KR101003531B1 - Nanoparticles comprising polythiophene or its derivatives enclosed by conductive polymers and method for preparing the same - Google Patents

Abstract

The present invention relates to a nanoparticle in which a polythiophene or a polythiophene derivative is surrounded by a polymer conductive emulsifier, and a method of manufacturing the same, in the presence of an aqueous solvent containing an oxidizing agent, in a region surrounded by a polymer conductive emulsifier, A polythiophene or polythiophene derivative capable of forming a luminescent film by producing an oxidative polymerization of an opene derivative to form a nanoparticle in which the polythiophene or polythiophene derivative is surrounded by a polymer conductive emulsifier is a polymer conductive emulsifier. The present invention relates to a nanoparticle and a method of manufacturing the same.

Polythiophene, polystyrene sulfonate, oxidizing agent, light emitting polymer, conductive emulsifier, nanoparticle

Description

Nanoparticles comprising polythiophene or its derivatives enclosed by conductive polymers and method for preparing the same

The present invention relates to a nanoparticle in which a polythiophene or a polythiophene derivative is surrounded by a polymer conductive emulsifier, and a method of manufacturing the same, in the presence of an aqueous solvent containing an oxidizing agent, in a region surrounded by a polymer conductive emulsifier, A polythiophene or polythiophene derivative capable of forming a luminescent film by producing an oxidative polymerization of an opene derivative to form a nanoparticle in which the polythiophene or polythiophene derivative is surrounded by a polymer conductive emulsifier is a polymer conductive emulsifier. The present invention relates to a nanoparticle and a method of manufacturing the same.

Nanotechnology is a technology that identifies and controls materials at the molecular and atomic level, and it is a technology that enables the transformation and modification of existing materials and the creation of new materials by appropriately combining atoms and molecules. Is recognized.

Nanomaterials are generally materials with a size of about 1 to 100 nanometers, and exhibit new electronic, magnetic, optical, and electrical properties not found in the solid state. Because of these properties, research on the manufacture of nanomaterials using metals, metal oxides, and inorganic materials has been continuously conducted. As a result, technologies for manufacturing nanometer-sized metal and inorganic semiconductor nanoparticles have been well established, and industrial applications are actively studied. It is becoming. On the other hand, in the case of organic polymer nanomaterials, it is difficult to mass-produce and the production of nanoparticles having a uniform size is relatively complicated, thereby limiting the application range. Overcoming these limitations and increasing interest in researches for producing and applying nanostructures of organic materials, researches for the preparation of nanostructures of conductive emulsifiers have also been actively conducted. In terms of electrically conductive materials, conductive emulsifiers have the potential to be used as substitutes for heavy loads, transparent conductive films, optical display devices, antistatic materials, and electromagnetic shielding materials. In order to enable this, not only high electrical conductivity but also improvement of workability, heat resistance, chemical resistance, and compatibility with commercial polymers are required. Recently, researches on improving the manufacturing method and improving the physical properties of well-known conductive emulsifiers such as polyaniline, polypyrrole, and polythiophene having excellent stability have been conducted, and are approaching the commercialization stage.

As an example of such an emulsion process, thiophene polymerization in an aqueous solution or continuous phase of alcohols is described by N. Toshima and S. Hara [Progress in Polymer Science , Vol. 20, pp. 155-183 (1995)] and M. Lapkowski [ Synthetic]. Metal , Vol. 407, pp. 41-43 (1991)].

However, in the above emulsion process, as a prerequisite, the continuous medium is an aqueous phase, and the yield in the aqueous continuous phase is remarkably low. The conductivity is also not measurable, and the polythiophene produced is insoluble in the organic solvent. There is a problem that the film can not be produced.

In addition, the Republic of Korea Patent No. 684913 describes the processability when preparing a granulated emulsion by polymerizing in an aqueous phase by using a very small amount of iron salt as an oxidizing agent in the aqueous phase and other oxidizing agents and emulsifiers that can be oxidized again when the iron salt is reduced. Techniques for producing polythiophene particles which are excellent and have improved particle luminescence properties from blue to red in the water phase are known.

However, the prior patent polymerized a thiophene monomer using a low molecular emulsifier, so that the final material prepared through the polymerization process will have a low molecular emulsifier as well as polythiophene nanoparticles, thereby forming the polythiophene nanoparticles. It serves to hinder its light emission and conductivity. In order to solve this problem, a process of removing the low molecular emulsifier has to be added.

