19.8 mmol) in an eggplant flask under an argon atmosphere, potassium carbonate (16.42 g, 118 mmol) and chloroform (40 ml) were added, and the mixture was cooled to 0 ° C. and stirred for 15 minutes, and bromine (15.8 g, 99.0 mmol) was added and reacted for 8 hours. The reaction was stopped with an aqueous sodium thiosulfate solution, extracted with dichloromethane three times, the organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. Purification by silica gel flash column chromatography (hexane: ethyl acetate = 6: 1 to 0: 1) gave 6-bromohexane-2-one (2.44 g, 13.6 mmol) in 69% yield (2 steps). Obtained. The structure of the product was confirmed by NMR and IR. The results are shown below. The Rf value of the product measured from the development position of thin layer chromatography is
Rf = 0.43 (hexane / ethyl acetate = 4/1)
Met.

[NMR spectral data]
¹ HNMR (400 MHz, ppm, CDCl ₃ , J = Hz) δ = 1.7-1.78 (2H, m), 1.83-1.90 (2H, m), 2.16 (3H, s) , 2.48 (2H, t, J = 7.3), 3.41 (2H, t, J6.5).
¹³ C NMR (100 MHz, ppm, CDCl ₃ ) δ = 2.16, 29.84, 31.92, 33.27, 42.43, 208.16.
[IR spectrum data]
IR (neat, cm ⁻¹ ) 2943, 2872, 1717, 1655, 1362, 1256, 1163, 725, 648, 559.

(3) Synthesis of 1-bromo-5,5-difluorohexane Under an argon atmosphere, 6-bromohexane-2-one (3.58 g, 20.0 mmol) and dichloromethane (15 ml) were placed in an eggplant flask. (2-Methoxyethyl) amino] sulfur trifluoride (7.52 g, 34.0 mmol) and ethanol (184 mg, 4.00 mmol) were added dropwise in this order, and the mixture was stirred at room temperature for 5 days. After confirming the absence of the substrate by evaluating the spectrum at the following detection position by gas chromatography, cooling to 0 ° C, adding water to stop the reaction, washing with water three times, and organic layer Was dried over anhydrous magnesium sulfate and filtered to obtain a reaction solution containing 1-bromo-5,5-difluorohexane.
GC (100 ° C, no temperature rise)
1-Bromo-5,5-difluorohexane ... 2.82 min.
6-Bromohexane-2-one ... 4.65 min.
(CH ₃ OCH ₂ CH ₂ ) ₂ NSF ₃ ... 2.98 min.

(4) Synthesis of ethyl (5,5-difluorohexyl) dimethylammonium bromide Under a argon atmosphere, 1-bromo-5,5-difluorohexane (1.01 g, 5.00 mmol shall be contained) is contained in the eggplant flask. The reaction solution and ethyldimethylamine (512 mg, 7.00 mmol) were added, and the mixture was heated to reflux at 100 ° C. for 24 hours. After cooling, the mixture was concentrated under reduced pressure, washed 5 times with an organic solvent (hexane: ethyl acetate = 4: 1), and then dried under reduced pressure to give brown sludge-like ethyl (5,5-difluorohexyl) dimethylammonium bromide as 1. .41 g was obtained. Since hexane and ethyl acetate could not be completely removed, no yield was determined. The structure of the product was confirmed by NMR and IR. The results are shown below.

[NMR spectral data]
¹ HNMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ = 1.48 (3H, t, J = 7.3), 1.61 (3H, t, J = 18.4), 1.63 ( 2H, quin, J = 7.8), 1.86 (2H, quin, J = 7.8), 1.93-2.02 (2H, m), 3.47 (2H, t, J = 11) .0), 3.55 (6H, s), 3.87 (2H, q, J = 7.3).
¹³ C NMR (126 MHz, ppm, CD ₃ OD, J = Hz) δ = 7.16, 19.44, 21.89, 22.21 (t, J _CF = 27.9), 36.80 (t, J _CF = 26.0), 49.81, 58.85, 68.07, 124.11 (t, J _CF = 237.1).
¹⁹ FNMR (470 MHz, ppm, CDCl ₃ , J = Hz) δ = 70.67 (sex, J _FF = 17.2).
[IR spectrum data]
IR (neat, cm ⁻¹ ) 2963, 2716, 2091, 1636, 1471, 1396, 1238, 1124, 1022, 916.

