JP2008074894A - Method for producing nano-particle of conductive polymer using ionic liquid and method for producing conductive polymer composite material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a nano-particle of a conductive polymer and to provide a method for producing a conductive polymer composite material using the method. <P>SOLUTION: The method for producing the nano-particle of the conductive polymer is carried out as follows. An ionic liquid containing an imidazole cation salt having substituents on both nitrogens is used as a solvent to synthesize a microparticle of the conductive polymer represented by structural formula 2 (wherein, R1 and R2 represent each independently any one kind selected from the group consisting of a hydrogen, a 1-15C alkyl group, a 1-15C ether group, a halogen atom and a benzene group; X represents a sulfur (S), an oxygen (O), a selenium (Se) or an NH; and n is an integer of 100-10,000). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing conductive polymer nanoparticles and a method for producing a conductive polymer composite material using the same, and more specifically, an ionic liquid containing a compound represented by the following structural formula 1 as a solvent. And a method for producing conductive polymer nanoparticles characterized by synthesizing fine particles of a conductive polymer represented by the following structural formula 2 and a conductive polymer represented by the following structural formula 2 obtained by this method. The present invention relates to a method for producing a conductive polymer composite material in which molecular nanoparticles are used as a material for vacuum forming materials having an antistatic and electromagnetic wave shielding function or other electronic components.

  Currently, polyaniline, polypyrrole, polythiophene, etc. are widely used as conductive polymer compounds. These compounds are easy to polymerize, and have excellent electrical conductivity, thermal stability and oxidation stability. Due to its nature, research on these substances has been extensive. This type of conductive polymer compound includes secondary battery electrodes, electromagnetic shielding materials, flexible electrodes, antistatic materials, anticorrosion coating agents, solid electrolytic capacitor electrolytes, etc. Is very diverse. However, this type of conductive polymer compound has a very high rigidity of the polymer chain in terms of structure, and the conductive polymer compound doped with an acid is charged. The interaction between the molecular chains is very strong and reduces processability, resulting in many limitations on practicality. This makes it impossible to use a normal method for processing plastics, that is, a method of processing by dissolving in a solvent or a method of applied processing. For this reason, eliminating these disadvantages is the most important issue in the practical application of conductive polymer compounds.

  Various methods have been proposed to eliminate such inconvenience of workability. First, the first method is a method for increasing the solubility of polyaniline by using a polyaniline that increases the molecular size of the partner anion of the positive child acid used when doping with acid. Actually, when camphorsulfonic acid or dodecylbenzenesulfonic acid is used as a polyaniline doping reagent, it is known that the solubility of polyaniline can be increased to some extent in metacresol, chloroform and xylene as organic solvents (Non-Patent Documents). 1). However, in this method, in synthesizing polyaniline, after being neutralized by reacting with ammonia water what is already doped with hydrochloric acid, it is again doped with an acid that increases the molecular size of the partner anion. There was a difficulty that was necessary. Moreover, this method has a drawback that it cannot be used at a practical level because the solubility cannot be increased unless a special technique is used.

  In the second method, after polyaniline is oxidatively polymerized in the presence of positive carboxylic acid, this is further treated with a base, the anti-doped polyaniline is dissolved in N-methylpyrrolidone, processed, and then positive. This is a method of re-doping with a ferric acid (see Non-Patent Document 2). However, this method has a drawback that the process becomes complicated because re-doping is essential.

  The third method is a method of increasing the solubility by bonding a polar substituent to a monomer and then polymerizing the monomer (see Non-Patent Document 3). However, this method has a drawback that the process of producing and purifying the monomer substitution product is complicated.

  The fourth method is a method in which the side chain of the monomer is replaced with a long alkyl chain to increase the solubility and the melt processing degree of the conductive polymer compound synthesized therefrom (see Non-Patent Document 4). However, this method is disadvantageous because it is difficult to synthesize the monomer and causes high cost.

  Finally, in the fifth method, in synthesizing the conductive polymer compound, particles of the polymer compound obtained by using polyvinyl alcohol, polyvinyl acetate, cellulose derivative or the like as the three-dimensional structure stabilizer are atomized. In this method, the polymer compound is dispersed in a solution (see Non-Patent Document 5). However, the compound such as polyvinyl alcohol used in this method has a defect that it functions only as a three-dimensional structure stabilizer and cannot function as a dopant when a polymer compound is synthesized.

