JP2011190292A - Ionic liquid-containing gel, manufacturing method of the same, and ionic conductor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ionic liquid-containing gel having excellent ion conductivity. <P>SOLUTION: The ionic liquid-containing gel comprises a fluoroalkyl group-bearing oligomer particle obtained by hydrolysis of a compound of general formula (1), and an ionic liquid. In the formula, R<SP>1</SP>and R<SP>2</SP>are each a -(CF<SB>2</SB>)p-Y group or a -CF(CF<SB>3</SB>)-[OCF<SB>2</SB>CF(CF<SB>3</SB>)]q-OC<SB>3</SB>F<SB>7</SB>group; R<SP>1</SP>and R<SP>2</SP>are the same group or a different group; Y's in R<SP>1</SP>and R<SP>2</SP>are each a hydrogen atom, a fluorine atom or a chlorine atom; p and q are each an integer of 0-10; R<SP>3</SP>, R<SP>4</SP>and R<SP>5</SP>are the same group or a different group and are each a 1-5C linear or branched alkyl group; and m is an integer of 2-3. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a gel containing an ionic liquid, a method for producing the gel, and an ionic conductor using the gel.

  An ionic liquid is a salt of a cation and an anion, which is a liquid at normal temperature and pressure, and has no boiling point. Some of them have been studied in the field of electrochemistry since the early 20th century. I came. However, other uses have not been studied.

  However, in the 1990s, when green chemistry began to be screamed, ionic liquids began to attract attention because they showed interesting properties such as non-flammability and non-volatility. Therefore, various ionic liquids have been developed. In recent years, research has been conducted on the use of ionic liquids as nonflammable, non-volatile and highly polar solvents.

  However, the use method of the ionic liquid has not been developed except for the use as a solvent, and a new use of the ionic liquid is expected in the future.

  One of the new uses of the ionic liquid is a functional material containing the ionic liquid. For this reason, the present inventors previously proposed powdery silica composite particles in which an ionic liquid is immobilized on the surface of particles that can be uniformly dispersed in a solvent or resin (see Patent Document 1).

  In recent years, a polymer material having high ion conductivity has attracted attention, and a polymer material having high ion conductivity in a solid state has attracted particular attention as an electrolyte for a next-generation lithium ion secondary battery.

  Non-Patent Document 1 below discloses gelling an ionic liquid with nanosilica particles.

JP 2007-270124 A (Claims)

J. et al. Phys. Chem. B 2008, 112, 9013-9019

According to Non-Patent Document 1, there is a problem that it is difficult to obtain a uniform gel unless a strong mixing means such as a homogenizer is used and vacuum drying is performed at 70 ° C. for 24 hours.
In the course of further developing a functional material containing an ionic liquid, the present inventors use a specific fluoroalkyl group-containing oligomer having an alkoxysilyl group and hydrolyze the alkoxysilyl group in a solvent. The fluoroalkyl group-containing oligomer particles obtained by the above method exhibit excellent dispersibility in ionic liquids. Further, when the fluoroalkyl group-containing oligomer particles and the ionic liquid are mixed, a gel containing the ionic liquid is easily obtained by mixing treatment such as ultrasonic treatment using the fluoroalkyl group-containing oligomer particles as a medium. The obtained fluoroalkyl group-containing oligomer particles have a high gel-forming ability with respect to an ionic liquid. Further, the inventors have found that the gel has excellent ionic conductivity, and have completed the present invention.

  Therefore, the subject of this invention is providing the ionic liquid containing gel which contains an ionic liquid and has the outstanding ionic conductivity. Moreover, the subject of this invention is providing the method which can manufacture this gel by an industrially advantageous method.

  That is, according to the first aspect of the present invention, an alkali is added to a reaction raw material solution containing a fluoroalkyl group-containing oligomer having an alkoxysilyl group represented by the following general formula (1) and a reaction solvent to An ionic liquid-containing gel produced by bringing a fluoroalkyl group-containing oligomer particle obtained by a hydrolysis reaction into contact with an ionic liquid.

