JP2011190291A - Polyaniline-containing nanocomposite particle and method for production thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyaniline-containing nanocomposite particle exhibiting excellent solubility in water and having excellent dispersibility in an organic solvent, and to provide a method for producing the same. <P>SOLUTION: The polyaniline-containing nanocomposite particle is produced by oxidation of aniline in the presence of a fluoroalkyl-containing oligomer represented by general formula (1); wherein R<SP>1</SP>and R<SP>2</SP>represent -(CF<SB>2</SB>)<SB>p</SB>-Y or -CF(CF<SB>3</SB>)-[OCF<SB>2</SB>CF(CF<SB>3</SB>)]<SB>q</SB>-OC<SB>3</SB>F<SB>7</SB>, which may be the same or different; Y represents a hydrogen atom, a fluorine atom or a chlorine atom, p and q represent integers of 0-10, R<SP>3</SP>represents a hydrogen atom or a methyl group; Z represents a group selected from -OH, -OC<SB>2</SB>H<SB>4</SB>SO<SB>3</SB>H or -NH<SB>2</SB>+C(CH<SB>3</SB>)<SB>2</SB>CH<SB>2</SB>SO<SB>3</SB>-; n represents an integer of 5-1,000. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to polyaniline-containing nanocomposite particles having excellent solubility in water and excellent dispersibility in an organic solvent, and a method for producing the same.

  Among a series of conjugated polymers, polyaniline is highly stable against air and moisture, and also exhibits high electrical conductivity, so secondary battery electrode materials, antistatic agents, solid electrolytic capacitor electrolytes, titanium dioxide It is a material that attracts attention in a wide range of fields such as electrical, electronic, mechanical, such as counter electrodes of dye-sensitized solar cells, electromagnetic shielding materials, active oxygen generating materials, optical recording elements, artificial muscle materials, and electrorheological fluid dispersants. is there.

  However, since ponianiline generally has low solubility in various solvents, many studies have been made to increase the solubility of ponianiline. For example, a method of performing redox polymerization of an aniline derivative having a sulfo group (m-aminobenzenesulfonic acid) and aniline (see, for example, Non-Patent Document 1), and when producing ponianiline by oxidation of aniline, A method in which a reaction is carried out by substituting para-substituted aniline (for example, see Patent Document 1), a method in which hydrogen peroxide is added to a solution composed of aniline and a transition metal or a transition metal compound to perform oxidative polymerization (for example, see Patent Document 2) ), A method of containing a cyclic perfluoroalkylene disulfonimide anion as dopan (for example, see Patent Document 3) and the like.

JP-A-2005-255905. Japanese Patent Laid-Open No. 06-200017. JP 2005-350525 A.

Synthetic Metals, 2002, 130, 1, 27-33.

  The inventors of the present invention have been actively researching the synthesis and properties of oligomers in which fluoroalkyl groups are introduced at both ends, and novel functional materials using the oligomers. The present inventors further conducted intensive research on a novel functional material having a fluoroalkyl group. By conducting a redox polymerization reaction of aniline in the presence of a specific fluoroalkyl group-containing oligomer, It was found that polyaniline-containing nanocomposite particles into which oligomer segments were introduced, and that the polyaniline-containing nanocomposite particles showed excellent solubility in water and excellent dispersibility in organic solvents. The present invention has been completed.

  That is, an object of the present invention is to provide polyaniline-containing nanocomposite particles having excellent solubility in water and excellent dispersibility in an organic solvent, and a method for producing the same. Another object of the present invention is to provide a method by which the nanocomposite particles can be produced by an industrially advantageous method.

  A first invention to be provided by the present invention is a polyaniline-containing nanocomposite produced by oxidizing aniline in the presence of a fluoroalkyl group-containing oligomer represented by the following general formula (1) Particles.

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 represents a hydrogen atom or a methyl group, Z represents a group selected from —OH, —OC ₂ H ₄ SO ₃ H or —NH ₂ ⁺ C (CH ₃ ) ₂ CH ₂ SO ₃ ^—. N Represents an integer of 5 to 1000.)
In addition, the second invention to be provided by the present invention is a polyaniline-containing nanostructure characterized by oxidatively polymerizing aniline with an oxidizing agent in the presence of a fluoroalkyl group-containing oligomer represented by the following general formula (1): This is a method for producing composite particles.