  For several years, heterocycle-like conductive polymers have been used effectively in electronic parts and various sensors as films or granules. Among heterocyclo compounds, polypyrrole and polythiophene are easy to synthesize, and the synthesized polymers have high electrical conductivity and excellent atmospheric stability. ing. Until now, synthesis methods such as an electrochemical polymerization method, a chemical oxidation method, and a gas phase polymerization method are generally known. However, these synthetic methods, like other conjugated conductive polymers, have the disadvantages that they do not progress in melting or dissolution and are difficult to process into a film, and are expensive, so they are often used. There were restrictions.

  In addition, most of the polymers synthesized by the chemical oxidation method are in the form of particles, and the polymers synthesized by the electrochemical method are usually produced in a thin film shape. The synthesis process is complicated and requires separate purification and doping steps. In any case, much research on the production of conductive polymers has progressed, especially in the case of conductive polymers that are in the form of particles, a composite that improves processability and physical properties when mixed with ordinary polymers. A method of producing a material has been proposed. Furthermore, as a method for producing a thin conductive composite film, an electrochemical polymerization method is widely known, but its processability is low, and there is a difficulty in production by a continuous process. In recent years, some gas phase polymerization methods have been introduced. In general, however, this method uses a normal polymer film in which an oxidant is dispersed as a host material, and sprays monomer vapor thereon. However, in this case, further problems such as prolonged reaction time have been raised.

The present inventors put an oxidant necessary for polymerization into an ionic liquid solvent and satisfy the necessary conditions such as temperature, and then synthesize a monomer (monomer) of a conductive polymer in a liquid form. As a result, conductive polymer particles of several tens of nanometers doped with a dopant at the same time as polymerization are provided, and synthesis and doping are simultaneously performed in a single process, and a high yield of 90% or more can be obtained. The present inventors have found that the process is simple and advantageous in obtaining an inexpensive conductive polymer composite. Furthermore, the inventors have found that these particles can be easily blended with other host polymers and can be used to produce conductive composite materials. The present invention has been completed based on these findings.
Synthetic Metal, 1992, 48, p91-97 J. Chem. Soc., Chem. Commun., 1989, p1736-1738 J. Electrochem. Soc., 1994, 141, L26 Synth. Met. 1988, 26, p267 Polymer, 1992, 33, p4857

  The object of the present invention is particularly excellent in electrical characteristics (for example, electrical conductivity can be expressed up to 300Ω by sheet resistance), and a conductive polymer whose particle size can be freely adjusted, particularly Another object of the present invention is to produce polypyrrole and polythiophene or a derivative thereof using an ionic liquid as a solvent, and provide it as a functional material for preventing static electricity and shielding electromagnetic waves such as materials for electronic parts and displays.

  In order to achieve the above object, the present invention synthesizes fine particles of a conductive polymer represented by the following structural formula 2 using an ionic liquid containing a compound represented by the following structural formula 1 as a solvent, and polymer nanoparticles. The present invention provides a method for producing conductive polymer nanoparticles, wherein the particle diameter is in the range of 10 to 500 nm.

In the formula, R ′ and R ″ each independently represent any one selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, an ether group, an alkoxy group, and an ester group, and Y ⁻ represents a monovalent group. Represents the anion.

  In the formula, R1 and R2 each independently represent any one selected from the group consisting of hydrogen, an alkyl group having 1 to 15 carbon atoms, an ether group having 1 to 15 carbon atoms, a halogen atom, and a benzene group. , X represents sulfur (S), oxygen (O), selenium (Se) or NH, and n is an integer of 100 to 10,000.

  In the above invention (invention 1), the substituents R ′ and R ″ of the compound represented by the structural formula 1 are each a hydrocarbon having 1 to 15 carbon atoms or a hydrocarbon containing 5 or less atoms outside carbon. Is preferably used (Claim 2), and the ionic liquid is preferably one selected from the group consisting of pyridinium, phosphonium, morpholinium, pyrrolidinium, pyrrolidonium, piperidinium and piperidinium derivatives (Claim 3). The ionic liquid is preferably a magnetic substance (Invention 4) In the invention (Invention 4), the anionic substance is preferably an iron chloride (Invention). 5).