Wherein R ¹ and R ² represent a — (CF ₂ ) p—Y group or a —CF (CF ₃ ) — [OCF ₂ CF (CF ₃ )] q—OC ₃ F ₇ group, and R ¹ And R ² may be the same group or different groups, Y in R ¹ and R ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are integers of 0 to 10. R ³ , R ⁴ and R ⁵ may be the same group or different groups, and R ³ , R ⁴ and R ⁵ are linear or branched alkyl groups having 1 to ⁵ carbon atoms. M is an integer of 2 to 3.)
In addition, the second invention to be provided by the present invention is the addition of an alkali to a reaction raw material solution containing a fluoroalkyl group-containing oligomer having an alkoxysilyl group represented by the following general formula (1) and a reaction solvent. An ionic liquid-containing gel comprising a step of obtaining a fluoroalkyl group-containing oligomer particle by performing a hydrolysis reaction of an alkoxysilyl group, and then a step of mixing the fluoroalkyl group-containing oligomer particle and an ionic liquid It is a manufacturing method.

Wherein R ¹ and R ² represent a — (CF ₂ ) p—Y group or a —CF (CF ₃ ) — [OCF ₂ CF (CF ₃ )] q—OC ₃ F ₇ group, and R ¹ And R ² may be the same group or different groups, Y in R ¹ and R ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are integers of 0 to 10. R ³ , R ⁴ and R ⁵ may be the same group or different groups, and R ³ , R ⁴ and R ⁵ are linear or branched alkyl groups having 1 to ⁵ carbon atoms. M is an integer of 2 to 3.)
A third invention to be provided by the present invention is an ionic conductor characterized by containing the ionic liquid-containing gel of the first invention.

  The gel of the present invention is a novel functional material in which an ionic liquid is immobilized, is excellent in ionic conductivity, and retains the excellent ionic conductivity inherent in the ionic liquid. The ionic liquid-containing gel can be used, for example, as a polymer electrolyte for lithium secondary batteries, capacitors, photoelectric conversion elements and the like. The gel can be produced industrially advantageously by simple mixing means such as ultrasonic treatment of the fluoroalkyl group-containing oligomer particles and the ionic liquid.

The scanning electron micrograph (SEM) which shows the surface state of the gel obtained by adding 1 mass%, 3 mass%, and 5 mass% of an ionic liquid (compound (B)), respectively. The figure which shows the relationship between the temperature in the ionic liquid containing gel obtained in Example 3, and a viscosity.

Hereinafter, the present invention will be described based on preferred embodiments thereof.
The ionic liquid-containing gel of the present invention is obtained by bringing fluoroalkyl group-containing oligomer particles into contact with an ionic liquid.

The fluoroalkyl group-containing oligomer particles have the following general formula (1)

Wherein R ¹ and R ² represent a — (CF ₂ ) p—Y group or a —CF (CF ₃ ) — [OCF ₂ CF (CF ₃ )] q—OC ₃ F ₇ group, and R ¹ And R ² may be the same group or different groups, Y in R ¹ and R ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are integers of 0 to 10. R ³ , R ⁴ and R ⁵ may be the same group or different groups, and R ³ , R ⁴ and R ⁵ are linear or branched alkyl groups having 1 to ⁵ carbon atoms. M is an integer of 2 to 3.)
It is obtained by hydrolyzing the alkoxysilyl group by adding an alkali to a reaction raw material solution containing a fluoroalkyl group-containing oligomer having an alkoxysilyl group and a reaction solvent.

  The fluoroalkyl group-containing oligomer having an alkoxysilyl group represented by the general formula (1) can be produced, for example, by reacting a trialkoxysilane such as trimethoxyvinylsilane with a fluoroalkanoyl peroxide (for example, JP 2002-338691 A).

  The alkali added to the reaction raw material solution is not particularly limited as long as it can hydrolyze the alkoxysilyl group, and examples thereof include ammonium hydroxide, sodium hydroxide, potassium hydroxide, and the like. Ammonium oxide is particularly preferably used because it is excellent in reactivity and can obtain the target product with high purity. The mixing amount of the alkali added to the reaction raw material solution is not particularly limited and is appropriately selected.

