KR102142457B1 - Organic-inorganic hybrid particles and method for manufacturing the same - Google Patents

Abstract

The organic-inorganic hybrid particles of the present invention include a core formed of organic polymer particles; And a shell formed by any one of a transition metal oxide, a post-transition metal oxide, a transition metal oxide composite, and a post-transition metal oxide composite, and covers the surface of the core, and has a density of 1.5 to 3.85 g.cm ³ . Have.

Description

Organic-inorganic hybrid particle and its manufacturing method {ORGANIC-INORGANIC HYBRID PARTICLES AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to an organic-inorganic hybrid particle having dispersion stability and a method of manufacturing the same.

As one of the ways to improve the performance of the device, it may be considered to introduce a coating layer on the surface of the components constituting the device. Since the coating layer provides the surface with properties that the surface of the part does not have, the device additionally has heterogeneous properties due to the coating layer in addition to the properties originally possessed.

The coating layer that further imparts heterogeneous properties to the surface may be formed by applying a coating liquid to the part or immersing the part in the coating liquid. In either case, the coating liquid contains particles that impart heterogeneous properties together with the solvent.

In order to form a uniform coating layer on the surface of the part, the dispersion stability of the particles is important. As a general method for securing dispersion stability of inorganic particles, there is a method of causing steric hindrance between inorganic particles by applying a dispersing agent, and causing inorganic particles to repel each other through this. This method is effective for preparing a dispersion such as a paint containing inorganic particles in a high concentration. However, when preparing a coating solution containing inorganic particles at a low concentration, this method is not suitable due to problems such as precipitation.

For example, Korean Patent Application Publication No. 10-2004-0027995 (2004.04.03.), which is a prior patent document, discloses a polyether diol dispersant that improves the steric hindrance effect. However, the dispersant of the prior patent document is limited to a pigment dispersant containing a high concentration of particles, as can be seen from the name of the invention.

Therefore, unlike paints, in preparing a coating solution containing inorganic particles at a low concentration, a method for securing dispersion stability of particles must be prepared.

An object of the present invention is to propose an organic-inorganic hybrid particle capable of securing dispersion stability in a solvent by maintaining a specific gravity lower than the original specific gravity of the inorganic particle while maintaining the properties of the inorganic particle and a method for producing the same.

The present invention is to provide an organic-inorganic hybrid particle having a configuration capable of stably maintaining an original shape even under external physical impact.

Another object of the present invention is to provide an appropriate size and an appropriate density of the core and the shell included in the organic-inorganic hybrid particles.

Another object of the present invention is to provide a manufacturing method capable of bonding the core and the shell of the organic-inorganic hybrid particles to each other by a physical or chemical method.

In order to achieve such an object of the present invention, the organic-inorganic hybrid particles according to an embodiment of the present invention include a core formed of organic polymer particles; And a shell formed by any one of a transition metal oxide, a post-transition metal oxide, a transition metal oxide composite, and a post-transition metal oxide composite, and covers the surface of the core, and has a density of 1.5 to 3.85 g.cm ³ . Have.

According to an example related to the present invention, the organic polymer particle is an aromatic vinyl-based monomer, an acrylic acid alkyl ester monomer having 1 to 20 carbon atoms, a methacrylic acid alkyl ester monomer having 1 to 20 carbon atoms, and a fluoro acrylic acid having 1 to 20 carbon atoms. It is formed by polymerizing at least one monomer selected from the group consisting of an alkyl ester monomer and a methacrylic acid fluoroalkyl ester monomer having 1 to 20 carbon atoms.

According to another example related to the present invention, the organic polymer particles are methyl methacrylate, styrene, divinyl benzene, butyl methacrylate, trimethylolmethane tetraacrylic. At least one selected from the group consisting of trimethylolmethane tetraacrylate, trimethylolmethane triacrylate, trimethylolbutane triacrylate, and ethylene glycol dimethacrylate.

According to another example related to the present invention, the diameter of the core is 200 nm to 500 nm.

