KR100350189B1 - Inorganic hallow typed micro oxide composition with membrance effect and fabrication method of composite compound using the same - Google Patents

Abstract

The present invention, by designing a hollow body of the inorganic oxide fine particles having a new concept of ultrafiltration (Membrane), by using the ultrafiltration effect, to improve the safety of the material, the handleability and the catalytic functionality by the reaction temperature, The present invention relates to a method for effectively preparing a composite compound (mixture) capable of facilitating its use as a stable functional material and improving the handling safety of pesticides and other harmful chemicals, and its application.

As a means for solving the above-mentioned objects, first, a hollow oxide was conceived, and a hollow particulate support was prepared by adjusting the thickness and pore size of the oxide wall. In the next step, the inorganic oxide fine particle hollow body having the ultrafiltration effect of the new concept and using the ultrafiltration effect, the inorganic fine particle oxide hollow body having an ultrafiltration effect in which a separate functional inorganic oxide is contained therein It was possible to provide a composition and a method for producing a composite compound using the same.

Description

FIELD OF THE INVENTION An inorganic particulate oxide hollow body composition having an ultrafiltration effect and a method for producing a composite compound using the same {INORGANIC HALLOW TYPED MICRO OXIDE COMPOSITION WITH MEMBRANCE EFFECT AND FABRICATION METHOD OF COMPOSITE COMPOUND USING THE SAME}

The present invention relates to a method for producing inorganic oxide fine particles having an ultrafiltration effect, and more particularly, in the manufacture of hollow spherical inorganic oxide fine particles which exhibit an ultrafiltration effect, inexpensive alkali silicate (Alkali) The present invention relates to an inorganic particulate oxide hollow body composition having an ultrafiltration effect using salt as a raw material and freely controlling the entry and exit of an effective substance into a hollow body, and a method for producing a composite compound using the same.

The curing catalyst added to the reactants is usually in particulate form or granule form. The curing catalyst in the form of particulates or granules plays a role of speeding up the reaction time, but it hardens before the end of the work process by curing the reactant itself, such as the heat of reaction is gradually generated by mixing with other reactants, increasing the viscosity. As a result, the entire reactant becomes unusable.

Pesticides are also used in the form of granules rather than particulates, but they are also difficult to handle and even dangerous.

In addition, in the case of cosmetics, ultrafine particles such as zinc oxide and titanium dioxide have been generally used until now to effectively block the wavelength of the ultraviolet ray that adversely affects the human body. However, ultrafine titanium oxide has a large effect of blocking ultraviolet rays, but when blended with a foundation, the finish of makeup becomes blue, resulting in unnaturalness, and ultrafine zinc oxide has high transparency but low UV blocking effect. Although ultrafine cerium oxide (ceria, CeO ₂ ) is being examined, the conventional technique has a strong cohesive force of cerium oxide powder, which makes it impossible to ultrafine and prevents UV blocking effect or has high catalytic activity when formulated in cosmetics. There was a difficulty in using it as a cosmetic material due to a change in scent or discoloration.

Accordingly, one object of the present invention is to provide an inorganic particulate oxide hollow body composition having an ultrafiltration effect capable of controlling the ultrafiltration function and a method of preparing a composite compound using the same.

Another object of the present invention is to provide an inorganic particulate oxide hollow body composition having an ultrafiltration effect to freely control the entry and exit of harmful substances into the hollow body, and a method for preparing a composite compound using the same.

Another object of the present invention is to not only facilitate handling by using a cheap material, but also inorganic fine particle oxide hollow body having an ultrafiltration effect which can realize a continuous reaction of a curing agent or a catalyst which requires a reaction time to be controlled as a whole. It is to provide a composition and a method for producing a composite compound using the same.

1 is a scanning electron microscope (SEM) photograph of an inorganic oxide (SiO ₂ ) microparticle hollow body having an ultrafiltration effect according to an embodiment of the present invention.

In order to achieve the above objects and advantages, according to an aspect of the present invention, the inorganic particulate oxide hollow body composition having an ultrafiltration effect and a method for producing a composite compound using the same, 0.01 to 2.0 mol / Kg of ammonia ion and 0.01 Forming microdroplets from an aqueous solution containing from 2.0 mol / Kg of halogen ions and having a first ion (M ^I ) having a first ionization tendency;

The first element than the ionization tendency lower first element (M ^II) to the chloride with stirring the fine droplet and silica (SiO ₂₎ is combined with the first oxide (M ^II O) of the second element M ^II O · forming a silicate of nSiO ₂ composition;

Melting an oxide (M ^II O) component with the second element from the silicate to form a member structure having pores corresponding to the vacancy corresponding to the oxide (M ^II O) position with the second element; It includes.