As the reaction solvent, one that dissolves the fluoroalkyl group-containing oligomer having an alkoxysilyl group represented by the general formula (1) is used, and examples thereof include lower alcohols such as methanol, ethanol, and isopropyl alcohol. Among these, methanol is particularly preferable from the viewpoint of improving the reaction efficiency.
The temperature at which the alkoxysilyl group is hydrolyzed is -5 to 50 ° C, preferably 0 to 30 ° C. If the reaction temperature is less than −50 ° C., the hydrolysis rate of the alkoxysilyl group becomes too slow, so that the reaction efficiency is poor, and if it exceeds 50 ° C., the dispersion stability of the resulting fluoroalkyl group-containing oligomer particles is low. Easy to be. The reaction time when the reaction raw material solution is mixed with an alkali to hydrolyze the alkoxysilyl group is not particularly limited and is appropriately selected, but is preferably 1 to 72 hours, and particularly preferably 1 to 72 hours. 24 hours.

  In the present invention, it is possible to recover the fluoroalkyl group-containing oligomer particles from the reaction solution by performing a solvent evaporation removal step of obtaining the fluoroalkyl group-containing oligomer particles by evaporating and removing the reaction solvent from the reaction solution. In the solvent evaporation removing step, the reaction solvent is evaporated and removed by heating to a temperature at which the reaction solvent evaporates under normal pressure or reduced pressure. Further, if necessary, it can be further dried to obtain fluoroalkyl group-containing oligomer particles.

  As a preferable physical property of the fluoroalkyl group-containing oligomer particles, the average particle size is 10 to 1000 nm, preferably 100 to 300 nm. When the average particle size is within the above range, it is preferable in terms of good dispersibility in the ionic liquid.

  The ionic liquid-containing gel of the present invention can be obtained by mixing and contacting the fluoroalkyl group-containing oligomer particles and the ionic liquid.

  The ionic liquid that can be used is not particularly limited as long as it is a salt of a cation and an anion, is a liquid at normal temperature (25 ° C.) and normal pressure (0.1 MPa), and has no boiling point. For example, examples of the cation constituting the ionic liquid include an amidinium cation, a guanidinium cation, a tertiary ammonium cation, a quaternary ammonium cation, and a phosphonium cation.

  Examples of the amidinium cation include an imidazolinium cation, an imidazolium cation, a tetrahydropyrimidinium cation, and a dihydropyrimidinium cation.

  Examples of the guanidinium cation include a guanidinium cation having an imidazolinium skeleton, a guanidinium cation having an imidazolium skeleton, a guanidinium cation having a tetrahydropyrimidinium skeleton, and a guanidinium cation having a dihydropyrimidinium skeleton. Nizinium cation and the like can be mentioned.

  Examples of the tertiary ammonium cation include methyl dilauryl ammonium.

  As the quaternary ammonium cation or phosphonium cation, those represented by the following general formula (2) can be used.

(In the formula, Q represents a P atom or an N atom.)
In the general formula (2), R ⁶ , R ⁷ , R ⁸ and R ⁹ are each a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an allyl group, or a phenyl group. Indicates. R ⁶ , R ⁷ , R ⁸ and R ⁹ may be a group containing a silica atom. When R ⁶ , R ⁷ , R ⁸ and R ⁹ are a cycloalkyl group or a phenyl group, for example, one of hydrogen atoms of a cycloalkyl ring or a benzene ring such as a 4-methylcyclohexyl group and a 4-methylphenyl group. Part may be substituted with an alkyl group. R ⁶ , R ⁷ , R ⁸ and R ⁹ may be the same group or different groups. R ⁶ , R ⁷ , R ^8, and R ⁹ are each a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an allyl group, or a phenyl group in which a part of hydrogen atoms are hydroxyl groups. It may be a group substituted with a substituent such as a group, an amino group, or an alkoxy group.