According to another example related to the present invention, the density of the core is 0.8 g.cm ³ to 2.0 g.cm ³ .

According to another example related to the present invention, the density of the core is 0.9 g.cm ³ to 1.1 g.cm ³ .

According to another example related to the present invention, the transition metal oxide or the transition metal of the transition metal oxide composite is scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), Iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), tantalum (Ta) and tungsten (W) Including at least one selected from the group consisting of, the post-transition metal oxide or the post-transition metal of the post-transition metal oxide composite, at least one selected from the group consisting of indium (In), tin (Sn), and germanium (Ge) Includes.

According to another example related to the present invention, the transition metal oxide complex or the post-transition metal oxide complex includes a transition metal oxide and a salt, and the salt is NaNO ₃ , KNO ₃ , Mg(NO ₃ ) ₂ . And at least one selected from the group consisting of Al(NO ₃ ) ₃ .

According to another example related to the present invention, the transition metal oxide composite or the post-transition metal oxide composite is a mixed crystal of two or more transition metal oxides, a mixed crystal of two or more post-transition metal oxides, or a transition metal oxide and a transition metal oxide. It is then formed as a mixed crystal of metal oxide.

According to another example related to the present invention, the thickness of the shell is 30 nm to 100 nm.

According to another example related to the present invention, the organic-inorganic hybrid particles have a density of 1.5 to 2.0 g.cm ³ .

According to another example related to the present invention, the core and the shell are physically coupled to each other by electrostatic attraction due to opposite charges.

According to another example related to the present invention, the core and the shell are chemically bonded to each other by a coupling agent.

According to another example related to the present invention, the transition metal oxide includes molybdenum trioxide (MoO ₃ ), and the molybdenum trioxide has an alpha phase (α-phase).

In addition, in order to realize the above object, the present invention discloses a method of manufacturing organic-inorganic hybrid particles. The manufacturing method includes: (a) forming organic polymer particles by polymerizing an organic monomer to prepare a core having a density of 0.8 to 2.0 g.cm ³ ; (b) forming a transition metal oxide, a post-transition metal oxide, a transition metal oxide composite, or a post-transition metal oxide composite on the surface of the core to produce a shell surrounding the surface of the core; And (c) performing a heat treatment to change the phase of the shell of the particles prepared in step (b) from the first phase to the second phase.

According to an example related to the present invention, in the step (a), an aromatic vinyl-based monomer, an acrylic acid alkyl ester monomer having 1 to 20 carbon atoms, a methacrylic acid alkyl ester monomer having 1 to 20 carbon atoms, and a fluorine acrylic acid having 1 to 20 carbon atoms At least one monomer selected from the group consisting of an alkyl ester monomer and a methacrylic acid fluoroalkyl ester monomer having 1 to 20 carbon atoms is polymerized to form the organic polymer particles.

According to another example related to the present invention, in step (b), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co) , Nickel (Ni), Copper (Cu), Indium (In), Tin (Sn), Germanium (Ge), Yttrium (Y), Zirconium (Zr), Niobium (Nb), Molybdenum (Mo), Tantalum (Ta) And at least one selected from the group consisting of tungsten (W) is used to perform the synthesis.

According to another example related to the present invention, in the step (b), stirring is performed during the reaction process of preparing the shell.

According to another example related to the present invention, step (c) is carried out at a temperature of 400 to 450° C. for 30 minutes or more, and the second phase has a lower dissolution rate to the solvent than the first phase.

According to another example related to the present invention, the first phase corresponds to a hydrate or a metastable phase, and the second phase corresponds to a stable phase.

According to the present invention having the above configuration, an organic polymer forms a core, and a transition metal oxide, etc. is a shell?? Therefore, the specific gravity of the organic-inorganic hybrid particles has a lower specific gravity than that of particles composed of only inorganic substances. Accordingly, dispersion stability of the particles can be ensured.