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 represents a hydrogen atom or a methyl group, Z represents a group selected from —OH, —OC ₂ H ₄ SO ₃ H or —NH ₂ ⁺ C (CH ₃ ) ₂ CH ₂ SO ₃ ^—. N Represents an integer of 5 to 1000.)
The third invention to be provided by the present invention is a gel produced by bringing the polyaniline-containing nanocomposite particles of the first invention into contact with an ionic liquid.

  A fourth invention to be provided by the present invention is an ionic conductor comprising the gel of the third invention.

According to the present invention, it is possible to provide a nanocomposite particle containing polyaniline that exhibits excellent solubility in water and excellent dispersibility in an organic solvent, and the polyaniline-containing nanocomposite particle. Electrode materials for secondary batteries, antistatic agents, electrolytes for solid electrolytic capacitors, counter electrodes for titanium dioxide dye-sensitized solar cells, electromagnetic shielding materials, active oxygen generators, optical recording elements, artificial muscle materials, electrorheological fluids It can be expected to be used in a wide range of fields such as electrical, electronic and mechanical dispersants.
Moreover, according to this invention, this polyaniline containing nanocomposite particle can be manufactured industrially advantageously.

  Moreover, when the polyaniline-containing nanocomposite particles of the present invention are brought into contact with an ionic liquid, a gel is formed, and an ionic liquid-containing gel excellent in ionic conductivity can be generated.

The UV spectrum chart of the aqueous solution (0.033 g / ml) which melt | dissolved the polyaniline containing nanocomposite particle | grains obtained in Examples 1-4.

  Hereinafter, the present invention will be described based on preferred embodiments thereof.

  The polyaniline-containing nanocomposite particles of the present invention are obtained by oxidizing aniline in the presence of a fluoroalkyl group-containing oligomer represented by 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 represents a hydrogen atom or a methyl group, Z represents a group selected from —OH, —OC ₂ H ₄ SO ₃ H or —NH ₂ ⁺ C (CH ₃ ) ₂ CH ₂ SO ₃ ^—. N Represents an integer of 5 to 1000.)
The fluoroalkyl group-containing oligomer represented by the general formula (1) is a component that imparts excellent solubility in water and excellent dispersibility in an organic solvent to the polyaniline-containing nanocomposite particles.

  The content of the fluoroalkyl group-containing oligomer represented by the general formula (1) is 0.01 to 100 parts by weight, preferably 1 to 50 parts by weight with respect to 1 part by weight of aniline. Within this range, it is preferable from the viewpoint that it is easy to obtain a product having particularly high solubility in water and dispersibility in various solvents.

  The fluoroalkyl group-containing oligomer represented by the general formula (1) is described in, for example, JP-A-2007-270124, JP-A-2009-209349, JP-A-2005-71694, 2003-257240, and the like. It is manufactured with reference to the method.

  An example of the production example is shown below. The following general formula (2):

(Wherein, ^{R 1} and ^{R 2,} the general formula (1) is the same as ^{R 1} and ^{R 2} in.) And peroxide -fluoroalkanoyl compound represented by the following general formula (3)

(Wherein, R ³ and Z are the same as R ³ and Z in the general formula (1).) A compound having a vinyl group represented by a raw material, in accordance with the following reaction formula (4), the general A fluoroalkyl group-containing oligomer represented by the general formula (1) is obtained by reacting a fluoroalkanoyl peroxide compound represented by the formula (2) with a compound having a vinyl group represented by the general formula (3). be able to.

(Wherein R ¹ , R ² , R ³ , Z and m are as defined above.)
Specific examples of the fluoroalkanoyl peroxide compound represented by the general formula (2) include diperfluoro-2-methyl-3-oxahexanoyl peroxide, diperfluoro-2,5-dimethyl-3,6 peroxide. -Dioxanonanoyl, diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide, diperfluorobutyryl peroxide, diperfluoroheptanoyl peroxide, diperfluorooctanoyl peroxide Etc. The fluoroalkanoyl peroxide compound represented by the general formula (2) is obtained by a known production method. For example, a fluoroalkyl group-containing acyl halide may be added to a fluorine-containing aliphatic solvent such as a fluorine-containing aromatic solvent or an alternative fluorocarbon. It can be easily obtained by reacting hydrogen peroxide in the presence of an alkali such as sodium hydroxide, potassium hydroxide, potassium hydrogen carbonate, sodium carbonate or potassium carbonate in a group solvent.

