KR100684913B1 - Preparation method of polythiophene nanoparticles and derivatives thereof by oxidation polymerization of thiophene emulsion in aqueous phase - Google Patents

Abstract

Provided is a method for preparing polythiophene nanoparticles and derivatives thereof, wherein the polythiophene nanoparticles and derivatives thereof have good processability and exhibit particle luminescence characteristics ranging from blue to red color in an aqueous phase according to a production process. The method for preparing polythiophene nanoparticles and derivatives thereof comprises the steps of: (1) adding thiophene or derivatives thereof, 25-55wt%, based on the weight of the thiophene or derivatives thereof, of an emulsifier, and 50-1000wt%, based on the weight of the thiophene or derivatives thereof, of a first oxidizer to 1000-1300wt%, based on the weight of the thiophene or derivatives thereof, of an acidic solution having a temperature of 20-50‹C and pH of 1-5, and mixing the admixture to prepare emulsion; (2) mixing the prepared emulsion with 0.1-10wt%, based on the weight of the thiophene or derivatives thereof, of a second oxidizer as an initiator, followed by stirring the mixture at 45-55‹C for 10-30 minutes to prepare seed emulsion; and (3) stirring the prepared seed emulsion at 50-55‹C for 6-12 hours to perform emulsion oxidation polymerization.

Description

Preparation Method of Polythiophene Nanoparticles and Derivatives Thereof by Oxidation Polymerization of Thiophene Emulsion in Aqueous Phase

1 is a view showing a mechanism for forming polythiophene nanoparticles or derivatives thereof according to the present invention;

2 is a flow chart showing a method for producing polythiophene nanoparticles or derivatives thereof according to the present invention;

3 is an electron micrograph of the polythiophene nanoparticles according to the present invention,

4 is a fluorescence spectrum of the polythiophene nanoparticles according to the present invention,

5 is a light emission photograph of the polythiophene nanoparticles according to the present invention.

The present invention relates to polythiophene nanoparticles or derivatives thereof and a method for preparing the same, and more particularly, to polythiophene nanoparticles or derivatives thereof prepared by oxidative polymerization of a thiophene emulsion and a method for producing the same.

Polythiophene is not soluble in organic solvents, so it is not easy to process, and the activity of molecules in the polymer backbone is limited, thereby affecting photochemical properties. Very unstable

In order to overcome this problem, it was necessary to develop a new thiophene synthesis process. Unlike the conventional process, the new thiophene synthesis process was performed through chemical synthesis, which is a well-known Kumada coupling, Aryl-aryl coupling reactions by metal catalysts, such as steel coupling and Suzuki coupling, have been commonly used to date.

However, the new synthesis method described above is difficult to commercialize due to various problems in the process, for example, a separate process of removing excess oxidant, and an additional reaction process called doping, which is difficult to commercialize. And problems such as expensive catalysts.

Therefore, by introducing an emulsion process for producing polythiophene, a method of lowering the production cost and simplifying the process to improve the processability and chemical stability of the polythiophene has been proposed.

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 Metals, 407, pp. 41-43 (1991)].

However, in the emulsion process, the continuous medium is a water phase as a prerequisite, the yield in such an aqueous solution continuous phase appears to be significantly low, there is a problem that the conductivity is also impossible to measure.

Recently, in order to overcome the above-mentioned problems, N. Balal and M. Biswas [Polymer International, Vol. 53, pp. 198-203 (2004)] have described suspension polymerization using monomers of N-vinylcarbazole and thiophene. It is disclosed that a copolymer can be prepared from polymerization. Nevertheless, the production of particles in dispersed form in the aqueous phase has a problem in that the thiophene monomer cannot be oxidized alone.

Such an emulsion process not only provides an amphiphilic domain that can oxidize thiophene, but also a nano-reactor that can provide process conditions to minimize the amount of iron salt (FeCl ₃ ). Play a role.

As an example of this technique, Korean Patent Laid-Open Publication No. 2003-0045686 discloses a redispersible or soluble product which can be obtained by freeze drying an aqueous dispersion of a latex comprising a polymer or copolymer of substituted or unsubstituted thiophene and a polyanion. Korean Patent Laid-Open Publication No. 2002-0040586 is prepared in anhydrous solvent or low moisture content solvent and adds a phase transfer catalyst (18-crown-6; increases the solubility of the oxidizer in the solvent) during the reaction to dry solvent or low moisture. A method for producing high quality polythiophenes that can be easily dissolved or dispersed in a content solvent is disclosed.