In addition, according to the present invention, the properties of the surface of the organic-inorganic hybrid particles are imparted by the transition metal oxide forming the shell, and the transition metal oxide or the like imparts antibacterial properties and deodorization properties to the surface of the particles.

In addition, according to the present invention, an appropriate density of the organic-inorganic hybrid particles can be set through an appropriate size and an appropriate density of the core and the shell.

In addition, according to the present invention, since the core acts as a buffer against external impact, the original shape of the organic-inorganic hybrid particles can be maintained in an application field in which the organic-inorganic hybrid particles are used.

1 is a conceptual diagram of an organic-inorganic hybrid particle proposed in the present invention.
2 is a flow chart showing a method of manufacturing an organic-inorganic hybrid particle proposed in the present invention.
3A to 3C are conceptual diagrams for explaining the effect of physical bonding and heat treatment between a core and a shell.

Hereinafter, an organic-inorganic hybrid particle and a method of manufacturing the same according to the present invention will be described in more detail with reference to the drawings.

In the present specification, the same or similar reference numerals are assigned to the same or similar configurations in different embodiments, and the description is replaced with the first description.

When an element is said to be "connected" or "connected" to another component, it is understood that other components may be directly connected to or connected to the other component, but there may be other components in between. It should be. On the other hand, when a component is referred to as being "directly connected" or "directly connected" to another component, it should be understood that there is no other component in the middle.

As used herein, a singular expression includes a plural expression unless the context clearly indicates otherwise.

1. Organic-inorganic hybrid particles

1 is a conceptual diagram of an organic-inorganic hybrid particle 100 proposed in the present invention.

The organic-inorganic hybrid particle 100 includes a core 110 and a shell 120.

The core 110 is disposed at the center of the organic-inorganic hybrid particle 100. The core 110 may have a shape corresponding to a sphere or a sphere.

The core 110 is formed of organic polymer particles having a density smaller than that of the shell 120. The density of the core 110 is 0.8 to 2.0 g.cm ³ , and preferably 0.9 to 1.1 g.cm ³ .

The organic polymer particles include (a) an aromatic vinyl monomer, (b) an acrylic acid alkyl ester monomer having 1 to 20 carbon atoms, (c) a methacrylic acid alkyl ester monomer having 1 to 20 carbon atoms, and (d) an acrylic acid having 1 to 20 carbon atoms. It is formed by polymerizing at least one monomer selected from the group consisting of a fluoroalkyl ester monomer, (e) a methacrylic acid fluoroalkyl ester monomer having 1 to 20 carbon atoms.

Examples of organic polymers formed by polymerizing the monomers include methylmethacrylate, styrene, divinyl benzene, butylmethacrylate, and trimethylolmethane tetraacrylate. , Trimethylolmethane triacrylate, trimethylolbutane triacrylate, and ethylene glycol dimethacrylate. The organic polymer particles may be formed of at least one selected from the group consisting of these.

The organic polymer particles have a density smaller than that of the shell 120. Therefore, on the premise of the same size, the organic-inorganic hybrid particles 100 are relatively lighter than those made of only inorganic substances.

Clusters formed of a plurality of organic polymer particles may constitute the core 110. In this case, the core 110 is formed of a plurality of spheres or a set of organic polymer particles having a shape similar to that of a sphere.

The shell 120 is formed to surround the surface of the core 110. Since the shell 120 is formed in a region other than the region in which the core 110 is to be disposed, the shell 120 has a shape similar to a hollow sphere or a hollow sphere.

The shell 120 is formed of any one of a transition metal oxide, a post-transition metal oxide, a transition metal oxide composite, and a post-transition metal oxide composite, which is heavier than the core 110.

Here, the transition metal oxide complex or the post-transition metal oxide complex refers to a mixture of two or more kinds of crystals, or additionally containing a salt in addition to the transition metal oxide or the post-transition metal oxide.

