KR20090106247A - Method for preparing core-shell nanoparticles comprising vinyl or acrylic polymer core and conducting polymer shell - Google Patents

Abstract

PURPOSE: A method for fabricating core-shell nanoparticles comprising vinyl-based or acrylic-based polymer core and conductive polymer shell is provided to exhibit high processability and to control the conductivity according to fabrication conditions. CONSTITUTION: A method for fabricating core-shell nanoparticles comprises the step of polymerizing vinyl-based or acrylic-based monomers, conductive polymers, and their derivative monomers in the presence of a water-soluble solvent containing radical initiator and oxidizer. The vinyl-based or acrylic-based monomers are selected from the group consisting of styrene, ethylene, propene, butadiene, polyvinyl chloride, vinyl acetate, vinyl alcohol, acrylonitrile, (meth)acrylic acid, alkyl(meth)acrylic acid, acrylamide, and their derivatives.

Description

Method for preparing core-shell nanoparticles comprising a vinyl or acrylic polymer core and a conductive polymer cell {Method for preparing core-shell nanoparticles comprising vinyl or acrylic polymer core and conducting polymer shell}

The present invention relates to a method for producing a core-cell structure nanoparticles comprising a vinyl or acrylic polymer core and a conductive polymer cell, and more particularly, a core formed by radical polymerization of a vinyl or acrylic monomer, an outer peripheral surface of the core. In addition to excellent conductivity in the solid state, including a cell containing a conductive polymer or a derivative thereof, which is formed in the outer wall of the core, the core is processed through a single process using a difference in polymerization rate of monomers and an emulsion-free polymerization method. The present invention relates to a method for producing a core-cell structured nanoparticle in which a cell is manufactured.

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 1-100 nanometers in size and exhibit new electronic, magnetic, optical, and electrical properties not found in 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 manufacturing and applying nanostructured materials of organic materials, researches for the production of nanostructured materials of conductive polymers have also been actively conducted. In view of the electrically conductive material, the conductive polymer has a possibility of being used as a substitute for a heavy load, a transparent conductive film, an optical display element, an antistatic material, an electromagnetic shielding material, and the like. 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 polymers, such as polyaniline, polypyrrole, and polythiophene, which are excellent in stability, have been conducted, and are approaching the commercialization stage. In this regard, particles of which vinyl or acrylic general purpose polymers (eg, polystyrene) having good physical properties are used as cores and conductive polymers (eg, polypyrrole) form cells are prepared to secure conductivity of the conductive polymers (eg, polypyrrole) and It also suggested a way to improve.

Such core-as an example for the production of cell nanoparticles Stuart F. Lascelles and Steven P. Armes [Journal of materials chemistry , 7 (8), p1349-1355 (1997)] and Jin-Baek Kim and Sung-Tek Lim [Polymer Bulletin, Vol. 37, p321-328 (1996)].

However, the method for preparing core-cell particles used in the preceding research has a drawback in that it takes a lot of cost and effort into the process as a two-step seed polymerization method in which a core is first prepared and then a cell is coated on the surface of the core.

The present invention is to overcome the above-mentioned problems of the prior art, an object of the present invention is to use the difference in the hydrophilicity of the conductive polymer and the vinyl or acrylic monomer in the droplets dispersed in the water phase core into the outer cell formed It is to provide a one-step core-cell structure nanoparticles and a method for producing the core-cell structure.

In order to achieve the above object, the present invention is a vinyl or acrylic monomer in the presence of an aqueous solvent containing a radical polymerization initiator and an oxidizing agent; And it provides a method for producing a nano-particles of the core-cell structure characterized in that the polymerization of the conductive polymer or a derivative thereof at the same time.

The invention also

A core containing a vinyl or acrylic monomer and an anionic group-containing vinyl or acrylic comonomer; And

It is provided on the outer circumferential surface of the core to provide a core-cell structure of nanoparticles comprising a cell containing a conductive polymer or a derivative thereof to form the outer wall of the core.