On the other hand, in the above-described prior art it is described that the solid content (wt%) of the polymer solution by dispersion is low, and can be obtained by freeze-drying to obtain a high concentration of solid content (wt%), but in the dispersion process low solid content ( wt%) has a problem that the granulation efficiency is low.

In addition, there is a method for producing 3,4-ethylenedioxythiophene through the water-insoluble emulsion polymerization as a method for producing a polythiophene, but because of the use of excess iron salt has a problem of chemical resistance, conductive or anti-static coating film, etc. If used as a product may adversely affect the quality of the product, there is a problem such as using an excessive dispersion stabilizer.

In addition, the polythiophene prepared by the prior art has a disadvantage in that it is difficult to process because it does not dissolve in the solvent and does not melt. In order to overcome such disadvantages, a study to improve the processability by introducing various side branches into the polythiophene Has been racing a lot.

As such a method, an aqueous process has been developed in the past, but it was impossible to control morphology in the form of a structure such as nanoparticles, and did not overcome the disadvantage of low processability of polythiophene or a derivative thereof.

Accordingly, the inventors of the present invention are to be differentiated from the process of polymerizing a substituted or unsubstituted thiophene monomer using an excess of iron salt in a conventional water-insoluble continuous phase during the research to overcome the above problems. When preparing a granulated emulsion by polymerizing in an aqueous phase using a very small amount of iron salt as an oxidizing agent and other oxidizing agents and emulsifiers which can be oxidized again when the iron salt is reduced, the processability is excellent and particle emission from blue to red in the aqueous phase is excellent. The present invention has been completed by focusing on the ability to produce polythiophene particles having improved properties.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and provides a nanoparticle of polythiophene nanoparticles or polythiophene derivatives prepared by an oxidative polymerization method using two oxidants having different oxidizing powers. There is.

In addition, the present invention has a technical problem to provide a method for producing polythiophene nanoparticles or polythiophene derivative nanoparticles using an oxidative polymerization method.

In one aspect, the present invention provides polythiophene nanoparticles or derivatives thereof having a size of 10 nm to 1 μm.

In another aspect, the present invention provides electronic materials, optical materials, toners and / or inks comprising polythiophene nanoparticles or derivatives thereof.

In another aspect, the present invention provides a method for preparing an thiophene or derivative thereof, i) 25 to 55% by weight of an emulsifier and 50 to 1000% by weight of a first oxidant, based on the weight of the thiophene or derivative thereof. Emulsion preparation step of mixing in an acid solution of pH 1 to 5 having a temperature range of 20 to 50 ℃ of 1000 to 1300% by weight of the thiophene or derivatives thereof, ii) a second as an initiator in the emulsion of step i) A seed emulsion preparation step of mixing an oxidizing agent in an amount of 0.1 to 10% by weight based on the weight of thiophene or a derivative thereof, followed by stirring at 45 to 55 ° C. for 10 to 30 minutes, i) a seed emulsion of step ii) of 50 to 55 ° C. It is stirred for 6 to 12 hours at a temperature to provide a method for producing a polythiophene or derivative particles thereof comprising an emulsion oxidation polymerization step.

The polythiophene nanoparticles or derivatives thereof according to the present invention have a size of 10 nm to 1 μm, and have good processability, and have particle emission characteristics from blue to red depending on the manufacturing process.

Meanwhile, the electronic material, optical material, toner and / or ink according to the present invention means an electronic material, an optical material, a toner and / or an ink including polythiophene or a derivative thereof, and a sugar containing such a structure. Any product in the industry would correspond to the electronic materials, optical materials, toners and / or inks according to the present invention, and preferred electronic materials include photovoltaic cells, capacitors (used as electrolytes) and printed circuits (PCBs). board coatings (previous metal plating can minimize environmental pollution) and / or antistatic agents (preventing static electricity generated on the surface of plastics, polymers, etc. through coating, etc.), and as a preferred optical material Are electroluminescent devices, for example organic light emitting diodes and displays, and particularly preferred optical materials include flat panel displays such as LCDs and the like. There is an organic electroluminescence (EL) device, a hole injecting layer or an emitting layer of an indium tin oxide (ITO) substrate.