(5) Synthesis of ethyl (5,5-difluorohexyl) dimethylammonium bis (trifluoromethanesulfonyl) imide In an eggplant flask under an argon atmosphere, ethyl (5,5-difluorohexyl) dimethylammonium bromide (1.37 g, 5.00 mmol), lithium bis (trifluoromethanesulfonyl) imide (1.44 g, 5.00 mmol), and acetone (5 ml) were added and stirred at room temperature for 24 hours for salt exchange. After concentration under reduced pressure, the organic solvent (hexane: ethyl acetate = 4: 1) and water were washed 5 times each and concentrated. Thereafter, acetone (5 ml) and activated carbon (1.0 g) were added, and the mixture was stirred at room temperature for 3 hours, and then the activated carbon was removed by Celite filtration. Subsequently, after passing through an alumina short column 5 times and concentrating under reduced pressure, vacuum drying at 50 ° C. for 24 hours and freeze-drying for 24 hours to obtain a yellow oily substance, the following formula (9),

Embedded image Ethyl (5,5-difluorohexyl) dimethylammonium bis (trifluoromethanesulfonyl) imide (1.) is a salt of an ethyl (5,5-difluorohexyl) dimethylammonium cation and a TFSI anion. 52 g, 3.21 mmol) was obtained with a yield of 41.2%. The structure of the ionic liquid 2 was confirmed by NMR and IR. The results are shown below.

[NMR spectral data]
¹ HNMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ = 1.48 (3H, t, J = 7.3), 1.61 (3H, t, J = 18.4), 1.63 ( 2H, quin, J = 7.8), 1.86 (2H, quin, J = 7.8), 1.93-2.02 (2H, m), 3.47 (2H, t, J = 11) .0), 3.55 (6H, s), 3.87 (2H, q, J = 7.3).
¹³ C NMR (126 MHz, ppm, CD3OD, J = Hz) δ = 7.16, 19.44, 21.89, 22.21 (t, J _CF = 27.9), 36.80 (t, J _CF = 26.0), 49.81, 58.85, 68.07, 121.18 (q, J _CF = 320.5), 124.11 (t, J _CF = 237.1).
¹⁹ FNMR (470 MHz, ppm, CDCl ₃ , J = Hz) δ = 70.91 (dsex, J _FF = 328.3, 17.3), 82.72 (d, J _FF = 201.5).
[IR data]
IR (neat, cm ⁻¹ ) 2961, 2885, 1742, 1396, 1333, 1139, 1057, 899, 791, 741.

<Example 3>
Ionic liquid 3 was synthesized by the following method using 1-methylimidazole instead of dimethylethylamine.

(1) Synthesis of 4-bromobutan-2-one In an argon atmosphere, aluminum chloride (4.00 g, 30.0 mmol) and dichloromethane (30 ml) were placed in an eggplant flask, cooled to −50 ° C., and then 3-bromopropionyl. Chloride (5.14 g, 30.0 mmol) was added and stirred for 30 minutes. The temperature was raised to −30 ° C., and after 2 hours, trimethylaluminum (1.4 M in n-hexane, 8.70 ml) was added dropwise, and the temperature was slowly returned from −30 ° C. to room temperature over 5 hours. After cooling to 0 ° C. and adding water to stop the reaction, extraction with dichloromethane was performed three times. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo using an evaporator. Purification by silica gel flash column chromatography (hexane: ethyl acetate = 6: 1 to 0: 1) gave 4-bromobutan-2-one (3.54 g, 23.4 mmol) in a yield of 78%. The structure of the product was confirmed by NMR and IR. The results are shown below. The Rf value of the product measured from the development position of thin layer chromatography is
Rf = 0.36 (hexane / ethyl acetate = 4/1)
Met.

[NMR spectral data]
¹ HNMR (400 MHz, ppm, CDCl ₃ , J = Hz) δ = 2.20 (3H, s), 3.05 (2H, t, J = 6.3), 3.55 (2H, t, J = 6.3).
¹³ C NMR (100 MHz, ppm, CDCl ₃ ) δ = 25.31, 30.23, 45.94, 205.38.
[IR spectrum data]
IR (neat, cm ⁻¹ ) 2978, 2916, 1717, 1366, 1335, 1267, 1159, 1007, 549.

(2) Synthesis of 1-bromo-3,3-difluorobutane Under an argon atmosphere, 4-bromobutan-2-one (3.02 g, 20.0 mmol) and dichloromethane (15 ml) were placed in an eggplant flask, and [bis ( 2-Methoxyethyl) amino] sulfur trifluoride (7.52 g, 34.0 mmol) and ethanol (184 mg, 4.00 mmol) were added dropwise in this order, and the mixture was stirred at room temperature for 5 days. After confirming the absence of the substrate by evaluating the spectrum at the following detection position by gas chromatography, cooling to 0 ° C, adding water to stop the reaction, washing with water three times, and organic layer Was dried over anhydrous magnesium sulfate and filtered to obtain a reaction solution containing 1-bromo-3,3-difluorobutane.
GC (100 ° C, no temperature rise)
1-bromo-3,3-difluorobutane ... 1.84 min.
4-Bromobutan-2-one ... 2.34 min.
(CH ₃ OCH ₂ CH ₂ ) ₂ NSF ₃ ... 2.98 min.

