KR100958539B1 - Fabrication of inorganic nanoparticle/polymer core-shell nanoparticle using interfacial seeded polymerization - Google Patents

Abstract

The present invention relates to inorganic nanoparticles / polymeric core-cell nanocomposites, wherein inorganic nanoparticles are used as a core component, a certain amount of inorganic nanoparticles are dispersed in an aqueous solution, and then dispersed inorganic nanoparticles. After the surface is modified hydrophobically using a silane coupling agent, an additional monomer and an initiator are introduced to form a polymer using interfacial seeded polymerization, which is limited on the surface of the inorganic nanoparticle at an appropriate temperature and time. It provides a method for producing a core-cell nanocomposite by coating the surface of the inorganic nanoparticles as a shell component.

According to the present invention, the inorganic nanoparticle / polymer core-cell composite can be manufactured in large quantities using a simple and inexpensive process. Moreover, the core-cell nanocomposites that can be produced in the present invention are not only limited to the size and shape of the core component, but can be prepared without limitation on the type and thickness of the polymer cell. In terms of process, the reaction proceeds in a non-volatile aqueous solution using a manufacturing method consisting of a simple process, and has the advantage of easy mass production and recovery of the nanocomposite.

 Interfacial Seed Polymerization, Core-Cell Composites, Polymer Cells, Inorganic Nanoparticles

Description

Fabrication method of inorganic nanoparticle / polymer core-cell nanocomposite using interfacial seed polymerization {Fabrication of inorganic nanoparticle / polymer core-shell nanoparticle using interfacial seeded polymerization}

The present invention, after the surface modification of the inorganic nanoparticles to the inorganic nanoparticles dispersed in an aqueous solution using a silane coupling agent to the surface of the inorganic nanoparticles hydrophobicly, by introducing a monomer and an initiator, the interfacial seeded polymerization occurs only limited to the surface The present invention relates to a method for preparing inorganic nanoparticles / polymer core-cell nanocomposites for coating inorganic nanoparticles using polymerization, wherein the inorganic nanoparticles are introduced by introducing a polymer thin film of about 2-50 nm onto the surface of the inorganic nanoparticles. We present a method for easily preparing a large amount of polymer core-cell nanoparticles.

Nanomaterials are defined as materials that range in size from 1 to 100 nanometers, and because of their large surface area, they exhibit excellent physical properties compared to conventional bulk materials. In particular, the titanium oxide and zinc oxide nanoparticles are applied to applications such as sunscreens and toxic substance removers because the properties of photocatalysts are remarkable in nanoparticles compared to conventional materials. When titanium oxide is introduced into a polymer and used, it is also possible to apply it as an e-paper that can express text when electricity is applied due to its white color and high dielectric constant. In addition, silica nanoparticles have been used in imaging fields such as liquid crystal displays (LCDs) that require a wide angle view for the purpose of widening the wide viewing angle by introducing a filler into a polymer.

However, since the surface of the inorganic nanoparticles is generally composed of hydrophilic groups, when the composite is formed with a hydrophobic polymer material, the inorganic nanoparticles cannot be uniformly dispersed in the polymer matrix due to the large difference in affinity at the interface between the two materials. As the inorganic nanoparticles are formed independently of each other, when the inorganic nanoparticles are applied as a filler to the polymer, the expected properties such as the response speed of the letters expressed during application to the electronic paper or the desired letters are not expressed. Compared to the reduced physical properties will appear. Therefore, as a method for improving this, many methods have been studied for improving the dispersibility and stability when the inorganic nanoparticle surface is coated with a polymer or applied as a filler in the polymer using a dispersant or a surfactant.

In the case of dispersing inorganic nanoparticles in a polymer using a dispersant or a surfactant, dispersants and surfactants exhibit disadvantages of inhibiting the physical properties of the polymer and process disadvantages such as complicated processes and expensive processes.

Coating the surface of the inorganic nanoparticles with a polymer includes a method of introducing a polymer thin film using vapor deposition polymerization, a method of dissolving the polymer in a solvent to coat the polymer on the surface of the nanoparticle, and dispersing the inorganic nanoparticle in a solvent. Thereafter, there is a method (polymerization number: 10-0643211-0000, South Korea) to proceed with the polymer coating by introducing a monomer to proceed with the polymerization.

