KR101419876B1 - Preparation of high-performance hybrid-polymer beads by 1 step polymerization - Google Patents

Abstract

The present invention relates to a process for producing a high performance organic-inorganic hybrid particle in a single process, and more particularly, to a process for producing a high performance organic-inorganic hybrid particle by mixing a silane monomer having an unsaturated carbon, a vinyl monomer having an unsaturated carbon, a crosslinking agent and an initiator, Inorganic hybrid hybrid beads in a single step by radical polymerization of the suspension prepared by adding the organic-inorganic hybrid beads to a suspension of the organic-inorganic hybrid beads.

The present invention relates to a method of copolymerizing a vinyl monomer containing acrylic, styrene or various unsaturated carbon and a specific silane monomer containing unsaturated carbon by a suspension polymerization method, to obtain a copolymer having a degree of crosslinking of 1 to 98% , An organic-inorganic hybrid polymer bead having a particle size of 1 to 50 占 퐉 and a particle size distribution of 5 to 30% of a coefficient of variation (CV) can be produced.

Polymer beads, silanes, polyalkyl silsesquioxanes, organic-inorganic hybrids, single processes, radical polymerization

Description

[0001] The present invention relates to a process for preparing a high-performance hybrid-polymer hybrid beads by 1 step polymerization,

The present invention relates to a method for manufacturing a single process of high performance organic-inorganic hybrid particles.

Polymer beads are generally manufactured by methods such as suspension polymerization, dispersion polymerization and emulsion polymerization. The polymer beads thus prepared are used for various purposes such as cosmetics, coating additives and the like, and the use of the polymer diffuser as a diffusion agent of a light diffusion plate or a light diffusion film is increasing.

However, polymer beads are disadvantageous in that they have poor solvent resistance to organic solvents such as toluene, methyl ethyl ketone, and n-butyl acetone when used as a diffuser for a light diffusion plate or a light diffusion film, There is a problem that yellowing occurs during processing. Further, in order to change the refractive index, the polymer structure itself must be changed or the monomer ratio of the copolymer must be changed, which is disadvantageous in compatibility with the entire composition.

Organic-inorganic hybrid particles have been developed as a solution to the organic polymer bead problem. Organic-inorganic hybrid particles containing silane have a three-dimensional crosslinked structure and are excellent in solvent resistance and heat resistance to organic solvents, and have a lower refractive index than conventional organic particles. .

Organic-inorganic hybrid particles are generally prepared using a sol-gel reaction method. The sol-gel method comprises two steps of a primary hydrolysis reaction and a secondary condensation reaction as shown in the following reaction formulas (1) and (2).

[Reaction Scheme 1]

[Reaction Scheme 2]

However, the hydroxy group of the final product according to the above-described method is an element that hinders long-term stability such as moisture absorption. Therefore, in order to overcome this problem, a surface modification process in which the hydroxy group of the final product is substituted with an alkyl group is added, which requires a total of three steps of reaction. This means that precise control in the first and second reactions is required, and it is accompanied by difficulty in reproducibility and mass production.

Accordingly, the present invention proposes a method of easily and reproducibly producing the organic-inorganic hybrid bead utilizing the merits of organic beads / inorganic beads by only one-step reaction.

Therefore, it is an object of the present invention to overcome the disadvantages of conventional polymer bead and organic-inorganic hybrid particle production method and to overcome the disadvantages of the conventional polymer bead and organic-inorganic hybrid particle production method. - < / RTI > inorganic hybrid beads.

To achieve these and other advantages and in accordance with the purpose of the present invention,

Inorganic hybrid particles in a single step by mixing a silane-based monomer having an unsaturated carbon, a vinyl monomer having an unsaturated carbon, a crosslinking agent and an initiator, adding a dispersion stabilizer and ion-exchanged water to radical polymerization of the suspension,

Organic hybrid beads comprising the organic-inorganic hybrid beads.

Preferably, the present invention relates to a method for producing an aqueous dispersion, which comprises mixing a silane-based monomer having an unsaturated carbon, a vinyl monomer having an unsaturated carbon, a crosslinking agent and an initiator to prepare a first solution as a monomer mixture, mixing the dispersion stabilizer and ion- After the solution is prepared, the suspension prepared by mixing the first solution and the second solution may be subjected to radical polymerization to prepare the organic-inorganic hybrid particles by a single polymerization process.

