KR100828720B1 - Method for producing mesoporous organosilica material using PEO-PLLA-PEO block copolymer and mesoporous organosilica material produced thereby - Google Patents

Abstract

The present invention relates to a method for producing a mesoporous organo-silica material using the PEO-PLGA-PEO block copolymer represented by the formula (1) as a structural derivative, and to the mesoporous organo-silica material, which is prepared by the method. It is about:

<Formula 1>

Wherein x, y and z are each the number of units of the polymer block.

According to the present invention, it is possible to provide a mesoporous organo-silica material having a surface area of 500 to 2,000 m ² / g and pores having a size of 5 to 10 nm arranged in a regular hexagon. In addition, according to the present invention, the mesoporous organo-silica material may be prepared into a powder and a film depending on the intended use.

Mesoporous, PEO-PLGA-PEO block copolymer, organo-silica

Description

Method for preparing mesoporous organosilica material using PEO-PLLA-PEO block copolymer and method for preparing mesoporous organosilica material produced by PEO-PLGA-PEO block copolymer and mesoporous organosilica material using the method }

Figure 1 shows the incineration X-ray scattering spectrum of the mesoporous phenylene-silica material prepared in one embodiment of the present invention.

Figure 2 shows the nitrogen adsorption-desorption isotherm of the mesoporous phenylene-silica material prepared in one embodiment of the present invention.

FIG. 3 shows a pore size distribution curve obtained from the adsorption isotherm of nitrogen shown in FIG. 2 using the Barrett-Joyner-Halenda (BJH) method.

Figure 4 shows the solid-state silicon nuclear magnetic resonance spectroscopy spectrum of the mesoporous phenylene-silica material prepared in one embodiment of the present invention.

The present invention relates to a method for producing a mesoporous organosilica material, and more particularly, the present invention relates to a novel method for producing a mesoporous organo-silica material having a high surface area and a predetermined size of pores in an orderly arrangement. A mesoporous organo-silica material produced by the present invention.

Since the release of M41S by Mobil in 1992, numerous studies have been carried out, including mesoporous pore structure analysis, the discovery of new pore structures, the expansion of pores, the introduction of new functional groups on silica walls and the introduction of metal oxides. Efforts are being made to complement the functions of surface reactivity with other materials, optical properties, mechanical properties, smooth insertion and selective separation of other materials, especially by thickening or imparting a uniform wall of silica. have.

The development of such a mesoporous molecular sieve material extends the pore size range by 2 to 50 nm, compared to existing materials having micropores such as zeolites. It opened up the possibility of solving the problems such as the reaction, adsorption, separation and cultivation of the limited nanometer molecules, biological substances such as proteins and cells, or the manufacture of metal oxides with large surface area.

The introduction of functional groups other than silica has been suggested to chemically reattach functional groups after preparation of mesoporous silica materials or to co-condensation of functional group precursors with silica precursors. There are limitations in introducing a non-uniform distribution in the interior or incorporating sufficient content for effective physical properties. In addition, when a functional group is newly provided, the hydration and polymerization rate of the functional group precursor different from the existing silica material, and compatibility in the reaction vessel with the silica material become new problems of polymerization.

Since 1999, regularly ordered mesoporous organosilica materials have been published, which use organic or organosiloxane precursors in which organic materials are bridged between silica and silica and are either existing or complemented cations. It has been shown that mesoporous organic silica materials of effectively ordered structure can be prepared using surfactants or block copolymers (T. Asefa, MJ MacLachlan, N. Coombs, GA Ozin, Nature, Vol. 402, p. 867, 1999).

