WO2014137134A1

WO2014137134A1 - Method for synthesizing core material used for synthesizing hollow nano-silica material

Info

Publication number: WO2014137134A1
Application number: PCT/KR2014/001765
Authority: WO
Inventors: 배재영; 윤태관; 권재민
Original assignee: 계명대학교 산학협력단
Priority date: 2013-03-05
Filing date: 2014-03-04
Publication date: 2014-09-12

Abstract

The present invention relates to a method for synthesizing core material nanoparticles used for synthesizing hollow nano-silica particles, and the method for synthesizing a nano-core material, comprises the steps of: (a) adding polyvinylpyrrolidone as a stabilizer to a distilled water solvent; (b) adding AIBA(2,2;-azobis dihydrochloride as an initiator; (c) adding styrene as a precursor; and (d) mixing the solution to which the stabilizer, the initiator, and the precursor are added for 24 hours at a temperature between 60 degrees to 80 degrees, wherein the particle size is adjusted by controlling the concentration of at least one of the solvent, the stabilizer, and the initiator. The present invention enables easy synthesis of core material nanoparticles having various sizes by using various synthesis techniques, and provides the method for synthesizing small core material nanoparticles by improving the steps to be simpler and more efficient.

Description

【Specification】

[Name of invention]

Synthesis method of core material used for synthesis of hollow nano silica material

Technical Field

The present invention relates to a method for synthesizing a core material, and more particularly, to a method for synthesizing a core material used for synthesizing a hollow nano silica material through a ratio of an additive material.

[Background]

Core-shell nanoparticles are applicable to various fields such as photonic crystals, catalysts, drug delivery, cosmetics or functional coating materials. Such core-shell nanoparticles generally comprise certain nanoparticles as a core and are prepared by coating the core surface with another material. The physicochemical properties of these core-shell nanoparticles can be controlled by fine-tuning the composition, size or structure of the core or coating layer (ie shell) surrounding the core.

For example, the shell can improve the stability and dispersibility of the core nanoparticles, and can control the surface charge, functionality, or reactivity of the core nanoparticles. In addition, core-shell nanoparticles having magnetic properties, optical properties, or catalytic functions may be manufactured according to the material of the shell.

Prior research papers (Frank Caruso, Advanced materials, 2001, vol 13, No 1.11—22) introduce various types of core-shell nanoparticles, for example a-Fe ₂ 0 ₃ , Ce0 ₂ or Si0 _2. Core-shell nanoparticles coated with polypyrrole on nanoparticles, a-Fe ₂ 0 ₃₎ Core-shell nanoparticles or Si0 ₂ nanoparticles coated with Si0 ₂ on gold (Au) or silver (Au) nanoparticles Core-shell nanoparticles coated with Au are introduced.

On the other hand, as a specific example of the core-shell nanoparticles, there are hollow particles in which all of the core nanoparticles have been removed, or particles having a hollow therein removed by removing a portion of the core nanoparticles. The hollow core-shell nanoparticles are applied to low refractive index materials, thermal insulation materials, or drug delivery capsules that require high porosity. It is possible.

A typical form of such hollow core-shell nanoparticles is a hollow core, which is surrounded by a shell made of a single film, and the hollow core-shell is made of a single film such as silica or magnesium fluoride. Various shell nanoparticles and methods for their preparation have been proposed.

For example, Japanese Unexamined Patent Publication No. JP 2002-160907 discloses hollow silica particles in which a core is hollow and surrounded by a shell of a silica film, and a method of manufacturing the same. In addition, US 2005-0244322A1 discloses hollow silica particles and a method of manufacturing the same, wherein the core is hollow and the shell is made of a porous silica membrane having a plurality of channels surrounding the hollow core. have.

In addition, Korean Patent Publication No. 0628033 discloses a vaporized magnesium fluoride particle and a method for producing the same, in which the core has a hollow shape and the core is surrounded by a shell of a magnesium fluoride film.

As such, the conventional hollow silica particles or the vaporized magnesium fluoride particles are all surrounded by a shell made of a hollow silica core or a magnesium fluoride film, and the single silica film or magnesium fluoride film has a dense structure or (FIG. 1A) The porous structure can be measured (FIG. 1B).

However, hollow silica spheres (HSS), which are widely used in the industry, have different particle sizes depending on the purpose and purpose of use. Since HSS particle size is influenced by the core used for synthesis, there is a need for a method for easily synthesizing HSS particles having various sizes using various synthesis methods.

In addition, HSS used in some industries tends to prefer smaller hollow sizes. PS particles of small size are very difficult and inefficient when using the conventional method.