(3) Synthesis of 1- (3,3-difluorobutyl) -3-methylimidazolium bromide 1-bromo-3,3-difluorobutane (3.46 g, 20.0 mmol) in an eggplant flask under an argon atmosphere And 1-methylimidazole (1.97 g, 24.0 mmol) were added, and the mixture was heated to reflux at 100 ° C. for 24 hours. After cooling, the mixture was concentrated under reduced pressure, washed 5 times with an organic solvent (hexane: ethyl acetate = 4: 1), and then dried under reduced pressure to give 1- (3,3-difluorobutyl) -3-methylimidazo as a black-brown oil. Lithium bromide (2.78 g, 10.9 mmol) was obtained in 54% yield (2 steps). The structure of the product was confirmed by NMR. The results are shown below.

[NMR spectral data]
¹ HNMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ = 1.60 (3H, t, J = 18.8), 1.89-1.98 (2H, m), 4.11 (3H, s), 4.42 (2H, t, J = 7.3), 7.51 (2H, d, J = 11.3), 10.60 (1H, s).
¹³ C NMR (126 MHz, ppm, CDCl ₃ , J = Hz) δ = 2.19 (t, J _CF = 26.5), 30.53, 37.41 (t, J _CF = 24.8), 43. 75, 122.64 (t, J _CF = 226.6), 136.09.
¹⁹ FNMR (470 MHz, ppm, CDCl ₃ , J = Hz) δ = 70.91 (sex, J _FF = 17.3).

(4) Synthesis of 1- (3,3-difluorobutyl) -3-methylimidazolium bis (trifluoromethanesulfonyl) imide 1- (3,3-difluorobutyl) -3-methyl in an eggplant flask under an argon atmosphere Imidazolium bromide (2.78 g, 10.9 mmol), lithium bis (trifluoromethanesulfonyl) imide (3.16 g, 11.0 mmol) and acetone (12 ml) were added and stirred for 24 hours at room temperature to give a salt. Exchange was performed. After concentration under reduced pressure, the organic solvent (hexane: ethyl acetate = 4: 1) and water were washed 5 times each and concentrated. Thereafter, acetone (12 ml) and activated carbon (1.5 g) were added, and the mixture was stirred at room temperature for 3 hours, and then the activated carbon was removed by Celite filtration. Subsequently, after passing through an alumina short column 5 times and concentrating under reduced pressure, vacuum drying at 50 ° C. for 24 hours and freeze-drying for 24 hours to obtain a reddish brown oily substance, the following formula (10),

1- (3,3-Difluorobutyl) -3-methylimidazolium cation and TFSI anion 1- (3,3-difluorobutyl) -3-methylimidazolium bis The ionic liquid 3 consisting of trifluoromethanesulfonyl) imide (1.52 g, 3.36 mmol) was obtained in a yield of 21.8%. The structure of the ionic liquid 3 was confirmed by NMR and IR. The results are shown below.

[NMR spectral data]
¹ HNMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ = 1.60 (3H, t, J = 18.8), 1.89-1.98 (2H, m), 4.11 (3H, s), 4.42 (2H, t, J = 7.3), 7.51 (2H, d, J = 11.3), 10.60 (1H, s).
¹³ C NMR (126 MHz, ppm, CDCl ₃ , J = Hz) δ = 2.19 (t, J _CF = 26.5), 30.53, 37.41 (t, J _CF = 24.8), 43. 75, 119.72 (q, J _CF = 320.9), 122.64 (t, J _CF = 226.6), 136.09.
¹⁹ FNMR (470 MHz, ppm, CDCl ₃ , J = Hz) δ = 69.44 (dsex, J _FF = 132.4, 17.3), 82.54 (d, J _FF = 241.8).
[IR spectrum data]
IR (neat, cm ⁻¹ ) 3123, 2853, 1560, 1331, 1136, 1057, 908, 843, 791, 615.

<Example 4>
Using 1-bromo-3,3-difluorobutane obtained by a method similar to that described in Example 3 and using the following method, 1- (3,3-difluorobutyl) pyridinium bis (trifluoromethanesulfonyl) ) An imide was synthesized.

(1) Synthesis of 1- (3,3-difluorobutyl) pyridinium = bromide In a argon flask, 1-bromo-3,3-difluorobutane (3.46 g, 20.0 mmol) is contained in an eggplant flask. The reaction solution and pyridine (1.90 g, 24.0 mmol) were added and heated to reflux at 100 ° C. for 24 hours. After allowing to cool, the mixture was concentrated under reduced pressure, washed 5 times with an organic solvent (hexane: ethyl acetate = 4: 1), dried under reduced pressure, and 1- (3,3-difluorobutyl) pyridinium bromide (94 0.2 mg, 0.37 mmol) was obtained with a yield of 1.9% (2 steps). The structure of the product was confirmed by NMR and IR. The results are shown below.

