KR20150076578A - preparation method for silica particles containing single or multiple functional groups and silica particles prepared thereby - Google Patents

Abstract

The present invention relates to a method for preparing silica particles containing functional groups and silica particles prepared thereby. More specifically, the present invention relates to a method which prepares silica particles containing functional groups by regulating process variables, such as reaction temperature, to conveniently control the size and distribution of silica particles. According to the present invention, a method of preparing silica particles uses water as a dissolvent with a small amount of catalyst, wherein the size of silicon particles can be regulated within a range of 0.5-5 μm, the distribution form thereof can be controlled easily, and uniform particles can be obtained at high yields. Also through a process of sintering, pure silica particles can be obtained in high yields, whose size is up to 5 times that of conventional silica particles. Silica particles containing at least one functional group or pure silica particles, have suitable structures for multifunction and sizes similar to bio materials, and exhibits no toxicity so that such silica particles can be employed biomedical areas, such as bio labelling.

Description

The present invention relates to a method for preparing silica particles having a functional group and silica particles prepared thereby,

The present invention relates to a process for preparing silica particles having functional groups and silica particles prepared thereby, and more particularly to a process for producing silica particles having a functional group by controlling the size and distribution of silica particles by controlling process parameters such as reaction temperature, To a process for producing silica particles having at least one functional group composed of particles of one size.

Silica is a substance with considerable utilization value throughout the whole business such as a desiccant, a cosmetic additive, a catalyst carrier, and a diaphragm for a display. As the industry becomes more and more advanced, demand for silica particles having various physical properties is increasing There is an increasing demand for the production of spherical monodispersed silica particles for improving the performance of various products using silica particles. Therefore, research on the control of size and distribution of silica particles is of interest.

Generally, spray pyrolysis using sodium silicate is known, but the sodium content is high and the porous silica particles are formed into polydisperse, which is insufficient in mechanical strength, resulting in breakage or a decrease in filling density.

In order to solve the above-mentioned problems, it has been proposed to add ammonia as a catalyst to a mixed solution containing tetraethylorthosilicate (TEOS), alcohol and water to induce hydrolysis and polycondensation reaction to form silica particles - Stover method, a kind of gel method, is known. Although this method can obtain spherical particles with a relatively monodisperse particle size distribution, the yield is very low and only particles with a size of less than 1 micrometer can be produced. This problem is a major cause of inhibiting the availability of silica particles (Non-Patent Document 1)

In addition, there is known a method for preparing spherical silica by controlling the stirring speed by adding a silicone oil as a dispersant as a starting material in the emulsification of sodium silicate as a starting material, but there is a disadvantage that uneven distribution of nanoparticles is exhibited. Patent Document 1)

In order to solve the above problems, silica nanoparticles are prepared by mixing a silica precursor with an organic solvent, and then ammonia water is added thereto to produce silica particles. The silica particles produced by changing the heating temperature in the above- It is described that the size of the particles can be controlled, but there is a problem that it is not suitable for producing functionalized silica particles (Patent Document 2).

Patent Document 1. Korean Patent Publication No. 2006-0097223 Patent Document 2: Korean Patent Publication No. 10-2013-0011505

Non-Patent Document 1. W. Stober., A. Fink and E. Bohn., J. Colloid Interface Sci., 26, 62 (1968)

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a silica precursor which is produced by controlling a process parameter such as a reaction temperature during a production process by adding a basic catalyst to a silica precursor through hydrolysis and polycondensation And to provide a method for producing silica particles having functional groups capable of controlling the size and distribution of silica particles.

Another object of the present invention is to provide a method for producing pure silica particles containing no functional groups by sintering silica particles having functional groups produced through the above-mentioned production method.

It is also an object of the present invention to provide silica particles having a functional group prepared to have a desired particle size through the above-mentioned production method, or pure silica particles obtained by sintering.

In order to accomplish the above object, the present invention provides a process for producing silica particles having a functional group comprising the steps of:

(I) preparing a mixed solution by adding a silica precursor and a basic catalyst to an aqueous solution; And

(II) stirring the mixed solution to perform hydrolysis and polycondensation to produce silica particles having at least one functional group.