For example, the transition metal oxide complex or the post-transition metal oxide complex may further include a salt in addition to the transition metal oxide or the post-transition metal oxide described above. Salts are NaNO ₃ , KNO ₃ , Mg(NO ₃ ) ₂ . And at least one selected from the group consisting of Al(NO ₃ ) ₃ . The morphology of the transition metal oxide complex or the post-transition metal oxide complex can be controlled by the salt.

In addition, the transition metal oxide composite or the post-transition metal oxide complex is formed of a mixed crystal of two or more transition metal oxides, a mixed crystal of two or more post-transition metal oxides, or a mixed crystal of a transition metal oxide and a post-transition metal oxide. Can be.

On the other hand, the transition metal of the shell 120 is scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), It contains at least one selected from the group consisting of copper (Cu), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), tantalum (Ta), and tungsten (W).

In addition, the post-transition metal of the shell 120 includes at least one selected from the group consisting of indium (In), tin (Sn), and germanium (Ge).

Since the shell 120 is formed on the surface of the organic-inorganic hybrid particles 100, the surface properties of the organic-inorganic hybrid particles 100 are imparted by the shell 120. When the organic-inorganic hybrid particles 100 are included in the coating layer on the surface of the parts constituting the device, the transition metal oxide, the post-transition metal oxide, the transition metal oxide composite, or the post-transition metal oxide composite is antibacterial and/or deodorizing on the surface. Provides property (odor removal performance).

For example, a transition metal oxide or a post-transition metal oxide reacts with moisture to exhibit acidity. Here, acidity is a concept including weak acidity (pH 5 to 6). The transition metal oxide generates an acidic or weakly acidic metallic acid through a catalytic reaction with moisture, and the acidic or weakly acidic metallic acid imparts antibacterial and deodorant properties to the surface.

Typical transition metals that impart antibacterial and deodorant properties to the surface are tungsten (W), molybdenum (Mo), and zirconium (Zr).

For example, when the transition metal of the transition metal oxide is made of molybdenum, the molybdenum oxide generates hydroxonium ions (H ₃ O ⁺ ) through a catalytic reaction with moisture. Hydrooxonium ions are acidic, so when they come into direct contact with the surface of bacteria, they cause sterilization.

In addition, metallic acids impart deodorization to the surface. For example, amine-based malodorous substances such as trimethylamine {trimethylamine, (CH ₃ ) ₃ N} are compounds with low odor intensity or odorless compounds TMAO{TMA N-oxide, (CH ₃ ) through oxidation reaction with metallic acids. ₃ NO}. As another example, aqueous ammonia (NH ₃ ), which is an odorous substance, may react with hydrogen cations when the acidity increases, and change into a form with low odor intensity (NH ₄ ⁺ ).

On the other hand, some transition metal oxides and post-transition metal oxides act as photocatalysts and impart antibacterial properties and deodorizing properties to neutral or basic surfaces regardless of moisture.

The photocatalyst receives light and acts as a catalyst. When light is irradiated on a photocatalyst, electrons and holes are generated. Electronics superoxide anion can react with oxygen present on the surface of the photocatalyst (O ₂ ^-) and create a hole will produce hydroxyl radicals (hydroxyl radical, OH) by reaction with moisture in the air. Since hydroxyl radicals have an excellent ability to oxidize and decompose organic substances, they decompose bacteria and change them into water and carbon dioxide. For this reason, the photocatalyst provides an antibacterial function.

In addition, bacteria cause odor. If bacteria are decomposed into odorless substances such as water and carbon dioxide, odors caused by bacteria can also be removed.

Representative transition metals that act as photocatalysts are zinc (Zn), titanium (Ti), and copper (copper, Cu). In addition, a typical post-transition metal acting as a photocatalyst is tin (Tin, Sn).

Moisture is required to generate hydroxyl radicals, but moisture in the air is sufficient. The catalytic reaction of the photocatalyst requires light, but not moisture. The light required for the catalytic reaction of the photocatalyst is sufficient only with light that exists in nature.