Wherein n, Sadamari the valence of the anion ^{(Y) (Y n-),} ( If n 1) when the valence of the anion (Y) ^{(Y n-)} is monovalent, quaternary ammonium cation Or the number of n in the formula of the phosphonium cation is 1, and the valence (Y ⁿ⁻ ) of the anion (Y) is divalent (when n is 2), the quaternary ammonium cation or the phosphonium cation in the formula The number of n is 2. And n is an integer of 1-2.

Examples of the anion constituting the ionic liquid include benzotriazole ion, fluorine ion, chlorine ion, bromine ion, iodine ion, BF ₄ ⁻ , PF ₆ ⁻ , PO ₂ (OMe) ₂ ⁻ , PS ₂ (OEt). is _SO ^{4 2-2-valent} anion such ^{_{as;) 2 -, (CO 2}} Me) 2 PhSO 3 -, CF 3 SO 3, HSO 4 - -, (CF 3 SO 2) 2 N 1 monovalent anion such as The anions exemplified here are preferred because they are easy to produce.

In the present invention, a preferable ionic liquid has a cation of tri-n-butyl-allylammonium salt, tri-n-butylmethylammonium salt, triethyldodecylammonium salt, tri-n-butyl {3- (trimethoxysilyl) propyl. } Ammonium salt, 1-butyl-3-methylimidazolium salt, 1-ethyl-3-methylimidazolium salt, ethylimidazolium salt, tri-n-butyl-allylphosphonium salt, tri-n-butylmethylphosphonium salt, Triethyldodecylphosphonium salt, tri-n-butyl {3- (trimethoxysilyl) propyl} phosphonium salt, tri-n-octyl {3- (trimethoxysilyl) propyl} phosphonium salt, tri-n-butyl (2-hydroxy) Ethyl) phosphonium salt and the anion is (C ^{_{3 SO 2) 2 N -,}} PF 6 -, HSO 4 -, CF 3 SO 3, a chloride ion, or is an iodide ion preferable because the resulting high ion conductivity.

  The mixing treatment of the fluoroalkyl group-containing oligomer particles and the ionic liquid is preferably performed by adding the fluoroalkyl group-containing oligomer particles to the ionic liquid. The amount of the fluoroalkyl group-containing oligomer particles added to the ionic liquid is not particularly limited as long as gelation is caused by the addition of the fluoroalkyl group-containing oligomer particles, and in many cases, 100 parts by weight of the ionic liquid 1-50 parts by weight, preferably 1-15 parts by weight, particularly preferably 5-10 parts by weight of fluoroalkyl group-containing oligomer particles. In particular, a gel containing 20 to 99.9% by mass, preferably 85 to 99% by mass, more preferably 90 to 95% by mass of an ionic liquid is preferably used as an ion conductor exhibiting excellent ion conductivity. Such an ionic conductor can be suitably used as a polymer electrolyte.

  The mixing treatment method may be carried out by a mechanical means such as a mixer that exerts a strong shearing force. However, in the present invention, the intended ionic liquid-containing gel can be easily obtained even by performing ultrasonic irradiation.

  The conditions for ultrasonic treatment vary depending on the amount of ionic liquid and fluoroalkyl group-containing oligomer particles used, etc., but in many cases, the ultrasonic power is 50 to 500 W, preferably 100 to 200 W, preferably 1 hour or more. , Preferably 2 to 24 hours.

  Since the ionic liquid-containing gel of the present invention has water repellency attributable to the fluoroalkyl group, it can be expected to be used as an additive for imparting water repellency to materials, and has excellent ionic conductivity. Therefore, it is particularly useful as an ionic conductor, and can be used as a polymer electrolyte such as a lithium secondary battery, a capacitor, and a photoelectric conversion element.

  Next, a polymer electrolyte using the ionic conductor of the present invention will be described.

  The polymer electrolyte of the present invention contains the ionic liquid-containing gel, and the polymer electrolyte has a gel-like form.

  In the present invention, the polymer electrolyte can contain water or an aprotic solvent as long as the form thereof is a gel.