In the step (II), the reaction temperature is controlled at 20 to 60 ° C to control the size and dispersion of silica particles.

The manufacturing method further comprises: (III) washing and drying the silica particles having the at least one functional group.

The drying in the step (III) is performed at a temperature of 30 to 250 ° C for 1 to 16 hours.

And the stirring speed is controlled at 30 to 100 rpm in the step (II), thereby controlling the size and dispersed form of the silica particles.

And controlling the molar concentration of the silica precursor to 0.2 to 1.0 M to control the size and the dispersed form of the silica particles.

The molar concentration of the basic catalyst is controlled to 13 to 60 mM to control the size and the dispersed form of the silica particles.

In the step (II), the hydrolysis reaction and condensation polymerization reaction time are controlled to 3 to 24 hours to control the size and dispersion form of the silica particles.

Wherein the basic catalyst is any one selected from the group consisting of triethylamine, ammonia water, and tetramethylammonium hydroxide.

Wherein the silica precursor is at least one selected from alkyl trimethoxysilane, silicon alkoxide, and mixtures thereof,

The alkyltrimethoxysilane may be selected from the group consisting of phenyltrimethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, aminopropyltrimethoxysilane, 3-glycidyloxypropyl tri Is selected from the group consisting of methoxysilane, chloropropyltrimethoxysilane, 2-phenylethyltrimethoxysilane, chloropropylmethoxysilane and 2-phenylethyltrimethoxysilane,

Wherein the silicon alkoxide is selected from the group consisting of tetraethylorthosilicate and tetramethylorthosilicate.

The present invention also provides a method for producing a silica particle, comprising the steps of: (I) preparing silica particles having a functional group according to the above production method; And (II) sintering the silica particles having the functional groups to prepare pure silica particles.

And drying the silica particles having the functional groups prepared in the step (I) at a temperature of 150 to 250 ° C for 1 to 2 hours.

The sintering of step (II) is performed at 200 to 600 ° C.

Further, the present invention provides silica particles having a functional group prepared by the above-mentioned method for producing silica particles having functional groups.

The size of the silica particles is 0.5 to 5.0 탆, and is characterized by being a polydisperse or monodisperse dispersed form.

In addition, the present invention provides pure silica particles which are produced through the above-mentioned process for producing pure silica particles.

According to this, in the process of producing silica particles using a small amount of catalyst and water as a solvent, it is possible to easily adjust the size of silica particles having functional groups to 0.5 to 5.0 μm without complicated equipment and process steps, It is possible to control easily, and uniform particles having a high yield can be obtained.

In addition, through the process of sintering the silica particles having at least one functional group obtained through the above-described method, pure silica particles having a particle size five times larger than that of the conventional silica particles can be obtained with high yield.

The silica particles or the pure silica particles having a functional group prepared according to such a production method have a structure suitable for a multifunctionality, have a size similar to that of a biomaterial, and have no toxicity, and thus can be applied to biomedical applications such as bio-labeling.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart illustrating the process for producing silica particles having at least one functional group according to the present invention. FIG.
2 is a flow chart showing a process for producing pure silica particles according to the present invention.
3 is a scanning electron microscope (SEM) photographing silica particles having phenyl groups prepared in Examples 1 to 9, in order to confirm the influence of the kind and concentration of the catalyst on the size and distribution pattern of the silica particles.
4 to 7 are graphs showing the effect of the reaction temperature, stirring speed, silica precursor concentration and reaction time on the size and distribution pattern of the silica particles, SEM).
8 to 10 are scanning electron microscopy (SEM) photographs of silica particles having vinyl groups prepared in Examples 28 to 38, in order to confirm the effect of reaction temperature, stirring speed and silica precursor concentration on the size and distribution form of silica particles SEM).
11 to 12 are scanning electron microscopy (SEM) photographs of silica particles having a mercer earthenware fabricated from Examples 39 to 46 in order to confirm the influence of the stirring speed and the silica precursor concentration on the size and distribution form of the silica particles. to be.
13 to 14 are scanning electron microscope (SEM) photographs of silica particles prepared in Examples 47 to 61, in order to confirm the effect of the stirring speed and the silica precursor concentration on the size and distribution form of the silica particles.
15 is an infrared spectrum graph of silica particles having two kinds of functional groups prepared from Example 28, Example 47, and Examples 59 to 61. Fig.
16 is a scanning electron microscope (SEM) photograph showing the size and distribution pattern of the silica particles prepared from Examples 62 to 67. Fig.
17 is an infrared spectrum graph of the silica particles prepared from Examples 62 to 67. Fig.