On the other hand, polystyrene sulfonate is commonly used as a buffer layer of an organic light emitting diode together with 3,4-polyethylene dioxythiophene. The long chains of polystyrene sulfonate give good solubility to water phases, which together with other polymer composites offers the advantage of making thin conductive films by spin coating. The synthesis of this 3,4-polyethylene dioxythiophene-polythiene sulfonate consists of radical polymerization. Ethylene dioxy thiophene monomers form cationic radicals by an initiator on a solution in which polystyrene sulfonate is dissolved, thereby causing radical polymerization. Herein, since polystyrene sulfonate has a charge opposite to polyethylene dioxythiophene because of sulfonate group, polystyrene sulfonate serves to impart electrical stability. The final material thus polymerized, polyethylene dioxythiophene-polystyrene sulfonate, is present in a dispersed state in the water phase. However, this method is expensive.

The present invention is to overcome the above-mentioned problems of the prior art, an object of the present invention is to disperse a polymer that is conductive and viscous and acts as an emulsifier in the aqueous phase to surround the polythiophene or polythiophene derivative To provide a nanoparticle and a method for producing the same.

Another object of the present invention is to provide a use of the nanoparticles for applying the nanoparticles to electronic materials, optical materials, printing materials, or films.

In order to achieve the above object, the present invention provides a nanoparticle characterized in that the polythiophene or polythiophene derivative is surrounded by a polymer conductive emulsifier.

The invention also

The present invention provides a method for producing nanoparticles of the present invention, wherein the thiophene or thiophene derivative is polymerized in a region surrounded by a polymer conductive emulsifier in the presence of an aqueous solvent containing an oxidizing agent.

The present invention also provides an electronic material comprising the nanoparticles of the present invention.

The present invention also provides an optical material comprising the nanoparticles of the present invention.

The invention also provides a printing material comprising the nanoparticles of the invention.

The present invention also provides a film characterized by containing polythiophene in the matrix of the polymer conductive emulsifier.

The invention also

Thiophene or thiophene derivatives in aqueous solvents; Polymer conductive emulsifiers; And adding an oxidant to form an emulsion;

Adding an initiator to the emulsion to form a seed emulsion;

Stirring the emulsion to prepare an nanoparticle emulsion in which the thiophene or thiophene derivative is emulsion oxidatively polymerized to surround the polythiophene or polythiophene derivative with a polymer conductive emulsifier; And

It provides a method for producing a film of the present invention comprising the step of heat-treating the nanoparticle emulsion.

Nanoparticles, characterized in that the polythiophene or polythiophene derivative of the present invention is surrounded by a polymer conductive emulsifier, have a size of 10 to 1000 nm and, unlike other polythiophenes, which generally do not form a film, After heat treatment at 30 to 200 ° C, a light emitting film in which nanoparticles of polythiophene or polythiophene derivatives are embedded in a polymer matrix is formed to be applied to an EL sheet electrode for a mobile phone, an electrode for a touch screen, and an organic EL device. have.

EMBODIMENT OF THE INVENTION Hereinafter, the structure of this invention is demonstrated concretely.

The present invention relates to nanoparticles wherein the polythiophene or polythiophene derivative is surrounded by a polymer conductive emulsifier.

The size of the nanoparticles is characterized in that 10 to 1000 nm.

The polythiophene derivative is not particularly limited, but a thiophene repeating unit is preferably substituted with at least one substituent selected from alkyl, alkoxy, carboxyl, sulfone, alkyleneoxy, or these.

In addition, the polymer conductive emulsifier is an emulsifier and plays a role as a conductive dopant, and is primarily mixed with thiophene or thiophene derivatives to impart stability of particles, and provides a domain for synthesizing thiophene or thiophene derivatives, Secondly, it can be used as a material for forming a luminescent film containing a polymer of a polythiophene nanoparticle or a thiophene derivative through a high temperature heat treatment after polymerization of the polythiophene or polythiophene derivative.

The polymer conductive emulsifiers include polystyrenesulfonate, polypara-toluenesulfonate (poly (p-toluenesulfonate)), polycamphorsulfonate, polydi (2-ethylhexyl) sulfosuccinate ( poly (di (2-ethylhexyl) sulfosuccinate)), or polydioleylsulfosuccinate, etc. may be used alone or in combination of two or more.

The invention also relates to a process for the preparation of the nanoparticles of the invention, characterized in that the thiophene or thiophene derivative is polymerized in the region surrounded by the polymer conductive emulsifier in the presence of an aqueous solvent containing an oxidizing agent.