Nanoparticles having a structure composed of a core of a vinyl or acrylic polymer prepared according to the present invention and a cell of a conductive polymer generally have good workability unlike an unsubstituted conductive polymer, and are 0.1012 depending on the size of the particles and the amount of doping. It shows a conductivity of S / cm to 10.1709 S / cm, it is possible to adjust the conductivity according to the manufacturing conditions.

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

The present invention provides a vinyl or acrylic monomer in the presence of an aqueous solvent containing a radical polymerization initiator and an oxidizing agent; And it relates to a method for producing a nano-particles of the core-cell structure characterized in that the polymerization of the monomer of the conductive polymer or derivatives thereof.

Nanoparticles having a core of a vinyl or acrylic polymer (eg polystyrene) and a cell of a conductive polymer (eg polypyrrole, polyaniline) according to the present invention are present in the form of latex, and the nanoparticles are prepared by an emulsion-free polymerization method. The core including the vinyl or acrylic polymer is polymerized by the radical polymerization method, and the cell containing the conductive polymer or the derivative thereof is polymerized by the oxidative polymerization method to prepare nanoparticles having a core-cell structure.

In this case, the nanoparticles are a first step of preparing a core having a core-cell structure and a second step of wrapping the core with a material constituting the cell. The cells are first formed and then the cores are filled to reduce the steps of the process for producing the particles, thereby reducing manufacturing costs and time.

The vinyl or acrylic monomer is more hydrophobic than the conductive polymer or derivative thereof dispersed in the aqueous phase, thereby entering the interior of the conductive polymer forming the cell to form a core.

Examples of the vinyl or acrylic monomers include styrene, ethylene, propene, butadiene, vinyl chloride, vinyl acetate, vinyl alcohol, acrylonitrile, (meth) acrylic acid, alkyl (meth) acrylic acid, acrylamide, and derivatives thereof. Two or more kinds can be used.

In addition, the monomer of the conductive polymer or derivative thereof is less hydrophobic than the vinyl or acrylic monomer dispersed in the water phase to form a cell on the outer surface of the core.

The conductive polymer may be acetylene, p-phenylene, thiophene, 3,4-ethylenedioxythiophene, pyrrole, aniline, p-phenylene vinylene, thienylene vinylene, or derivatives thereof as starting materials. Polyacetylene, poly (p-phenylene), polythiophene, poly (3,4-ethylenedioxy thiophene: PEDOT)), polypyrrole, polyaniline, poly (p-phenylene vinylene), poly (Thienylene vinylene) or polymer derivatives thereof.

In addition, the derivative of the conductive polymer that can be used for cell formation is preferably the polymer or the derivative thereof is a conductive polymer in which substituents such as an alkyl group, an alkoxy group, a carboxyl group, or a sulfone group are substituted alone or in two or more kinds.

The conductive polymer or derivative thereof is preferably mixed in an amount of 5 to 200 parts by weight based on 100 parts by weight of the vinyl or acrylic monomer. When the range is less than 5 parts by weight, it is difficult to form a core-cell structure due to insufficient amount to wrap around the core, and when it exceeds 200 parts by weight, an excess of conductive polymer is present to form particles of only conductive polymer. do.

In the method for producing a nano-particle having a core-cell structure according to the present invention, in order to impart the stability of the particles, it is to include an anionic group-containing vinyl or acrylic comonomer as a comonomer to be polymerized together with the vinyl or acrylic monomer. desirable.

The anionic group-containing vinyl-based or acrylic comonomer is preferably used alone or in combination of two or more metal salts of (meth) acrylic acid, styrene sodium sulfonate or metal salts of alkyl (meth) acrylic acid. More preferably, a vinyl or acrylic monomer in which an anion substituent is substituted is preferable.