Meanwhile, the transition metal oxide or the like should have a stable phase on the surface of the organic-inorganic hybrid particles 100. Here, a transition metal oxide or the like means a transition metal oxide, a post-transition metal oxide, a transition metal oxide composite, and a post-transition metal oxide composite. And the stable phase means a phase having a relatively low dissolution degree in a solvent compared to other phases that a transition metal oxide may have.

For example, when the transition metal that will form the shell 120 is molybdenum (Mo), the molybdenum forms molybdic acid (MoO ₃ ·2H ₂ O) in the process of being synthesized as a transition metal oxide, Molybdenumic acid has a hexagonal or beta-phase. After the molybdenum acid is heat-treated, molybdenum trioxide (MoO ₃ ) becomes molybdenum trioxide, and molybdenum trioxide is phase-changed to an alpha phase (α-phase) having a lower dissolution rate than the hexagonal or beta phase.

The density of the transition metal oxide forming the shell 120 is 4 g.cm ³ or more. For example, the density of molybdenum trioxide (MoO ₃ ) is 4.69 g.cm ³ , the density of zinc oxide (ZnO) is 5.61 g.cm ³ , and the density of tungsten oxide (WO) is 7.16 g. cm ³ .

The density of the organic-inorganic hybrid particles 100 including the core 110 formed of organic polymer particles and the shell 120 such as transition metal oxide is 1.5 to 3.8 g.cm ³ . Preferably, the density of the organic-inorganic hybrid particles 100 is 1.5 to 2 g.cm ³ . As the density of the organic-inorganic hybrid particles 100 decreases, the organic-inorganic hybrid particles 100 may have improved dispersion stability in the solvent of the coating solution.

In order for the density of the organic-inorganic hybrid particles 100 to have the above range, the diameter of the core 110 must be in the range of 200 nm to 500 nm, and the thickness of the shell 120 must be in the range of 30 nm to 100 nm.

When several embodiments of the organic-inorganic hybrid particles 100 including a core 110 having a density of 0.9 g.cm ³ to 1.1 g.cm ³ and a shell 120 having a density of 5 are listed as shown in Table 1 , The density of the organic-inorganic hybrid particles 100 are all within the range of 1.5 to 3.85 g.cm ³ .

Example diameter
(nm) volume
(nm ³ ) Volume ratio density
(g/cm ³ ) Full weight
(g) Overall density
(g/cm ³ ) One core 200 4186666.7 0.296296 0.9 0.266667 3.785185 Core+shell 300 9943333.3 0.703704 5 3.518519 2 core 500 6541666.7 0.839619 0.9 0.755657 1.557561 Core+shell 530 12495630 0.160381 5 0.801904 3 core 200 4186666.7 0.296296 1.1 0.325926 3.844444 Core+shell 300 9943333.3 0.703704 5 3.518519 4 core 500 65416666.7 0.839619 1.1 0.923581 1.725485 Core+shell 530 12495630 0.160381 5 0.801904

Meanwhile, the core 110 and the shell 120 of the organic-inorganic hybrid particle 100 may be physically or chemically bonded to each other at the mutual interface.

Physical coupling refers to electrostatic attraction due to opposite charges. For example, if the core 110 is formed of an organic polymer having a positively charged functional group and exhibits a negative charge during the synthesis of the shell 120, the core 110 and the shell 120 are formed by electrostatic attraction due to opposite charges. Can be physically combined.

Chemical bonding refers to bonding by a coupling agent. When a coupling agent is added during the synthesis of the organic-inorganic hybrid particles 100, the core 110 and the shell 120 may be chemically bonded.

When the core 110 is disposed at the center of the organic-inorganic hybrid particle 100, the core 110 acts as a buffer layer against external physical impact. Therefore, when the organic-inorganic hybrid particle 100 is used as an additive for an extruded or extruded product, the organic-inorganic hybrid particle 100 can maintain its original shape even with external physical impact.

2. Manufacturing method of organic-inorganic hybrid particles

Hereinafter, a method of manufacturing the organic-inorganic hybrid particles will be described.

2 is a flow chart showing a method of manufacturing an organic-inorganic hybrid particle proposed in the present invention.