Preferably, the method for preparing nanoparticles of the present invention comprises the following steps:

Thiophene or thiophene derivatives in aqueous solvents; Polymer conductive emulsifiers; And adding an oxidant to form an emulsion;

Adding an initiator to the emulsion to form a seed emulsion; And

Stirring the seed emulsion to emulsion oxidize the thiophene or thiophene derivative.

The thiophene or thiophene derivative is a starting material for preparing a polythiophene or polythiophene derivative through a polymerization reaction, and is not particularly limited as long as it is a thiophene or thiophene derivative commonly used in the art. More preferably, the thiophene derivative may be one in which the thiophene repeating unit is substituted with at least one substituent selected from alkyl, alkoxy, carboxyl, sulfone, and alkyleneoxy.

The polymer conductive emulsifiers include polystyrenesulfonate, polypara-toluenesulfonate (poly (p-toluenesulfonate)), polycamphorsulfonate, polydi (2-ethylhexyl) sulfosuccinate ( poly (di (2-ethylhexyl) sulfosuccinate)), or polydioleylsulfosuccinate, etc. may be used alone or in combination of two or more.

The amount of the polymer conductive emulsifier is preferably 0.01 to 500 parts by weight based on the weight of the thiophene or thiophene derivative. If the content is less than 0.01 parts by weight, the micelle formation concentration does not act as an emulsifier, so that the polymerization of the nanoparticles cannot be induced and the particles aggregate. If the content exceeds 500 parts by weight, the amount of the emulsifier becomes excessive. It may be difficult to form the nanoparticles.

In addition, when the initiator is reduced by oxidizing the thiophene or thiophene derivative, the oxidant functions to oxidize the reduced initiator again to give the initiator an oxidizing power.

The oxidizing agent is not particularly limited, but H ₂ O ₂ , (NH ₄ ) ₂ S ₂ O ₈ , or O ₂ Peroxides, such as HMnO ₄ , HNO ₃ , or HClO ₄ Oxygen acids, such as F ₂ , Cl ₂ , or Br ₂ It is preferable that they are halogens, such as these, or a mixture thereof.

The amount of the oxidizing agent added is preferably 10 to 1000 parts by weight based on the weight of the thiophene or thiophene derivative. If the content is less than 10 parts by weight, the reaction for reducing the initiator does not occur well, the polymerization degree of the polymer nanoparticles is lowered, if the content exceeds 1000 parts by weight may occur a phenomenon that the degree of polymerization is lowered, there is a fear of deterioration of the physical properties.

In addition, the aqueous solvent is deionized water (Deionized water, DI Water) or an acidic solution prepared by adding an acid to water to prepare a pH of 1 to 5. The deionized water has an acidity of pH 1 to 5 by sequentially passing through a cation and an anion exchange resin. In addition, the acid to prepare an acidic solution of pH 1 to 5 by adding to the water is not particularly limited as long as it is an acid commonly used in the art, preferably sulfuric acid, nitric acid or hydrochloric acid may be used alone or two or more kinds. More preferably sulfuric acid.

The aqueous solvent is preferably included 500 to 2000 parts by weight based on the weight of the thiophene or thiophene derivative. If the content is less than 500 parts by weight, the polymer mixture may not be sufficiently dissolved. If the content is more than 2000 parts by weight, the solid content of the polymer may be lowered, thereby lowering the physical properties of the synthesized particles.

In addition, the initiator serves to oxidize the thiophene or thiophene derivative, although not particularly limited, a metal oxide is preferred.

As the metal oxide, H ₄ Fe (III) NO ₈ S ₂ / H ₂ O ₂ , H ₄ Fe (III) NO ₈ S ₂ / O ₂ , H ₄ Fe (III) NO ₈ S ₂ / HMnO ₄ , H ₄ Fe (III) NO ₈ S ₂ / F ₂ , H ₄ Fe (II) NO ₈ S ₂ / H ₂ O ₂ , H ₄ Fe (II) NO ₈ S ₂ / O ₂ , H ₄ Fe (II) NO ₈ S ₂ / HMnO ₄ , H ₄ Fe (II) NO ₈ S ₂ / F ₂ , FeCl ₃ / H ₂ O ₂ , FeCl ₃ / O ₂ , FeCl ₃ / HMnO ₄ , FeCl ₃ / F ₂ , FeCl ₂ / Iron complexes (III) and iron complexes such as H ₂ O ₂ , FeCl ₂ / O ₂ , FeCl ₂ / HMnO ₄ , FeCl ₂ / F ₂ , CuCl ₂ / H ₂ O ₂ , CuCl ₂ / HMnO ₄ ), Iron salt (III), iron salt (II), copper chloride (II) or a mixture thereof, or the like can be used alone or in combination of two or more thereof.