[NMR spectral data]
¹ HNMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ = 1.71 (3H, t, J = 19.2), 2.81-2.90 (2H, m), 5.29 (2H, t, J = 6.5), 8.10 (2H, t, J = 6.9), 8.52 (1H, t, J = 7.8), 9.59 (2H, d, J = 5) .5).
¹³ C NMR (125 MHz, ppm, CD3OD, J = Hz) δ = 2.89 (t, J _CF = 25.9), 39.16 (t, J _CF = 25.0), 43.93, 124.45 (T, J _CF = 238.9), 129.48, 142.97, 146.47.
¹⁹ FNMR (470 MHz, ppm, CDCl ₃ , J = Hz) δ = 70.86 (sex, J _FF = 17.3).
[IR spectrum data]
IR (neat, cm ⁻¹ ) 2635, 2347, 2104, 1612, 1582, 1539, 1489, 1400, 1030, 912.

  Subsequently, in the same manner as in Example 3, lithium = bis (trifluoromethanesulfonyl) imide was reacted to perform salt exchange, and the following formula (11),

An ionic liquid composed of 1- (3,3-difluorobutyl) pyridinium bis (trifluoromethanesulfonyl) imide, which is a salt of a 1- (3,3-difluorobutyl) pyridinium cation and a TFSI anion 4 was obtained in a yield of 15.8%.

<Example 5>
Except for using 2,2,3,3,4,4,5,5-octafluoropentanesulfate ammonium instead of LiTFSI, the same method as in Example 1, the following formula (13),

Ethyl which is a fluorinated sulfate salt of ethyl (3,3-difluorobutyl) dimethylammonium cation and 2,2,3,3,4,4,5,5-octafluoropentanesulfate anion having the structure represented by The ionic liquid 5 consisting of (3,3-difluorobutyl) dimethylammonium = 2,2,3,3,4,4,5,5-octafluoropentanesulfonylimide was obtained in a yield of 32.3%. The structure of the ionic liquid 5 was confirmed by ¹ HNMR.

<Example 6>
Using 1-bromo-3,3-difluorobutane obtained by the same method as described in Example 3, ionic liquid 6 was synthesized by the following method.

(1) Synthesis of 1- (3,3-difluorobutyl) -2,3-dimethylimidazolium bromide In an argon atmosphere, 1-bromo-3,3-difluorobutane (5.19 g, 30.0 mmol) was added to an eggplant flask. A reaction solution containing 1) and 1,2-dimethylimidazole (3.46 g, 36.0 mmol) were added and heated to reflux at 100 ° C. for 24 hours. After cooling, the mixture was concentrated under reduced pressure, washed 5 times with an organic solvent (hexane: ethyl acetate = 4: 1), dried under reduced pressure, and 1- (3,3-difluorobutyl) -2,3-dimethyl as a black solid. Imidazolium bromide (2.50 g, 9.29 mmol) was obtained in 31% yield (2 steps). The structure of the product was confirmed by NMR. The results are shown below.

[NMR spectral data]
¹ HNMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ = 1.68 (3H, t, J = 18.8), 2.40-2.50 (2H, m), 2.65 (3H, s), 3.83 (3H, s), 4.35 (2H, t, J = 6.9), 7.23 (1H, d, J = 2.2), 7.32 (1H, d, J = 2.3).
¹³ C NMR (100 MHz, ppm, CDCl ₃ , J = Hz) δ = 9.13, 23.32 (t, J _CF = 28.1), 34.97, 36.89 (t, J _CF = 24.8) ), 42.17 (t, J _CF = 5.0), 120.53, 122.49, 122.49 (t, J _CF = 238.2).
¹⁹ FNMR (470 MHz, ppm, CDCl ₃ , J = Hz) δ = 70.75 (sex, J _FF = 17.3).

(2) Synthesis of 1- (3,3-difluorobutyl) -2,3-dimethylimidazolium = bis (trifluoromethanesulfonyl) imide 1- (3,3-difluorobutyl) -2 in an eggplant flask under an argon atmosphere , 3-dimethylimidazolium bromide (2.50 g, 9.29 mmol), lithium bis (trifluoromethanesulfonyl) imide (2.73 g, 9.51 mmol), and acetone (10 ml) were added for 24 hours at room temperature. Salt exchange was performed with stirring. After concentration under reduced pressure, the organic solvent (hexane: ethyl acetate = 4: 1) and water were washed 5 times each and concentrated. Thereafter, acetone (10 ml) and activated carbon (1.5 g) were added, and the mixture was stirred at room temperature for 3 hours, and then the activated carbon was removed by Celite filtration. Subsequently, after passing through an alumina short column 5 times and concentrating under reduced pressure, vacuum drying at 50 ° C. for 24 hours and freeze-drying for 24 hours to obtain a brown oily product, the following formula (14),

1- (3,3-difluorobutyl) which is a salt of a 1- (3,3-difluorobutyl) -2,3-dimethylimidazolium cation and a bis (trifluoromethanesulfonyl) imide anion having a structure represented by The ionic liquid 6 consisting of) -2,3-dimethylimidazolium bis (trifluoromethanesulfonyl) imide (3.22 g, 6.86 mmol) was obtained in a yield of 74%. The structure of the ionic liquid 6 was confirmed by NMR and IR. The results are shown below.