(S100) First, a core of organic polymer particles is prepared by polymerizing an organic monomer. The core is manufactured to have a density of 0.8 to 2.0 g.cm ^{3 and} a size of several hundred nanometers. Organic monomers that can be used in the manufacture of the core were previously described in FIG. 1.

In the polymerization, an emulsion polymerization method may be used, and a dispersant and a crosslinking agent may be added to the solvent as additives for polymerization.

(S200) Next, a shell such as a transition metal oxide is synthesized on a surface of a transition metal oxide or the like on the surface of the core. The transition metal and the post-transition metal that can be used in the manufacture of the shell have been previously described in FIG.

As a method of synthesizing the shell, methods such as acid precipitation, hydrothermal, solvothermal reaction, etc. may be used. The shell is synthesized to surround the surface of the core. Strong agitation can be achieved in this process.

The bonding at the mutual interface between the core and the shell can be made physically or chemically. Physical bonding is by electrostatic attraction, and chemical bonding is by coupling agents.

When the shell is formed around the core, the shell may be in the form of a dihydrate or a metastable phase. Therefore, heat treatment is required to form a solid film on the surface of the particles.

(S300) Finally, heat treatment is performed to change the phase of the shell of the previously prepared particles from the first phase to the second phase. The second phase is a stable phase with a lower degree of dissolution to the solvent than the first phase. The heat treatment may be performed at a temperature of 400 to 450° C. for 30 minutes or more.

3A to 3C are conceptual diagrams for explaining the effect of physical bonding and heat treatment between a core and a shell.

First, referring to FIG. 3A, transition metal oxide particles 120 ′ having a negative charge around the core 110 having a positive charge are synthesized. The transition metal oxide particles 120 ′ to be synthesized may have a dihydrate state or a metastable phase.

In FIG. 3B, strong stirring is performed during the process of synthesizing the transition metal oxide particles 120'. By vigorous stirring, the probability that particles having different charges are mutually adsorbed by electrostatic attraction may increase. Therefore, the synthesized transition metal oxide particles 120 ′ are adsorbed on the surface of the core.

Referring to FIG. 3C, the transition metal oxide is converted into a stable phase around the core through heat treatment to form the shell 120, and the organic-inorganic hybrid particles 100 are manufactured.

The manufacturing method described above has several options, such as a method of synthesizing a shell, a method of combining a core and a shell, and the like. Hereinafter, two of the various options will be described. However, in both embodiments, organic-inorganic hybrid particles comprising polystyrene as a core and molybdenum trioxide (MoO ₃ ) as a shell are prepared.

Water is used as a solvent, CTAB (Cetrimonium bromide, 0.5 wt.% of water) is used as a dispersant, and a polystyrene core is produced through emulsion polymerization. When 1wt.% of DVB (divinylbenzene) is added as a crosslinking agent during emulsion polymerization, the polymerized polystyrene has a crosslinked form. The polystyrene core is a particle having a size of several hundred nanometers, the surface of the polystyrene core has an NH ₂ functional group, and NH ₃ ⁺ forms a positive charge on the surface of the core.

Next, the synthesis of molybdenum trioxide shell uses a hydrothermal method. Ethanol 10mL, 1-octadecene (20mL), oleic acid (oleic acid) 10mL, oleylamine (oleylamine) 1mL is used as a solvent. After mixing 2 g of previously polymerized polystyrene in a solvent, 0.18 g of ammonium heptamolybdate tetrahydrate is dissolved in 4 mL of an acidic aqueous solution having a pH of 3, and then slowly mixed. Ammonium heptamolybdate tetrahydrate corresponds to a precursor that will constitute a molybdenum trioxide shell.

The mixing reaction is performed in an autoclave, and the mixing reaction is performed at 180° C. for 24 hours. Transition metal oxide particles having a size of 5-50 nm are synthesized on the surface of the polymer core by mixing reaction. Transition metal oxide particles formed on the surface of the core have a negative charge. In particular, strong stirring may be performed during the mixing reaction process in order to allow the transition metal oxide particles to be adsorbed on the surface of the core. In particular, it is possible to induce uniform adsorption by controlling the ratio of the core and the shell.