As described above, the production and application of mesoporous materials are increasing. The development of new structural derivatives in the design of new mesoporous materials is the best way to pioneer applications through the manufacture of materials with new structures and functional groups. It is considered an important part. Pluronic PEO-PPO-PEO triblock copolymers sold by BASF, Germany, have been used since 1998 to increase the pore size and increase the silica wall thickness. It is a commercially available polymer resin that is sold on a large scale and has been easily studied in combination with basic silica precursors such as tetraethyl orthosilicate (TEOS), and SBA-15 and SBA-16 are well known and representative. Silica materials with hexagonal and cubic structure (US Pat. No. 6,027,706; US Pat. No. 6,054,111; D. Zhao, J. Feng, Q. Huo, N. Melosh, GH Fredrickson, BF Chmelka, GD Stucky, Science, Vol. 279, p. 548, 1998).

Organics such as TEOS are beginning to be used to prepare structural derivatives or hybrids with organic silica, which are suitable for enhancing pore size and material stability over the use of low molecular weight surfactants, compared to using low molecular weight surfactants. It has been reported that the reaction with organic silica material is not easy or in a more limited range compared to the case where no silica precursor is used.

A process in which phenylene is chemically bonded to silica to form a mesoporous material was first introduced using octadecyltrimethyl-ammonium chloride (ODDTMA) surfactants containing cationic amines (S. Inagaki, S. Guan). , T. Ohsuna, T. Terasaki, Nature, Vol. 416, p. 304, 2002). The preparation of mesoporous phenylene-silica materials not only expands the selectivity as a catalyst use, but also adds sulfuric acid groups to the walls, and thus it is considered that the application of the battery to the electrolyte or acid catalyst is possible. However, to date, no method has been introduced to increase the pore and silica wall thickness, and to produce a stable and membrane.

Accordingly, the present inventors have repeatedly studied to solve the problems of the prior art, using a PEO-PLGA-PEO triblock copolymer as a pore-forming derivative, and by adjusting its molecular weight and block fraction, constant surface area and orderly arrangement The present invention has been completed by confirming that hexagonal mesoporous organo-silica materials having pores of size can be prepared.

Accordingly, an object of the present invention is to distribute the organic material such as phenylene uniformly on the silica wall by chemical bonding, and can be prepared in the form of powder and a thin film of a few millimeters thick depending on the intended use, high surface area and orderly arrangement It is to provide a method for producing a mesoporous organo-silica material having pores of a certain size.

Another object of the present invention is to provide a mesoporous organo-silica material produced by the above method.

In order to achieve the object of the present invention, the present invention provides a method for producing a mesoporous organo-silica material using the PEO-PLGA-PEO block copolymer represented by the formula (1) as a structural derivative:

<Formula 1>

Wherein x, y and z are each the number of units of the polymer block.

In order to achieve another object of the present invention, the present invention provides a mesoporous organo-silica material produced by the above method.

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

One aspect of the invention is directed to a method of making a mesoporous organo-silica material. Method for producing a mesoporous organo-silica material according to an aspect of the present invention is characterized by using the PEO-PLGA-PEO block copolymer represented by the formula (1) as a structural derivative:

<Formula 1>

Wherein x, y and z are each the number of units of the polymer block.

The PLGA chain of the PEO-PLGA-PEO block copolymer used in the present invention is a biologically stable material with FDA approval, and when the block copolymer with the PEO block forms a special sol-gel phase transition depending on the temperature in the aqueous solution It is a substance that has been studied a lot as a biological drug release or drug carrier due to the behavior (US Patent No. 6,201,072, Republic of Korea Publication No. 2001-0030891).

However, no attempt has been made to produce mesoporous organosilica materials using the PEO-PLGA-PEO block copolymer. The present invention provides a method for preparing a mesoporous organosilica material using a PEO-PLGA-PEO block copolymer in which a PLGA block having an increased hydrophobicity than the hydrophobicity of the PPO block in a conventional PEO-PPO-PEO block copolymer is introduced. Use as structural derivatives can lead to more efficient reactions of organic silica precursors only on PEO blocks.

The preparation method of the present invention is mesoporous organo-silica, such as ethane-silica, thiophene-silica and phenylene-silica by the sol-gel synthesis method using the PEO-PLGA-PEO triblock copolymer represented by the formula (1) Material may be provided.