The initiator can be incorporated directly as an initiator into a mixture of starting materials for the polymerization, for example thiophene or thiophene derivatives, emulsifiers, oxidants and acidic solution mixtures of pH 1 to 5, but acidic solutions of pH 1 to 5 Preferably, a mixture of the starting materials is dissolved in deionized water (DI Water) and / or organic solvents such as chloroform, ethyl acetate, hexane, cyclohexane, petroleum ether, methylene chloride, and the like. It can be mixed with.

The amount of the initiator added is preferably 0.1 to 10 parts by weight based on the weight of the thiophene or thiophene derivative. If the content is less than 0.1 part by weight, the polymerization rate is very slow, and if it exceeds 10 parts by weight, the polymerization rate and the electrical conductivity are increased, but the physical properties of the polythiophene or polythiophene derivatives prepared, for example, light intensity and electricity Luminescence intensity decreases.

The invention also relates to electronic materials, optical materials, or printing materials comprising the nanoparticles of the invention.

Nanoparticles characterized in that the polythiophene or polythiophene derivative of the present invention is surrounded by a polymer conductive emulsifier is an electronic material, optical material, toner, ink, organic light emitting material, energy conversion and energy storage material, antistatic material, It can be used without limitation, such as a charge control material, an electrically conductive layer material, a pattern manufacturing material or a printing ink material.

In addition, the electronic material, optical material, toner and / or ink and the like refer to an electronic material, an optical material, a toner and / or an ink including a conductive emulsifier (for example, polystyrene sulfonate) or a derivative thereof, and such a configuration It is not particularly limited as long as it is a conventional product in the art, and preferably, it is preferable that the electronic material is a photovoltaic cell, a capacitor (used as an electrolyte), and a printed circuit board (PCB) substrate coating material (conventional metal plating is generally used to prevent environmental pollution). Can be minimized) and / or antistatic agent (to prevent static electricity generated on the surface of plastics, polymers, etc. through coating, etc.), and electroluminescent devices such as organic light emitting diodes and displays Particularly preferred optical materials include flat panel displays such as LCDs, organic electroluminescence (EL) devices, and indium tin oxide (ITO) substrates. Include hole injection layer (hole injecting layer) or a light emitting layer (emitting layer).

The invention also relates to a film characterized by containing polythiophene in the matrix of the polymer conductive emulsifier.

The luminescent film, for example, a film of polystyrene sulfonate containing polythiophene nanoparticles or derivatives thereof emits light in a wavelength range of about 580 nm when irradiated with an excitation wavelength of 420 nm. The phenomenon seems. In addition, since the polystyrene sulfonate is conductive, the film may be applied to an EL sheet electrode for a mobile phone, an electrode for an EL billboard, an electrode for a touch screen, an electrode for a backlight, and the like.

The invention also

Thiophene or thiophene derivatives in aqueous solvents; Polymer conductive emulsifiers; And adding an oxidant to form an emulsion;

Adding an initiator to the emulsion to form a seed emulsion;

Stirring the seed emulsion to emulsion oxidize the thiophene or thiophene derivative to prepare a nanoparticle emulsion in which the polythiophene or polythiophene derivative is surrounded by a polymer conductive emulsifier; And

It relates to a method for producing a film of the present invention comprising the step of heat-treating the nanoparticle emulsion.

The manufacturing method of the film of the present invention will be described in detail step by step.

In a first step, the thiophene or thiophene derivative; 0.01 to 500 parts by weight of the polymer conductive emulsifier relative to the weight of the thiophene or thiophene derivative; And 10 to 1000 parts by weight of an oxidizer relative to the weight of the thiophene or thiophene derivative is added to an acid solution having a pH of 1 to 5 having a temperature range of 20 to 50 ° C. to prepare an emulsion.

In a second step, a seed emulsion is prepared by mixing an initiator in the emulsion of the first step in an amount of 0.1 to 10 parts by weight based on the weight of a thiophene or a thiophene derivative, followed by stirring at 45 to 55 ° C. for 10 to 30 minutes.

The seed emulsion refers to a form in which particles are present therein, and thiophene is grown to a critical chain length to form a seed inside the emulsion.