The thiophene according to the present invention is a starting material prepared from polythiophene through a polymerization reaction, and any thiophene may be used as long as it is commonly used in the art.

The thiophene derivative according to the present invention may be a thiophene derivative as long as it is a substance derived from the thiophene, but is preferably substituted with an alkyl group, an ethoxy group, a carboxyl group, a sulfone group or at least one substituent selected therefrom. Thiophene is good.

The emulsifier according to the present invention is mixed with the thiophene or thiophene derivative to impart stability of the particles, and any emulsifier commonly used in the art may be used to achieve this purpose. Anionic linear alkylbenzene sulfonates (LAS), alpha-olefin sulfonates (AOS), alkylsulfates (AS), alkyl ether sulfates (AES), secondary alkenes sulfonates (SAS), soaps, methyl It is preferable to use ether sulfonate (MES), phosphate or at least one substance selected from them, preferably alkylsulfate, and the amount thereof is preferably 25 to 55% by weight based on the total weight of thiophene or derivatives thereof.

The second oxidizing agent according to the present invention is for oxidizing the thiophene or thiophene derivative, and any oxidizing agent capable of achieving this object may be used, but preferably a metal oxide such as FeCl ₃ / H ₂ O ₂ , FeCl ₃ / O ₂ , FeCl ₃ / HMnO ₄ And iron complexes such as FeCl ₃ / F ₂ , CuCl ₂ / H ₂ O ₂ , CuCl ₂ / HMnO ₄ , iron salts, or copper (II) chlorides, or mixtures thereof, and the like may be used for the thiophene or derivatives thereof. It is preferable to use 0.1 to 10% by weight relative to the weight.

Here, if the amount of the second oxidant is less than 0.1% by weight based on the weight of the thiophene or derivatives thereof, the rate of polymerization is very slow. If the amount of the amount of the second oxidant is more than 10% by weight, the rate of polymerization and electrical conductivity are increased, but the polythiophene is produced. Or derivative properties thereof, for example, light intensity and electroluminescent intensity are reduced.

The second oxidant according to the invention can also be incorporated directly as an initiator into a mixture of starting materials for the polymerization, for example thiophene or a derivative thereof, an emulsifier, a first oxidant and an acid solution mixture of pH 1-5. In particular, it may be mixed in a mixture of the starting materials in a state dissolved in an acidic solution of pH 1 to 5, preferably deionized water (ID Water) and / or an organic solvent.

At this time, the acid solution and / or organic solvent of the pH 1 to 5 is preferably used 5 to 100% by weight based on the total weight of the acid solution of pH 1 to 5.

On the other hand, the first oxidizing agent according to the present invention is to oxidize the reduced second oxidant when the second oxidant is reduced by oxidizing the thiophene or thiophene derivative, so that the second oxidant has an oxidizing power, for this purpose Although any may be used as long as it can achieve, preferably an oxidizing agent having a relatively higher oxidizing power than the second oxidizing agent is preferable. Therefore, the peroxides are recommended [H ₂ O ₂ , (NH ₄ ) ₂ S ₂ O ₈ , O ₂ ] or oxygen acids [HMnO ₄ , HNO ₃ , HClO ₄ ], halogens [F ₂ , Cl ₂ , Br ₂ ] or mixtures thereof are preferred, the amount of thiophene or thi 50 to 1000% by weight based on the weight of the opene derivative is good.

On the other hand, it will be described the manufacturing method of the polythiophene nanoparticles or derivatives thereof according to the present invention having the above-described configuration.

First, in a macroscopic view, the polythiophene emulsion according to the present invention is present in the form of particles, and the particles, preferably nanoparticles, are polymerized through an oxidation method to form polythiophene or derivative particles thereof, preferably polythiophene. Prepared from nanoparticles or derivatives thereof.

In this case, the particles, preferably nanoparticles are configured to oxidize thiophene or derivatives thereof at the interface, so that the particles are preferably referred to as an oxidative polymerization emulsion process collectively in the method for producing the particles, preferably nanoparticles. can do.