[NMR spectral data]
¹ HNMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ = 1.68 (3H, t, J = 18.8), 2.40-2.50 (2H, m), 2.65 (3H, s), 3.83 (3H, s), 4.35 (2H, t, J = 6.9), 7.23 (1H, d, J = 2.2), 7.32 (1H, d, J = 2.3).
¹³ C NMR (100 MHz, ppm, CDCl ₃ , J = Hz) δ = 9.13, 23.32 (t, J _CF = 28.1), 34.97, 36.89 (t, J _CF = 24.8) ), 42.17 (t, J _CF = 5.0), 119.69 (q, J _CF = 320.9), 120.53, 122.49, 122.49 (t, J _CF = 238.2) ).
¹⁹ FNMR (470 MHz, ppm, CDCl ₃ , J = Hz) δ = 68.69 (sex, J _FF = 17.3), 82.83.
[IR spectrum data]
IR (neat, cm ⁻¹ ) 3153, 2957, 1593, 1541, 1333, 1140, 1059, 908, 740, 617.

<Example 7>
Using 1-bromo-5,5-difluorohexane obtained by the same method as described in Example 2, ionic liquid 7 was synthesized by the following method.

(1) Synthesis of 1- (5,5-difluorohexyl) -3-methylimidazolium = bromide 1-bromo-5,5-difluorohexane (2.01 g, 10.0 mmol) in an eggplant flask under an argon atmosphere And 1-methylimidazole (985 mg, 12.0 mmol) were added, and the mixture was heated to reflux at 100 ° C. for 24 hours. After standing to cool, the solution was concentrated under reduced pressure, washed 5 times with an organic solvent (hexane: ethyl acetate = 4: 1), dried under reduced pressure, and 1- (5,5-difluorohexyl) -3-methylimidazo in the form of a dark brown sludge. 2.90 g of a crude product of lithium bromide was obtained. Since hexane and ethyl acetate could not be completely removed, no yield was determined. The structure of the product was confirmed by NMR and IR. The results are shown below.

[NMR spectral data]
¹ HNMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ = 1.57 (2H, q, J = 7.8), 1.60 (3H, t, J = 18.8), 1.89− 1.97 (2H, m), 2.03 (2H, quin, J = 7.4), 4.11 (3H, s), 4.42 (2H, t, J = 7.3), 7. 51 (2H, d, J = 13.3), 10.60 (1H, s).
¹³ C NMR (126 MHz, ppm, CD3OD, J = Hz) δ = 20.55, 30.47 (t, J _CF = 27.8), 30.75, 36.66, 38.00 (t, J _CF = 25.9), 50.48, 123.55, 124.95, 125.44 (t, J _CF = 237.1), 137.90.
¹⁹ FNMR (470 MHz, ppm, CDCl ₃ , J = Hz) δ = 70.64 (sex, J _FF = 17.3).
[IR spectrum data]
IR (neat, cm ⁻¹ ) 2955, 2874, 1709, 1572, 1396, 1240, 1173, 1132, 885, 623.

(2) Synthesis of 1- (5,5-difluorohexyl) -3-methylimidazolium = bis (trifluoromethanesulfonyl) imide 1- (5,5-difluorohexyl) -3-methyl in an eggplant flask under an argon atmosphere Put a crude product of imidazolium bromide (2.83 g, 10.0 mmol), lithium bis (trifluoromethanesulfonyl) imide (2.87 g, 10.0 mmol) and acetone (10 ml). Salt exchange was performed by stirring at room temperature for an hour. After concentration under reduced pressure, the organic solvent (hexane: ethyl acetate = 4: 1) and water were washed 5 times each and concentrated. Thereafter, acetone (10 ml) and activated carbon (1.0 g) were added, and the mixture was stirred at room temperature for 3 hours, and then the activated carbon was removed by Celite filtration. Subsequently, after passing through an alumina short column 5 times and concentrating under reduced pressure, vacuum drying at 50 ° C. for 24 hours and freeze-drying for 24 hours to obtain the following formula (15),

An ionic liquid 7 having a structure represented by the formula: 1- (5,5-difluorohexyl) -3-methylimidazolium = bis (trifluoromethanesulfonyl) imide (2.88 g, 5.96 mmol) was obtained at a yield of 60%. (3 steps). The structure of the ionic liquid 7 was confirmed by NMR and IR. The results are shown below.