In the present invention, first, a spherical fine particle carrier was produced by spheroidizing an oxide in a hollow form and adjusting the wall thickness and pore diameter of the oxide. The reaction used in the present invention can be explained by the tendency to become a cation when the metal is in contact with water or a solution, that is, the standard electrode potential of the metal. For example, M ^I selected from the first group consisting of Li, Na, K, Cs, etc. is a different cationic species, for example M selected from the second group consisting of Ca, Mg, Al, NH _4, etc. ^{When contacted} with the electrolyte solution containing ^II , the ion substitution reaction recorded below is used to proceed to the right as the ionization tendency of M ^I is larger than M ^II .

M ^Ⅰ (undissociated) + M ^Ⅱ (Ion) → M ^Ⅰ (Ion) + M ^Ⅱ (undissociated or evaporated)

On the basis of this ion exchange reaction, a nonpolar and protonic solvent having a dielectric constant (20 ° C.) of 5 or less is used as a dispersion medium, and an aqueous solution containing M ^I is forcibly dispersed in the dispersion medium, thereby providing a stable emulsion. It can manufacture. In this case, an emulsifier may be used to obtain a more stable emulsion.

The emulsion obtained in this way is in a relatively stable state, and as shown in the above reaction scheme, in the next step, hollow microparticles can be prepared by reacting the electrolyte solution containing M ^II with the emulsion obtained in the first step. By adjusting the value of "n" in the general formula of the starting material M ^I ₂ O.nSiO ₂ , it is possible to control the pore water and the specific surface area of the fine particles. (Spherical oxide fine particles having a membrane structure).

Alternatively, it is also possible to use flammable polymers instead of adjusting the "n" value.

The spherical oxide fine particles of the membrane structure prepared in the above process are in equilibrium in the atmosphere, but when a pressure difference occurs between the inside and the outside of the membrane, the surrounding materials move from a high pressure to a low place to equilibrate. Using the principle, an organic precursor such as an oxide precursor solution containing M ^III (Al, Ce, Zr, Ti, Co, Ni, Cr, etc.), or zinc pyrithione, triphenylphosphine (Tri phenyl) When spherical oxide fine particles having a membrane structure are put into a solution of a reactive curing catalyst such as phosphine, a pressure difference is generated, and the precursor solution moves through the membrane wall into the hollow interior. As a mechanism for generating such a pressure difference, it is also possible to use a syringe, a piston, or the like.

Hereinafter, the preparation and application of spherical inorganic oxide fine particles having an ultrafiltration effect according to the present invention and a composite mixture (compound) using the ultrafiltration effect thereof will be described in more detail with reference to Examples.

Example 1

Spherical oxide fine particles having an ultrafiltration effect were prepared by the following formulation.

Li ₂ O · 5.8H ₂ O with respect to the composition of lithium silicate to the total weight of aqueous solution containing 20% by weight was mixed with methanol (Methanol) 3% by weight, 0.1Mol relative to the total weight of the obtained water-methanol mixed solution / Kg of ammonium chloride (NH ₄ Cl) was added as a starting material.

Weigh 300 grams of 1-Hexan with a dielectric constant of 20 ° C., and add 1% by weight of a solvent of Sobitan-mono-Oleite with an HLB value of 3 in advance. Melted. 50 grams of an aqueous starting material solution prepared according to the above-described procedure was added to the mixture, and microscopic droplets were prepared by irradiating an ultrasonic vibrator for about 20 minutes. The ultrasonic vibrator used at this time had a specification of 1.8 KW and 20 kHz. The microdroplets thus produced had a particle diameter of about 2 to 3 mu m.

On the other hand, 1000 g of 3 mol / L calcium chloride (CaCl ₂ ) aqueous solution was used as an electrolyte material having less ionization tendency than lithium silicate having a composition of starting material Li ₂ O · 5.8H ₂ O so that the reaction proceeded to the right side in the reaction scheme mentioned. After preparing and slowly stirring, the emulsion prepared beforehand was gradually added, stirred for about 2 hours, and left standing to obtain CaO.SiO ₂ powder as a reaction product. The powder had an average particle diameter of 2.5 µm, a specific surface area of 250 m 2 / g, an apparent specific gravity of 0.7, excellent flow characteristics, and white spherical oxide fine particles.