  Specific examples of the compound having a vinyl group represented by the general formula (3) include acrylic acid, methacrylic acid, 2-acryloxyethanesulfonic acid, 2-methacryloxyethanesulfonic acid, 2-acrylamido-2-methyl. Examples thereof include propanesulfonic acid and 2-methacrylamide-2-methylpropanesulfonic acid.

  Examples of the method of reacting the fluoroalkanoyl peroxide compound represented by the general formula (2) and the compound having a vinyl group represented by the general formula (3) include those represented by the general formula (3). The compound having a vinyl group is dissolved in an inert solvent, and then, under stirring, the fluoroalkanoyl peroxide compound represented by the general formula (2) is mixed, and then heated to 40 to 50 ° C., Examples include a method of aging and then performing purification.

  Aniline is oxidatively polymerized with an oxidizing agent in the reaction solvent in the presence of the fluoroalkyl group-containing oligomer represented by the general formula (1).

  Examples of the oxidizing agent include manganese dioxide, ammonium peroxodisulfate, sodium peroxodisulfate, potassium peroxodisulfate, chromyl chloride, hydrogen peroxide, ferric salt, iodate, and the like. When ammonium peroxodisulfate is used, it is particularly preferably used from the viewpoint of obtaining excellent polyaniline-containing nanocomposite particles in various solvents.

  The addition amount of the oxidizing agent is 1 to 1.5, preferably 1 to 1.23 in terms of molar ratio to aniline.

  As the reaction solvent, a solvent that dissolves the fluoroalkyl group-containing oligomer represented by the general formula (1), aniline, and an oxidizing agent and is not oxidized by the oxidizing agent is used. Water is most preferably used, but alcohols such as methanol and ethanol, nitriles such as acetonitrile, polar solvents such as N-methyl-2-pyrrolidone and dimethyl sulfoxide, ethers such as tetrahydrofuran, acetic acid, etc. Organic acids can also be used. A mixed solvent of these organic solvents and water can also be used.

  The reaction conditions in the oxidation polymerization reaction of aniline are a reaction temperature of 0 to 50 ° C., preferably 5 to 50 ° C., and a reaction time of 2 hours or longer, preferably 10 to 30 hours.

  After completion of the oxidative polymerization reaction, the reaction solution is mixed with an organic solvent such as tetrahydrofuran in which the polyaniline-containing nanocomposite particles obtained are insoluble and re-precipitated, and further centrifuged to recover the target product as a precipitate. It can be washed and then dried to obtain polyaniline-containing nanocomposite particles.

  The polyaniline-containing nanocomposite particle of the present invention has a repeating structural unit represented by the following general formula (5), and the polyaniline is doped with a fluoroalkyl group-containing oligomer represented by the general formula (1). The present inventors speculate.

(In the formula, A represents a fluoroalkyl group-containing oligomer represented by the general formula (1). The molar ratio of x: y is 0.1: 100 to 1:50.)
The content of the fluoroalkyl group-containing oligomer represented by the general formula (1) in the polyaniline-containing nanocomposite particles is preferably 1 to 95% by weight, particularly preferably 2 to 90% by weight. The content of the fluoroalkyl group-containing oligomer in the polyaniline-containing nanocomposite particles of the present invention can be determined by thermogravimetric analysis.

  In addition, as another preferable physical property of the polyaniline-containing nanocomposite particles of the present invention, the average particle size is preferably 10 to 900 nm, particularly preferably 20 to 500 nm. When the average particle size is within the above range, it is preferable from the viewpoint of excellent solubility in water and good dispersibility in various organic solvents.