  In the above invention (Invention 1), the monomer of the compound represented by Structural Formula 2 is preferably any one selected from the group consisting of pyrrole, thiophene, furan and derivatives thereof. (Claim 6). In the above invention (invention 6), the monomer is preferably a conjugated substance having aniline or pi bond (invention 7).

  Furthermore, in the said invention (invention 1), it is preferable that the said ionic liquid is mixed with another organic solvent, and the said ionic liquid is contained at least 50% or more at the time of superposition | polymerization (invention 8), The conductive polymer nanoparticles represented by the structural formula 2 are preferably mixed with at least 1% or more of another substance and used as an additive to a coating material or another material (claim 9).

  In addition, the present invention provides a conductive polymer nanoparticle represented by the structural formula 2 obtained by the method according to claim 1, a vacuum forming material with an antistatic and electromagnetic shielding function, or other electronic component material. The present invention provides a method for producing a conductive polymer composite material characterized by being used as (claim 10). In the said invention (invention 10), the said vacuum forming material or the raw material of another electronic component is a polyester (PET, A-PET, PBT, or PET-G), a polycarbonate (PC), a polystyrene (PS), and a polyurethane. It is preferably blended with a host polymer different from any one selected from the group (claim 11). In the above invention (Invention 1), the shape of the conductive polymer is preferably a tube or a rod (Invention 12).

  According to the present invention, an oxidizing agent or the like necessary for polymerization is placed in an ionic liquid solvent, and after satisfying necessary conditions such as temperature, the conductive polymer monomer (monomer) is mixed in a liquid state. So synthesis is easy. In addition, by providing conductive polymer particles of several tens of nanometers doped with a dopant simultaneously with polymerization, synthesis and doping can be simultaneously performed in a single process, and a high yield of 90% or more can be obtained. The process is simple and advantageous in obtaining an inexpensive conductive polymer composite. Furthermore, these particles can be easily blended with other host polymers and can be used to produce conductive composite materials. Furthermore, the conductive polymer nanoparticles obtained by the present invention are useful as an alternative to a conductive material using carbon nanotubes. Moreover, according to the present invention, conductive polymer nanoparticles can be synthesized more economically and can be used for various applications.

Hereinafter, the present invention will be described in detail.
The present invention provides a conductive polymer nano-particle characterized in that the ionic liquid containing the compound represented by the structural formula 1 is used as a solvent to synthesize conductive polymer fine particles represented by the structural formula 2. Provide a method.

  In the present invention, as the substituents R ′ and R ″ of the compound represented by the structural formula 1, it is preferable to use a hydrocarbon having 1 to 15 carbon atoms or an imidazole type, and the ionic liquid is In particular, it is preferably any one selected from the group consisting of pyridinium, phosphonium, morpholinium, pyrrolidinium, pyrrolidonium, piperidinium and piperidinium derivatives centering on imidazole series.

Further, in the present invention, the ionic liquid is preferably a magnetic material, more preferably, anionic substances are iron chloride compounds (FeCl ₄ containing iron ^- ions) it is.

  In the present invention, the monomer of the compound represented by the structural formula 2 is preferably any one selected from the group consisting of pyrrole, thiophene, furan and derivatives thereof, more preferably The monomer is an aniline or conjugated substance having a pi bond.

  Furthermore, in the present invention, the ionic liquid is used by being mixed with another organic solvent, and the ionic liquid is preferably contained at least 50% or more at the time of polymerization, and the structure obtained by the above method is used. It is preferable to mix the conductive polymer nanoparticles represented by Formula 2 with at least 1% or more of other substances and use them as an additive to a coating material or other materials.