In the case of vapor deposition polymerization, a manufacturing process that requires the vaporization of monomers is additionally required, and thus, the manufacturing process is complicated and disadvantages in producing a large amount of particles.

The reaction process of dissolving the polymer in the solvent is a process risk because most of the polymer material is dissolved in a volatile solvent, there is a disadvantage that the polymer is present in the polymer alone as well as the surface of the inorganic nanoparticles.

The method of dispersing in the solvent carried out in the laboratory and proceeding the polymerization (Registration No.:10-0643211-0000, Republic of Korea) is a process risk that the solvent that dissolves the polymer and the solvent that dissolves the monomer are mostly volatile. Since the weight part of is limited to 1 part by weight based on 100 parts by weight of the solvent, it has a large limit in mass production. In addition, since the monomer and the initiator are added in separate steps, the process is complicated, and such a complicated process has a large weak point in mass production as well as the weight part of the low inorganic nanoparticles.

In particular, when considering the various applications such as wide viewing angle, electronic paper, etc. of the inorganic nanoparticles in which the inorganic nanoparticles are introduced into the polymer as a filler, it is required to have a high yield in the preparation of the inorganic nanoparticles / polymer core-cell nanocomposites. . Since the preparation by the above method is limited to only the surface of the inorganic nanoparticles, and the introduction of the polymer is not performed, when the weight of the inorganic nanoparticles is conducted at 1 part by weight or more based on 100 parts by weight of the solvent, the inorganic nanoparticles / polymer core -The entanglement of the cell nanocomposites occurs, and the introduced polymer is present on the surface of the inorganic nanoparticles as well as the polymer alone. Therefore, the production of inorganic nanoparticles / polymer core-cell nanocomposites by the conventional method is difficult to exhibit a high yield, which leads to difficulties in mass production and application to industry.

Therefore, for the production of inorganic nanoparticles / polymer core-cell nanocomposites, only a surface of inorganic nanoparticles can be coated with a polymer, but a simple, inexpensive, safe process for mass production and easy recovery This is strongly demanded.

An object of the present invention is to solve the problems of the prior art by coating the inorganic nanoparticles with a polymer using an interfacial seeded polymerization (interfacial seeded polymerisation) that proceeds only on the surface of the inorganic nanoparticles inorganic nanoparticles / polymer core To produce cell nanocomposites.

After numerous experiments and in-depth studies, the present inventors have made a method very different from the known methods, dispersing inorganic nanoparticles in an aqueous solution, modifying the surface of the nanoparticles hydrophobicly, and introducing monomers and initiators. By inducing polymerization only on the surface of the inorganic nanoparticles / polymer core-cell nanocomposite was confirmed that it is possible to produce and led to the present invention.

The present invention utilizes interfacial seed polymerization in which inorganic nanoparticles having a size of several nanometers to several micrometers are limited only on the surface thereof, and thus, polymethylmethacrylate, polydivinylbenzene, and polyacryl It will be described by coating with ronitrile (polyacrylonitrile), polyethylene glycol methacrylate (polyethylglycolmethacrylate).

Method for producing inorganic nanoparticles coated with a polymer according to the present invention,

(A) dispersing inorganic nanoparticles in an aqueous solution;

(B) introducing a silane coupling agent to the surface of the inorganic nanoparticles in the dispersion aqueous solution to modify the hydrophobicity; And,

(C) adding a monomer and an initiator to the aqueous solution to make it adsorb on the surface of the hydrophobically modified inorganic nanoparticles; And,

(D) allowing the polymerization to occur only at the surface in the reaction solution; And,

(E) drying the obtained reaction material to recover inorganic nanoparticles coated with a polymer.

Polymer coating method of inorganic nanoparticles through interfacial seed polymerization that proceeds in a limited way on the surface of the inorganic nanoparticles according to the present invention is a completely new method that has not been reported so far, it is remarkable to independently stand out the polymers caused by the conventional method In addition, when the polymer coating, the aggregation of the prepared inorganic nanoparticles / polymer core-cell nanocomposites can also be prevented. In addition, since the experiment is carried out under the condition that the amount of the inorganic nanoparticles is added up to 5 parts by weight with respect to 100 parts by weight of the aqueous solution, the inorganic nanoparticles / polymer core-cell nanocomposites can be mass-produced. It proceeds in aqueous solution and has the advantage of simple process to add monomer and initiator simultaneously. It is easy to recover because inorganic nanoparticle / polymer core-cell nanocomposite with hydrophobic surface sinks in water after polymerization. Unlike the preparation method of the inorganic nanoparticles / polymer core-cell nanocomposite coated with a variety of polymers in a very easy method can be prepared.