In addition, the method for producing a polythiophene or a derivative thereof according to the present invention is an emulsification process including a general emulsion polymerization method, for example, radicals using a persulfide system and an azobis system according to a method for initiating monomers. Initiation method, oxidation initiation method using metal-based oxidizing agents such as Cu (II), Fe (III) and Cerium (IV), bissellate / Fe (III), bisselate / Ag (I) and Cu (II) / Although the oxidation initiation method such as thiocellate may be used, the thiophene used as a starting material, or a derivative thereof, requires a high oxidizing power and is specifically designed to minimize the effect of dislocation metals on the physical properties of the polymer produced after polymerization. The emulsion oxidation polymerization method using a second oxidizing agent, preferably a metal oxidizing agent, or the like according to the present invention as an oxidation initiator will be described.

Thus, the method for producing a polythiophene nanoparticles or derivatives thereof according to the present invention in detail,

I) a thiophene or derivative thereof, 25 to 55% by weight of the emulsifier and 50 to 1000% by weight of the first oxidant relative to the weight of the thiophene or derivative thereof, the weight of the thiophene or derivative thereof Emulsion preparation step of mixing in the acid solution of pH 1 to 5 having a temperature range of 20 to 50 ℃ of 1000 to 1300% by weight,

Ii) preparing a seed emulsion, in which the second oxidizing agent is mixed with 0.1 to 10% by weight based on the weight of thiophene or derivative thereof as an initiator in the emulsion of step i) and stirred at 45 to 55 ° C. for 10 to 30 minutes,

Iii) stirring the seed emulsion of step ii) at a temperature of 50-55 ° C. for 6-12 hours to include an emulsion oxidation polymerization step.

If necessary, the emulsion particles, preferably the emulsion nanoparticles prepared through step iii) are dried to produce polythiophene nanoparticles or derivatives thereof.

Here, the second oxidant of step ii) 5 to 100% by weight of the acidic solution of pH 1 to 5, preferably deionized water or the pH 1 to 5 of the total weight of the acidic solution of pH 1 to 5, if necessary 5 to 100% by weight of an organic solvent, preferably chloroform, ethyl acetate, hexane, cyclohexane, petroleum ether, and methylene chloride, in an organic solvent, relative to the total weight of the acidic solution, and specifically organic In the case of a solvent, it can be mixed into the emulsion in a supersaturated form and then stirred to prepare a seed emulsion.

In this case, when the second oxidant is supersaturated in the organic solvent, it is preferable to dissolve the second oxidant in the organic solvent in an ultrasonic bath for 10 to 20 minutes in order to increase the dissolving power.

If necessary, when the second oxidant of step ii) is dissolved in the organic solvent and mixed into the emulsion, the seed emulsion is separately stirred between 45 ° C. and 50 ° C. for 10-30 minutes or 10 minutes between step ii) and step iii). ^{The method} may further include removing the organic solvent by reducing the pressure to ^-2 to 100 Torr.

Meanwhile, an acidic solution having a pH of 1 to 5 in which thiophene or a derivative thereof, an emulsifier, and a first oxidant are mixed according to the present invention may be deionized water (ID water) or pH by adding acid to water. It can be used a solution prepared from to 5, the deionized water is prepared by sequentially passing through the cation and anion exchange resin has an acidity of pH 1 to 5.

Herein, an acid for preparing an acidic solution having a pH of 1 to 5 by adding to water may be any acid that is commonly used in the art, but preferably at least one or more substances selected from sulfuric acid, nitric acid or hydrochloric acid. Is recommended, sulfuric acid is recommended.

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

The thiophene according to the present invention is a starting material for producing polythiophene through a polymerization reaction, and any thiophene may be used as long as it is commonly used in the art.

The thiophene derivative according to the present invention may be a thiophene derivative as long as it is a substance derived from thiophene, but is preferably substituted with an alkyl group, an ethoxy group, a carboxyl group, a sulfone group or at least one substituent selected therefrom. Thiophene is good.

The emulsifier according to the present invention is mixed with the thiophene or thiophene derivative to impart stability of the particles, and any emulsifier commonly used in the art may be used to achieve this purpose. It is preferable to use at least one substance selected from linear alkylbenzene sulfonates, alpha-olefin sulfonates, alkyl sulfates, alkyl ether sulfates, secondary alkenes sulfonates, soaps, methyl ether sulfonates, phosphates or the like which are anionic It is preferable to use alkyl sulfate, and the amount thereof is preferably 25 to 55% by weight based on the total weight of thiophene or derivatives thereof.