The comonomer may be included in an amount of 0.01 to 300 parts by weight, more preferably 0.1 to 100 parts by weight, and most preferably 1 to 20 parts by weight, based on 100 parts by weight of the vinyl or acrylic monomer. When the content range is less than 0.01 parts by weight, the content of comonomers that impart stability of the particles may be insufficient, leading to a decrease in storage stability. When the content is more than 300 parts by weight, the comonomers may act as an electrolyte, thereby interfering between particles. Agglomeration can occur.

In addition, the aqueous solvent for dissolving the polymer mixture is not particularly limited, but deionized water is preferably used. More specifically, the aqueous solvent may be used deionized water having a temperature range of 50 to 90 ℃. In addition, the aqueous solvent may be used an acidic solution having a pH of 1 to 5.

The deionized water is preferably included 5 to 15 parts by weight based on 1 part by weight of the polymer mixture. Within the above range, the polymer mixture is sufficiently dissolved.

As a radical polymerization initiator added for radical polymerization of the vinyl or acrylic monomers and comonomers thereof, peroxides such as potassium persulfate and benzoyl peroxide, derivatives of peroxides, aromatic azo compounds of benzene groups or benzene derivatives, or oxidation / reduction An initiator etc. can be used individually or in 2 or more types.

The radical polymerization initiator is preferably added in 0.01 to 1 parts by weight based on 100 parts by weight of vinyl or acrylic. More preferably, it is 0.05-0.5 weight part. If the content is less than 0.01 parts by weight, the initiator may not be sufficient to generate an unreacted styrene monomer. If the content is more than 1 part by weight, low molecular weight polystyrene may be polymerized to deteriorate physical properties.

In addition, an initiator for oxidative polymerization of the conductive polymer or derivative thereof may include a first oxidizing agent of a metal oxide. The first oxidant may be directly incorporated as an initiator or added to the core-cell preparation solution, preferably in a state of being dissolved in deionized water (DI Water) and / or an organic solvent.

Preferably, the first oxidizing agent is 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) chloride, mixtures thereof, and the like, may be used alone or in combination.

The first oxidant is preferably included in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the conductive polymer or its derivative. If the content range is less than 0.05 parts by weight, the polymerization rate may drop. If the content is more than 10 parts by weight, the polymerization rate and the electrical conductivity may increase, but the physical properties of the conductive polymer or derivative thereof may be reduced.

In addition, the first oxidizing agent is preferably added to the emulsion of the first step in a state dissolved in 5 to 100 parts by weight of water or an organic solvent with respect to 100 parts by weight of deionized water. As the organic solvent, chloroform, ethyl acetate, hexane, cyclohexane, petroleum ether, ethylene chloride, or the like may be preferably used.

In addition, in the case where the first oxidant is supersaturated in the organic solvent, it is preferable to dissolve the oxidizer in the organic solvent in an ultrasonic bath for 10 to 20 minutes in order to increase the dissolving power.

In the case of using the organic solvent to dissolve the first oxidizing agent in the polymerization step, the step of removing the organic solvent by stirring the mixed solution for 10 to 30 minutes at 45 to 50 ℃ or reduced pressure to a pressure of 10 ^-2 to 100 Torr It may include.

In addition, when the first oxidant is reduced by oxidizing the conductive polymer or a derivative thereof, the first oxidant may include a second oxidant to oxidize the reduced first oxidant again to have an oxidizing power.

The second oxidant is not particularly limited as long as it can achieve the above object, but preferably an oxidant having a relatively higher oxidizing power than the first oxidant.

The second oxidizing agent is H ₂ O ₂ , (NH ₄ ) ₂ S ₂ O ₈ And O ₂ Peroxides such as HMnO ₄ , HNO ₃ and oxygen acids such as HClO ₄ , or F ₂ , Cl ₂ And halogens such as Br ₂ may be used alone or in combination of two or more thereof.