Hereinafter, the present invention will be described in more detail.

One aspect of the present invention provides a method for producing silica particles having at least one functional group comprising the steps of:

(I) adding a silica precursor and a basic catalyst to an aqueous solution to prepare a mixed solution, and

And (II) stirring the mixed solution to perform a hydrolysis reaction and a polycondensation reaction to produce silica particles having at least one functional group.

Here, by controlling the reaction temperature and the stirring speed in the step (II), the size and the dispersed form of the silica particles to be produced can be controlled.

The manufacturing method of the present invention will be described in more detail with reference to FIG.

First, in step I), a basic catalyst is added to a silica precursor having the same or different functional groups in an aqueous solution to prepare a mixed solution.

At this time, the basic catalyst may be any one selected from the group consisting of triethylamine, ammonia water, and tetramethylammonium hydroxide, and the dispersed form of the silica particles to be produced may vary depending on the type of the catalyst. That is, when triethylamine is used as a catalyst, silica particles having a monodispersed form are prepared, and when ammonia water is used as a catalyst, silica particles having a double dispersed form are prepared, and tetramethylammonium hydroxide is used as a catalyst When used, it can be confirmed that silica particles having a polydispersed form can be produced.

At this time, the molar concentration of the basic catalyst may be 13.0 to 56.0 mM. The pH of the mixed solution is preferably adjusted to be in the range of 10 to 13 through the addition of the basic catalyst.

In addition, the silica precursor used in the present invention may be an alkyltrimethoxysilane, a silicon alkoxide, or a mixture thereof. More specifically, the alkyltrimethoxysilane may be phenyltrimethoxysilane, vinyltrimethoxysilane, 3- Mercaptopropyltrimethoxysilane, methyltrimethoxysilane, aminopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, chloropropyltrimethoxysilane, 2-phenylethyltrimethoxysilane, chloro Propylmethoxysilane, 2-phenylethyltrimethoxysilane, and the silicon alkoxide may be any one selected from the group consisting of tetraethylorthosilicate and tetramethylorthosilicate, Or more. Depending on the structure of the silica particles to be produced, the mixing ratio of two or more kinds of silica precursors to be used can be appropriately selected.

The volume ratio of the silica precursor to be mixed in step I) is controlled to 5-15: 5-15 to control the size and dispersed form of the silica particles.

Next, in step II) of the present invention, the hydrolysis reaction and the condensation polymerization reaction of the mixed solution obtained in step I) are carried out to produce silica particles having at least one functional group. At this time, the size of the silica particles having at least one functional group generated by controlling the reaction temperature at 20 to 60 ° C can be controlled within the range of 0.5 to 5.0 μm.

The size of the silica particles having at least one functional group generated by controlling the agitation speed in the hydrolysis reaction and the condensation polymerization step at 30 to 100 rpm can be controlled within the range of 0.5 to 5.0 mu m

The size of the silica particles having at least one functional group generated by controlling the silica precursor concentration at 0.20 to 0.83 M in the step (II) hydrolysis and polycondensation may be controlled within the range of 0.5 to 5.0 mu m

Also, the size of the silica particles having at least one functional group generated by controlling the reaction time in the hydrolysis and polycondensation step of II) for 3 to 24 hours may be adjusted within the range of 0.5 to 5.0 μm.

In addition, step (III) may further comprise filtering, washing and drying the silica particles having the functional groups obtained in the step (II). At this time, the drying is preferably performed at a temperature of 30 to 250 ° C for 1 to 16 hours.

In another aspect of the present invention, there is provided a process for producing pure silica comprising the steps of:

The present invention also relates to a method for producing silica particles comprising the steps of: preparing silica particles having functional groups in accordance with the process for preparing silica particles having functional groups; and II) sintering the silica particles having functional groups to prepare pure silica particles. A process for producing silica particles is provided.