The present invention relates to a method for producing conductive particles in which an ionic liquid is used as a solvent, and a liquid polymer such as polypyrrole, polythiophene, polyfuran and derivatives thereof and a conductive polymer material such as polyaniline are directly polymerized into particles of a certain size and Regarding its application. Here, the ionic liquid refers to a liquid composed only of ions, and is generally composed of a huge cation containing nitrogen and a smaller anion. Such a structure reduces the lattice energy of the crystal structure, resulting in a low melting point and a high boiling point. In particular, it exists as a liquid at room temperature, and is non-volatile, non-flammable, stable as a liquid at temperatures up to 400 ° C., high solubility of organic and inorganic substances, high electrical conductivity, etc. It is a new concept cleaning medium with unique characteristics. Further, since 100% complete recovery by layer separation after use is possible, it is also called “GREEN SOLVENT (green solution)”. The ionic liquid is composed of an organic cation and an anion. Typical examples of the cation include imidazolinium, pyridinium, ammonium, phosphonium and the like. In recent years, morpholinium, pyrrolidinium, pyrrolidonium, piperidinium , Tend to expand to piperidinium and the like. Here, anion substances having various structures such as NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , and FeCl ₄ ⁻ are included. Among the ionic liquid substances that can be used according to the present invention, the structure of the imidazolinium derivative is represented by the following structural formula 1.

In the formula, R ′ and R ″ are each independently any one selected from the group consisting of an alkyl group having 1 to 15 carbon atoms, an ether group, an alkoxy group, and an ester group, and Y ⁻ is 1 It is a valent anion.

In the above structural formula 1, examples of Y ⁻ include anionic substances having various structures such as NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , and FeCl ₄ ^−. .

  The present invention is particularly excellent in electrical characteristics (for example, electrical conductivity can be developed up to 300Ω in terms of surface resistance), and a conductive polymer whose particle size can be freely adjusted, particularly polypyrrole. In addition, polythiophene or a derivative thereof can be produced using an ionic liquid as a solvent. Moreover, this can be used as a functional material for preventing static electricity and shielding electromagnetic waves in materials for electronic components and displays. That is, according to the present invention, an oxidant necessary for polymerization is placed in an ionic liquid solvent, and after satisfying necessary conditions such as temperature, the monomer (monomer) of the conductive polymer is mixed in a liquid state. As a result, conductive polymer particles of several tens of nanometers that are easily synthesized and doped with a dopant simultaneously with polymerization are obtained. As a result, synthesis and dope are simultaneously performed in a single process, and a high yield of 90% or more can be obtained. Therefore, the process is simple and advantageous in obtaining an inexpensive conductive polymer composite. It is.

  Furthermore, these particles can be easily blended with other host polymers, and a conductive composite material can be easily produced. The conductive polymer material that can be produced according to the present invention is mainly a conjugated polymer having a heterocyclic structure, and includes polypyrrole and derivatives thereof, polythiophene and derivatives thereof, polyfuran and derivatives thereof, and polyselenophene and derivatives thereof. Derivatives and the like. These are represented by the following structural formula 2.

  In the above formula, R1 and R2 are each independently any one selected from the group consisting of hydrogen, an alkyl group having 1 to 15 carbon atoms, an ether group having 1 to 15 carbon atoms, a halogen atom, and a benzene group. Yes, X is sulfur (S), oxygen (O), selenium (Se), or NH, and n is an integer from 100 to 10,000.

  The ionic liquid used in the present invention is based on the structure represented by the structural formula 1 above, and 1-ethyl-3-methylimidazolinium tetrafluoroborate, 1-ethyl-3-methylimidazolinium ethyl sulfate, 1-ethyl Ethyl-3-methylimidazolinium iron chloride, 1-hexyl-3-methylimidazolinium trifluoroethane sulfate, 1-aryl-3-butylimidazolinium tetrafluoroborate, 1-ethylpyridinium bromide, 1-butylpyridinium Hexafluorophosphate or the like can be used, and these can be combined to increase the yield depending on the application. In some cases, a magnetic ionic liquid having magnetism may be used. Anions that can be used at this time can include iron (trivalent ions).

The conjugated polymer obtained according to the present invention has an electric conductivity of about 10 ² to 10 ⁻² S / cm, and the particle size varies depending on the synthesis time and reaction temperature conditions. Larger particles can be obtained at higher temperatures than at lower temperatures. In particular, when pyrrole is used as a monomer, factors such as reaction time, reaction temperature, reaction solvent, and oxidizing agent greatly affect the microstructure and electrical conductivity of the synthesized conductive polymer.