The particles (core + shell) formed by this process were washed three or more times through filtering or centrifugation, and then lyophilized and heat-treated in powder form at 400° C. for 1 hour. The shell particles before heat treatment have a hexagonal or beta phase because they are synthesized from the surface of the core to molybdic acid (MoO ₃ ·2H ₂ O). However, after the heat treatment, the shell particles correspond to a stable phase and have an alpha phase with very low dissolution to water.

Water is used as a solvent and ascorbic acid (0.5 wt.% of water) is used as a dispersant, and a polystyrene core is produced through emulsion polymerization. When 1wt.% of DVB (divinylbenzene) is added as a crosslinking agent during emulsion polymerization, the polymerized polystyrene has a crosslinked form. The polystyrene core is a particle size of several hundred nanometers, and the surface of the polystyrene core has ascorbic acid functionality. The particles of the polystyrene core may be adjusted to a size of 50 nm by adjusting the content of the dispersant as necessary.

Next, the synthesis of molybdenum trioxide shell uses a hydrothermal method. 0.2 g of ammonium heptamolybdate tetrahydrate is mixed with 2 g of polystyrene suspension. Ammonium heptamolybdate tetrahydrate corresponds to a precursor that will constitute a molybdenum trioxide shell.

The mixing reaction is performed in an autoclave, and the mixing reaction is performed at 180° C. for 24 hours. Transition metal oxide particles are synthesized from the surface of the polymer core by a mixing reaction using ascorbic acid as a catalyst.

The particles (core + shell) formed by this process were washed three or more times through filtering or centrifugation, then lyophilized and heat-treated at 400° C. for 1 hour in powder form. The shell particles before heat treatment have a hexagonal or beta phase because they are synthesized from the surface of the core to molybdic acid (MoO ₃ ·2H ₂ O). However, after the heat treatment, the shell particles correspond to a stable phase and have an alpha phase with very low dissolution to water.

If molybdenum trioxide is synthesized by the acid precipitation method, a hexagonal phase having a size of several micrometers in the form of a rod will be synthesized. However, when tungsten oxide (WO ₃ ) is mixed during the preparation of the precursor, the size can be adjusted to tens to hundreds of nanometers. The mixing ratio for mixing tungsten oxide is advantageous from 1:1 to 1:3, but it can be synthesized in various compositions as needed.

The organic-inorganic hybrid particles and their manufacturing method described above are not limited to the configuration and method of the above-described embodiments, and all or part of the embodiments are selectively combined so that various modifications can be made. It can also be configured.

Claims (20)