Wherein the silica particles having functional groups may have a single or multifunctional group depending on the silica precursor to be mixed.

Here, the step (I) includes the same manufacturing process as that of the silica particles having the functional group, so that the above description will be referred to. However, it is preferable to dry the silica particles having the functional groups prepared in the step (I) at a temperature of 150 to 250 ° C. for 1 to 2 hours. If the silica particles are out of the range, the silica particles are not formed properly in the following sintering step Cracking can occur.

Thereafter, the silica particles having the functional groups produced in the step (I) are sintered in the step (II) to prepare pure silica particles. At this time, the sintering temperature can be performed at 200 to 600 ° C for 1 to 3 hours, more preferably at 300 to 600 ° C for 1 to 3 hours. At this time, the size of the pure silica particles generated by controlling the sintering temperature and time can be controlled. When the silica particles having the functional groups are sintered as in the above production method, they can be produced to have a particle size up to 5 times larger than that of the conventional silica particles, and the functional groups can be removed and converted to SiO ₂ . However, in the case of silica particles having a phenyl group, when the sintering temperature exceeds 400 ° C, the particle size decreases and pure silica particles in which phenyl groups have been removed can be obtained. On the other hand, when the sintering temperature is lower than 400 ° C, it is important to select an appropriate sintering temperature since silica particles without phenyl groups can be obtained.

Another aspect of the present invention provides silica particles having at least one functional group prepared by the above process. Such silica particles having a functional group contain at least one functional group uniformly outside the particle and have a uniform size through hydrolysis and polycondensation reaction depending on the type of functional group, Sensors, drug delivery materials, and the like.

According to another aspect of the present invention, there is provided pure silica particles produced by the above-described production method.

Hereinafter, the present invention will be described in more detail based on the following examples.

Example  One.

After mixing 100 ml of ion-exchanged water into a 250 ml three-necked flask, 13.9 mM triethylamine was added to adjust the pH to 12, and the mixture was stirred for 10 minutes. Next, 20 ml of phenyltrimethoxysilane (0.1 mol) was added and mixed at a stirring rate of 75 rpm for 8 hours to conduct hydrolysis and condensation polymerization at 30 to 60 ° C. The turbidity changed drastically with the lapse of time, and silica particles having a phenyl group were prepared.

The silica particles having the phenyl group were filtered, washed with ion-exchanged water and dried in a vacuum oven at 50 DEG C for 8 hours to obtain silica particles having a controlled particle size.

Example  2 to 9

Silica particles having a controlled particle size were obtained by performing the same method as in Example 1 except that the kind and concentration of the catalyst used were changed as shown in Table 1 below.

Example  10 to 27.

The procedure of Example 1 was repeated except that the concentration of the silica precursor used, the reaction temperature, the stirring speed and the reaction time were changed as shown in Table 2, .

Example  28 to 38.

Except that vinyltrimethoxysilane was used instead of phenyltrimethoxysilane in the silica precursor in Example 1 and the concentration, reaction temperature and stirring rate of the silica precursor were changed as shown in Table 3 below. The procedure of Example 1 was followed to obtain silica particles having a particle size-regulated vinyl group.

Example  39 to 46.

The procedure of Example 1 was repeated except that 3-mercaptopropyltrimethoxysilane was used instead of phenyltrimethoxysilane and the silica precursor concentration, reaction temperature, and stirring rate were changed as shown in Table 4 , Silica particles having a controlled particle size were obtained.

Example  47 to 61.

In Example 1, two kinds of silica precursors were used instead of phenyltrimethoxysilane as a silica precursor, and the reaction temperature and the mixing ratio of the silica precursor were changed as shown in Table 5, 1, silica particles having two kinds of functional groups whose particle sizes were controlled were obtained.

Example  62 to 67.

The procedure of Example 1 was repeated except that the silica particles were dried at 200 ° C for 12 hours instead of drying at 50 ° C for 2 hours to obtain silica particles having a controlled particle size The temperature was raised to 300, 400, 500 and 600 ° C at a rate of 5 ° C / min in an atmospheric and nitrogen atmosphere, and then sintered for 2 hours to obtain silica particles.