  The method for synthesizing conductive polymer particles by polymerization in an ionic liquid according to the present invention can be performed under a temperature condition of 0 to 120 ° C., and from synthesis to particle formation is performed in a single step. There are features. Further, no additional process is required for chemical doping. The synthesized conductive polymer nanoparticles can be separated and recovered by simple layer separation from the magnetic ionic liquid, and alcohols may be added for layer separation. In order to diversify the polymer particle structure and improve the yield, various ionic liquids can be mixed, and two or three types of anions can be mixed and used.

  After the polymerization, washing is performed to remove unreacted monomers and impurities. In this case, the usable solvent usually includes alcohols, but depending on the case, water may be used. Such a series of processes can be performed stepwise or continuously, and can be processed by a series of operation processes from polymerization to particle formation.

  The conductive polymer particles obtained according to the present invention maintain a purity of 99% or more and are excellent in conductivity. In addition, it exhibits stable characteristics in ordinary organic solvents such as alcohols.

  After completion of the reaction, the separated and recovered conductive polymer particles are dried in a vacuum dryer at 60 ° C. or lower in consideration of the deformation of the dopant. The synthesized conductive polymer particles have an affinity with most polymer materials such as polyurethane, polyvinyl chloride, polyester, nylon, ABS resin, polystyrene, and polyvinyl alcohol as host polymer materials and are easily mixed. It is a feature that it is done. For this reason, these synthetic polymer materials can be blended with the host polymer described above to produce a composite material.

  They have electrical conductivity, are easy to manufacture as antistatic or electromagnetic shielding films or sheets, and are excellent in moldability, so they can be used for vacuum molded products or other processed products. is there. In addition to excellent moldability as a molded product, it has mechanical strength, and in the case of polypyrrole, it has high thermal and chemical stability in the atmosphere, and has attracted much attention so far.

  In the present invention, the conductive polymer nanoparticle represented by the structural formula 2 obtained by the above method is used as a vacuum forming material with an antistatic and electromagnetic wave shielding function or an element of other electronic components. A method for producing a polymer composite material is provided.

  At this time, the material of the vacuum forming material or other electronic component is any one selected from the group consisting of polyester (PET, A-PET, PBT or PET-G), polycarbonate (PC), polystyrene (PS) and polyurethane. It is preferably blended with a host polymer different from one kind.

  In the present invention, sheet resistance is measured by a four-terminal method, reliability is tested under high temperature and high humidity conditions of 85 ° C./85% RH, and in the case of composite, hardness is measured by measuring pencil strength. Went. Evaluation of thermal stability was performed using a TGA2050 analyzer (manufactured by DuPont) at a heating rate of 10 ° C./min in a measurement range of 30 to 500 ° C. The shape of the particles could be observed with an optical microscope.

  The conductive particles obtained according to the present invention show slight differences due to polymerization conditions and chemical structure differences of the polymer. In the case of electrical conductivity, the minimum is 300 Ω / □ to the maximum 1000 Ω / □, and the particle size can be freely adjusted by the reaction time, temperature and the like. When a conductive polymer composite is prepared by mixing with another host polymer, it can be used as an antistatic film, an electromagnetic wave shielding film, or an electromagnetic wave shielding sheet. Furthermore, in the case of this composite, the conductivity can be maintained up to 3 to 5 times stretching, and it also has the characteristics as a molding material.

  In recent years, it has been reported that the application can be expanded to materials for displays as well as for transporting semiconductor IC chips or precision electronic devices (shipping trays or carrier tapes). However, for these materials, a method of forming a film by a separate coating process after polymerizing the conductive polymer itself has been used so far. Furthermore, a metal thin film formed by vacuum deposition is used as a transparent conductive material. However, although these exhibit excellent performance as electrode materials, they are difficult to use as materials that require secondary processing such as vacuum forming, and have the disadvantage of high manufacturing costs. Further, in some cases, it is considered useful as a substitute for a conductive material using carbon nanotubes, and the nanoparticles of the conductive polymer can be provided at a lower cost and for various uses.