[NMR spectral data]
¹ HNMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ = 1.57 (2H, q, J = 7.8), 1.60 (3H, t, J = 18.8), 1.89− 1.97 (2H, m), 2.03 (2H, quin, J = 7.4), 4.11 (3H, s), 4.42 (2H, t, J = 7.3), 7. 51 (2H, d, J = 13.3), 10.60 (1H, s).
¹³ C NMR (126 MHz, ppm, CD3OD, J = Hz) δ = 20.55, 30.47 (t, J _CF = 27.8), 30.75, 36.66, 38.00 (t, J _CF = 25.9), 50.48, 119.75 (q, J _CF = 320.8), 123.55, 124.95, 125.44 (t, J _CF = 237.1), 137.90.
¹⁹ FNMR (470 MHz, ppm, CDCl ₃ , J = Hz) δ = 70.87 (dsex, J _FF = 242.4, 17.3), 82.69 (d, J _FF = 133.2).
[IR spectrum data]
IR (neat, cm ⁻¹ ) 3123, 2964, 1576, 1396, 1333, 1198, 1138, 1059, 740, 617.

<Example 8>
Using 1-bromo-5,5-difluorohexane obtained by the same method as described in Example 2, ionic liquid 8 was synthesized by the following method.

(1) Synthesis of 1- (5,5-difluorohexyl) -2,3-dimethylimidazolium = bromide 1-bromo-5,5-difluorohexane (419 mg, 2.08 mmol) in an eggplant flask under argon atmosphere And a reaction solution containing 1,2-dimethylimidazole (240 mg, 2.50 mmol), and heated to reflux at 100 ° C. for 24 hours. After standing to cool, the solution was concentrated under reduced pressure, washed 5 times with an organic solvent (hexane: ethyl acetate = 4: 1), dried under reduced pressure, and 1- (5,5-difluorohexyl) -2,3-dimethyl as a brown solid. 640 mg of a crude product of imidazolium bromide was obtained. The structure of the product was confirmed by NMR and IR. The results are shown below.

[NMR spectral data]
¹ HNMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ = 1.59 (2H, quin, J = 7.8), 1.60 (3H, t, J = 18.3), 1.85 1.98 (2H, m), 2.14 (2H, quin, J = 2.3), 2.84 (3H, s), 4.02 (3H, s), 4.31 (2H, t, J = 7.4), 7.65 (1H, d, J = 2.3), 7.68 (1H, d, J = 2.3).
¹³ C NMR (126 MHz, ppm, CD3OD, J = Hz) δ = 9.88, 20.64, 23.48 (t, J _CF = 23.0), 30.35, 35.65, 38.07 (t , J _CF = 25.9), 43.14, 122.13, 123.65, 125.25 (t, J _CF = 237.1), 145.87.
¹⁹ FNMR (470 MHz, ppm, CDCl ₃ , J = Hz) δ = 70.75 (sex, J _FF = 17.3).
[IR spectrum data]
IR (neat, cm ⁻¹ ) 1587, 1541, 1398, 1337, 1256, 1226, 1184, 1132, 910, 669.

(2) Synthesis of 1- (5,5-difluorobutyl) -2,3-dimethylimidazolium = bis (trifluoromethanesulfonyl) imide 1- (5,5-difluorohexyl) -2 in an eggplant flask under an argon atmosphere , 3-Dimethylimidazolium bromide (618 mg, 2.08 mmol) crude, lithium bis (trifluoromethanesulfonyl) imide (603 mg, 2.10 mmol) and acetone (3 ml) were added. Salt exchange was performed by stirring at room temperature for an hour. After concentration under reduced pressure, the organic solvent (hexane: ethyl acetate = 4: 1) and water were washed 5 times each and concentrated. Thereafter, acetone (3 ml) and activated carbon (0.5 g) were added, and the mixture was stirred at room temperature for 3 hours, and then the activated carbon was removed by Celite filtration. Subsequently, after passing through an alumina short column 5 times and concentrating under reduced pressure, vacuum drying at 50 ° C. for 24 hours and freeze-drying for 24 hours to obtain a brown oily product, the following formula (16),

An ionic liquid 8 having a structure represented by the formula: 1- (5,5-difluorohexyl) -2,3-dimethylimidazolium = bis (trifluoromethanesulfonyl) imide (808 mg, 1.62 mmol) was obtained at a yield of 78%. (3 steps). The structure of the ionic liquid 8 was confirmed by NMR and IR. The results are shown below.

[NMR spectral data]
¹ HNMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ = 1.59 (2H, quin, J = 7.8), 1.60 (3H, t, J = 18.3), 1.85 1.98 (2H, m), 2.14 (2H, quin, J = 2.3), 2.84 (3H, s), 4.02 (3H, s), 4.31 (2H, t, J = 7.4), 7.65 (1H, d, J = 2.3), 7.68 (1H, d, J = 2.3).
¹³ C NMR (126 MHz, ppm, CD3OD, J = Hz) δ = 9.88, 20.64, 23.48 (t, J _CF = 23.0), 30.35, 35.65, 38.07 (t , J _CF = 25.9), 43.14, 119.12 (q, J _CF = 321.3), 122.13, 123.65, 125.25 (t, J _CF = 237.1), 145 .87.
¹⁹ FNMR (470 MHz, ppm, CDCl ₃ , J = Hz) δ = 71.05 (dsex, J _FF = 351.2, 17.3), 82.64 (d, J _FF = 167.0).
[IR spectrum data]
IR (neat, cm ⁻¹ ) 3152, 2963, 1591, 1541, 1396, 1333, 1194, 1138, 1059, 617.