3 is a scanning electron microscope (SEM) photographing silica particles having phenyl groups prepared in Examples 1 to 9, in order to confirm the effect of the type and concentration of the catalyst on the size and distribution pattern of the silica particles, The measured particle sizes and distribution patterns are shown in Table 1.

number Catalyst type Catalyst concentration
(mM) Particle size
(탆) Distribution type Example 1 Triethylamine 13.9 3.42 ± 0.07 Monostable Example 2 27.8 3.01 + 0.04 Monostable Example 3 55.5 2.02 ± 0.06 Monostable Example 4 ammonia 13.9 0.61 ± 0.06 ~
1.42 ± 0.03 Bimodal Example 5 27.8 0.62 ± 0.05 ~
1.66 + 0.03 Bimodal Example 6 55.5 0.58 ± 0.06 ~
1.37 + 0.03 Bimodal Example 7 Tetramethylammonium hydroxide 13.9 2.8 ± 0.80 Dispersed Example 8 27.8 2.70 ± 0.65 Dispersed Example 9 55.5 2.15 + - 0.41 Dispersed

Referring to FIG. 3 and Table 1, it can be seen that the silica particles having phenyl groups prepared in Examples 1 to 3 have a monodispersed distribution shape, and the particle size decreases with increasing catalyst concentration. The silica particles having phenyl groups prepared in Examples 4 to 6 had a bimodal distribution shape, and no change in particle size was observed depending on the concentration of the catalyst.

In addition, it can be seen that the silica particles having a phenyl group prepared in Examples 7 to 9 have a polydisperse distribution shape, and the particle size becomes smaller as the concentration of the catalyst increases.

As a result, it can be confirmed that it is most preferable to use triethylamine as a catalyst in order to produce silica particles having a phenyl group having a uniform particle size showing a monodisperse distribution pattern.

4 to 7 are graphs showing the effect of the reaction temperature, stirring speed, silica precursor concentration and reaction time on the size and distribution pattern of the silica particles, SEM), and the measured particle sizes and distribution types are shown in Table 2. [

Reaction temperature
(° C) Stirring speed
(rpm) Silica precursor concentration
(M) Reaction time
(hr) Particle size (탆) Distributed form Example 10 30 75 0.83 12 3.01 Monostable Example 11 40 75 0.83 12 2.52 Monostable Example 12 50 75 0.83 12 1.66 Dispersed Example 13 60 75 0.83 12 Gel type Example 14 30 30 0.83 12 1.72 Dispersed Example 15 30 50 0.83 12 2.66 Monostable Example 16 30 100 0.83 12 4.11 Monostable Example 17 30 75 0.20 12 1.51 Monostable Example 18 30 75 0.41 12 2.25 Monostable Example 19 30 75 0.63 12 2.68 Monostable Example 20 30 75 0.83 3 2.12 Dispersed Example 21 30 75 0.83 4 2.28 Dispersed Example 22 30 75 0.83 7 2.38 Dispersed Example 23 30 75 0.83 8 2.71 Dispersed Example 24 30 75 0.83 9 2.84 Monostable Example 25 30 75 0.83 10 2.93 Monostable Example 26 30 75 0.83 11 2.95 Monostable Example 27 30 75 0.83 24 3.04 Monostable

Referring to Figs. 4 to 7 and Table 2, the silica particles having a phenyl group prepared from Examples 10 to 11 each had a particle size of 3.01 and 2.52 占 퐉 and exhibited a monodispersed form, and the silica particles prepared from Examples 12 to 13 The silica particles having a phenyl group are 1.66 mu m in size and can be confirmed to have a polydisperse or gel form.

This is considered to be because the higher the reaction temperature, the faster the rate of hydrolysis and polycondensation reaction is, and thus the more nuclei are produced. The silica particles having the phenyl group prepared at the highest reaction temperature (Example 13) And gel-like particles are produced. Particularly, when it is produced at a reaction temperature of 50 ° C, it can be obtained in the form of a gel when the stirring speed is high or when the concentration of the catalyst is high.

This means that the reaction temperature can be controlled at 30 to 40 占 폚 so that the monodispersed silica particles having a phenyl group can be adjusted to have a particle size of 2.52 to 3.01 占 퐉.