A core formed of organic polymer particles; And
A transition metal oxide, a post-transition metal oxide, a transition metal oxide composite, and a post-transition metal oxide composite, and includes a shell surrounding the surface of the core,
The core is formed of organic polymer particles having a smaller density than the shell,
Organic-inorganic hybrid particles having a density of 1.5 to 3.85 g.cm ³ . The method of claim 1,
The organic polymer particles include an aromatic vinyl monomer, an acrylic acid alkyl ester monomer having 1 to 20 carbon atoms, a methacrylic acid alkyl ester monomer having 1 to 20 carbon atoms, an acrylic acid fluoroalkyl ester monomer having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Organic-inorganic hybrid particles, characterized in that formed by polymerizing at least one monomer selected from the group consisting of methacrylic acid fluoroalkyl ester monomers. The method of claim 1,
The organic polymer particles are methyl methacrylate, styrene, divinyl benzene, butyl methacrylate, trimethylolmethane tetraacrylate, trimethylolmethane tri Organic-inorganic hybrid particles, characterized in that formed of at least one selected from the group consisting of acrylate (trimethylolmethane triacrylate), trimethylolbutane triacrylate, and ethylene glycol dimethacrylate. The method of claim 1,
Organic-inorganic hybrid particles, characterized in that the diameter of the core is 200 nm to 500 nm. The method of claim 1,
Organic-inorganic hybrid particles, characterized in that the density of the core is 0.8 g.cm ³ to 2.0 g.cm ³ . The method of claim 1,
Organic-inorganic hybrid particles, characterized in that the density of the core is 0.9 g.cm ³ to 1.1 g.cm ³ . The method of claim 1,
The transition metal oxide or the transition metal of the transition metal oxide composite is scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), Including at least one selected from the group consisting of nickel (Ni), copper (Cu), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), tantalum (Ta) and tungsten (W),
The post-transition metal oxide or the post-transition metal of the post-transition metal oxide composite is an organic-inorganic hybrid comprising at least one selected from the group consisting of indium (In), tin (Sn), and germanium (Ge). particle. The method of claim 1,
The transition metal oxide complex or the post-transition metal oxide complex includes a transition metal oxide and a salt,
The salt is NaNO ₃ , KNO ₃ , Mg(NO ₃ ) ₂ . And Al(NO ₃ ) ₃ Organic-inorganic hybrid particles comprising at least one selected from the group consisting of. The method of claim 1,
The transition metal oxide composite or the post-transition metal oxide composite is formed of a mixed crystal of two or more transition metal oxides, a mixed crystal of two or more post-transition metal oxides, or a mixed crystal of a transition metal oxide and a post-transition metal oxide. Organic-inorganic hybrid particles characterized by. The method of claim 1,
Organic-inorganic hybrid particles, characterized in that the thickness of the shell is 30 nm to 100 nm. The method of claim 1,
The organic-inorganic hybrid particles, characterized in that the organic-inorganic hybrid particles have a density of 1.5 to 2.0 g.cm ³ . The method of claim 1,
The organic-inorganic hybrid particles, wherein the core and the shell are physically bonded to each other by electrostatic attraction due to opposite charges. The method of claim 1,
The organic-inorganic hybrid particles, characterized in that the core and the shell are chemically bonded to each other by a coupling agent. The method of claim 1,
The transition metal oxide comprises molybdenum trioxide (MoO ₃ ), and the molybdenum trioxide has an alpha phase (α-phase). (a) polymerizing an organic monomer to form organic polymer particles to prepare a core having a density of 0.8 to 2.0 g.cm ³ ;
(b) forming a transition metal oxide, a post-transition metal oxide, a transition metal oxide composite, or a post-transition metal oxide composite on the surface of the core to prepare a shell surrounding the surface of the core; And
(c) performing a heat treatment to change the phase of the shell of the particles prepared in step (b) from the first phase to the second phase; Including,
The first phase corresponds to a hydrate or a metastable phase, and the second phase corresponds to a stable phase (stable phase). The method of claim 15,
In the step (a), an aromatic vinyl monomer, an acrylic acid alkyl ester monomer having 1 to 20 carbon atoms, a methacrylic acid alkyl ester monomer having 1 to 20 carbon atoms, an acrylic acid fluoroalkyl ester monomer having 1 to 20 carbon atoms, and 1 to 20 carbon atoms A method for producing organic-inorganic hybrid particles, comprising polymerizing at least one monomer selected from the group consisting of four methacrylic acid fluoroalkyl ester monomers to form the organic polymer particles. The method of claim 15,
In step (b), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) , Indium (In), tin (Sn), germanium (Ge), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), tantalum (Ta) and tungsten (W) selected from the group consisting of A method for producing an organic-inorganic hybrid particle, characterized in that the synthesis is performed using at least one. The method of claim 15,
In the step (b), a method for producing organic-inorganic particles, characterized in that stirring is performed during a reaction process for producing a shell. The method of claim 15,
The step (c) is carried out for 30 minutes or more at a temperature of 400 to 450°C,
The second phase is a method for producing an organic-inorganic hybrid particle, characterized in that it has a lower elution degree to the solvent than the first phase. delete

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