<Example 9>
Using 1-bromo-5,5-difluorohexane obtained by the same method as described in Example 2, 1- (5,5-difluorohexyl) pyridinium bromide was synthesized by the following method.

(1) Synthesis of 1- (5,5-difluorohexyl) pyridinium = bromide Reaction solution containing 1-bromo-5,5-difluorohexane (419 mg, 2.08 mmol) in an eggplant flask under an argon atmosphere And pyridine (197 mg, 2.50 mmol) were added, and the mixture was heated to reflux at 100 ° C. for 24 hours. After allowing to cool, the mixture was concentrated under reduced pressure, washed 5 times with an organic solvent (hexane: ethyl acetate = 4: 1), and then dried under reduced pressure to give 1- (5,5-difluorohexyl) pyridinium bromide ( 164 mg, 0.65 mmol) was obtained in 31% yield (2 steps). The structure of the product was confirmed by NMR and IR. The results are shown below.

[NMR spectral data]
¹ HNMR (500 MHz, ppm, CDCl ₃ , J = Hz) δ = 1.59 (3H, t, J = 18.4), 1.64 (2H, quin, J = 7.8), 1.91− 2.01 (2H, m), 2.17 (2H, quin, J = 7.8), 5.12 (2H, t, J = 7.8), 8.14 (2H, t, J = 6) .9), 8.54 (1H, t, J = 7.5), 9.66 (2H, d, J = 5.9).
¹³ C NMR (125 MHz, ppm, CD3OD, J = Hz) δ = 20.43, 23.45 (t, J _CF = 27.8), 32.00, 37.93 (t, J _CF = 25.0) 42.98, 125.39 (t, J _CF = 237.5), 129.51, 145.98, 146.95.
¹⁹ FNMR (470 MHz, ppm, CDCl ₃ , J = Hz) δ = 70.77 (sex, J _FF = 17.3).
[IR spectrum data]
IR (neat, cm ⁻¹ ) 2943, 2872, 1709, 1634, 1582, 1489, 1396, 1235, 1136, 887.

  Subsequently, in the same manner as in Example 8, lithium = bis (trifluoromethanesulfonyl) imide was reacted to perform salt exchange, and the following formula (17),

An ionic liquid 9 composed of 1- (5,5-difluorohexyl) pyridinium bis (trifluoromethanesulfonyl) imide having a structure represented by the formula:

<Example 10>
In the same manner as in Example 3 using 1-bromo-3,3-difluorobutane, N-methylpiperidine, and lithium bis (trifluoromethanesulfonyl) imide, the following formula (18),

The ionic liquid 10 consisting of 1- (3,3-difluorobutyl) -1-methylpiperidinium = bis (trifluoromethanesulfonyl) imide having a structure represented by

<Example 11>
In the same manner as in Example 3 using 1-bromo-3,3-difluorobutane, N-methylpyrrolidine, and lithium bis (trifluoromethanesulfonyl) imide, the following formula (19),

The ionic liquid 11 consisting of 1- (3,3-difluorobutyl) -1-methylpyrrolidinium = bis (trifluoromethanesulfonyl) imide having the structure represented by

<Comparative Example 1>
An ionic liquid composed of 1-ethyl 3-methylimidazolium tetrafluoroborate (BF ₄ ) (manufactured by Kanto Chemical) was used.

  Table 1 shows a list of ionic liquids obtained in each Example and Comparative Example 1. Table 2 shows the results of the potential window, electrical conductivity, viscosity, hydrophilicity, water content, and glass transition temperature evaluated by the above-described methods for each of Examples and Comparative Example 1.

  From the results shown in Table 2, it can be seen that the ionic liquid according to each example has a wider potential window than the ionic liquid according to Comparative Example 1. In addition, the ionic liquids according to the respective examples have slightly higher viscosities than those of Comparative Example 1, but each has a viscosity of about 3P or lower as measured by an E-type viscometer, and has a low viscosity. Was obtained.

  From the results shown in Table 2, it can be seen that the ionic liquid according to Comparative Example 1 was hydrophilic, whereas the ionic liquid obtained in each Example showed hydrophobicity. From the results shown in Table 2, the ionic liquid according to Comparative Example 1 contained 1200 ppm of water, whereas the ionic liquid according to each Example contained only 650 ppm or less of water.

  From the results shown in Table 2, the ionic liquid according to each example has an electric conductivity of 1.5 mS / cm or more, although the electric conductivity is lower than that of the ionic liquid according to comparative example 1, and the electric conductivity It can be seen that the desired degree can be secured.

  From the results shown in Table 2, the glass transition temperature of each of the ionic liquids according to each example is −74 ° C. or less, which is significantly lower than the glass transition temperature of 11 ° C. of the ionic liquid according to Comparative Example 1. there were.