The inorganic nanoparticles used in step (A) are not particularly limited, and polymer particles may be used in addition to the inorganic nanoparticles. In particular, inorganic nanoparticles such as silica (SiO ₂ ), titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO), iron oxide (Fe ₂ O ₃ ), and lead sulfide (PbS) are preferable. The diameter of the inorganic nanoparticles is not particularly limited and is preferably 5-500 nanometers, and is applicable to particles of micro size. The shape is not limited to a specific shape, but spherical particles or acicular particles are preferable. In the case of silica nanoparticles, commercialized silica colloidal solutions such as Ludox TM-40, HS-40, and SM-30 may be used, and various sizes and sizes may be obtained using a conventionally known sol-gel method. Silica particles in the form may also be prepared and used. In the case of titanium oxide, commercially available titanium oxide nanoparticles such as Degussa P-25 can be used, and titanium oxide particles of various sizes and shapes can be prepared and used by using a commonly known sol-gel method. It may be. In the case of zinc oxide, both commercially available zinc oxide nanoparticles and nanoparticles prepared by the sol-gel method can be used.

When dispersing the inorganic nanoparticle particles on the aqueous solution, the addition amount of the inorganic nanoparticles is preferably 1 to 5 parts by weight based on 100 parts by weight of the aqueous solution. If the amount of the inorganic nanoparticles is less than 1 part by weight, problems in the manufacturing process cost due to excessive use of the aqueous solution may occur. If the amount is more than 5 parts by weight, the core-cell nanoparticles may not be easily dispersed or finally prepared in the aqueous solution. Problems such as clumping together may occur.

The temperature at which the inorganic nanoparticles are dispersed in the aqueous solution is not particularly limited, but the temperature is 1 to 30 ° C., and the dispersion time is preferably 10 to 100 minutes.

The silane coupling agent used in step (B) is not limited to a specific kind, but may be one that can hydrophobically modify the surface properties of the dispersed inorganic nanoparticles. In particular, chlorodimethylvinylsilane, 3-methacryloxypropyl trimethoxysilane ([3- (methacrylyloxy) propyl] trimethoxysilane), and the like are preferable. The addition amount of the silane coupling agent may be added in a weight ratio of one hundredth to one tenth of the inorganic nanoparticles, but is not limited to these ranges and may be more or less than the above ranges.

The temperature of the hydrophobic reforming reaction is not particularly limited, but proceeds at a temperature of 1 to 50 ° C., and the reforming reaction time is preferably 1 to 12 hours.

The type of monomer in step (C) is not limited to a particular monomer, but it is important to select a monomer suitable for the purpose to be prepared. Particularly vinyl monomers such as methyl methacrylate, styrene, divinylbenzene , Acrylonitrile and vinyl carbazole are preferred. Also pyromellitic dianhydride (PMDA) and 4,4-oxydianiline (ODA) which can be used as monomers of polyimide, monomers of thermosetting resins such as epoxy, phenol, Formaldehyde can also be used, monomers of the conductive polymers pyrrole, aniline, thiophene. 3,4'- ethylene dioxythiophene etc. are also preferable.

The addition amount of the monomer may be added in a weight ratio of 1/10 to 2 times the inorganic nanoparticles, but is not limited to these ranges may be more or less than the above ranges.

Said initiator is not limited to a specific kind, What is necessary is just to consider the kind of monomer, and may use it. In particular, a radical initiator using pyrolysis or an oxidizing agent by an oxidation-reduction reaction is preferable, and in the present invention, in the case of radical polymerization, 2,2'-azobisisobutyronitrile or 2,2'-azobis- which is a radical initiator is preferred. [2- (2-imidazolin-2-yl) -propane] dihydrochloride, benzoylperoxide and the like are preferable. The oxidizing agent is preferably ammonium persulfate or iron trichloride. The addition amount of the initiator is used in the amount known in the art for the amount necessary for the conventional polymerization reaction, for example, may be added in a weight ratio of 1/100 to 1/10 of the monomer, but is not limited to these ranges And may be more or less than the above range.