[Detailed Description of the Invention]

[Technical problem]

The problem of the present invention to solve the above problems is to be utilized in various industries Since the HSS particles have different particle sizes depending on the purpose and use of the HSS particles, it is intended to provide a method for easily synthesizing HSS particles having various sizes using various synthesis methods. That is, to provide a method for synthesizing the core material particles used in the synthesis of HSS particles of various sizes by adjusting the ratio of the additives, and to provide a condition for synthesizing the particles of the same size in different proportions.

In addition, it is intended to provide a method for synthesizing small-size core material nanoparticles by simply and efficiently improving the process by adding a new material.

Technical Solution

A feature of the present invention for solving the above problems is a method for synthesizing a nanocore material, comprising: (a) adding polyvinylpyrrolidone (PVP) as a stabilizer to a distilled water solvent; (b) adding ΑΙΒΑ (2,2'-azobis dihydrochloride) as an initiator; (c) adding styrene as a precursor; (d) stirring the solution to which the stabilizer, the initiator, and the precursor are added at 60 to 80 degrees for 24 hours, wherein the size of the particles is controlled by adjusting the concentration of at least one of the solvent, the stabilizer, and the initiator. It is characterized by.

Here, the core material is preferably polystyrene (PS), and the step (d) may include forming a 10% NaOH solution; It is preferable to include the step of mixing the NaOH solution and the styrene in a 1: 1 ratio to remove the inhibitor in the styrene.

Preferably, the step ( _a ) may include adding the molar ratio of PVP to 0.001 to 0.0030, and the step (b) may add the molar ratio of AIBA to 0.01 to 0.1. Can be.

In addition, it is preferable to adjust the size of the particles by adjusting the concentration of the solvent to 0.1M to 0.4M, and the solvent is preferably a mixed solvent in which distilled water and acetone are mixed at a ratio of 1: 1.

[Favorable effect]

The present invention can be easily synthesized core material nanoparticles of various sizes using a variety of synthetic methods, and simply and efficiently improve the process Provided is a method for synthesizing small-sized core material nanoparticles. [Brief Description of Drawings]

1 is a view showing the structure of a hollow nano silica particles having a conventional core shell structure,

2 is a view showing the flow of the core material synthesis method used in the synthesis of hollow nano silica material according to an embodiment of the present invention,

3 is a TEM photograph showing the size of the PS particles synthesized core material by adjusting the concentration of PVP according to an embodiment of the present invention,

4 is a TEM photograph showing the size of various PS particles synthesized by core material by adjusting the concentration of AIBA according to an embodiment of the present invention,

5 is a TEM photograph showing the size of various PS particles synthesized by core material by adjusting the concentration of a solvent according to an embodiment of the present invention,

6 is a TEM photograph showing the size of various PS particles synthesized with a core material using a mixed solvent according to an embodiment of the present invention.

[Best form for implementation of the invention]

Figure 2 is a view showing the flow of the core material synthesis method used in the synthesis of hollow nano silica material according to an embodiment of the present invention. As shown in Figure 2, the core material synthesis method according to an embodiment of the present invention, (a) adding a polyvinylpyrrolidone (PVP) as a stabilizer to the distilled water solvent (S100); (b) adding ΑΙΒΑ (2,2'- azobis dihydrochloride) as an initiator (S200); (c) adding styrene as a precursor (S300); (d) stirring the solution to which the stabilizer, the initiator, and the precursor are added at 60 to 80 degrees for 24 hours (S400), wherein the concentration of at least one of the solvent, stabilizer, and initiator is adjusted to It is characterized by adjusting the size.

As such, the present invention proposes a method of controlling the size of the core material used for synthesizing the hollow nano-silica material, and by adjusting the concentration of any one of a solvent, a stabilizer, and an initiator. Suggest ways to adjust. [Form for implementation of invention]

Advantages and features of the present invention, and a method for achieving the same will be described with reference to embodiments described below in detail with the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. However, the present embodiments are provided to explain in detail enough to easily implement the technical idea of the present invention to those skilled in the art.

In the drawings, the embodiments of the present invention are not limited to the specific forms shown and are exaggerated for clarity. In addition, parts denoted by the same reference numerals throughout the specification represent the same components.