  From these results, the ionic liquid according to the present invention has a unique structure in which two fluorine atoms are bonded to one carbon atom, thereby maintaining desired performance in potential window, hydrophobicity, and electrical conductivity. However, it can be seen that the properties of low viscosity and extremely low glass transition temperature are imparted.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  As described above, the ionic liquid according to the present invention can be widely used as various electrical device materials and various reaction solvents.

2 is a diagram showing an FT-IR chart of the ionic liquid 1 obtained in Example 1. FIG. 1 is a diagram showing a DSC chart of an ionic liquid 1 obtained in Example 1. FIG. 2 is a diagram showing a TGA chart of the ionic liquid 1 obtained in Example 1. FIG.

Claims (19)

Ri Do a cation component and an anion component, it a ionic liquid, wherein the two fluorine atoms in one of the carbon atoms forming the cationic component is attached,
The cationic component is ammonium, imidazolium, pyridinium, pyrrolidinium, pyrrolium, pyrazinium, pyrimidinium, triazonium, triazinium, quinolinium, isoquinolinium, indolinium, quinoxalinium, piperazinium, oxazolinium, thiazolinium, morpholinium, piperazine, sulfonium, phosphonium, and , At least one of the substitutable hydrogen atoms of these cations is an aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, carboxyl group, ester group, ether group, acyl group or amino group One or more selected from the group consisting of derivatives substituted with
And the following formula (3),

(In formula (3), X is a divalent group, and is an aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, carbonyl group, ester group, ether group, acyl group, imino group. , A group containing one or more selected from the group consisting of a carboxyl group and an amino group.)
Only contains the chemical structure shown in,
The anion component is a bis (trifluoromethylsulfonyl) imide anion atomic group, CHF ₂ —CF ₂ —CH ₂ OSO ₃ ^— atomic group, CHF ₂ — (CF ₂ ) ₃ —CH ₂ OSO ₃ ^— atomic group, CF _{3. - (CF 2) 2 -CH 2} OSO 3 - _{atomic, CF 3 - (CF 2)} 6 -CH 2 OSO 3 - _{atomic, CHF 2 -CF 2 -CH 2 SO} 3 - atomic, _CHF 2 - ( _{CF 2) 3 -CH 2 SO 3} - _{atomic, CF 3 - (CF 2)} 2 -CH 2 SO 3 - _{atomic, CF 3 - (CF 2)} 6 -CH 2 SO 3 - atomic, and, CF _{3 - (CF 2) 3 -} (CH 2) 2 SO 3 - atomic, one or more atomic ionic liquids characterized by containing Mukoto selected from the group consisting of. The anion component contains an R _B —SO _V ^— atomic group (where v is an integer from 2 to 4, and R _B is an aromatic compound or aliphatic compound having 1 to 50 carbon atoms). The ionic liquid according to claim 1 . The anion component is carboxy anion (-COO ^-) ionic liquid according to claim 1 or 2, characterized in that it comprises a. The ionic liquid according to claim 1, which has a structure represented by the following formula (8).

The ionic liquid according to claim 1, which has a structure represented by the following formula (9).

The ionic liquid according to claim 1, which has a structure represented by the following formula (10).

The ionic liquid according to claim 1, which has a structure represented by the following formula (11).

The ionic liquid according to claim 1, which has a structure represented by the following formula (12).

The ionic liquid according to claim 1, which has a structure represented by the following formula (13).

The ionic liquid according to claim 1, which has a structure represented by the following formula (14).

The ionic liquid according to claim 1, which has a structure represented by the following formula (15).

The ionic liquid according to claim 1, which has a structure represented by the following formula (16).

The ionic liquid according to claim 1, which has a structure represented by the following formula (17).

The ionic liquid according to claim 1, which has a structure represented by the following formula (18).

The ionic liquid according to claim 1, which has a structure represented by the following formula (19).

A manufacturing method for obtaining the ionic liquid according to any one of claims 1 to 15
The method for producing an ionic liquid, wherein the production of the cationic component includes a fluorination step in which only a ketone group of a halogenated keto hydrocarbon or a derivative thereof is fluorinated using a fluorination reagent. The halogenated keto hydrocarbon is a halogenated-2-ketoalkane;
The ionic liquid according to claim 16 , wherein in the fluorination step, the fluorination reagent is used to undergo a reaction of fluorinating only the ketone group at the terminal 2-position of the halogenated-2-ketoalkane. Production method. The derivative of the halogenated keto hydrocarbon is a halogenated-2-keto hydrocarbon derivative;
17. The fluorination step according to claim 16 , wherein the fluorination step passes through a reaction of fluorinating only the ketone group at the terminal 2-position of the halogenated-2-keto hydrocarbon derivative using the fluorination reagent. A method for producing an ionic liquid. An electrolytic capacitor comprising the ionic liquid according to any one of claims 1 to 15 or the ionic liquid obtained by the method for producing an ionic liquid according to any one of claims 16 to 18 .

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