Next, the spherical oxide fine particles obtained in this manner were dissolved in a 2N-HCl solution to dissolve the CaO component, thereby obtaining a member structure having pores as many as the CaO vacancies.

In addition, the spherical oxide fine particles having such ultrafiltration effect were placed in a 0.5 Mol / L cerium (III) nitrate solution prepared in advance, and a pressure of 1 kg / cm 2 was applied to the entire system, thereby providing a member of the spherical inorganic oxide fine particles. Cerium (III) Nitrate solution was loaded into the spherical body through the rain wall, and 1Mol / ℓ-NH ₄ OH solution was added dropwise to neutralize it gradually.Then, it was washed again and dried at 105 ℃ for 24 hours and 900 ℃ for 2 hours. Spherical inorganic oxide mixture fine particles containing Cerium (IV) Oxide embedded therein were prepared through a calcination process.

This fine powder not only has excellent flow characteristics, but also has no catalytic activity on the surface of the powder because cerium oxide is not derived from the outside, and thus it is useful for cosmetics. In particular, ultraviolet light in the wavelength range of 300 to 400 nm can be irradiated. In this case, since the internal cerium oxide can express its functionality, it is excellent in its ability as an ultraviolet (UV-A) blocker of general plastic which is easily deteriorated by ultraviolet rays.

Example 2

Spherical inorganic oxide fine particles having an ultrafiltration effect were prepared by the following formulation.

₂ % by weight of methanol was mixed with respect to the total weight of the aqueous solution containing 20% by weight of sodium silicate having a composition of Na ₂ O.3.3H ₂ O, and 0.05 Mol / Kg of the total weight of the water-methanol mixed solution obtained. Ammonia was added to make the starting material.

300 grams of 1-hexane having a dielectric constant (20 ° C.) of 2 was weighed, and 1 wt% of a solvent was dissolved in advance of 1 wt% of a solvent having a HLB value of 3 (Sorbitan-mono-Oleite). 50 grams of an aqueous starting material solution prepared according to the above-described procedure was added to the mixture, and microscopic droplets were prepared by irradiating an ultrasonic vibrator for about 20 minutes. The ultrasonic vibrator used at this time had a specification of 1.8 KW and 20 kHz. The microdroplets thus produced had a particle size of about 4 to 5 mu m.

On the other hand, as mentioned above, in order to proceed to the right side of the reaction scheme, an electrolyte material having less ionization tendency than the starting material Na ₂ O · 3.3H ₂ O composition soda silicate aqueous solution of 3 mol / L magnesium chloride (MgCl ₂ ) 1000 A gram was prepared, and an emulsion prepared in advance was gradually added while stirring, followed by stirring for about 2 hours and allowed to stand, thereby obtaining MgO.SiO ₂ powder as a reaction product. The powder had an average particle diameter of 4.5 µm, a specific surface area of 150 m 2 / g, an apparent specific gravity of 0.9, excellent flow characteristics, and white spherical oxide fine particles.

Next, the spherical oxide fine particles obtained in this way were dissolved in a 2N-HNO ₃ solution to dissolve the MgO component, so that it was possible to have a member structure having pores as many as the MgO vacancies.

In addition, the spherical oxide fine particles having such ultrafiltration effect were put in a 0.5 Mol / L titanium (IV) chloride solution prepared in advance, and a pressure of 1 kg / cm 2 was applied to the whole system to apply a member of the spherical inorganic oxide fine particles. Titanium (IV) chloride solution was loaded into the spherical body through the rain wall, and 5Mol / L-ammonium hydroxide (NH ₄ OH) solution was added dropwise to neutralize gradually, washed again, dried at 105 ° C for 12 hours, Spherical inorganic oxide fine particles containing titanium (IV) oxide (Titanium (IV) Oxide) were prepared through a calcination process at 1000 ° C. for 2 hours.

This fine powder has excellent flow characteristics, and since titanium oxide is not derived from the outside, it also eliminates catalytic activity on the surface of the powder, which makes it useful for cosmetics. In particular, ultraviolet light in the wavelength range of 280 to 350 nm can be irradiated. In this case, since the internal titanium oxide can express its functionality, it is excellent in its ability as an ultraviolet (UV-B) blocker of general plastic which is easily deteriorated by ultraviolet rays.