  In the present invention, an oxidant is mixed with an ionic liquid to react a pyrrole monomer, and then a precipitate is separated and recovered to obtain conductive polypyrrole polymer particles. Next, impurities are removed from this and vacuum dried. As a result, conductive polymer polypyrrole particles are obtained, which show high electrical conductivity values, are stable in organic solvents, and have no change in electrical conductivity even during high temperature treatment at 200 ° C. or higher.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are merely for illustrating the present invention, and the content of the present invention is not limited to the following examples.

[Example 1]
3% by weight of ferric chloride (FeCl ₃ ) as an oxidant is mixed with 100% by weight of 1-ethyl-3-methylimidazolinium tetrafluoroborate as an ionic liquid, and pyrrole is heated at a temperature of 60 ° C. The monomer was allowed to react for 60 minutes by adding 10% by weight. Next, the precipitate was separated and recovered, and conductive polypyrrole polymer particles having an average particle diameter of 500 nm were recovered.

In order to remove impurities, it was washed with 50 g of methanol and vacuum-dried for 1 hour under a temperature condition of 60 ° C. to obtain 9.5 g of dark brown conductive polymer polypyrrole particles. The obtained conductive polymer polypyrrole particles have a high electric conductivity of about 10 ² S / cm, are stable in organic solvents, and change in electric conductivity even during high-temperature treatment at 200 ° C. or higher. I was not able to admit.

[Example 2]
100 g of 1-hexyl-3-methylimidazolinium trifluoroethane sulfate was used as the ionic liquid, and 10% by weight of a pyrrole monomer was added to a ferric chloride (FeCl ₃ ) solvent at 60 ° C. for 60 minutes. Then, the precipitate was separated and recovered to obtain 8.7 g of conductive polypyrrole polymer particles. The obtained conductive polypyrrole polymer particles had an average particle size of 80 nm.

Example 3
9 g of a blue polythiophene derivative was obtained in the same manner as in Example 1 except that a thiophene derivative monomer was used. The obtained polythiophene derivative had an electrical conductivity of about 10 ² S / cm, which was higher than that of polypyrrole, and exhibited plate-like particles of about 800 nm.

Example 4
8.2 g of a blue polythiophene derivative was obtained in the same manner as in Example 2 except that the thiophene derivative monomer was used. The obtained polythiophene derivative had an electric conductivity of about 10 ² S / cm, which was higher than that of polypyrrole, and exhibited plate-like particles of about 120 nm.

Example 5
Transparent brown conductive polymer particles were obtained in the same manner as in Example 1 except that Cu (ClO ₄ ) ₂ was synthesized by dissolving Cu (ClO ₄ ) ₂ as an oxidizing agent. At this time, the yield was as low as about 75%. The electrical conductivity of the obtained conductive polymer particles was similar to that of Example 1.

Example 6
1-ethyl-3-methylimidazolinium iron chloride was used as the ionic liquid, and the pyrrole monomer was added at 10% by weight under the temperature condition of 20 ° C. and reacted for 60 minutes, and then the precipitate was separated and recovered. Except that, conductive polypyrrole fine particles having an average particle diameter of 60 nm were obtained in the same manner as in Example 1 above. As a result, 8 g of dark brown conductive polymer polypyrrole particles were obtained. The obtained conductive polymer polypyrrole particles had the same electrical conductivity as that of Example 1 and polymerization in a low temperature process, and therefore a phenomenon that the particle size was remarkably reduced was observed.

Example 7
7.8 g of a blue polythiophene derivative was obtained in the same manner as in Example 6 except that a thiophene derivative monomer was used instead of the pyrrole monomer. The obtained polythiophene derivative had slightly higher electrical conductivity than that of polypyrrole, and exhibited plate-like particles of about 80 nm.

Example 8
Polystyrene having a molecular weight of 80,000 to 120,000 as a host polymer is 100% by weight, and 5% by weight of a conductive polymer composition obtained according to Example 1 is melt-mixed to obtain a light brown composite. Cast and observed for mixing and electrical properties. As a result, the mixed state showed a very uniform surface, and the electric conductivity was about 10 ⁸ Ω / □ in terms of surface resistance. In addition, although the transparent brown conductive polymer sheet was obtained, this also showed favorable moldability.