The second oxidizing agent according to the present invention is for oxidizing the thiophene or thiophene derivative, and any oxidizing agent capable of achieving this object may be used, but preferably a metal oxide such as FeCl ₃ / H ₂ O ₂ , FeCl ₃ / O ₂ , FeCl ₃ / HMnO ₄ And iron complexes such as FeCl ₃ / F ₂ , CuCl ₂ / H ₂ O ₂ , CuCl ₂ / HMnO ₄ , iron salts, or copper (II) chlorides, or mixtures thereof, and the like may be used for the thiophene or derivatives thereof. It is preferable to use 0.1 to 10% by weight relative to the weight (see Fig. 1).

In particular, the second oxidant according to the invention can be incorporated directly as an initiator into a mixture of starting materials for the polymerization, for example thiophene or derivatives thereof, emulsifiers, first oxidants and acidic solution mixtures of pH 1-5. However, it may be mixed in a mixture of the starting materials, in particular dissolved in an aqueous solution, preferably an acidic solution of pH 1 to 5 and / or an organic solvent. At this time, the aqueous solution and / or the organic solvent is preferably used 5 to 100% by weight based on the total weight of the acid solution of the pH 1 to 5.

The first oxidizing agent according to the present invention is to oxidize the reduced second oxidant again when the second oxidant is reduced by oxidizing a thiophene or thiophene derivative so that the second oxidant has an oxidizing power. Any one can be used as long as it can be achieved. Preferably, an oxidant having a relatively higher oxidizing power than the second oxidant is preferable. H ₂ O ₂ , (NH ₄ ) ₂ S ₂ O ₈ and Peroxides such as O ₂ or oxygen acids such as HMnO ₄ , HNO ₃ and HClO ₄ or halogens such as F ₂ , Cl ₂ and Br ₂ may be used, and the amount thereof is 50 to the weight of the thiophene or thiophene derivative. To 1000% by weight is preferred (see Figure 1).

On the other hand, the polythiophene or polythiophene derivative nanoparticles according to the present invention prepared by the above-described method has good processability, and exhibits the light emission characteristics of particles from blue to red in the water phase according to the manufacturing process, the electronic materials, optical materials, It may be used in toners and / or inks, and further, may be applied to organic light emitting materials, energy conversion and energy storage materials, antistatic materials, charge control materials, electroconductive layer materials, pattern manufacturing materials, printing ink materials, and the like.

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 are not intended to limit the scope of the present invention by these examples.

<Example 1>

6 g of SLS [Duksan Co., Ltd.], an emulsifier, was mixed with 135 g of deionized water prepared by sequentially passing distilled water through a cation and an anion exchange resin, followed by stirring to completely dissolve the emulsifier.

Then, an emulsion was prepared by mixing 27 g of 50% hydrogen peroxide [Dongyang Steel Chemical, South Korea] and 12 g of thiophene [Sigma-Aldrich, USA] as a first oxidant.

Then, 18 mg of iron salt (FeCl ₃ ) [Kanto, Japan], which is a second oxidant, was mixed with 15 g of deionized water to prepare a mixed solution containing a second oxidant, and then mixed with the emulsion. The seed emulsion was prepared by reacting at a temperature of about 20 minutes.

The seed emulsion mixture was then stirred for 12 hours at a temperature of 50 ° C. in a closed reactor to prepare polythiophene particles in emulsion state.

Then, the polythiophene particles in the emulsion state prepared above were dried in a range of room temperature to 70 ° C to prepare polythiophene particles.

As a result, the conversion rate of the polythiophene emulsion was 99%, and the prepared polythiophene particle size was 90 nm to 350 nm.

Here, the prepared polythiophene particle size showed a difference according to the drying method, which is shown in FIG. 3. At this time, the particle size was measured by an electron microscope [JSM-6500F, Jeol, Japan].

As shown in FIG. 3, (a) represents polythiophene particles dried at 70 ° C., (b) represents polythiophene particles dried at room temperature, and the difference in particle size described above is due to general internal molecular interaction ( intermolecule interaction).

<Example 2>

48g of 50% hydrogen peroxide [Dongyang Steel Chemical, South Korea] instead of 27g of 50% hydrogen peroxide [Dongyang Steel Chemical, Korea] of Example 1 was used as the initiator. 18 mg of iron salt (FeCl ₃ ) [Kanto, Japan] as an oxidizing agent was mixed with 15 g of deionized water to prepare a mixed solution containing a second oxidizing agent, which was mixed with the emulsion and then heated to about 20 at a temperature of 50 ° C. The reaction was carried out for minutes to prepare a seed emulsion.