The stirring time for the adsorption is preferably 5 to 120 minutes, the temperature at the time of stirring is preferably carried out at a temperature of 1 to 30 ℃. If the agitation time is less than 5 minutes, the monomers may not be sufficiently adsorbed on the surface of the hydrophobically modified inorganic nanoparticles, and if it is 120 minutes or more, the process time is long, which is undesirable in terms of process time and cost.

The reaction time required for the polymerization in step (D) is preferably 1 to 24 hours, similar to the polymer polymerization reaction time, but is not limited thereto, and may be shorter or longer than the above range depending on the type of monomer. The temperature required for the polymerization may be 5 to 100 degrees, but may be higher or lower than the above range depending on the type of monomer or the type of initiator.

The drying method in step (E) may use a number of methods, but it is preferable to dry under normal temperature and atmospheric pressure if possible in order to prevent the produced particles from agglomeration in the drying step. However, the present invention is not limited thereto, and an appropriate method may be used depending on the humidity and temperature of the laboratory and the type of solvent used.

EXAMPLE

Although specific examples of the present invention will be described with reference to the following Examples, the scope of the present invention is not limited thereto.

Example 1

1.0 g of silica nanoparticles having a diameter of 7 nm were dispersed in 50 ml of distilled water, and 0.2 g of chlorodimethylvinyl silane was additionally introduced, and surface modification was performed to make the surface of the silica nanoparticles hydrophobic while stirring for 6 hours. 0.5 g of methyl methacrylate and 0.01 g of 2,2'-azobisisobutyronitrile were simultaneously added to the reaction solution, followed by stirring for 1 hour to be adsorbed onto the surface of hydrophobically modified silica nanoparticles. The mixed solution was polymerized at 70 ° C. for 12 hours. After the polymerization was completed, in order to collect only the precipitate from the reaction solution, the solution other than the precipitate was removed and dried at room temperature to recover the core-cell nanoparticles.

As a result of analyzing silica / polymer nanoparticles having a core-cell structure using a transmission electron microscope (TEM), a polymethylmethacrylate layer having a thickness of about 2 nm was formed on the surface of the titanium oxide particles. I could confirm it. Also After checking through the Fourier change infrared spectroscopy (FT-IR) devices to ensure that the polymerization is conducted, poly methylmethacrylate representative peak of C = O peak in the acrylate is 1730 cm ^- poly methylmethacrylate through what is observed in ¹ It was confirmed that the acrylate was successfully applied to the surface of the silica nanoparticles. (Figure 1)

[Example 2]

As in Example 1, 1.0 g of silica nanoparticles having a diameter of 22 nm was dispersed in 50 ml of distilled water, and surface modification was performed with 0.2 g of chlorodimethylvinyl silane, followed by 0.5 g of methyl methacrylate and 2,2. 0.01 g of '-azobisisobutyronitrile was added and then polymerized at 70 ° C for 12 hours.

As a result of analyzing the prepared silica / polymer core-cell nanoparticles having a core-cell structure using a transmission electron microscope (TEM), a polymethylmethacrylate layer having a thickness of about 2 nm was formed on the surface of the silica nanoparticles. It was confirmed that the generated. (Figure 2)

Example 3

As in Example 1, 1.0 g of silica nanoparticles having a diameter of 50 nm were dispersed in 50 ml of distilled water, and surface modification was performed with 0.2 g of chlorodimethylvinyl silane, followed by 0.5 g of methyl methacrylate and 2,2. 0.01 g of '-azobisisobutyronitrile was added and then polymerized at 70 ° C for 12 hours.

As a result of analyzing the prepared silica / polymer core-cell nanoparticles having a core-cell structure using a transmission electron microscope (TEM), a polymethylmethacrylate layer having a thickness of about 5 nm was formed on the surface of the silica nanoparticles. It was confirmed that the generated. (Figure 3)

Example 4

As in Example 1, 1.0 g of silica nanoparticles having a diameter of 200 nm were dispersed in 50 ml of distilled water, and surface modification was performed with 0.2 g of chlorodimethylvinyl silane, followed by 0.5 g of methyl methacrylate and 2,2. 0.01 g of '-azobisisobutyronitrile was added and then polymerized at 70 ° C for 12 hours.