The present invention also provides an organic-inorganic hybrid bead comprising a polymer represented by the following Formula 3:

(3)

Wherein R ¹ to R ⁴ are each independently an acrylic group; A methacryl group; Amide group; A straight chain or branched alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; An alkylene group having 2 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Or an aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group, or an amide group;

R ⁵ and R ⁶ are each independently an acrylic group; A methacryl group; Amide group; A straight chain or branched alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; An alkylene group having 2 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Alkoxycarbonyl having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Or an aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group, or an amide group;

R < ⁷ > is a linear or branched alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Or an aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group, or an amide group;

R ¹ to R ⁴ may not simultaneously be an amide group, an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or an unsubstituted aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms, and R ¹ to R ⁴ At least one of them has a substituent comprising a double bond,

m and n are each an integer of 500 to 100,000.

The organic-inorganic hybrid beads may have a degree of crosslinking of 1 to 98% and a particle size of 1 to 50 탆. The bead may have a coefficient of variation (CV) of 5 to 30%.

Hereinafter, the present invention will be described in detail.

The present invention can simplify the two-step reaction of the conventional hydrolysis and polycondensation reaction in the synthesis of the silane-based polymer, and can prevent terminal hydroxyl groups, which are inevitably generated in the conventional methods, Inorganic hybrid beads and a method of producing the same.

The present invention provides a method for preparing various types of organic-inorganic hybrid beads by radical suspension polymerization using a silane monomer having an unsaturated carbon introduced therein, as shown in the following reaction formula (3).

[Reaction Scheme 3]

Wherein R ¹ to R ⁴ are each independently an acrylic group; A methacryl group; Amide group; A straight chain or branched alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; An alkylene group having 2 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Or an aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group, or an amide group;

R ⁵ and R ⁶ are each independently an acrylic group; A methacryl group; Amide group; A straight chain or branched alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; An alkylene group having 2 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Alkoxycarbonyl having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Or an aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group, or an amide group;

R ⁷ is a linear or branched alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Or an aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group, or an amide group;

R ¹ to R ⁴ may not simultaneously be an amide group, an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or an unsubstituted aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms, and R ¹ to R ⁴ At least one of them has a substituent comprising a double bond,

m and n are each an integer of 500 to 100,000.

According to the present invention, the particles can have a network structure based on 100% covalent bond, without depending only on the secondary bonding force and partial primary bonding force (covalent bond) between the amide group and the silane group. In addition, the organic-inorganic hybrid particles can be produced by a single radical polymerization in the production method.

The method for producing the organic-inorganic hybrid bead of the present invention comprises the steps of: a) a silane-based monomer having at least one unsaturated carbon, b) a vinyl monomer having at least one unsaturated carbon, c) a dispersion stabilizer, d) ) Crosslinking agent and, if necessary, f) a co-solvent.

At this time, in the case of the present invention, preparation steps for preparing monomer mixture and aqueous mixture wool are carried out using each compound.

That is, in the present invention, a silane-based monomer having at least one unsaturated carbon, a vinyl monomer having at least one unsaturated carbon and a crosslinking agent are mixed and stabilized, and a radical initiator is added thereto to prepare a first solution as a monomer mixture .

Further, in the present invention, a dispersion stabilizer and ion-exchanged water are mixed and, if necessary, a cosolvent is added to prepare a second solution which is an aqueous mixture.

Then, the first solution and the second solution are mixed and mixed at 200 rpm or more for 1 to 5 hours to prepare a suspension, and then the suspension is homogenized. At this time, it is more preferable that the mixing time is 1 to 3 hours and the stirring speed is 200 to 2000 rpm.

Then, the suspension is subjected to radical suspension polymerization at 40 to 95 ° C. for 2 to 24 hours while stirring the suspension at 50 to 500 rpm. At this time, it is more preferable that the radical polymerization is carried out at a stirring speed of 100 to 300 rpm, at a temperature of 50 to 90 ° C, and for 5 to 18 hours.

After completion of the reaction, the polymer beads are separated by filtration, washed with ion exchange water three to four times, dehydrated and dried at 70 ° C. for 24 hours to obtain final organic-inorganic hybrid beads.

In the first solution, the silane-based monomer having at least one unsaturated carbon is preferably at least one compound selected from the group consisting of compounds represented by the following general formula (1).