The silica particles having a phenyl group prepared in Example 10 and Examples 15 to 16 had particle sizes of 3.01, 2.66 and 4.11 占 퐉 and monodispersed shapes, respectively, and had 1.72 占 퐉 particles having a phenyl group prepared from Example 14 Size and polydisperse shape.

This means that the stirring speed can be controlled at 50 to 100 rpm so that the monodisperse type silica particles having a phenyl group can be adjusted to have a particle size of 2.66 to 4.11 mu m. As described above, it can be confirmed that the production of silica particles in gel form can be inhibited by controlling the stirring speed under specific temperature conditions.

From this, it can be confirmed that it is preferable to control the silica particles having a phenyl group in monodisperse form to a stirring speed range of 50 to 100 rpm in order to control the particle size within the range of 2.66 to 4.11 mu m.

In addition, it can be seen that the silica particles having phenyl groups prepared from Example 10 and Examples 17 to 19 have larger particle sizes as the concentration of the silica precursor increases. By controlling the concentration of the silica precursor to 0.20 to 0.83 M, the monodispersed silica particles having a phenyl group can be controlled to have a particle size of 1.51 to 3.01 μm.

The silica particles having a phenyl group prepared in Examples 20 to 23 each had a polydisperse shape with a particle size of 2.12 to 2.71 탆, and the silica particles having a phenyl group prepared in Example 10 and Examples 24 to 27, respectively It can be confirmed that it has a monodispersed form having a particle size of 2.84 to 3.04 mu m. More specifically, a solute is precipitated on a nucleus formed in a silica precursor mixed solution, and nucleation occurs. At this time, the growth proceeds until the solute concentration reaches the saturation point. According to the speed equation that can be classified into the speed determination step and the speed adjustment step, the reaction speed is slow at a reaction temperature of 30 ° C or less, A time of 8 hours or more is required to confirm the growth. Therefore, when the reaction time is increased, silica particles having a large and uniform phenyl group can be obtained.

Thus, the reaction time can be controlled within the range of 3 to 8 hours to adjust the polydisperse type silica particles having a phenyl group to have a particle size of 2.12 to 2.71 mu m, and the reaction time can be controlled for 9 to 24 hours, The monodisperse type silica particles can be adjusted to have a particle size of 2.84 to 3.04 mu m.

FIGS. 7 to 9 are scanning electron microscopy (SEM) photographs of silica particles having vinyl groups prepared in Examples 28 to 38, in order to confirm the effect of reaction temperature, stirring speed and silica precursor concentration on the size and distribution form of silica particles SEM), and the particle sizes and distribution types measured thereby are shown in Table 3.

Reaction temperature
(° C) Stirring speed
(rpm) Silica precursor
density
(M) Particle size (탆) Distributed form Example 28 30 30 0.83 1.56 / 1.11 Monodispersed / Example 29 40 30 0.83 1.61 Monostable Example 30 50 30 0.83 1.44 Monostable Example 31 60 30 0.83 0.65 Monostable Example 32 30 50 0.83 1.36 Monostable Example 33 30 75 0.83 1.69 Monostable Example 34 30 100 0.83 2.04 Monostable Example 35 30 75 0.20 1.12 Monostable Example 36 30 75 0.41 1.99 Monostable Example 37 30 75 0.63 1.25 Monostable Example 38 30 75 0.83 2.06 Monostable

Referring to Figures 7 to 9 and Table 3, the vinyl group-containing silica particles prepared from Examples 28 to 31 were produced with particle sizes of 1.11 or 1.56, 1.61, 1.44 and 0.65 占 퐉, respectively, Which means that the size of the recorded particles decreases. That is, the higher the reaction temperature, the faster the rate of hydrolysis and polycondensation, and the more nuclei are formed.

The silica particles having vinyl groups prepared from Example 28 and Examples 32 to 34 were produced with particle sizes of 1.11 or 1.56, 1.36, 1.69 and 2.04 μm, respectively. When the reaction temperature was low, And it was confirmed that the formation of gel could be inhibited by the stirring speed although it did not greatly affect the particle size.