The seed emulsion mixture was then stirred for 12 hours at a temperature of 50 ° C. in a closed reactor to prepare polythiophene particles in emulsion state.

As a result, the conversion rate of the polythiophene emulsion was 96%, and the prepared polythiophene particle size was 10 to 50 nm.

<Example 3>

A mixed solution containing the second oxidant was prepared by mixing 18 mg of iron salt (FeCl ₃ ) [Kanto, Japan], which is the second oxidant of Example 1, in 15 g of deionized water. Instead, 18 mg of iron salt (FeCl ₃ ) [Kanto, Japan] was saturated in 20 g of methylene chloride to prepare a mixed solution containing a second oxidant.

Here, in the preparation of the mixed solution containing the second oxidant, iron salt in methylene chloride for 10 minutes using an ultrasonic bath (SH-1025, Saehan Ultrasonic Industries, Korea) to increase the physical dissolving power of iron salt Dissolve for 20 minutes.

Then, the seed emulsion was stirred at about 48 ° C. for 30 minutes to remove the organic solvent that saturated the iron salt contained in the prepared seed emulsion.

As a result, the conversion rate of the polythiophene emulsion was 98%, and the produced polythiophene particle size was 90 to 350 nm.

<Example 4>

In the same manner as in Example 1, 135g of acidic solution of pH 1.8 to 2.2 was used instead of 135g of deionized water of Example 1.

In this case, the acid solution was prepared by installing a pH meter [420A, Orion, USA] in an aqueous solution, and dropping a small amount of sulfuric acid [Samjeon, Korea] and acidifying the pH of the aqueous solution to 1.8 to 2.2.

Then, 18 mg of iron salt (FeCl ₃ ) [Kanto, Japan], which is the second oxidant of Example 1, was mixed with 15 g of deionized water to prepare a mixed solution containing the second oxidant, instead of iron salt (FeCl ₃ ) [ Kanto, Japan] A mixed solution containing a second oxidant was prepared by mixing 18 mg of 15 mg of an acidic solution having a pH of 1.8 to 2.2.

As a result, the conversion rate of the polythiophene emulsion was 98%, and the produced polythiophene particle size was 90 to 350 nm.

<Example 5>

After installing a pH meter [420A, Orion, USA] in an aqueous solution, a small amount of sulfuric acid [Samjeon, South Korea] was added dropwise and acidified to pH 1.8-2.2 of the aqueous solution to prepare an acidic solution.

Then, 6 g of SLS [Duksan Co., Ltd.], which is an emulsifier, was mixed with 135 g of the acidic solution maintained at 25 ° C., followed by stirring to completely dissolve the emulsifier.

Then, an emulsion was prepared by mixing 27 g of 50% hydrogen peroxide [Dongyang Steel Chemical, South Korea] and 12 g of thiophene [Sigma-Aldrich, USA] as a first oxidant.

Then, 18 mg of iron salt (FeCl ₃ ) [Kanto, Japan], a second oxidizing agent, was saturated in 20 g of methylene chloride to prepare a mixed solution containing a second oxidizing agent, which was then mixed in the emulsion. The seed emulsion was prepared by reacting at a temperature of about 20 minutes.

Here, in the preparation of the mixed solution containing the second oxidant, 10 minutes of iron salts in methylene chloride using an ultrasonic bath (SH-1025, Saehan Ultrasonic Industries, Korea) to increase the physical dissolving power of iron salts. Dissolve for 20 minutes.

Then, the seed emulsion was stirred at about 48 ° C. for 30 minutes to remove the organic solvent that saturated the iron salt contained in the prepared seed emulsion.

The seed emulsion mixture was then stirred for 12 hours at a temperature of 50 ° C. in a closed reactor to prepare polythiophene particles in emulsion state.

As a result, the conversion rate of the polythiophene emulsion was 96%, and the produced polythiophene particle size was 90 to 350 nm.

<Example 6>

In the same manner as in Example 5, in order to remove the organic solvent saturating the iron salt contained in the seed emulsion of Example 5, instead of stirring the seed emulsion at about 48 ℃ for 30 minutes at a pressure of about 100 Torr pressure to reduce the organic solvent Removed.