[Chemical Formula 1]

In the above formula, R ¹ to R ⁴ are substituents having at least one unsaturated hydrocarbon capable of radical polymerization including vinyl, acrylic, methacrylic or styrene,

Each independently an acryl group; A methacryl group; Amide group; A straight chain or branched alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; An alkylene group having 2 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Or an aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group, or an amide group;

R ¹ to R ⁴ may not simultaneously be an amide group, an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or an unsubstituted aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms, and R ¹ to R ⁴ At least one of which has a substituent comprising a double bond.

The vinyl monomer having at least one unsaturated carbon is preferably a compound represented by the following formula (2).

(2)

Wherein R ⁵ and R ⁶ are each independently an acrylic group; A methacryl group; Amide group; A straight chain or branched alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; An alkylene group having 2 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Alkoxycarbonyl having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Or an aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group, or an amide group; And

R ⁷ is a linear or branched alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Alkoxycarbonyl having 1 to 20 carbon atoms; Or an aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group, or an amide group.

The silane-based monomer having at least one unsaturated carbon is preferably an organic compound containing 1 to 6 unsaturated carbons and having ₂ to ₂₀ carbon atoms. Further, a Si compound substituted with an organic substance having properties such as an acrylic type or a urethane type is also preferable. Optionally, the monomers may be used in admixture of two or more. For example, the silane-based monomer may be 1-methylmethacrylate-trimethoxysilane, 1-methylmethacrylate-triethoxysilane, or the like.

The silane-based monomer having at least one unsaturated carbon is preferably used in an amount of 10 to 100 parts by weight based on 100 parts by weight of the vinyl monomer. If the content is less than 10 parts by weight, there is a problem that thermal and mechanical properties are insufficient. If the content is more than 100 parts by weight, there is a problem in particle stability.

The vinyl monomer having at least one unsaturated carbon atom is preferably a radical polymerizable monomer containing 1 to 6 unsaturated carbon atoms, and is preferably an organic compound having C ₂ to C ₂₀ . Monomers having properties such as acrylic type and urethane type are also preferable. Alternatively, two or more kinds of the monomers may be mixed and used. For example, the vinyl monomers include methyl methacrylate, methyl acrylate, butyl acrylate, urethane acrylate, benzyl methacrylate, cyclohexyl acrylate, and styrene.

The crosslinking agent is a compound containing two or more unsaturated carbon atoms, and examples thereof include 1,2-ethanediol diacrylate, 1,3-propanediol diacrylate, 1,3-butanediol diacrylate, 1,4 Butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, divinylbenzene, ethylene glycol diacrylate, propylene glycol diacrylate, butylene glycol diacrylate, tri Ethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, polybutylene glycol diacrylate, allyl acrylate, 1,2-ethanediol dimethacrylate, 1,3-propanediol dimethacrylate, Butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, relay , Propylene glycol dimethacrylate, butylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, triethylene glycol At least one member selected from the group consisting of methacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate, allyl methacrylate, and diallyl maleate Can be used.

The crosslinking agent is used in an amount of 1 to 50 parts by weight, preferably 1 to 35 parts by weight, based on 100 parts by weight of the vinyl monomer. If the content of the crosslinking agent exceeds 50 parts by weight, it is difficult to control the heat of reaction. If the content of the crosslinking agent is less than 1 part by weight, it can not be expected to serve as a crosslinking agent.

The radical initiator may be selected from a fat-soluble initiator and a water-soluble initiator. As the fat-soluble initiator, at least one selected from the group consisting of benzoyl peroxide, azobisisobutyronitrile, azobiscenyl butyronitrile and azobiscyclohexanecarbonitrile can be used. As the water-soluble initiator, at least one selected from the group consisting of potassium persulfate, sodium persulfate, ammonium persulfate, and azo-based water-soluble initiator may be used.

The radical initiator is used in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the vinyl monomer. If the amount of the radical initiator is less than 0.1 parts by weight, the degree of completion of the reaction decreases. When the amount of the radical initiator exceeds 3 parts by weight, it is difficult to control the reaction heat.

In the second solution, the dispersion stabilizer may be at least one selected from the group consisting of polyvinyl pyrrolidone, polyvinyl methyl ether, polyethyleneimide, polyacrylic acid, polyvinyl alcohol, vinyl acetate copolymer, ethyl cellulose, hydroxypropyl cellulose, silica, , And the like, and they may be used alone or in combination of two or more.