The vinyl group-containing silica particles prepared from Examples 35 to 38 were produced with particle sizes of 1.12, 1.99, 1.25 and 2.06 μm, respectively, and the particle size of the vinyl group-containing silica particles prepared from Example 36 was the largest. That is, the larger the amount of silica precursors participating in the growth process, the smaller the amount of silica precursors participating in nucleation, the larger the silica particle size.

When the reaction temperature is 30 ° C and the stirring speed is 75 rpm, the silica particles having a vinyl group having a vinyl group can be controlled to have a particle size of 1.12 to 2.06 μm by controlling the silica precursor concentration to 0.20 to 0.83 M have.

10 to 11 are scanning electron microscope (SEM) photographs of silica particles having a mercaptoester prepared from Examples 39 to 46 in order to confirm the influence of the stirring speed and the silica precursor concentration on the size and distribution form of the silica particles. , And the measured particle size and distribution pattern are shown in Table 4.

Reaction temperature
(° C) Stirring speed
(rpm) Silica precursor concentration
(M) Particle size
(탆) Distributed form Example 39 30 75 0.20 1.99 Dispersed Example 40 30 75 0.41 4.09 Dispersed Example 41 30 75 0.63 4.80 Dispersed Example 42 30 75 0.83 5.60 Dispersed Example 43 30 30 0.83 3.83 Dispersed Example 44 30 50 0.83 2.95 Dispersed Example 45 30 75 0.83 3.37 Dispersed Example 46 30 100 0.83 4.83 Dispersed

10 to 11 and Table 4, it can be seen that the silica particles having a mercapto group prepared from Examples 39 to 46 have a particle size about twice as large as those of silica particles having other functional groups. It is considered that the mercapto pottery has a larger hydrophilicity than the other functional groups, and the nucleation time is longer, thereby forming particles having a large and broad distribution pattern.

It can be seen that the silica particles having the mercapto-containing particles prepared from Examples 39 to 42 have an increased particle size as the stirring speed is increased, and the silica particles having the mercapto-containing particles prepared from Examples 43 to 46 have a silica precursor concentration It can be seen that the particle size increases according to the particle size.

13 to 14 are scanning electron microscope (SEM) photographs of the silica particles prepared in Examples 47 to 61 in order to confirm the influence of the stirring speed and the silica precursor concentration on the size and distribution form of the silica particles, The size and distribution of the measured particles are shown in Table 5.

Reaction temperature
(° C) Mixing ratio of silica precursor (V / V) Particle size (탆) Distributed form PTMS VTMS TEOS MPTMS Example
47 30 10 10 - - 2.16 Monostable Example
48 40 10 10 - - 2.26 Monostable Example 49 50 10 10 - - 1.77 Monostable Example 50 60 10 10 - - 0.85 Monostable Example 51 30 10 - 10 - 0.76 Monostable Example 52 40 10 - 10 - 0.86 Monostable Example 53 50 10 - 10 - 1.95 Monostable Example 54 60 10 - 10 - 1.69 Monostable Example 55 30 10 - - 10 2.46 Monostable Example 56 40 10 - - 10 2.58 Monostable Example 57 50 10 - - 10 1.65 Monostable Example 58 60 10 - - 10 1.3-1.95 Dispersed Example 59 30 20 - - - 3.98 Monostable Example 60 30 15 5 - - 1.60 Monostable Example 61 30 5 15 - - 1.65 Monostable PTMS: phenyltrimethoxysilane, VTMS: vinyltrimethoxysilane, TEOS: tetraethylorthosilicate, MPTMS: 3-mercaptopropyltrimethoxysilane

13 to 14 and Table 5, the silica particles having two kinds of functional groups prepared from Examples 47 to 58 have different particle sizes depending on the reaction temperature. This means that the particle size of the silica particles having one functional group is decreased because the hydrolysis and polycondensation reaction rate increases at the reaction temperature to form more nuclei. On the other hand, when the volume ratio of TEOS to PTMS is 1: 1, the results are in contradiction.

The silica particles having one or two functional groups prepared from Examples 28, 47, 59, 60 and 61 can be confirmed to have a reduced particle size as the volume ratio of vinyltrimethoxysilane is increased. Further, as a result of washing and sintering with acetone, it was confirmed that not only the particle size was reduced but also the organic solvent was not dissolved.