Alternatively, instead of titanium (IV) oxide, Cerium (III) precursors such as Cerium (III) Chloride, Cerium (III) Nitrate, Cerium (III) Sulfate, etc. are dissolved to have an ultrafiltration effect. After the pores of the inorganic oxide fine particles of the spherical body and the inside are supported by the pressure difference with the solution, they can be encapsulated as Cerium (IV) Oxide by a process of neutralization, drying and calcination under appropriate conditions.

Selectively, Zirconium (IV) Oxide precursors such as Zirconyl (ZrO ^{+ 2} ) Chloride, Zirconyl (ZrO ^{+ 2} ) Sulfate, Zirconyl (ZrO ^{+ 2} ) Nitrate, and Zirconium Tetrachloride Soluble Salts dissolve and have ultrafiltration effect. After the pores of the inorganic oxide fine particles and the inside are supported by a pressure difference with the solution, they may be encapsulated as Zirconium (IV) oxide by a neutralization, drying, and calcining step under appropriate conditions.

Moreover, in order to raise the production efficiency of a clathrate mixture, the organic surfactant of HLB1-6 can also be used.

1 is a scanning electron microscope (SEM) photograph of a hollow body of inorganic oxide (SiO ₂ ) particles having an ultrafiltration effect according to Examples 1 and 2 described above.

Example 3

100 grams of spherical inorganic oxide fine particles having an ultrafiltration effect obtained in Examples 1 and 2 were prepared.

100 g of TPP (Tri Phenyl Phosphine) powder used as an epoxy curing accelerator is placed in 300 g of a 1-hexane solution, and the temperature is raised to 80 ° C. to make a liquid.

While maintaining the temperature of the TPP solution as it is, 100 grams of the particulate inorganic oxide prepared in advance is gradually added while stirring. After holding for about 30 minutes, and rapidly filtered using a temperature-controlled Buffner Funnel, and poured a new 80 ℃ 1-hexane solution two to three times on the filter paper to adhere to the particulate inorganic oxide surface Clean the TPP. When this is cooled to room temperature, up to about 50% of TPP is present inside the hollow body of the particulate inorganic oxide.

When it is used as a curing accelerator for epoxy, the reaction due to heat of mixing does not occur at 83 ° C or lower, which is the melting point of TPP, and melts around 85 ° C as the heat curing reaction proceeds. This becomes high and eventually pushes through the member wall of the hollow body to the surface of the particulate inorganic oxide to serve as a cure accelerator in the system.

As described above, the present invention uses a cheap silicate alkali salt as a raw material in the production of hollow spherical inorganic oxide fine particles exhibiting the ultrafiltration effect, and also the M ₂ O / SiO ₂ Mole ratio in the silicate alkali salt By controlling the reaction time to adjust the wall thickness of the hollow microparticles and thereby the ultrafiltration function can be adjusted, and finally, by using it can freely control the entry and exit of the effective material. Therefore, after preparing the hollow spherical inorganic oxide fine particles, it is not only to facilitate handling, but also to react as a whole by providing a complex mixture (compound) in which an unusable pesticide or hazardous chemicals are generally supported therein. Better effects can be obtained by delaying the catalyst to control the time, or by implementing a continuous reaction of the curing agent.

In addition, in the case of a commonly used hazardous substance and a material having low stability, it is difficult to handle and also has a limitation in handling, but in the case of a composite mixture (compound) using spherical inorganic oxide fine particles having an ultrafiltration effect obtained in the present invention, Ease of handling can be realized, and other catalytically active oxides can maintain the safety of the product, which means that the field of application in the relevant industry is very wide.

Claims (9)