The expression “and / or” is used herein to mean at least one of the components listed before and after. In addition, singular forms also include the plural unless specifically stated otherwise in the text. Also, as used herein, components, steps, operations, and elements referred to as "comprising" or "comprising" mean the presence or addition of one or more other components, steps, operations, elements, and devices. Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

2 is a view showing the flow of the core material synthesis method used in the synthesis of hollow nano silica material according to an embodiment of the present invention. As shown in Figure 2, the core material synthesis method according to an embodiment of the present invention, (a) adding a polyvinylpyrrolidone (PVP) as a stabilizer to the distilled water solvent (S100); (b) adding ΑΙΒΑ (2,2'- azobis dihydrochloride) as an initiator (S200); (c) adding styrene as a precursor (S300); (d) stirring the solution to which the stabilizer, the initiator and the precursor are added at 60 to 80 degrees for 24 hours (S400), wherein the size of the particles is controlled by adjusting the concentration of at least one of the solvent, the stabilizer and the initiator. It characterized in that to adjust.

As described above, the present invention proposes a method of controlling the size of the core material used for synthesizing the hollow nano silica material, and by adjusting the concentration of any one of a solvent, a stabilizer, and an initiator, How to adjust Suggest.

As described above, hollow silica particles (HSS), which are widely used in the industry, have different particle sizes depending on the purpose and purpose of use, and the HSS particle size is determined by the core material used in the synthesis. Since it is most affected, the method of controlling the size of the core material and synthesizing it is an important issue.

Therefore, in an embodiment of the present invention, in the method of synthesizing nanocore materials in the range of 100 nm to 250 nm, a method of easily synthesizing core material particles having various sizes by controlling the concentration or ratio of additives is proposed. The conditions which synthesize | combine particle | grains in a different ratio are proposed.

In addition, the HSS used in some industries tends to prefer a smaller hollow size. In the method of synthesizing nanocore material having a very small size of 100 nm or less, the embodiment of the present invention is new to the conventional synthesis method. We propose a method for synthesizing nano-core materials by simply and efficiently improving the process by adding materials. Nano core material synthesis process

In the embodiment of the present invention, distilled water is used as the solvent, PVP, AIBA, and styrene are sequentially added to the solvent, followed by stirring at about 70 degrees for a predetermined time to synthesize polystyrene.

Specifically, as shown in Figure 2, (P) (P) polyvinylpyrrolidone (PVP) is added as a stabilizer using a distilled water as a solvent in the step (S100) at a constant molar ratio of the size of the particles.

(b) In step (S200), ΑΙΒΑ (2,2'- azobis dihydrochloride), which is used as an initiator, is added to the PVP-added solution at a molar ratio that corresponds to the particle size.

(c) In step S300, precursor styrene is added to the solution to which PVP and AIBA are added.

(d) In step (S400), the solution in which the additive is added to the solvent is stirred at about 7 CTC for 24 hours to synthesize polystyrene nanocore material particles.

Here, NaOH is used as a precursor to remove the inhibitor inside the styrene. After preparing a 10% NaOH solution, the mixture is mixed with styrene at a ratio of 1: 1, and the inhibitor is separated. In this case, the inhibitor is used for chemical reaction, physiological action, etc. It refers to an interfering substance and, depending on the type of reaction, is called an antioxidant, a corrosion inhibitor, a polymerization inhibitor, a cocatalyst, a catalyst poison, a metabolic antagonist.

Styrene (styrene) used as a precursor in the embodiment of the present invention has an inhibitor therein, it can act to reduce the reaction required for the synthesis, it is preferable to separate the extract agent in advance by mixing the NaOH solution Do. Core material synthesis method used in the synthesis of hollow nano-silica material according to an embodiment of the present invention is to control the size of the core material nanoparticles by controlling the concentration of at least one of a stabilizer, an initiator and a solvent. .

Hereinafter, an embodiment of a method of synthesizing the core material nanoparticles by the size of the additive material by adjusting the type and concentration will be described. Example 1

Polystyrene (PS) of the core material by controlling the molar ratio of polyvinylpyrrolidone (PVP) to 0.0001-0.0030 as a stabilizer in the additive material to synthesize the nanoparticle size of the core material used for the synthesis of the hollow silica material. The particle size can be synthesized from 100nm to 200nm.

Stabilizers are added to prevent or change the state of chemicals or chemicals, and are used in various chemical industries such as gunpowder, synthetic resins, and food.

In an embodiment of the present invention, a polyvinylpyrrolidone (PVP) is used as a stabilizer, in order to induce interaction between the core nanoparticles and the shell particles, a so-called glue or adhesive polymer coating on the surface of the core nanoparticles is performed. In order to easily wrap the surface of the core nanoparticles coated with the polymer material, the shell composed of a plurality of particles.

Figure 3 is a TEM photograph showing the size of the PS particles synthesized core material by adjusting the concentration of PVP according to an embodiment of the present invention. As shown in Figure 3, by adjusting the concentration of the stabilizer PVP according to an embodiment of the present invention it can be clearly seen that the core material nanoparticles having a size of 100nm ~ 200nrrt was synthesized. Example 2

In order to synthesize PS particles as nanoparticles of various sizes of core materials, the embodiment of the present invention controls the size of PS particles to 120 nm to 250 nm by controlling the ratio of ΑΙΒΑ (2,2 '-azobis dihydrochloride) as an initiator to 0.01 to 0.10. It is possible to synthesize by adjusting.