In the present invention, the number of units x of the block copolymer block is 16, y is an integer of 3 to 7, z is an integer of 25 to 35, the number average molecular weight of the block copolymer is 3,500 to 7,000 Daltons It is preferable.

The method for producing mesoporous organo-silica according to the present invention may specifically include the following steps:

a) preparing an aqueous solution by mixing PEO-PLGA-PEO block copolymer represented by Chemical Formula 1 with distilled water, alcohol and acid;

b) reacting the organic-silica precursor mixed with the aqueous solution;

c) hydrothermally reacting the material obtained in step b); And

d) filtering and washing the material obtained in step c) to remove the block copolymer and to dry the final material.

In step a), the PEO-PLGA-PEO triblock copolymer may be prepared by synthesis. For example, the synthesis of the PEO-PLGA-PEO triblock copolymer is prepared by dissolving D, L-lactide and glycolide precursors in an ethyl acetate solution, filtration and purification through recrystallization. After synthesis of PLGA blocks to a certain length through ring opening polymerization, a double-block copolymer was synthesized by hydrogen ion bonding with mPEG having a methoxy (CH ₃ O-) group attached to one end of PEG. The coalescing may be performed by linking hexamethylene diisocianate with each other via a medium.

When the number of units x of the block copolymer block is 16, y is an integer of 3 to 7, z is an integer of 25 to 35, and the number average molecular weight of the block copolymer is 3,500 to 7,000 Daltons, Formula 1 In addition to the PEO-PLGA-PEO block copolymers represented, PLGA-PEO biblock copolymers having a physical form different from that of Chemical Formula 1 and triblock copolymers of PLGA-PEO-PLGA type may also be used as structural derivatives.

The aqueous solution prepared in step a) may include 2 to 2.5 wt% of PEO-PLGA-PEO block copolymer, 0.3 to 7.4 wt% of acid, 0 to 6.7 wt% of alcohol, and the remaining water.

The organo-silica precursor may be one or more materials selected from the group consisting of materials represented by Formula 2 and materials represented by Formula 3:

<Formula 2>

R ¹ _i R ² _j MO _{4 -ij}

<Formula 3>

R ¹ _k R ² _l O _{3 -k- l} MSMO _{3 -k- l} R ¹ _k R ² _l

In which R ¹ And Each R ² is independently an alkyl group having 1 to 10 carbon atoms; O is an alkoxy group having 1 to 5 carbon atoms; M is Si or Ti atom; S is an alkylene group having 1 to 15 carbon atoms, or a thiophene group having 5 to 40 carbon atoms, an alkylthiophene group, a phenylene group, an alkylphenylene group, an arylphenylene group, an arylene group, an alkylarylene group or an arylalkylene group; i and j are each independently integers of 0 to 3 satisfying 0 ≦ i + j ≦ 3, and k and l are each independently integers of 0 to 2 satisfying 0 ≦ k + l ≦ 2.

Examples of the organic silica precursors are methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, Trimethylethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, bis (trichlorosilyl) methane, 1,2-bis (Trichlorosilyl) ethane (1,2-bis (trichlorosilyl) ethane), bis (trimethoxysilyl) methane (bis (trimethoxysilyl) methane), 1,2-bis (triethoxysilyl) ethane (1,2 -bis (triethoxysilyl) ethane), 1,4-bis (trimethoxysilyl) benzene (1,4-bis (trimethoxysilyl) benzene), 1,4-bis (trimethoxysilylethyl) benzene (1,4- bis (trimethoxysilylethyl) benzene), 1,4-bis (triethoxysilyl) benzene (1,4-b is (triethoxysilyl) benzene), 1,4-bis (triethoxysilylethyl) benzene (1,4-bis (triethoxysilylethyl) benzene), 2,5-bis (trimethoxysilyl) thiophene (2,5- bis (trimethoxysilyl) thiophene), 2,5-bis (triethoxysilyl) thiophene, 4,4-bis (trimethoxysilyl) biphenyl (2,5- bis (trimethoxysilyl) biphenyl), 4,4-bis (triethoxysilyl) biphenyl (2,5-bis (triethoxysilyl) biphenyl) and the like.