Forming microdroplets from an aqueous solution containing 0.01 to 2.0 mol / Kg of ammonia ions and 0.01 to 2.0 mol / Kg of halogen ions and having a first element (M ^I ) having a first ionization tendency; The first element than the ionization tendency lower first element (M ^II) to the chloride with stirring the fine droplet and silica (SiO ₂₎ is combined with the first oxide (M ^II O) of the second element M ^II O · forming a silicate of nSiO ₂ composition; Melting an oxide (M ^II O) component with the second element from the silicate to form a member structure having pores corresponding to the vacancy corresponding to the oxide (M ^II O) position with the second element; Inorganic particulate oxide hollow composition having an ultrafiltration effect, characterized in that it comprises a and a method for producing a composite compound using the same. The method of claim 1, wherein the forming of the micro droplets, M ^I ₂ O · nH ₂ O of from 10 to silicic acid alkali aqueous solution of 50% by weight containing a silicate alkali in the composition of about 2 to 3% by weight relative to the total weight of the mixture of methanol (Methanol), and the obtained water-methanol mixed solution Providing a starting material to which a predetermined amount of ammonia or ammonia chloride (NH ₄ Cl) is added relative to the total weight of; 300 grams of 1-hexane having a dielectric constant of 20 ° C. was weighed, and 1% by weight of a solvent of Sobitan-mono-Oleite having an HLB value of 3 was dissolved in advance. Adding 50 grams of the starting material aqueous solution and mixing; Irradiating and stirring the ultrasonic vibrator for about 20 minutes, wherein the aqueous alkali silicate solution is an inorganic particulate oxide having an ultrafiltration effect, characterized in that it is produced using a nonpolar solvent having a dielectric constant (20 ° C) of 5 or less. Hollow body composition and method for producing a composite compound using the same. The method according to claim 1 or 2, wherein in the forming of the member structure, the solution used to dissolve the M ^II O component is one selected from the group consisting of 2N-HCl and 2N-HNO ₃ solution. An inorganic particulate oxide hollow body composition having an ultrafiltration effect of a hollow form and a method of preparing a composite compound using the same. The method of claim 1, wherein the first element is one selected from the group consisting of Li, Na, K, Cs, the second element is one selected from the group consisting of Ca, Mg, Al, NH ₄ An inorganic fine particle oxide hollow-body composition having an ultrafiltration effect and a method for producing a composite compound using the same. Forming microdroplets from an aqueous solution containing 0.01 to 2.0 mol / Kg of ammonia ions and 0.01 to 2.0 mol / Kg of halogen ions and having a first element (M ^I ) having a first ionization tendency; The first element than the ionization tendency lower first element (M ^II) to the chloride with stirring the fine droplet and silica (SiO ₂₎ is combined with the first oxide (M ^II O) of the second element M ^II O · forming a silicate of nSiO ₂ composition; Melting an oxide (M ^II O) component with the second element from the silicate to form a member structure having pores corresponding to the vacancy corresponding to the oxide (M ^II O) position with the second element; ; Enveloping a selected oxide into the spherical oxide fine particles; And An inorganic fine particle oxide hollow-body composition having an ultrafiltration effect, and a method for producing a composite compound using the same, comprising the step of containing a tippy inside the oxide fine particles. The method of claim 5, wherein the inclusion of the selected oxide, Cerium (III) precursors such as Cerium (III) Chloride, Cerium (III) Nitrate, Cerium (III) Sulfate, etc. are dissolved, and the pressure difference between the pores of the spherical inorganic oxide fine particles having the ultrafiltration effect and the solution After the supporting process, the inorganic fine particle oxide hollow body composition having an ultrafiltration effect, and a method for producing a composite compound using the same, characterized in that it is included as Cerium (IV) Oxide by a process of neutralization, drying and calcination under appropriate conditions. . The method of claim 5, wherein the inclusion of the selected oxide, Pores of inorganic oxide fine particles of spherical bodies having ultrafiltration effect by dissolving Titanium Oxide precursors such as Titanium-based soluble salts of Titanium (II), Titanium (III) and Titanium (IV) and Titanyl (TiO ^{+ 2} ) -soluble salts And an inorganic fine particle oxide hollow body having an ultrafiltration effect, which is supported by a pressure difference with a solution therein and then embedded in a titanium (IV) oxide by neutralization, drying, and calcining under appropriate conditions. A composition and a method for producing a composite compound using the same. The method of claim 5, wherein the inclusion of the selected oxide, Zirconium (IV) Oxide precursors such as Zirconyl (ZrO ⁺² ) Chloride, Zirconyl (ZrO ⁺² ) Sulfate, Zirconyl (ZrO ⁺² ) Nitrate, and Zirconium Tetrachloride Soluble Salts Inorganic fine particles having an ultrafiltration effect, characterized in that the fine particles are supported by the pressure difference with the solution in the pores and the inside thereof, and then, they are encapsulated as Zirconium (IV) Oxide by a process of neutralization, drying and calcination under appropriate conditions. Oxide hollow body composition and method for producing a composite compound using the same. The method of preparing an inorganic fine particle oxide hollow composition having an ultrafiltration effect and a composite compound using the same according to claim 5, wherein an organic surfactant of HLB1 to 6 is used to increase the production efficiency of the inclusion mixture.