Wherein the initiator is a substance used to initiate a chain reaction. Initiators include substances that easily generate radicals by heat or light (for example, benzoyl peroxide), water, and the like that easily react with ions to generate ions (for example, BF (sub) 3 (/ sub)). In the embodiment of the present invention, it is preferable to use ΑΙΒΑ (2,2'- azobis (2-methylpropionamidine) dihydrochloride) as an initiator.

4 is a TEM photograph showing the size of various PS particles synthesized by core material by adjusting the concentration of AIBA according to an embodiment of the present invention. As shown in Figure 4, by controlling the concentration of the stabilizer PVP according to an embodiment of the present invention it can be clearly seen that the core material nano-indenter having a size of 120nm ~ 250nm was synthesized. Example 3

Synthetic method for controlling the size of the core material nanoparticles by adjusting the concentration of the solvent, when the concentration of the solvent is adjusted to 0.1M to 0.4M, it is possible to control the size of the PS particles of the core material nanoparticles to 100nm to 200nm Do. 5 is a TEM photograph showing the size of various PS particles synthesized by core material by adjusting the concentration of a solvent according to an embodiment of the present invention. As shown in FIG. 5, it can be clearly seen that various core material nanoparticles having a size of 120 nm to 250 nm were synthesized by adjusting the concentration of a solvent according to an embodiment of the present invention. Example 4

In an embodiment of the present invention, a mixed solvent of acetone and water is used to synthesize PS particles, which are core material nanoparticles having a size of 100 nm or less. At this time, the ratio of water and acetone is adjusted to the ratio of 1: 1 to proceed with the synthesis.

6 is a TEM photograph showing the size of various PS particles synthesized with a core material using a mixed solvent according to an embodiment of the present invention. As shown in FIG. 6 In accordance with an embodiment of the present invention, it is apparent that the size of PS particles, which is a core material, is synthesized to 100 nm or less using a mixed solvent in which acetone and water are mixed 1: 1. While the invention has been shown and described in connection with specific embodiments thereof, it is well known in the art that various modifications and changes can be made without departing from the spirit and scope of the invention as indicated by the claims. Anyone who owns it can easily find out.

Industrial Applicability

The present invention relates to a method for synthesizing a core material, and more particularly, to a method for synthesizing a core material used for synthesizing a hollow nano-silica material through a ratio of additives.

Claims

[Patent Claims]

[Claim 1]

In the method of synthesizing nano core materials,

(a) adding polyvinylpyrrolidone (PVP) as a stabilizer to the distilled water solvent;

(b) adding ΑΙΒΑ (2,2'- azobis dihydrochlorkle) as an initiator;

(c) adding styrene as a precursor;

(d) stably stirring the solution to which the initiator and precursor are added at 60 to 80 degrees for 24 hours,

Core material synthesis method used in the synthesis of hollow nano-silica material, characterized in that for controlling the size of the particles by adjusting the concentration of at least one of the solvent, stabilizer and initiator.

[Claim 2]

The method of claim 1,

The core material is a polystyrene (polystyrene: PS) core material synthesis method used in the synthesis of hollow nano-silica material, characterized in that.

[Claim 3]

The method of claim 1,

In step (d),

Forming a 10% NaOH solution;

The NaOH solution and the styrene (styrene) by mixing in a ratio of 1: 1, the core material synthesis method used for synthesizing the hollow nano-silica material, characterized in that it comprises the step of removing the inhibitor in the styrene.

[Claim 4]

The method according to any one of claims 1 to 3,

In step (a),

It is added by setting the molar ratio of the PVP to 0.001 to 0.0030. A method for synthesizing core materials used to synthesize hollow nano silica materials.

[Claim 5]

According to any one of claims U to 13,

Step (b) is

Core material synthesis method used for the synthesis of hollow nano-silica material, characterized in that the addition of the molar ratio of the AIBA to 0.01 to 0.1.

[Claim 6]

The method according to any one of claims 1 to 3,

Core material synthesis method used in the synthesis of hollow nano-silica material, characterized in that the size of the particles by controlling the concentration of the solvent to 0.1M to 0.4M.

[Claim 7]

The method according to any one of claims 1 to 3,

The solvent,

A method for synthesizing a core material used for synthesizing a hollow nano silica material, characterized in that the mixed solvent is a 1: 1 mixture of distilled water and acetone.