As a result of analyzing the prepared silica / polymer core-cell nanoparticles having a core-cell structure using a transmission electron microscope (TEM), a polymethylmethacrylate layer having a thickness of about 20 nm was formed on the surface of the titanium oxide particles. It was confirmed that the generated.

Example 5

As in Example 1, 0.5 g of silica nanoparticles having a diameter of 7 nm were dispersed in 50 ml of distilled water, and surface modification was performed with 0.2 g of chlorodimethylvinyl silane, followed by 0.5 g of methyl methacrylate and 2,2. 0.01 g of '-azobisisobutyronitrile was added and then polymerized at 70 ° C for 12 hours.

As a result of analyzing the prepared silica / polymer core-cell nanoparticles having a core-cell structure using a transmission electron microscope (TEM), a polymethylmethacrylate layer having a thickness of about 4 nm was formed on the surface of the titanium oxide particles. It was confirmed that the generated.

Example 6

As in Example 1, 2.0 g of silica nanoparticles having a diameter of 7 nm were dispersed in 50 ml of distilled water, and surface modification was performed with 0.2 g of chlorodimethylvinyl silane, followed by 0.5 g and 2,2 of methyl methacrylate. 0.01 g of '-azobisisobutyronitrile was added and then polymerized at 70 ° C for 12 hours.

As a result of analyzing the prepared silica / polymer core-cell nanoparticles having a core-cell structure using a transmission electron microscope (TEM), a polymethylmethacrylate layer having a thickness of about 1 nm was formed on the surface of the silica nanoparticles. It was confirmed that the generated.

Example 7

In the same manner as in Example 1, 1.0 g of silica nanoparticles having a diameter of 7 nm were dispersed in 50 ml of distilled water, and surface modification was performed with 0.2 g of 3-methacryloxypropyltrimethoxysilane, followed by methyl methacrylate. 0.5 g and 0.01 g of 2,2'-azobisisobutyronitrile were added, followed by polymerization at 70 DEG C for 12 hours.

As a result of analyzing the prepared silica / polymer core-cell nanoparticles having a core-cell structure using a transmission electron microscope (TEM), a polymethylmethacrylate layer having a thickness of about 2 nm was formed on the surface of the silica nanoparticles. It was confirmed that the generated.

Example 8

As in Example 1, 1.0 g of silica nanoparticles having a diameter of 7 nm was dispersed in 50 ml of distilled water, and surface modification was performed with 0.2 g of chlorodimethylvinyl silane, followed by 0.5 g of divinylbenzene and 2,2 '. 0.01 g of azobisisobutyronitrile was added, followed by polymerization at 70 ° C. for 12 hours.

As a result of analyzing the prepared silica / polymer core-cell nanoparticles having a core-cell structure using a transmission electron microscope (TEM), a polymethylmethacrylate layer having a thickness of about 2 nm was formed on the surface of the silica nanoparticles. It was confirmed that the generated.

Example 9

As in Example 1, 1.0 g of silica nanoparticles having a diameter of 7 nm were dispersed in 50 ml of distilled water, and surface modification was performed with 0.2 g of chlorodimethylvinyl silane, followed by 0.5 g of acrylonitrile and 2,2. 0.01 g of '-azobisisobutyronitrile was added and then polymerized at 70 ° C for 12 hours.

As a result of analyzing the prepared silica / polymer core-cell nanoparticles having a core-cell structure using a transmission electron microscope (TEM), a polymethylmethacrylate layer having a thickness of about 2 nm was formed on the surface of the silica nanoparticles. It was confirmed that the generated.

Example 10

As in Example 1, 1.0 g of silica nanoparticles having a diameter of 7 nm were dispersed in 50 ml of distilled water, and surface modification was performed with 0.2 g of chlorodimethylvinyl silane, followed by 0.5 g of acrylonitrile and 2,2. 0.01 g of '-azobisisobutyronitrile was added and then polymerized at 70 ° C for 12 hours.

As a result of analyzing the prepared silica / polymer core-cell nanoparticles having a core-cell structure using a transmission electron microscope (TEM), a polymethylmethacrylate layer having a thickness of about 3 nm was formed on the surface of the silica nanoparticles. It was confirmed that the generated.