The second oxidant is preferably included in an amount of 50 to 1000 parts by weight based on 100 parts by weight of the conductive polymer or a derivative thereof. When the range is less than 50 parts by weight, there is a risk that the role of the first oxidant as a catalyst may not be sufficiently performed. When the amount is more than 1000 parts by weight, the first oxidant may be hindered to lower the polymerization rate of the conductive polymer.

In the method for producing a core-cell structured nanoparticles according to the present invention, a vinyl or acrylic monomer; Monomers of conductive polymers or derivatives thereof; Radical polymerization initiators; And the order of mixing or adding the oxidizing agent is not particularly limited, vinyl or acrylic monomers; Optionally anionic group-containing vinyl or acrylic comonomers; And mixing monomers of the conductive polymer or derivatives thereof in deionized water; and

It is preferred to include adding a radical polymerization initiator for producing a core and an oxidizing agent for producing a cell to the mixture.

In addition, the method may further include drying the prepared core-cell structured nanoparticles prepared through the polymerization step at room temperature to 80 ° C.

The invention also

A core containing a vinyl or acrylic polymer and an anion group-containing vinyl or acrylic polymer; And

The present invention relates to a core-cell structured nanoparticle including a cell containing a conductive polymer or a derivative thereof formed on an outer circumferential surface of the core to form an outer wall of the core.

The core-cell nanoparticles of the present invention have a size of 10 nm to 1 μm, have good dispersibility and processability, and have a conductivity of 0.1012 S / cm to 10.1709 S / cm in a solid state depending on the amount of dopant.

The nano-particles of the core-cell structure according to the present invention are electronic materials, optical materials, toners, inks, organic light emitting materials, energy conversion and energy storage materials, antistatic materials, charge control materials, electroconductive layer materials, pattern manufacturing materials or Printing ink material can be used without limitation.

Core particles of the present invention, for example, nanoparticles having a structure composed of a core of polystyrene and a cell of a conductive polymer (eg, polypyrrole) have good processability, and are manufactured from 0.1012 S / cm to 10.1709 depending on the manufacturing process. It has a conductivity of S / cm, so it can be used in electronic materials, optical materials, toners and / or inks, and furthermore, organic light emitting materials, energy conversion and energy storage materials, antistatic materials, charge control materials, electroconductive layer materials, It can be applied to pattern manufacturing materials, printing ink materials and the like.

In the present invention, an electronic material, an optical material, a toner and / or an ink means an electronic material, an optical material, a toner and / or an ink including a conductive polymer (eg, polypyrrole) or a derivative thereof, and includes such a configuration. It is not particularly limited as long as it is a conventional product in the art, and preferably, it is possible to minimize environmental pollution by replacing photovoltaic cells, capacitors (used as electrolytes) and printed circuit board (PCB) substrate coatings (conventional metal plating as an electronic material). And / or antistatic agents (to prevent static electricity generated on surfaces of plastics, polymers, etc. through coatings, etc.), electroluminescent devices such as organic light emitting diodes and displays, Particularly preferred optical materials include hole injection in flat panel displays such as LCDs, organic electroluminescence (EL) devices, and indium tin oxide (ITO) substrates. And the like (hole injecting layer) or a light emitting layer (emitting layer).

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>

0.12 g of a comonomer, NaSS (styrene sodium sulfonate), was added to 190 g of deionized water prepared by sequentially passing distilled water through a cation and an anion exchange resin, and then stirred in a reactor to completely dissolve it.

Next, 6 g of pyrrole (Acros Organics, Belgium) as a first monomer and 12 g of styrene (Junsei Chemical, Japan) as a second monomer were added to the mixture, 50% hydrogen peroxide [Dongyang Co., Ltd.] Cheil Chemical, South Korea] 15g was added and stirred for about 5 minutes until completely mixed.