The organo-silica precursor may be mixed in the range of 15 to 100 moles based on 1 mole of PEO-PLGA-PEO block copolymer.

The reaction of step b) may be carried out by vigorously stirring for 0.5-2 hours at a temperature of 30 ~ 50 ℃.

The hydrothermal reaction of step c) may be performed by standing for 20 to 24 hours at a temperature of 80 ~ 100 ℃.

In step c), the membrane can be obtained as the final material by allowing evaporation of the reaction vessel and adjusting the evaporation rate.

The filtration of step d) is performed by a filtration device, and the washing is performed by sequentially flowing 100 to 500 mL of ethanol, distilled water and acetone into the filtration device for 20 to 30 minutes, or 250 to 300 mL of ethanol per 1 g of precipitate. And 36% hydrochloric acid aqueous solution of 5-15 g may be carried out by stirring for 7-10 hours.

Another aspect of the invention relates to a mesoporous organo-silica material characterized by being produced by the process according to the invention.

The organo-silica material may be an ethane-silica material, a thiophene-silica material or a phenylene-silica material.

In addition, the organo-silica material may be an organo-silica powder or an organo-silica membrane.

In addition, the organic-silica material may have a surface area of 500 ~ 2,000 m ² / g and the pores of 5 ~ 10 nm size are arranged in a regular hexagon.

Hereinafter, the present invention will be described in more detail with reference to Examples. Since these examples are only for illustrating the present invention, the scope of the present invention is not to be construed as being limited by these examples.

<Example 1>

PEO - PLGA - PEO Of triblock copolymer  synthesis

500 mL of ethyl acetate purified with calcium hydride (CaH ₂ ) was heated to 70 ° C. in a 1,000 mL Erlenmeyer flask, and 100 g of D, L-lactide was added to dissolve completely with stirring. The lactide solution was filtered under argon gas using a 500 mL suction flask, and the filtered solution and precipitates were dissolved again by raising the temperature and completely recrystallized into a styrofoam box and a refrigerator. 50 g of glycolide was also recrystallized at 300C using 300 mL of ethyl acetate. 40.5 g of polyethylene glycol having a molecular weight of 750 methoxy group at one end was dissolved in a 1,000 mL three-necked round bottom flask containing 700 mL toluene and distilled at 120 ° C. 54. 6 g and 4.9 g of purified lactide and glycolide, respectively, were prepared and placed in a 1000 mL round bottom flask containing polyethylene glycol at a temperature of 60 ° C. at room temperature and completely dissolved. After adding 0.6 g of Stannos octoate, the reaction was performed by stirring a magnetic bar in an argon gas atmosphere at a temperature of 120 ° C. for 24 hours. The reaction temperature was lowered to 40 ° C and 4.37 mL hexamethylene diisocianate was added and reacted in an argon atmosphere for 24 hours.

 The material obtained in the reactor was dissolved in 200 mL of dichloromethane and placed in a 5,000 mL flask containing 3,000 to 4,500 mL of diethylene ether, and allowed to stand for 2 days to precipitate. The precipitated solution was placed in a 250 mL polyethylene container to remove almost water vapor with a dryer and then kept in vacuum for about 10 days to completely remove the residue in the precipitate. In order to synthesize block copolymers having different block fractions, polymerization was performed by changing the contents of lactide, glycolide, and ethylene glycol participating in the reaction to obtain a final material in the same experimental procedure. When preparing the diblock copolymer, the hexamethylene diisocyanate reaction step of the above embodiment may be excluded.

As a result of peak quantitative analysis of the hydrogen atom nuclear magnetic resonance spectroscopy spectrum of the polymer obtained in the above example, the number of blocks of lactic acid and glycolic acid in the chain was 30 and 4, respectively. The number of units of ethylene oxide blocks located on both sides of the triblock copolymer was 16. The molar ratio of lactic acid in the PLGA block was 0.89 and the weight ratio of the polyethylene block was 37% of the total block weight. The number average molecular weight and the degree of polymerization dispersion (PDI) of the polyethylene wax identified by gel permeation chromatography were 5,200 Daltons and 1.26, respectively.