Example 11

As in Example 1, 1.0 g of silica nanoparticles having a diameter of 7 nm were dispersed in 50 ml of distilled water, and surface modification was performed with 0.2 g of chlorodimethylvinyl silane, followed by 0.5 g of methyl methacrylate and 2,2. 0.01 g of '-azobis [2- (2-imidazolin-2-yl) -propane] dihydrochromide was added and then polymerized at 50 ° C. for 12 hours.

As a result of analyzing the prepared silica / polymer core-cell nanoparticles having a core-cell structure using a transmission electron microscope (TEM), a polymethylmethacrylate layer having a thickness of about 2 nm was formed on the surface of the silica nanoparticles. It was confirmed that the generated.

Example 12

As in Example 1, 1.0 g of titanium oxide nanoparticles having a diameter of 50 nm were dispersed in 50 ml of distilled water, and surface modification was performed with 0.2 g of chlorodimethylvinyl silane, followed by 0.5 g of methyl methacrylate and 2, 0.01 g of 2'-azobisisobutyronitrile was added and then polymerized at 70 ° C for 12 hours.

Titanium oxide / polymer core-cell nanoparticles having a core-cell structure were analyzed using a transmission electron microscope (TEM). As a result, a polymethyl methacrylate layer having a thickness of about 4 nm was formed of titanium oxide nanoparticles. It was confirmed that it was produced on the surface.

Example 13

As in Example 1, 2.0 g of titanium oxide nanoparticles having a diameter of 50 nm were dispersed in 50 ml of distilled water, and surface modification was performed with 0.2 g of chlorodimethylvinyl silane, followed by 0.5 g of methyl methacrylate and 2, 0.01 g of 2'-azobisisobutyronitrile was added and then polymerized at 70 ° C for 12 hours.

Titanium oxide / polymer core-cell nanoparticles having a core-cell structure were analyzed using a transmission electron microscope (TEM). As a result, a polymethyl methacrylate layer having a thickness of about 2 nm was formed of titanium oxide nanoparticles. It was confirmed that it was produced on the surface.

Example 14

As in Example 1, 1.0 g of titanium oxide needle-shaped nanomaterial having a diameter of 50 nm was dispersed in 50 ml of distilled water, and surface modification was performed with 0.2 g of chlorodimethylvinyl silane, followed by 0.5 g of methyl methacrylate and 0.01 g of 2,2'-azobisisobutyronitrile was added and then polymerized at 70 ° C for 12 hours.

Titanium oxide / polymer core-cell nanoparticles having a core-cell structure were analyzed using a transmission electron microscope (TEM). As a result, a polymethylmethacrylate layer having a thickness of about 2 nm was formed of titanium oxide needle-shaped nanoparticles. It was confirmed that it was formed on the surface of the material.

Example 15

As in Example 1, 1.0 g of zinc oxide nanoparticles having a diameter of 50 nm were dispersed in 50 ml of distilled water, and surface modification was performed with 0.2 g of chlorodimethylvinyl silane, followed by 0.5 g of methyl methacrylate and 2, 0.01 g of 2'-azobisisobutyronitrile was added and then polymerized at 70 ° C for 12 hours.

As a result of analyzing the prepared zinc oxide / polymer core-cell nanoparticles having a core-cell structure using a transmission electron microscope (TEM), a polymethyl methacrylate layer having a thickness of about 5 nm was formed of zinc oxide nanoparticles. It was confirmed that it was produced on the surface.

Example 16

In the same manner as in Example 1, 2.0 g of zinc oxide nanoparticles having a diameter of 50 nm were dispersed in 50 ml of distilled water, and surface modification was performed with 0.2 g of chlorodimethylvinyl silane, followed by 0.5 g of methyl methacrylate and 2, 0.01 g of 2'-azobisisobutyronitrile was added and then polymerized at 70 ° C for 12 hours.

As a result of analyzing the prepared zinc oxide / polymer core-cell nanoparticles having a core-cell structure using a transmission electron microscope (TEM), a polymethyl methacrylate layer having a thickness of about 2 nm was formed of zinc oxide nanoparticles. It was confirmed that it was produced on the surface.