The content of the dispersion stabilizer is not particularly limited, but is preferably 0.1 to 5 parts by weight based on the whole aqueous mixture.

Further, the ion-exchanged water may be included in the balance with respect to the entire water-based mixture.

The co-solvent may be used in an amount of 1 to 40 parts by weight based on the entire water-based mixture. In this case, the content of the ion exchange water may also be included as the remainder.

The present invention also provides an organic-inorganic hybrid bead comprising a polymer represented by the following formula (3).

(3)

In the above formulas, R ¹ to R ⁷ , m and n are as defined above.

The organic-inorganic hybrid beads according to the present invention can be prepared according to the above-described method, and have a polymer form, not a composition form. In addition, the beads of the present invention can prevent phase separation by using the hydrogen bonding force and the chemical bonding force of the vinyl monomers and the silane monomers. Such organic-inorganic hybrid beads have a degree of crosslinking of 1 to 98% and a particle size of 1 to 50 탆. In addition, the organic-inorganic hybrid beads may have a coefficient of variation (CV) of 5 to 30%.

The organic-inorganic hybrid beads according to the present invention have an average particle diameter of 1 to 50 탆, C.V. It has a particle size distribution within 5 ~ 30%. It can easily produce a copolymer with an organic substance, polyalkyl silsesquioxane by a one-step process, and is excellent in thermal stability and solvent resistance, ), A light diffusing agent for a light diffusion plate, a surface lubricating agent in the coating material field, a water repellency, an oil repellency imparting agent, and an anti-blocking agent for paints and cosmetics.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to Examples. However, the following Examples are provided for easier understanding of the present invention, but the present invention is not limited to these Examples.

≪ Example 1 >

100 parts by weight of methyl methacrylate, 20 parts by weight of 1-methylmethacrylate-trimethoxysilane, 0.3 part by weight of azobisisobutyronitrile as an initiator, and 10 parts by weight of 1,2-ethanediol diacrylate as a crosslinking agent Was added to prepare a first solution which was a monomer mixture.

Then, 96 parts by weight of ion-exchanged water was added to 4 parts by weight of polyvinyl alcohol to prepare a second solution as an aqueous mixture.

Thereafter, the first solution and the second solution were mixed to prepare a suspension.

The prepared suspension was subjected to radical polymerization at a temperature of 70 캜 for 13 hours to prepare an organic-inorganic hybrid bead.

≪ Example 2 >

A suspension was prepared in the same manner as in Example 1, except that 50 parts by weight of 1-methylmethacrylate-trimethoxysilane was used in the preparation of the first solution as the monomer mixture.

≪ Example 3 >

A suspension was prepared in the same manner as in Example 1, except that 99.7 parts by weight of 1-methylmethacrylate-trimethoxysilane was used in the preparation of the first solution as the monomer mixture.

≪ Comparative Example 1 &

A suspension was prepared in the same manner as in Example 1 except that 1-methylmethacrylate-trimethoxysilane was not used in Example 1.

<Experimental Example 1>

The Coefficient of Variation (C.V. value) was obtained by the following formula using a particle size distribution measuring apparatus (Coulter Electronics, Multisizer 3) for Examples 1 to 3 and Comparative Example 1. The results are shown in Table 1.

[Equation 1]

C.V. (%) = (standard deviation of particle diameter / average particle diameter of particle) 占 100

[Table 1]

Si compound (parts by weight) Average particle diameter (um) C.V (%) Example 1 20 15.0 12 Example 2 50 14.5 13 Example 3 99.7 13.8 13 Comparative Example 1 0 15.3 30

As shown in Table 1, it can be seen that the organic-inorganic hybrid beads of Examples 1 to 3 according to the present invention have micron-sized particle diameters uniformly. On the other hand, in Comparative Example 1, the average particle diameter was similar to that of the present invention, but the value of the coefficient of variation was large and the particle diameters were not uniform.

<Example 4>

100 parts by weight of methyl methacrylate, 20 parts by weight of 1-methylmethacrylate-trimethoxysilane, 0.25 parts by weight of azobisisobutyronitrile as an initiator, and 10 parts by weight of 1,2-ethanediol diacrylate as a crosslinking agent To prepare a first solution which is a monomer mixture.

Subsequently, 2.8 parts by weight of polyvinyl alcohol and 1.2 parts by weight of polyvinyl pyrrolidone 30k were added 96 parts by weight of ion-exchanged water to prepare a second solution as an aqueous mixture.