<Example 2>

Mesoporous  Preparation of Silica Materials

0.5 g of the EO ₁₆ (L ₃₀ G ₄ ) EO ₁₆ triblock copolymer prepared in Example 1 was mixed with 16.55 g of distilled water, 1.5 g of ethanol and 4.45 g of 37% by weight of hydrochloric acid, and 0.98 to 1.30 g of TEOS was added and stirred for 30 minutes at a reaction temperature of 30 ° C. The white precipitate was reacted in a 95 ° C. water bath for 24 hours, and then the precipitate was filtered through a suction flask with ethanol, distilled water and acetone to remove the block copolymer. As a result of incineration X-ray scattering experiment, the d-spacing was 91.0∼93.8 Å and the two-dimensional hexagonal cylinder structure with peaks of (100), (110), and (200) existed at the positions of the crystal lattice, respectively. The BET surface area, Barett-Joyner-Halenda (BJH) pore volume and pore size obtained from the adsorption isotherm obtained by nitrogen adsorption-desorption isotherm were 970-990 m ² / g, 1.60-1.80 cm ³ / g, 8.4-9 nm, respectively. Value was shown.

<Example 3>

Mesoporous  Preparation of Ethane-Silica Materials

0.5 g of EO ₁₆ (L ₃₀ G ₄ ) EO ₁₆ or EO ₁₆ (L ₂₉ G ₇ ) EO ₁₆ triblock copolymer prepared in Example 1 was 18.78 to 19.78 g of distilled water, 0.5 to 1.5 g of ethanol, Mixed with 2.22 g of 37% by weight hydrochloric acid and reacted at 45-50 ° C. by adding 0.80-1.11 g of 1,2-bis (triethoxysilyl) ethane (BTESE) Magnetic stirring for 30 minutes at temperature. After reacting the white precipitate in a 95 ℃ water bath for 24 hours, the precipitate was filtered through a suction flask with ethanol, distilled water, acetone to remove the block copolymer. As a result of incineration X-ray scattering experiment, the d-spacing was 96.7 ~ 106.3 Å and the two-dimensional hexagonal cylinder structure in which the peaks of (100), (110), and (200) existed at the position of the crystal lattice, respectively. The BET surface area, Barett-Joyner-Halenda (BJH) pore volume and pore size obtained from the adsorption isotherm obtained by nitrogen adsorption-desorption isotherm were 1,496-1,797 m ² / g, 2.34-2.77 cm ³ / g, and 7.6-8.5 nm, respectively. Value was shown. The high surface area of the ethane silica material indicates the selective efficiency of the PEO-PLGA-PEO block copolymers used in the present invention.

<Example 4>

Mesoporous  Preparation of Thiophene-Silica Materials

0.5 g of EO ₁₆ (L ₃₀ G ₄ ) EO ₁₆ or EO ₁₆ (L ₂₉ G ₇ ) EO ₁₆ triblock copolymer prepared in Example 1 was 20.69 to 22.28 g of distilled water, 0 to 0.7 g of ethanol, Mixed with 0.22 to 1.11 g of 37% by weight hydrochloric acid, and 0.73 to 0.76 g of 2,5-bis (triethoxysilyl) thiophene (BTEST) was added at 40 캜. Magnetic stirring was performed for 60 minutes at the reaction temperature. The white precipitate was reacted in a 95 ° C. water bath for 24 hours, and then stirred for about 8 hours using about 250 mL of ethanol and 9 g of 36% hydrochloric acid solution per g of precipitate to remove the block copolymer as a structural derivative. The evaporation rate was controlled by allowing solution evaporation during the reaction at 95 ° C., resulting in a membrane of 1 to 3 mm. The results of incineration X-ray scattering showed that the d-spacing was 81.7-84.8 Å and the two-dimensional hexagonal cylinder structure where the peaks of (100), (110), and (200) existed at the positions of the crystal lattice, respectively. The BET surface area, Barett-Joyner-Halenda (BJH) pore volume and pore size obtained from the adsorption isotherm obtained by nitrogen adsorption-desorption isotherm were 492 ~ 760 m ² / g, 0.65 ~ 0.80 cm ³ / g, and 5.7 ~ 6.5 nm, respectively. Value was shown.