Example 17

As in Example 1, 2.0 g of iron oxide nanoparticles having a diameter of 7 nm were dispersed in 50 ml of distilled water, and surface modification was performed with 0.2 g of chlorodimethylvinyl silane, followed by 0.5 g of methyl methacrylate and 2,2. 0.01 g of '-azobisisobutyronitrile was added and then polymerized at 70 ° C for 12 hours.

Analysis of the prepared iron oxide / polymer core-cell nanoparticles having a core-cell structure using a transmission electron microscope (TEM) revealed that a polymethylmethacrylate layer having a thickness of about 2 nm was formed on the surface of the iron oxide nanoparticles. It was confirmed that the generated.

Example 18

As in Example 1, 2.0 g of tin oxide nanoparticles having a diameter of 50 nm were dispersed in 50 ml of distilled water, and surface modification was performed with 0.2 g of chlorodimethylvinyl silane, followed by 0.5 g of methyl methacrylate and 2, 0.01 g of 2'-azobisisobutyronitrile was added and then polymerized at 70 ° C for 12 hours.

The prepared tin oxide / polymer core-cell nanoparticles having a core-cell structure were analyzed using a transmission electron microscope (TEM). As a result, a polymethyl methacrylate layer having a thickness of about 2 nm was formed of tin oxide nanoparticles. It was confirmed that it was produced on the surface.

Example 19

As in Example 1, 2.0 g of lead sulfide nanoparticles having a diameter of 50 nm were dispersed in 50 ml of distilled water, and surface modified with 0.2 g of chlorodimethylvinyl silane, followed by 0.5 g of methyl methacrylate and 2, 0.01 g of 2'-azobisisobutyronitrile was added and then polymerized at 70 ° C for 12 hours.

The lead sulfide / polymer core-cell nanoparticles having the prepared core-cell structure were analyzed using a transmission electron microscope (TEM). As a result, a polymethyl methacrylate layer having a thickness of about 2 nm was formed of the lead sulfide nanoparticles. It was confirmed that it was produced on the surface.

1 is a result of Fourier transform infrared spectroscopy of silica / polymer core-cell nanoparticles prepared in Example 1 of the present invention;

2 is a transmission electron micrograph of the silica / polymer core-cell nanoparticles prepared in Example 2 of the present invention;

3 is a transmission electron micrograph of the silica / polymer core-cell nanoparticles prepared in Example 3 of the present invention.

Claims (9)

Dispersing the inorganic nanoparticles in an aqueous solution; Introducing a silane coupling agent to the surface of the inorganic nanoparticles in the dispersed aqueous solution to modify the hydrophobicity; And, Adding a monomer and an initiator to the aqueous solution to make it adsorb on the surface of the hydrophobically modified inorganic nanoparticles; And, Allowing the polymerization to occur only at the surface of the hydrophobic inorganic nanoparticle solution in which the monomer and the initiator are adsorbed; And, A method for producing an inorganic nanoparticle / polymer core-cell nanocomposite, comprising recovering inorganic nanoparticles coated with a polymer by drying an aqueous solution in which polymerization is limited to only the surface. The method according to claim 1, wherein the inorganic nanoparticles as core materials are silica, titanium oxide, zinc oxide, tin oxide, iron oxide or lead sulfide nanoparticles. The method of claim 1, wherein the core material is an inorganic nanoparticle having a size of several nanometers to several tens of micrometers. The method according to claim 1, wherein the addition amount of the inorganic nanoparticles is 1 to 5 parts by weight based on 100 parts by weight of the aqueous solution. The method of claim 1, wherein the silane coupling agent is selected from chlorodimethylvinylsilane and 3-methacryoxypropyltrimethoxysilane capable of hydrophobically modifying the surface of the hydrophilic inorganic nanoparticles. Manufacturing method. The method of claim 1, wherein the monomer is selected from the group consisting of methyl methacrylate, acrylonitrile, divinylbenzene, and copolymerized polymers thereof, which can form linear and crosslinked polymers. Manufacturing method. The method of claim 1, wherein the initiator is a radical initiator 2,2'-azobisisobutyronitrile, 2,2'-azobis- [2- (2-imidazolin-2-yl) -propane] dihydro Method for producing one of the chromide. The method according to claim 1, wherein the polymerization temperature is 40 to 100 degrees Celsius. The method according to claim 1, wherein in the polymerization, the polymerization time is 1 hour to 24 hours.

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