Next, 0.009 g of iron salt (FeCl ₃ ) [Kanto, Japan] was mixed with 10 g of deionized water as an oxidizing agent for oxidative polymerization of the pyrrole of the mixture being stirred in the reactor, and a styrene mixed solution containing oxidant As a initiator for radical polymerization, 0.012 g of potassium persulfate (KPS), Junsei Chemical, Japan was mixed with 10 g of deionized water to prepare a mixed solution containing a radical initiator, which was then stirred in the reactor. It was injected into the mixture.

The mixture was stirred at a temperature of 80 ° C. for 5 hours in a closed reactor to prepare core-cell nanoparticles, which were dried at 80 ° C. to produce core-cell nanoparticles.

As shown in FIG. 3, the prepared core-cell nanoparticles exhibited a diameter of 200 to 260 nm when confirmed by SEM and TEM, and a conductivity of 0.1120 S / cm when sufficiently doped with hydrochloric acid.

<Example 2>

A core-cell structured nanoparticle was prepared according to the same method as Example 1 except for mixing 0.36 g instead of 0.12 g of NaSS (styrene sodium sulfonate), which is the comonomer of Example 1.

The core-cell structure of the nanoparticles prepared therefrom is shown in FIG. 1 through a transmission electron microscope.

In addition, a scanning electron micrograph of the core-cell structure of the nanoparticle (a) and the conductive polymer (b) obtained by melting the core of the nanoparticle is shown in FIG. 2.

As shown in FIG. 3, the prepared core-cell nanoparticles exhibited a diameter of 150 to 200 nm when confirmed by SEM and TEM, and a conductivity of 1.7467 S / cm when sufficiently doped with hydrochloric acid.

<Example 3>

A core-cell structured nanoparticle was prepared in the same manner as in Example 1 except that 0.6 g of 0.1SS of NaSS (styrene sodium sulfonate), which is the comonomer of Example 1, was incorporated.

As shown in FIG. 3, the prepared core-cell nanoparticles showed 120-150 nm in diameter when confirmed by SEM and TEM, and showed conductivity of 7.5580 S / cm when sufficiently doped with hydrochloric acid.

<Example 4>

A core-cell structured nanoparticle was prepared in the same manner as in Example 1 except that 1.2 g of 0.1SS of NaSS (styrene sodium sulfonate), which is the comonomer of Example 1, was incorporated.

As shown in FIG. 3, the prepared core-cell nanoparticles exhibited a diameter of 100 to 120 nm when confirmed by SEM and TEM, and a conductivity of 8.6737 S / cm when sufficiently doped with hydrochloric acid.

<Example 5>

A core-cell structured nanoparticle was prepared according to the same method as Example 1 except for mixing 2.4 g instead of 0.12 g of NaSS (styrene sodium sulfonate), which is the comonomer of Example 1.

As shown in FIG. 3, the prepared core-cell nanoparticles exhibited a diameter of 70 to 100 nm when confirmed by SEM and TEM, and a conductivity of 10.1709 S / cm when sufficiently doped with hydrochloric acid.

1 is a transmission electron micrograph showing a core-cell structure of a nanoparticle having a structure composed of a cell of a vinyl or acrylic polymer core and a conductive polymer or a derivative thereof according to Example 2 of the present invention.

Figure 2 is a nanoparticle (a) having a structure consisting of a cell of a vinyl or acrylic polymer core and a conductive polymer or a derivative thereof according to the second embodiment of the present invention, and the conductive polymer (b) by melting the core of the nanoparticles Scanning electron micrograph.

Figure 3 is a graph showing the conductivity of the nanoparticles having a structure consisting of a cell of a vinyl or acrylic polymer core and a conductive polymer or a derivative thereof according to an embodiment of the present invention.