15 is an infrared spectrum graph of silica particles having one or two functional groups prepared from Examples 28, 47, 59, 60, and 61, in which an elastic stretching region of -OH was observed at 3420 cm ^-1 , The peak of -O was observed to be low by the condensation polymerization of the silica particles prepared on the basis of the toxic silane. -CH ₃ of vinyltrimethoxysilane was observed at 3060 cm ^-1 and 2950 cm ^-1 by the methyl group of the aliphatic compound. When the concentration of vinyltrimethoxysilane was high, 1410 cm ^-1 , which means C≡C bond, was observed. Typically, peaks at 3060 cm ^-1 , 1430 cm ^-1 and 1055 cm ^-1 refer to CH, C═C and Si-O-Si bonds of an aromatic compound, respectively.

16 is a scanning electron microscope (SEM) photograph showing the size and distribution pattern of the silica particles prepared from Examples 62 to 67. Fig. Referring to this, the embodiment 63 to the silica particles having a phenyl group prepared from 67 was reduced to a particle size dramatically depending on the sintering temperature, which hayeotgeona additional polycondensation reaction to take place, it could not be polymerized Si-OH or Si-O ^- Therefore, it is considered that the particle size is reduced.

17 is an infrared spectrum graph of the silica particles prepared from Examples 62 to 67. It can be confirmed that the silica particles prepared from Examples 66 and 67 were removed from phenyl groups and converted to SiO ₂ .

Claims (13)

(I) preparing a mixed solution by adding a silica precursor and a basic catalyst to an aqueous solution; And
(II) stirring the mixed solution to perform hydrolysis and polycondensation to prepare silica particles having at least one functional group,
And controlling the size and the dispersed form of the silica particles by controlling the reaction temperature to 20 to 60 ° C in the step (II). The method according to claim 1,
The method further comprises: (III) washing and drying the silica particles having the at least one functional group,
Wherein the drying is carried out at a temperature of 30 to 250 DEG C for 1 to 16 hours. The method according to claim 1,
And controlling the stirring speed at 30 to 100 rpm in the step (II) to adjust the size and the dispersed form of the silica particles. The method according to claim 1,
Wherein the molar concentration of the silica precursor is controlled to 0.2 to 1.0 M to control the size and dispersion form of the silica particles. The method according to claim 1,
Wherein the basic catalyst is controlled at a molar concentration of from 13 to 60 mM to control the size and the dispersed form of the silica particles. The method according to claim 1,
Wherein the size and the dispersed form of the silica particles produced by controlling the hydrolysis reaction and condensation polymerization reaction time in the step (II) are controlled. The method according to claim 1,
Wherein the basic catalyst is any one selected from the group consisting of triethylamine, ammonia water and tetramethylammonium hydroxide. The method according to claim 1,
Wherein the silica precursor is at least one selected from alkyl trimethoxysilane, silicon alkoxide, and mixtures thereof,
The alkyltrimethoxysilane may be selected from the group consisting of phenyltrimethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, aminopropyltrimethoxysilane, 3-glycidyloxypropyl tri Is selected from the group consisting of methoxysilane, chloropropyltrimethoxysilane, 2-phenylethyltrimethoxysilane, chloropropylmethoxysilane and 2-phenylethyltrimethoxysilane,
Wherein the silicon alkoxide is selected from the group consisting of tetraethylorthosilicate and tetramethylorthosilicate. ≪ RTI ID = 0.0 > 11. < / RTI > (I) preparing silica particles having functional groups according to the production method of the above-mentioned (1); And
(II) sintering the silica particles having the functional groups to prepare pure silica particles. 10. The method of claim 9,
Wherein the silica particles having the functional groups prepared in the step (I) are dried at a temperature of 150 to 250 DEG C for 1 to 2 hours. 10. The method of claim 9,
Wherein the sintering in step (II) is performed at 200 to 600 ° C. 8. A silica particle having a functional group prepared by a production method according to any one of claims 1 to 8,
Wherein the silica particles have a size of 0.5 to 5.0 mu m and are in a polydisperse or monodisperse dispersed form. A pure silica particle produced by the process according to claim 9 or 11.

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