As a result, the conversion rate of the polythiophene emulsion was 96%, and the produced polythiophene particle size was 90 to 350 nm.

<Example 7>

The same method as in Example 6 was carried out, but nitrogen (N ₂ ) gas was continuously purged in the reactor during the depressurization process of Example 6.

As a result, the conversion rate of the polythiophene emulsion was 50%, and the prepared polythiophene particle size was 10 to 100 nm.

<Example 8>

The polythiophene nanoparticle emulsion prepared according to Example 1 was mixed with deionized water at a ratio of 1: 3000 and then measured by a photoluminescence photometer [RF-5301PC, Shimadzu, Japan].

The result is shown in FIG.

Example 9

The polythiophene nanoparticle emulsion prepared according to Example 2 was used instead of the polythiophene nanoparticle emulsion prepared according to Example 1 in the same manner as in Example 8.

The result is shown in FIG.

As shown in FIG. 4, the maximum light emission wavelength of Example 8 was red light emission at 477 nm, and the maximum light emission wavelength of Example 9 was blue light emission at 449 nm under an excitation wavelength of 365 nm.

As shown in Fig. 5, Example 8 showed red particle emission and Example 9 showed blue particle emission under excitation wavelength conditions of 365 nm.

As described above, those skilled in the art will understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features. Therefore, the embodiments described above are to be understood as illustrative and not restrictive in all aspects. The scope of the present invention should be construed that all changes or modifications derived from the meaning and scope of the following claims and equivalent concepts rather than the detailed description are included in the scope of the present invention.

Polythiophene or derivatives thereof prepared according to the present invention are nano-sized particles, and generally have good processability unlike unsubstituted polythiophene, and exhibit particle emission characteristics ranging from blue to red depending on the manufacturing process. It is possible to adjust the light emission color according to the manufacturing conditions.

Claims (16)

delete delete delete delete delete delete delete delete i) 25 to 55% by weight of the thiophene or derivative thereof, 25 to 55% by weight of the emulsifier and 50 to 1000% by weight of the first oxidant relative to the weight of the thiophene or derivative thereof Emulsion preparation step of mixing in an acid solution of pH 1 to 5 having a temperature range of 20 to 50 ℃ of 1000 to 1300% by weight, Ii) preparing a seed emulsion, in which the second oxidizing agent is mixed with 0.1 to 10% by weight based on the weight of thiophene or derivative thereof as an initiator in the emulsion of step i) and stirred at 45 to 55 ° C. for 10 to 30 minutes, V) stirring the seed emulsion of step ii) at a temperature of 50 to 55 ° C. for 6 to 12 hours to produce a polythiophene or derivative particle thereof comprising an emulsion oxidation polymerization step. The method of claim 9, The acid solution of pH 1 to 5 is a method of producing a polythiophene or derivative particles thereof characterized in that the solution is a mixture of deionized water or acid with water. The method of claim 9, Polythiophene or polythiophene derivative, characterized in that the second oxidant of step ii) is dissolved in an aqueous solution or organic solvent of 5 to 100% by weight relative to the total weight of the acidic solution of pH 1 to 5 Method for Producing Particles. The method of claim 11, Between the step ii) and step iii) further comprising the step of removing the organic solvent by stirring the seed emulsion at 45 to 50 ℃ for 10 to 30 minutes or reduced pressure to a pressure of 10 ^-2 to 100 Torr Method for preparing thiophene or derivative particles thereof. The method according to any one of claims 9 to 12, Method for producing a polythiophene or derivative particles thereof, characterized in that the oxidizing power of the first oxidant is higher than the oxidizing power of the second oxidant. The method according to any one of claims 9 to 12, Method for producing a polythiophene or derivative particles thereof, characterized in that the second oxidant is a metal oxidant. The method according to any one of claims 9 to 12, The first oxidizing agent is a method for producing polythiophene or derivative particles thereof, characterized in that peroxides, oxygen acids, halogens or mixtures thereof. The method according to any one of claims 9 to 12, The emulsifier is at least one material selected from linear alkylbenzene sulfonates, alpha-olefin sulfonates, alkyl sulfates, alkyl ether sulfates, secondary alkenes sulfonates, soaps, methyl ether sulfonates, phosphates or Method for producing polythiophene or derivative particles thereof.

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