Example 9
The method of Example 1 above, except that the ionic liquid and a solvent in which methyl alcohol, isobutyl alcohol and ethyl cellosolve were mixed in a ratio of 6: 3: 1 were mixed at a mixing ratio of 3: 1. And performed in the same manner. As a result, it was confirmed that the separation ability of the conductive polymer particles was greatly increased.

Example 10
Polyester (PET) having a molecular weight of 100,000 to 150,000 as a host polymer was 100% by weight, and 5% by weight of a conductive polymer composite obtained according to Example 1 was melt-mixed to obtain a composite. The resulting composite was similar in mixing and electrical properties to that of Example 8.

Example 11
The same procedure as in Example 2 was performed except that a polyolefin-based resin was used as the host polymer.

Example 12
The procedure was the same as in Example 1 except that 2,3-dihydrothio-3,4-dioxin (EDOT) monomer was used. At this time, the reaction temperature was adjusted to 40 ° C. As a result, the polymerization state and electrical characteristics were similar to those in Example 1.

Example 13
A green polymer material was obtained in the same manner as in Example 1 except that the aniline monomer was used. The obtained polymerized material had irregularity of particles at several tens of nm, but no change in electrical characteristics was observed.

Claims (12)

Using an ionic liquid containing a compound represented by the following structural formula 1 as a solvent, fine particles of a conductive polymer represented by the following structural formula 2 are synthesized, and the particle size of the polymer nanoparticles is in the range of 10 to 500 nm. A method for producing conductive polymer nanoparticles, characterized by comprising:

(Independently of R 'and R ", wherein represents any one selected from the group consisting of alkyl group, an ether group, an alkoxy group and an ester group, of 1 to 15 carbon atoms, Y ^- is 1 Represents a valent anion.)

(Wherein R1 and R2 each independently represents any one selected from the group consisting of hydrogen, an alkyl group having 1 to 15 carbon atoms, an ether group having 1 to 15 carbon atoms, a halogen atom, and a benzene group. X represents sulfur (S), oxygen (O), selenium (Se) or NH, and n is an integer of 100 to 10,000.   As the substituents R ′ and R ″ of the compound represented by the structural formula 1, hydrocarbons having 1 to 15 carbon atoms or hydrocarbons having 5 or less carbon atoms are used, respectively. Item 2. A method for producing conductive polymer nanoparticles according to Item 1.   The conductive polymer nanoparticles according to claim 1, wherein the ionic liquid is any one selected from the group consisting of pyridinium, phosphonium, morpholinium, pyrrolidinium, pyrrolidonium, piperidinium, and piperidinium derivatives. Method.   The method for producing conductive polymer nanoparticles according to claim 1, wherein the ionic liquid is a magnetic substance.   The method for producing conductive polymer nanoparticles according to claim 4, wherein the ionic liquid is an anionic substance of iron chloride.   2. The conductive polymer according to claim 1, wherein the monomer of the compound represented by Structural Formula 2 is any one selected from the group consisting of pyrrole, thiophene, furan, and derivatives thereof. A method for producing nanoparticles.   The method for producing conductive polymer nanoparticles according to claim 6, wherein the monomer is an aniline or conjugated substance having a pi bond. The ionic liquid is used by being mixed with another organic solvent,
The method for producing conductive polymer nanoparticles according to claim 1, wherein the ionic liquid is contained at least 50% or more during polymerization.   The conductive polymer nanoparticle represented by the structural formula 2 is mixed with at least 1% or more of another substance and used as an additive to a coating material or another material. For producing functional polymer nanoparticles.   The conductive polymer nanoparticles represented by the structural formula 2 obtained by the method according to claim 1 are used as a vacuum forming material with an antistatic and electromagnetic shielding function or as a material for other electronic components, A method for producing a conductive polymer composite material.   The material of the vacuum forming material or other electronic component is any one selected from the group consisting of polyester (PET, A-PET, PBT or PET-G), polycarbonate (PC), polystyrene (PS) and polyurethane. The method of claim 10, wherein the method is blended with a different host polymer.   The method for producing conductive polymer nanoparticles according to claim 1, wherein the shape of the conductive polymer is a tube shape or a rod shape.