  The ponianiline-containing nanocomposite particles of the present invention exhibit high solubility in water and high dispersibility in organic solvents. The polyaniline-containing nanocomposite particles of the present invention having such characteristics include electrode materials for secondary batteries, antistatic agents, electrolytes for solid electrolytic capacitors, counter electrodes for titanium dioxide dye-sensitized solar cells, electromagnetic shielding materials, active oxygen It can be expected to be used in a wide range of fields such as electrical materials, optical recording elements, artificial muscle materials, electrorheological fluid dispersants, etc.

  The ponianiline-containing nanocomposite particles of the present invention can form a gel when mixed and contacted with an ionic liquid, thereby generating a gel containing 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, one represented by the following general formula (6) can be used.

(In the formula, Q represents a P atom or an N atom.)
In the general formula (8), 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, amino group or alkoxy.

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 ponianiline-containing nanocomposite particles and the ionic liquid is preferably performed by adding the ponianiline-containing nanocomposite 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 to 50 parts by weight, preferably 1 to 15 parts by weight, particularly preferably 4 to 10 parts by weight of fluoroalkyl group-containing oligomer particles. In particular, a gel containing 20 to 99.9% by mass, preferably 85 to 90% by mass, and more preferably 90 to 96% 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 of ultrasonic treatment vary depending on the amount of ionic liquid and polyaniline-containing nanocomposite particles used, etc., but in many cases, the output of ultrasonic waves is 50 to 500 W, preferably 100 to 200 W, preferably 1 hour or more, Preferably it is 2 to 24 hours.

  Since the gel containing the ionic liquid obtained in 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 the material. Since it has ionic conductivity, it is particularly useful as an ionic conductor. For example, it can also be used as a polymer electrolyte for lithium secondary batteries, capacitors, photoelectric conversion elements and the like.

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

  The polymer electrolyte of the present invention contains the 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 Examples.
(Preparation of fluoroalkyl group-containing oligomer)
(Synthesis Example 1)

A 1 L three-necked flask was charged with 29.4 g (0.41 mol) of acrylic acid and 500 ml of AK-225, and further at room temperature with perfluoro-2-methyl-3-oxahexanoyl peroxide ([C ₃ F ₇ 334 g (perfluoro-2-methyl-3-oxahexanoyl peroxide 0.05 mol) of a 10% AK-225 solution of —O—CF (CF ₃ ) —CO—O—] ₂ ) was charged. Then, it heated up to 45 degreeC, stirring, after aging for 5 hours, stirring was stopped and it left still overnight. After standing, it was concentrated, washed with AK-225, filtered, and vacuum dried at 50 ° C. to obtain an oligomer represented by the general formula (a) (abbreviation: RF-ACA oligomer). . In addition, the number average molecular weight by gel permeation chromatography (GPC, polystyrene conversion) was 2770.
AK-225: Asahi Glass Co., Ltd., non-flammable fluorine-based solvent, structural formula CF ₃ CF ₂ CHCl ₂ / CClF ₂ CF ₂ CHClF
(Synthesis Example 2)

In Synthesis Example 1, an oligomer (abbreviation; represented by the above general formula (b)) was prepared under the same reaction conditions as in Synthesis Example 1 except that 2-methacryloxyethanesulfonic acid (MES) (0.41 mol) was used as the acrylic acid. RF-MES oligomer) was obtained. The number average molecular weight determined by gel permeation chromatography (GPC, converted to polyethylene glycol) was 12,000.
(Synthesis Example 3)

  An oligomer represented by the above general formula (c) under the same reaction conditions as in Synthesis Example 1 except that acrylic acid was changed to 2-acrylamido-2-methylpropanesulfonic acid (AMPS) (0.41 mol) in Synthesis Example 1. (Abbreviation: RF-AMPS oligomer) was obtained. In addition, since it gelled with respect to water, methanol, and THF, the number average molecular weight could not be measured.

{Examples 1 to 4}
The amount of aniline (Wako Pure Chemical Industries, Ltd.) shown in Table 1 is added to 10 ml of the aqueous solution containing the RF-AMPS oligomer shown in Table 1 prepared above, and the mixture is stirred for 30 minutes at room temperature (25 ° C.). Got. Next, 20 ml of an aqueous solution containing the amount of ammonium peroxodisulfate (APS) shown in Table 1 was added to the mixed solution, and the mixture was reacted at room temperature (25 ° C.) for 24 hours with a magnetic stirrer.