The initiator is 5 to 100 parts by weight of an acid solution of pH 1 to 5, preferably deionized water or 5 to 100 parts by weight of an acid solution of pH 1 to 5 relative to the total weight of the acid solution of pH 1 to 5 Alternatively, the seed emulsion may be prepared by being mixed with the emulsion in a state of being dissolved in an organic solvent, followed by stirring.

At this time, when the initiator is supersaturated in the organic solvent, it is preferable to dissolve the initiator in the organic solvent in an ultrasonic bath (sonication bath) for 10 to 20 minutes to increase the dissolving power.

In addition, when the initiator of the second step is dissolved in the organic solvent and mixed into the emulsion, the seed emulsion is separately stirred at 45 to 50 ° C. for 10 to 30 minutes or 10 to ² to 100 between the second and third steps. The method may further include removing the organic solvent by reducing the pressure to a torr pressure.

In a third step, the seed emulsion of the second step is stirred at a temperature of 50 to 60 ℃ for 10 to 20 hours to perform the emulsion oxidation polymerization.

In a fourth step, the nanoparticles of the polythiophene or polythiophene derivative surrounded by the polymer conductive emulsifier polymerized through the process of the third step are 30 to 200 ℃, more preferably 130 to 170 ℃ for 5 to 20 minutes The light emitting film was prepared by embedding nanoparticles of polythiophene or polythiophene derivative in the matrix of the polymer conductive emulsifier.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are only for illustrating the present invention in detail, and the scope of the present invention is not limited by these examples.

≪ Example 1 >

0.4 g of polystyrene sulfonate [Sigma-Aldrich, USA] as an emulsifier and a conductive dopant was mixed with 45 g of 25 ° C. deionized water prepared by sequentially passing distilled water through a cation and an anion exchange resin, followed by stirring to completely dissolve the emulsifier. .

An emulsion was prepared by mixing 50 g of hydrogen peroxide [Dongyang Iron and Chemical Co., Ltd.] and 15 g of thiophene [Across Organics, Belgium] as a oxidant.

18 mg of iron salt (FeCl ₃ ) [Sigma-Aldrich, USA] as an initiator was mixed with 5 g of deionized water to prepare a mixed solution containing an initiator, which was mixed with the emulsion and reacted at a temperature of 50 ° C. for about 20 minutes. Seed emulsion was prepared.

The seed emulsion mixture was stirred at a temperature of 50 ° C. for 20 hours in a closed reactor to prepare polythiophene particles in an emulsion state.

The polythiophene particles in the emulsion state prepared above were dried at room temperature to prepare polythiophene particles.

As a result, the conversion rate of the polythiophene emulsion was 99%, and as shown in FIG. 2, the size of the prepared polythiophene particles (a) was about 52 nm as determined by scanning electron microscopy.

<Example 2>

In the same manner as in Example 1, but the amount of the polystyrene sulfonate [Sigma-Aldrich, USA] of the emulsifier of Example 1 was used in 1.7g.

As a result, the conversion rate of the polythiophene emulsion was 99%, and as shown in FIG. 2, the size of the prepared polythiophene particles (b) was about 49 nm as confirmed by scanning electron microscopy.

<Example 3>

In the same manner as in Example 1, but the amount of the polystyrene sulfonate [Sigma-Aldrich, USA] of the emulsifier of Example 1 was used in 3.5g.

As a result, the conversion rate of the polythiophene emulsion was 99%, and as shown in FIG. 2, the size of the prepared polythiophene particles (c) was about 40 nm as confirmed by scanning electron microscopy.

<Example 4>

The same procedure as in Example 1 was conducted, except that 5.2 g of the polystyrene sulfonate [Sigma-Aldrich, USA], which was an emulsifier of Example 1, was used.

As a result, the conversion rate of the polythiophene emulsion was 99%, and as shown in FIG. 2, the size of the prepared polythiophene particle (d) was about 32 nm as confirmed by scanning electron microscopy.

<Example 5>

In the same manner as in Example 1, but the amount of the polystyrene sulfonate [Sigma-Aldrich, USA] which is the emulsifier of Example 1 was used in 7.0g.

As a result, the conversion rate of the polythiophene emulsion was 95%, and as shown in FIG. 2, the size of the polythiophene particles (e) prepared when examined by a scanning electron microscope was about 20 nm.

<Example 6>

As shown in FIG. 2, the polythiophene emulsion surrounded by polystyrene sulfonate, which is an emulsifier and a conductive dopant synthesized by the method of Examples 1 to 5, was heat-treated at a high temperature of 150 ° C. for 10 minutes to contain polythiophene nanoparticles. A polystyrene sulfonate film about 1 μm thick was prepared.