  Examples of the aprotic solvent include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, 1,2-dimethoxyethane, tetrahydroxyfuran, 2- Methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxymethane, dioxolane derivative, sulfolane, 3-methyl-2-oxazolidinone , Propylene carbonate derivative, tetrahydrofuran derivative, diethyl ether, 1,3-propane sultone, methyl propionate, propionic acid A mixed solvent of one or more aprotic organic solvents chill and the like.

Furthermore, the polymer electrolyte of the present invention can be used in combination with other electrolytes. Other electrolytes are not particularly limited as long as they are soluble in aprotic solvents, but for example, LiClO ₄ , LiCl, LiBr, LiI, LiBF ₄ , LiPF ₆ , LiCF ₃ SO ₃ , LiAsF ₆ , LiAlCl ₄ , LiB (C ₆ H ₆ ) ₄ , CF ₃ SO ₃ Li, LiSbF ₆ , LiB ₁₀ Cl ₁₀ , LiSiF ₆ , LiN (SO ₂ CF ₃ ) ₂ , LiC (SO ₂ CF ₃ ) ₂ , LiN (CF ₃ SO ₃ ) ₂ , lithium lower fatty acid carboxylate, lithium chloroborane, lithium 4-phenylborate and the like, and these lithium salts are used alone or in combination. Of these lithium salts, LiN (CF ₃ SO ₃ ) ₂ , CF ₃ SO ₃ Li, and LiPF ₆ are preferable from the viewpoint of ionic conductivity of the electrolyte, and LiN (CF ₃ SO ₃ ) ₂ is particularly preferable. A preferable addition amount of these lithium salts is not particularly limited as long as the effects of the present invention are not impaired.

  The polymer electrolyte of the present invention can be suitably used as a polymer electrolyte for lithium secondary batteries, capacitors, photoelectric conversion elements and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
(Preparation of fluoroalkyl group-containing oligomer having alkoxysilyl group)
Trimethoxyvinylsilane (2.3 g) is added to 150 g of AK-225 solution containing perfluoro-2-methyl-3-oxahexanoyl peroxide (5.1 g), and the reaction is performed at 45 ^° C. for 5 hours under a nitrogen atmosphere. went. After completion of the reaction, the reaction solution was removed, followed by distillation to obtain 3.0 g of a fluoroalkyl group-containing oligomer (abbreviation: RF-VM oligomer) included in the target general formula (1). The results are shown in Table 1. AK-225 is an incombustible fluorine-based solvent manufactured by Asahi Glass Co., Ltd., and its structural formula is represented by CF ₃ CF ₂ CHCl ₂ / CClF ₂ CF ₂ CHClF.

* In Table 1, the molecular weight is a number average molecular weight determined by gel permeation chromatography (GPC, polystyrene conversion).

{Examples 1 to 4}
(Preparation of fluoroalkyl group-containing oligomer particles)
20 ml of methanol was put into a 50 ml sample bottle, then 0.1 g of RF-VM oligomer and 5 ml of NH ₃ (25 wt%) were added, and the mixture was stirred with a magnetic stirrer at room temperature for 5 hours, and the solvent was removed by an evaporator. . Subsequently, vacuum drying was performed for 1 day to obtain fluoroalkyl group-containing oligomer particles (yield 78%).

  The average particle diameter of the obtained fluoroalkyl group-containing oligomer particles was measured by using a light scattering photometer (DLS-6000HL manufactured by Otsuka Electronics Co., Ltd.) after being redispersed in methanol.

(Preparation of gel)
By adding the fluoroalkyl group-containing oligomer particles to the ionic liquid, the minimum amount of fluoroalkyl group-containing oligomer particles necessary for forming a gel (hereinafter referred to as “minimum gelation concentration”) was determined. The experimental method is as follows.

The fluoroalkyl group-containing oligomer particles prepared above were added to 0.5 g of various ionic liquids, and it was confirmed whether a gel was formed (25 ° C.) by applying ultrasonic waves at 120 W for 12 hours. Moreover, the state of the formed gel was visually observed.
Moreover, the used ionic liquid used the following chemical formula (A)-(D).