After completion of the reaction, the reaction solution was added to an excess amount of 500 ml of tetrahydrofuran to perform reprecipitation. The precipitate was decanted and centrifuged to remove the solvent, and then vacuum-dried at 50 ° C. to obtain dark green powder particles. The powdery particles were dissolved in water, and the UV spectrum was measured.
It is known that Poaron (see the following general formula (B)) has an absorption spectrum at 404 to 446 nm, and Bipolaron (see the following general formula (A)) has an absorption spectrum at 773 to 943 nm (for example, Synthetic Metals, 2002). 130, No. 1, pp. 27-33).

  What was obtained by the present invention was confirmed to be ponianiline-containing nanocomposite particles containing a fluoroalkyl group-containing oligomer because they have maximum absorption spectra at 430 nm and 790 nm. The UV spectrum chart is shown in FIG.

Note) APS indicates ammonium peroxodisulfate.
<Evaluation of polyaniline-containing nanocomposite particles>
About the polyaniline containing nanocomposite particle sample obtained in Examples 1-4, the average particle diameter and content of RF-AMPS oligomer were measured.
(Evaluation of average particle size)
The obtained polyaniline-containing nanocomposite particles were redispersed in water and measured using a light scattering photometer (DLS-6000HL manufactured by Otsuka Electronics).
(Measurement of RF-AMPS oligomer content)
The obtained polyaniline-containing nanocomposite particles were determined by thermogravimetric analysis.

{Examples 5 to 9}
The amount of aniline (Wako Pure Chemical Industries) shown in Table 3 was added to 10 ml of the aqueous solution containing the amount of RF-ACA oligomer shown in Table 3 prepared above, and the mixture was stirred for 30 minutes at room temperature (25 ° C.). Got. Next, 20 ml of an aqueous solution containing the amount of ammonium peroxodisulfate (APS) shown in Table 1 was added to the mixed solution, and the mixture was reacted at room temperature (25 ° C.) for 24 hours with a magnetic stirrer.

  After completion of the reaction, the reaction solution was added to an excess amount of 500 ml of tetrahydrofuran to perform reprecipitation. After removing the solvent by decantation and centrifugation, the precipitate was subjected to vacuum drying at 50 ° C. to obtain a sample of nanocomposite particles containing dark green polyaniline.

Note) APS indicates ammonium peroxodisulfate.
<Evaluation of polyaniline-containing nanocomposite particles>
About the polyaniline containing nanocomposite particle sample obtained in Examples 5-9, the average particle diameter and content of RF-ACA oligomer were measured.
(Evaluation of average particle size)
The obtained polyaniline-containing nanocomposite particles were redispersed in water and measured using a light scattering photometer (DLS-6000HL manufactured by Otsuka Electronics).
(Measurement of RF-ACA oligomer content)
The obtained polyaniline-containing nanocomposite particles were determined by thermogravimetric analysis.

{Examples 10 to 13}
The amount of aniline (Wako Pure Chemical Industries) shown in Table 5 is added to 10 ml of the aqueous solution containing the RF-MES oligomer shown in Table 5 prepared above, and the mixture is stirred for 30 minutes at room temperature (25 ° C.). Got. Next, 20 ml of an aqueous solution containing the amount of ammonium peroxodisulfate (APS) shown in Table 5 was added to the mixture, and the reaction was carried out for 24 hours at room temperature (25 ° C.) with a magnetic stirrer.

  After completion of the reaction, the reaction solution was added to an excess amount of 500 ml of tetrahydrofuran to perform reprecipitation. After removing the solvent by decantation and centrifugation, the precipitate was subjected to vacuum drying at 50 ° C. to obtain a sample of nanocomposite particles containing dark green polyaniline.

Note) APS indicates ammonium peroxodisulfate.
<Evaluation of polyaniline-containing nanocomposite particles>
About the polyaniline containing nanocomposite particle sample obtained in Examples 10-13, the average particle diameter and content of RF-MES oligomer were measured.
(Evaluation of average particle size)
The obtained polyaniline-containing nanocomposite particles were redispersed in water and measured using a light scattering photometer (DLS-6000HL manufactured by Otsuka Electronics).
(Measurement of RF-MES oligomer content)
The obtained polyaniline-containing nanocomposite particles were determined by thermogravimetric analysis.