Thereafter, the first solution and the second solution were mixed to prepare a suspension.

The prepared suspension was subjected to radical polymerization at a temperature of 70 캜 for 13 hours to prepare an organic-inorganic hybrid bead.

&Lt; Example 5 >

Methylmethacrylate-trimethoxysilane was used as a monomer in the preparation of the first solution which was a monomer mixture, 3.7 parts by weight of polyvinyl alcohol as a dispersion stabilizer in the preparation of the second solution, 30 parts by weight of polyvinylpyrrolidone 30K 1.8 By weight was used in place of the above-mentioned solution.

&Lt; Example 6 >

Methylmethacrylate-trimethoxysilane was used as a monomer in the preparation of the first solution, which was a monomer mixture, and 2.6 parts by weight of polyvinyl alcohol and 1.4 parts by weight of polyvinylpyrrolidone 30K The procedure of Example 4 was repeated to prepare a suspension.

&Lt; Example 7 >

In the preparation of the first solution, which is a monomer mixture, 1-methylmethacrylate-trimethoxysilane 99.75 And 1.5 parts by weight of polyvinyl alcohol and 1.2 parts by weight of polyvinylpyrrolidone 30K were used as a stabilizer in the preparation of the second solution and a suspension was prepared in the same manner as in Example 4. [

<Experimental Example 2>

With respect to Examples 4 to 7, coefficient of variation (CV value) was measured in the same manner as in Experimental Example 1, and the results are shown in Table 2.

[Table 2]

Si compound 2
(Parts by weight) Stabilizer 1 (parts by weight)
(Polyvinyl alcohol) Stabilizer 2 (parts by weight)
(Polyvinylpyrrolidone 30K) Average particle diameter (um) C.V (%) Example 4 0 2.8 1.2 15.2 7 Example 5 25 3.7 1.8 5.0 5 Example 6 50 2.6 1.4 15.1 8 Example 7 99.75 1.5 1.2 30.3 7

As shown in Table 2 above, it can be seen that the organic-inorganic hybrid beads according to the present invention can obtain micron-sized particle sizes with a monodisperse distribution.

<Experimental Example 3>

The stability of each of the beads of Examples 4 to 7 was evaluated after 0 hours, 1 hour, 2 hours, 3 hours, 4 hours, 6 hours, 8 hours, and 24 hours after the dispersion in toluene and n-butyl acetate, The results are shown in Figures 1 and 2.

The stability was evaluated at a fixed time of 50 rpm using Brookfield viscometer spindle No. 2, and the measured value was expressed in terms of viscosity (cP%). The viscosity was measured over time to confirm the solvent resistance.

As shown in FIGS. 1 and 2, as the content of the Si-compound increases, the solvent resistance increases. By controlling the weight ratio of the Si-compound, a product having excellent solvent resistance can be produced.

<Experimental Example 4>

Repeatability test was conducted by repeating the experiment five times under the experimental conditions of Example 6. The results for each scale are shown in Table 3 below.

[Table 3]

Lot NO. Scale (L) Average particle diameter (um) C.V (%) One One 15.1 8 2 5 15.0 7 3 10 15.1 8 4 20 15.3 8 5 20 15.3 8

As shown in Table 3, it can be seen that the organic-inorganic hybrid beads according to the present invention can reproducibly obtain micron-sized particle sizes in a monodisperse distribution.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the results of solvent resistance of toluene of an organic-inorganic hybrid bead of the present invention. FIG.

2 is a graph showing the results of solvent resistance of the organic-inorganic hybrid bead of the present invention to n-butyl acetate.

Claims (13)

Inorganic hybrid particles in a single process by mixing a silane-based monomer having an unsaturated carbon, a vinyl monomer having an unsaturated carbon, a crosslinking agent and an initiator, adding a dispersion stabilizer and ion-exchanged water to radical polymerization; / RTI &gt; Wherein the unsaturated carbon-containing silane-based monomer is at least one selected from the group consisting of compounds represented by the following formula (1): &lt; EMI ID = [Chemical Formula 1]