(In the formula, allyl represents an allyl group, n-Bu represents an n-butyl group, Me represents a methyl group, and n-Do represents an n-dodecyl group.)
Moreover, the scanning electron micrograph (SEM) which shows the surface state of the gel obtained by adding 1 mass%, 3 mass%, and 5 mass% of an ionic liquid (compound (B)), respectively is shown in FIG.
From the results of FIG. 1, in the system in which 1% by mass to 3% by mass of fluoroalkyl group-containing oligomer particles are added, fibrous aggregates are not sufficiently formed, and fluoroalkyl group-containing oligomer particles are observed in some places. . On the other hand, it was confirmed that the fibrous aggregate was completely formed when 5% by mass of the minimum gelation concentration was added.

{Comparative Example 1}
30 wt% silica nanoparticles (methanol dispersion, average particle diameter 11 nm) were distilled to remove methanol to obtain silica nanoparticles (average particle diameter 10 nm).
The silica nanoparticles prepared above were added to 0.5 g of an ionic liquid (chemical formula (C)) in an amount of 1 wt% up to 10 wt% and subjected to ultrasonic waves at 120 W for 12 hours. No gel was formed (25 ° C.). .

{Comparative Examples 2-3}
(Preparation of silica composite particles)
A 50 ml sample bottle is filled with 20 ml of methanol, then a commercial coupling agent; 0.10 g of C ₆ F ₁₃ C ₂ H ₄ Si (OEt) ₃ , 2.3 mmol of tetraethoxysilane (TEOS), NH ₃ (25 wt% 5 ml was added, and the mixture was stirred with a magnetic stirrer at room temperature for 5 hours, and the solvent was removed with an evaporator. Subsequently, vacuum drying was performed for 1 day to obtain silica composite particles.
The average particle size of the obtained silica composite particles was redispersed in methanol and measured using a light scattering photometer (DLS-6000HL manufactured by Otsuka Electronics). As a result, the average particle size was 216 ± 42 nm.
The content of coupling agent in the resulting silica composite particles is 71 wt%, Si content was 29 wt% as SiO _2.
The content of the coupling agent was determined by elemental analysis of F. The SiO ₂ content was determined by thermogravimetric analysis.

(Preparation of gel)
Silica composite particles were added to the ionic liquid by the same operation method as in Examples 1 to 4, and the minimum gelation concentration was determined. Moreover, the state of the formed gel was visually observed.

{Reference Examples 1-3}
(Preparation of silica composite particles)
20 ml of methanol is put into a 50 ml sample bottle, then 0.1 g of RF-VM oligomer, 3.3 wt g of 30 wt% silica nanoparticles (methanol dispersion, average particle diameter 11 nm), 2.3 mmol of tetraethoxysilane (TEOS), NH ₃ ( 25 wt%) 5 ml was added, and the mixture was stirred with a magnetic stirrer at room temperature for 5 hours, and the solvent was removed with an evaporator. Subsequently, vacuum drying was performed for 1 day to obtain silica composite particles.
The average particle size of the obtained silica composite powdery particles was redispersed in methanol and measured using a light scattering photometer (DLS-6000HL manufactured by Otsuka Electronics). As a result, the average particle size was 133 ± 33 nm. .
Further, the content of the fluoroalkyl group-containing oligomer in the obtained silica composite particles 5 wt%, Si content was 95 wt% as SiO _2.
The content of the fluoroalkyl group-containing oligomer was determined by elemental analysis of F. The SiO ₂ content was determined by thermogravimetric analysis.

(Preparation of gel)
Silica composite particles were added to the ionic liquid by the same operation method as in Examples 1 to 4, and the minimum gelation concentration was determined. Moreover, the state of the formed gel was visually observed.

From the results in Table 2, the minimum gelation concentration of the ionic liquids of Reference Examples 1 to 3 was 35 to 40% by mass. By using the fluoroalkyl group-containing oligomer particles of the present invention, the ionic liquid was gelled. It can be seen that uniform gelation is obtained at a relatively low concentration of 5 to 10% by mass.