<Evaluation of solubility>
The resulting polyaniline-containing nanocomposite particles were evaluated for solubility in each solvent. The results are shown in Table 7. Further, the solubility of polyaniline not containing a fluoroalkyl group-containing oligomer was also tested, and the results are also shown in Table 7.
The symbols in the table indicate the following.
◎; melted, ○ good dispersion, △; partial dispersion, ×; hardly dispersed

Note) AK225 is: 1: 1 mixture of CF ₃ CF ₃ CHCl ₂ and CClF ₂ CF ₂ CHClF, THF; tetrahydrofuran, dichloroethane; 1,2-dichloroethane (CH ₂ ClCH ₂ Cl), DMF; dimethyl Formamide <Evaluation of gelation of ionic liquid>
By adding the polyaniline-containing nanocomposite particles to the ionic liquid, the minimum amount of polyaniline-containing nanocomposite particles necessary for forming a gel (hereinafter referred to as “minimum gelation concentration”) was determined. The experimental method is as follows.

  A gel is formed (25 ° C.) by adding the polyaniline-containing nanocomposite particles of Example 1 and Example 10 prepared above to 0.5 g of various ionic liquids and applying ultrasonic waves at 120 W for 12 hours. I confirmed whether or not.

  Moreover, the used ionic liquid used the following chemical formula (a1)-(a6).

(Evaluation of ionic conductivity)
The obtained ionic liquid-containing gel sample was placed in a Pyrex (registered trademark) glass cell, an upper electrode made of brass was sandwiched between the lower electrodes, and the conductivity was measured at 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 9 also shows the ionic conductivity when the ionic liquid is used alone.

According to the present invention, it is possible to provide a nanocomposite particle containing polyaniline that exhibits excellent solubility in water and excellent dispersibility in an organic solvent, and the polyaniline-containing nanocomposite particle. Electrode materials for secondary batteries, antistatic agents, electrolytes for solid electrolytic capacitors, counter electrodes for titanium dioxide dye-sensitized solar cells, electromagnetic shielding materials, active oxygen generators, optical recording elements, artificial muscle materials, electrorheological fluids It can be expected to be used in a wide range of fields such as electrical, electronic and mechanical dispersants.
Moreover, according to this invention, this polyaniline containing nanocomposite particle can be manufactured industrially advantageously.
Moreover, when the polyaniline-containing nanocomposite particles of the present invention are brought into contact with an ionic liquid, a gel is formed, and an ionic liquid-containing gel excellent in ionic conductivity can be generated.

Claims (7)

Polyaniline-containing nanocomposite particles produced by oxidizing aniline in the presence of a fluoroalkyl group-containing oligomer represented by 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 represents a hydrogen atom or a methyl group, Z represents a group selected from —OH, —OC ₂ H ₄ SO ₃ H or —NH ₂ ⁺ C (CH ₃ ) ₂ CH ₂ SO ₃ ^—. N Represents an integer of 5 to 1000.)   2. The polyaniline-containing nanocomposite particle according to claim 1, having an average particle size of 10 to 900 nm. The manufacturing method of the polyaniline containing nanocomposite particle | grains characterized by oxidatively polymerizing aniline with an oxidizing agent in presence of the fluoroalkyl group containing oligomer represented by 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 represents a hydrogen atom or a methyl group, Z represents a group selected from —OH, —OC ₂ H ₄ SO ₃ H or —NH ₂ ⁺ C (CH ₃ ) ₂ CH ₂ SO ₃ ^—. N Represents an integer of 5 to 1000.)   The method for producing polyaniline-containing nanocomposite particles according to claim 3, wherein the oxidizing agent is ammonium peroxodisulfate.   A gel produced by bringing the polyaniline-containing nanocomposite particles according to any one of claims 1 and 2 and an ionic liquid into contact with each other.   An ionic conductor comprising the gel according to claim 5.   An ionic conductor characterized by being used as a polymer solid electrolyte.