Wherein R ¹ to R ⁴ are each independently an acrylic group; A methacryl group; Amide group; A straight chain or branched alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; An alkylene group having 2 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Or an aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group, or an amide group; R ¹ to R ⁴ may not simultaneously be an amide group, an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or an unsubstituted aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms, and R ¹ to R ⁴ At least one of which has a substituent comprising a double bond. The method according to claim 1, wherein the method comprises mixing a silane-based monomer having an unsaturated carbon, a vinyl monomer having an unsaturated carbon, a crosslinking agent and an initiator to prepare a first solution as a monomer mixture, mixing the dispersion stabilizer with ion- Inorganic hybrid beads, comprising the steps of: preparing a second solution which is a mixture of a first solution and a second solution and then subjecting the suspension prepared by mixing the first solution and the second solution to radical polymerization to prepare an organic- &Lt; / RTI &gt; delete 3. The method of producing an organic-inorganic hybrid bead according to claim 2, wherein the unsaturated carbon-containing silane-based monomer is used in an amount of 10 to 100 parts by weight based on 100 parts by weight of the vinyl monomer. The method for producing an organic-inorganic hybrid bead according to claim 1, wherein the unsaturated carbon-containing vinyl monomer is a compound represented by the following formula (2). (2)

Wherein R ⁵ and R ⁶ are each independently an acrylic group; A methacryl group; Amide group; A straight chain or branched alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; An alkylene group having 2 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Alkoxycarbonyl having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Or an aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group, or an amide group; And R ⁷ is a linear or branched alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Alkoxycarbonyl having 1 to 20 carbon atoms; Or an aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group, or an amide group. 2. The composition of claim 1, wherein the crosslinking agent is selected from the group consisting of 1,2-ethanediol diacrylate, 1,3-propanediol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, Diethylene glycol diacrylate, butylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, diethylene glycol diacrylate, diethylene glycol diacrylate, diethylene glycol diacrylate, Acrylate, polypropylene glycol diacrylate, polybutylene glycol diacrylate, allyl acrylate, 1,2-ethanediol dimethacrylate, 1,3-propanediol dimethacrylate, 1,3-butanediol di Methacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, Butylene glycol Polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate, triethylene glycol methacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, Wherein the at least one compound is at least one compound selected from the group consisting of polypropylene glycol dimethacrylate, polybutylene glycol dimethacrylate, allyl methacrylate, and diallyl maleate. The method for producing an organic-inorganic hybrid bead according to claim 2, wherein the cross-linking agent is used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the vinyl-based monomer. 3. The method of producing an organic-inorganic hybrid bead according to claim 2, wherein the dispersion stabilizer is used in an amount of 0.1 to 5 parts by weight based on the whole aqueous mixture. The method of claim 1, wherein the dispersion stabilizer is selected from the group consisting of polyvinyl pyrrolidone, polyvinyl methyl ether, polyethylene imide, polyacrylic acid, polyvinyl alcohol, vinyl acetate copolymer, ethyl cellulose, hydroxypropyl cellulose, silica and siloxane Wherein at least one selected from the group consisting of the organic-inorganic hybrid beads is used. The method of claim 1 wherein the initiator is selected from the group consisting of benzoyl peroxide, azobisisobutyronitrile, azobiscenyl butyronitrile, azobiscyclohexanecarbonitrile, potassium persulfate, sodium persulfate, ammonium persulfate, Wherein at least one selected from the group consisting of an initiator and an initiator is used. Organic-inorganic hybrid beads comprising a polymer represented by Formula 3: (3)

Wherein R ¹ to R ⁴ are each independently an acrylic group; A methacryl group; Amide group; A straight chain or branched alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; An alkylene group having 2 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Or an aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group, or an amide group; R ⁵ and R ⁶ are each independently an acrylic group; A methacryl group; Amide group; A straight chain or branched alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; An alkylene group having 2 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Alkoxycarbonyl having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Or an aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group, or an amide group; R ⁷ is a linear or branched alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group or an amide group; Or an aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms which is unsubstituted or substituted with an acryl group, a methacryl group, or an amide group; R ¹ to R ⁴ may not simultaneously be an amide group, an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or an unsubstituted aromatic or alicyclic hydrocarbon having 5 to 20 carbon atoms, and R ¹ to R ⁴ At least one of them has a substituent comprising a double bond, m and n are each an integer of 500 to 100,000. 12. The organic-inorganic hybrid bead according to claim 11, wherein the bead has a degree of crosslinking of 1 to 98% and a particle size of 1 to 50 占 퐉. 12. The organic-inorganic hybrid bead according to claim 11, wherein the beads have a coefficient of variation (CV) of 5 to 30%.

Images