When the film was irradiated with an excitation wavelength of 420 nm, it showed luminescence in the wavelength region of about 580 nm.

1 illustrates a mechanism for forming nanoparticles of polythiophene or polythiophene derivatives using polystyrene sulfonate, an emulsifier and a conductive dopant according to the present invention.

2 is an average size of 52 nm (a), 49 nm (b), and 40 nm of polythiophene nanoparticles oxidatively polymerized using polystyrene sulfonate, an emulsifier and a conductive dopant according to Examples 1 to 5 of the present invention. c) Scanning microscope photographs of 32 nm (d) and 20 nm (e).

3 is a scanning micrograph showing a cross section of a film obtained by heat treatment of a polythiophene emulsion oxidatively polymerized using polystyrene sulfonate as an emulsifier and a conductive dopant according to Example 6 of the present invention.

Claims (19)

A nanoparticle, wherein the polythiophene or polythiophene derivative is surrounded by a polymer conductive emulsifier. The method of claim 1, The nanoparticles have a size of 10 to 1000 nm. The method of claim 1, The polythiophene derivative is a nanoparticle, characterized in that the thiophene repeating unit is substituted with at least one substituent selected from alkyl, alkoxy, carboxyl, sulfone, and alkyleneoxy. The method of claim 1, The polymer conductive emulsifier is polystyrenesulfonate, polypara-toluenesulfonate (poly (p-toluenesulfonate)), polycamphorsulfonate, polydi (2-ethylhexyl) sulfosuccinate (poly (di (2-ethylhexyl) sulfosuccinate) and at least one selected from polydioleylsulfosuccinate. A method for producing a nanoparticle according to claim 1, wherein the thiophene or thiophene derivative is polymerized in a region surrounded by a polymer conductive emulsifier in the presence of an aqueous solvent containing an oxidizing agent. The method of claim 5, wherein the nanoparticle manufacturing method The thiophene or thiophene derivative in an aqueous solvent; The polymer conductive emulsifier; And adding the oxidant to form an emulsion; Adding an initiator to the emulsion to form a seed emulsion; And A method for producing nanoparticles, comprising stirring the seed emulsion to emulsion oxidize the thiophene or thiophene derivative. The method of claim 6, The thiophene derivative is a method for producing nanoparticles, characterized in that the thiophene repeating unit is substituted with at least one substituent selected from alkyl, alkoxy, carboxyl, sulfone and alkyleneoxy. The method of claim 6, The polymer conductive emulsifier is polystyrenesulfonate, polypara-toluenesulfonate (poly (p-toluenesulfonate)), polycamphorsulfonate, polydi (2-ethylhexyl) sulfosuccinate (poly (di (2-ethylhexyl) sulfosuccinate)), and a method for producing nanoparticles, characterized in that at least one selected from polydioleylsulfosuccinate. The method of claim 8, The addition amount of the polymer conductive emulsifier is a method for producing nanoparticles, characterized in that 0.01 to 500 parts by weight based on the weight of the thiophene or thiophene derivative. The method of claim 6, The oxidizing agent is a method for producing nanoparticles, characterized in that peroxides, oxygen acids, halogens or mixtures thereof. The method of claim 10, The amount of the oxidizing agent is 10 to 1000 parts by weight based on the weight of the thiophene or thiophene derivative. The method of claim 6, The aqueous solvent is a method for producing nanoparticles, characterized in that it comprises 500 to 2000 parts by weight based on the weight of the thiophene or thiophene derivative. The method of claim 6, The initiator is a method for producing nanoparticles, characterized in that the metal oxide. The method of claim 13, The amount of the initiator added is 0.1 to 10 parts by weight based on the weight of the thiophene or thiophene derivative. An electronic material comprising the nanoparticles of claim 1. An optical material comprising the nanoparticles of claim 1. Printing material comprising the nanoparticles of claim 1. A film comprising polythiophene in a matrix of a polymer conductive emulsifier. Thiophene or thiophene derivatives in aqueous solvents; Polymer conductive emulsifiers; And adding an oxidant to form an emulsion; Adding an initiator to the emulsion to form a seed emulsion; Stirring the emulsion to emulsion oxidize the thiophene or thiophene derivative to prepare a nanoparticle emulsion in which the polythiophene or polythiophene derivative is surrounded by the polymer conductive emulsifier; And 19. The method of claim 18, further comprising heat treating the nanoparticle emulsion.

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