(Evaluation of ionic conductivity)
The ionic liquid-containing gels obtained in Examples 1 to 4 and Reference Examples 1 to 3 were placed in a Pyrex (registered trademark) glass cell, the upper electrode made of brass was sandwiched between the lower electrodes, and the conductivity was room temperature (25 ° C. ). Moreover, the thickness of the gel was measured using the micro head. From these measured values, ionic conductivity (σ) was calculated. Table 3 also shows the ionic conductivity when the ionic liquid is used alone.

As a result of Table 3, the ionic-containing gel of the present invention has substantially the same conductivity as the ionic liquid-containing gel of the reference example, and the electric conductivity is substantially the same as compared with the case of using the ionic liquid alone. I understand that there is.

(Temperature dependence)
About the ionic liquid containing gel obtained in Example 3, the viscosity for every temperature was measured and the result is shown in FIG. The viscosity at each temperature of the ionic liquid (compound (C)) alone was also measured and collectively shown in FIG.

  From the results in FIG. 2, it was observed that the viscosity decreased with increasing temperature. It was observed that the viscosity was higher than that of the ionic liquid alone under the low temperature condition, but almost the same value was observed under the high temperature condition. This is presumably because the ionic liquid is bound by the fibrous aggregate at a low temperature, but the aggregate is loosened at a high temperature to form a colloidal dispersion solution.

  The gel of the present invention is a novel functional material in which an ionic liquid is immobilized, is excellent in ionic conductivity, and retains the excellent ionic conductivity inherent in the ionic liquid. The ionic liquid-containing gel can be used, for example, as a polymer electrolyte for lithium secondary batteries, capacitors, photoelectric conversion elements and the like. The gel can be produced industrially advantageously by simple mixing means such as ultrasonic treatment of the fluoroalkyl group-containing oligomer particles and the ionic liquid.

Claims (7)

A fluoroalkyl group-containing product obtained by adding an alkali to a reaction raw material solution containing a fluoroalkyl group-containing oligomer having an alkoxysilyl group represented by the following general formula (1) and a reaction solvent and hydrolyzing the alkoxysilyl group An ionic liquid-containing gel, which is produced by bringing oligomer particles into contact with an ionic liquid.

Wherein R ¹ and R ² represent a — (CF ₂ ) p—Y group or a —CF (CF ₃ ) — [OCF ₂ CF (CF ₃ )] q—OC ₃ F ₇ group, and R ¹ And R ² may be the same group or different groups, Y in R ¹ and R ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are integers of 0 to 10. R ³ , R ⁴ and R ⁵ may be the same group or different groups, and R ³ , R ⁴ and R ⁵ are linear or branched alkyl groups having 1 to ⁵ carbon atoms. M is an integer of 2 to 3.)   The ionic liquid-containing gel according to claim 1, wherein the ionic liquid contains 20 to 99.9% by mass. A fluoroalkyl group-containing oligomer obtained by adding an alkali to a reaction raw material solution containing a fluoroalkyl group-containing oligomer having an alkoxysilyl group represented by the following general formula (1) and a reaction solvent and hydrolyzing the alkoxysilyl group A method for producing an ionic liquid-containing gel, comprising a step of obtaining particles, and then a step of mixing the fluoroalkyl group-containing oligomer particles and the ionic liquid.

Wherein R ¹ and R ² represent a — (CF ₂ ) p—Y group or a —CF (CF ₃ ) — [OCF ₂ CF (CF ₃ )] q—OC ₃ F ₇ group, and R ¹ And R ² may be the same group or different groups, Y in R ¹ and R ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are integers of 0 to 10. R ³ , R ⁴ and R ⁵ may be the same group or different groups, and R ³ , R ⁴ and R ⁵ are linear or branched alkyl groups having 1 to ⁵ carbon atoms. M is an integer of 2 to 3.)   The method for producing an ionic liquid-containing gel according to claim 3, wherein the reaction solvent is methanol.   The said mixing process is performed by ultrasonic irradiation, The manufacturing method of the ionic liquid containing gel of Claim 3 characterized by the above-mentioned.   An ionic conductor comprising the ionic liquid-containing gel according to claim 1. The ionic conductor according to claim 6, which is used as a polymer solid electrolyte.