Claims (18)

A method for producing a core-cell structured nanoparticle, comprising polymerizing a monomer of a vinyl or acrylic monomer and a conductive polymer or derivative thereof in the presence of an aqueous solvent containing a radical polymerization initiator and an oxidizing agent. The method of claim 1, The vinyl or acrylic monomer is selected from the group consisting of styrene, ethylene, propene, butadiene, vinyl chloride, vinyl acetate, vinyl alcohol, acrylonitrile, (meth) acrylic acid, alkyl (meth) acrylic acid, acrylamide and derivatives thereof. Core-cell structure nanoparticles manufacturing method characterized in that the species or more. The method of claim 1, The monomer of the conductive polymer is at least one member selected from the group consisting of acetylene, p-phenylene, thiophene, 3,4-ethylenedioxythiophene, pyrrole, aniline, p-phenylene vinylene, and thienylene vinylene A method for producing a nanoparticle having a core-cell structure. The method of claim 1, The monomer of the derivative of the conductive polymer is a method of producing a core-cell structure nanoparticles, characterized in that the monomer of the conductive polymer is substituted with one or more substituents selected from the group consisting of alkyl, alkoxy, carboxyl and sulfone groups. The method of claim 1, The conductive polymer or derivative thereof is a core-cell structure nanoparticle manufacturing method characterized in that it comprises 5 to 200 parts by weight based on 100 parts by weight of the vinyl or acrylic monomer. The method of claim 1, A core-cell structure characterized by further polymerizing at least one anionic group-containing vinyl-based or acrylic comonomer selected from the group consisting of metal salts of (meth) acrylic acid, styrene sodium sulfonate and metal salts of alkyl (meth) acrylic acid. Nanoparticles manufacturing method. The method of claim 6, Anion group-containing vinyl-based or acrylic comonomer is a method for producing a core-cell structure nanoparticles, characterized in that it comprises 0.01 to 300 parts by weight based on 100 parts by weight of the vinyl or acrylic monomers. The method of claim 1, Aqueous solvent is 5 to 15 parts by weight based on 1 part by weight of the polymer mixture, characterized in that the core-cell structure manufacturing method of nanoparticles. The method of claim 1, The radical polymerization initiator is at least one selected from the group consisting of peroxide potassium persulfate, benzoyl peroxide, peroxide derivatives, benzene groups or aromatic azo compounds of benzene derivatives and oxidation / reduction initiators. Manufacturing method. The method of claim 1, The radical polymerization initiator is added to 0.01 to 1 part by weight based on 100 parts by weight of the vinyl or acrylic monomers. The method of claim 1, The oxidizing agent is a method for producing a nano-particles of the core-cell structure, characterized in that the metal oxide. The method of claim 1, Oxidizing agent is a core-cell structure nanoparticles manufacturing method characterized in that it comprises 0.05 to 10 parts by weight based on 100 parts by weight of the conductive polymer or derivatives thereof. The method of claim 1, The oxidizing agent is a core-cell structure manufacturing method of nanoparticles, characterized in that mixed with the emulsion in a state dissolved in 5 to 100 parts by weight of water or an organic solvent with respect to 100 parts by weight of deionized water. The method of claim 11, The oxidizing agent further comprises at least one second oxidizing agent selected from the group consisting of peroxides, oxygen acids, halogens or mixtures thereof. The method of claim 14, The second oxidizing agent is a core-cell structure nanoparticles manufacturing method characterized in that it comprises 50 to 1000 parts by weight based on 100 parts by weight of the conductive polymer or derivatives thereof. The method of claim 1, Core-cell nanoparticle manufacturing method further comprises the step of drying the core-cell nanoparticles prepared through the polymerization step at room temperature to 80 ℃. A core containing a copolymer comprising a vinyl or acrylic monomer and an anionic group containing vinyl or acrylic comonomer; And Core particles of the core-cell structure provided on the outer peripheral surface of the core comprising a cell containing a conductive polymer or a derivative thereof to form the outer wall of the core. The method of claim 17, A nano-particle having a size of 10 nm to 1 μm, and having a conductivity of 0.1012 S / cm to 10.1709 S / cm in a solid state.

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