<Example 5>

Mesoporous Phenylene Preparation of Silica Materials

0.5 g of EO ₁₆ (L ₃₀ G ₄ ) EO ₁₆ or EO ₁₆ (L ₂₉ G ₇ ) EO ₁₆ triblock copolymer prepared in Example 1 was 20.69 to 21.98 g of distilled water, 0.3 to 0.7 g of ethanol, Mix with 0.22 to 1.11 g of 37% by weight hydrochloric acid, and add 0.72 to 0.83 g of 2,5-bis (triethoxysilyl) benzene (BTESB) to react at 40 ° C. Magnetic stirring was carried out at a temperature of 60-80 minutes. The white precipitate was reacted in a 95 ° C. water bath for 24 hours, and then stirred for about 8 hours using about 250 mL of ethanol and 9 g of 36% hydrochloric acid solution per g of precipitate to remove the block copolymer as a structural derivative. The evaporation rate was controlled by allowing solution evaporation during the reaction at 95 ° C., resulting in a membrane of 1 to 3 mm.

Figure 1 shows the incineration X-ray scattering spectrum of the mesoporous phenylene-silica material prepared in this example. As shown in Fig. 1, the results of incineration X-ray scattering experiments show that the d-spacing is 84.8 to 90.0 Hz, and the two-dimensional hexagonal shape in which the peaks of (100), (110), and (200) exist at the positions of the crystal lattice, respectively. The cylinder structure is shown.

Figure 2 shows the nitrogen adsorption-desorption isotherm of the mesoporous phenylene-silica material prepared in this embodiment, Figure 3 is a Barret-Joyner-Halenda (BJH) method from the adsorption isotherm of the nitrogen It shows the pore size distribution curve obtained by using (pore size distribution curve). As shown in Figs. 2 and 3, the BET surface area, the Barett-Joyner-Halenda (BJH) pore volume, and the pore size obtained from the adsorption isotherm by nitrogen adsorption-desorption isotherms are respectively 646 to 996 m ² / g, 0.76 to 1.02 cm ³ / g, the value was 6.4 ~ 7.0 nm.

Figure 4 shows the solid-state silicon nuclear magnetic resonance spectroscopy spectrum of the mesoporous phenylene-silica material prepared in one embodiment of the present invention. As shown in FIG. 4, the Q peak did not appear and the form of T-bonded silica was confirmed.

As can be seen from the results of the above embodiment, the present invention is a PLGA block reinforced with hydrophobicity compared to the method for producing a mesoporous organo-silica material using a conventionally used PEO-PPO-PEO block copolymer By using the prepared block copolymer, it is possible to introduce various organic materials of mesoporous organo-silica material having a surface area of 500 to 2,000 m ² / g and large pores of 5 to 10 nm in a regular hexagonal arrangement. Depending on the intended use, it may be prepared from powders and membranes.

While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and variations fall within the scope of the appended claims. It is also natural.

As described above, according to the present invention, it is possible to provide a mesoporous organo-silica material having a surface area of 500 to 2,000 m ² / g and 5 to 10 nm pores arranged in a regular hexagon. In addition, according to the present invention, the mesoporous organo-silica material may be prepared into a powder and a film depending on the intended use.

Claims (13)

Method for preparing a mesoporous organo-silica material using the PEO-PLGA-PEO block copolymer represented by Formula 1 as a structural derivative: <Formula 1>

In the above formula, x, y and z are each the number of units of the polymer block, The number of units of blocks of the block copolymer x is 16, y is an integer of 3 to 7, z is an integer of 25 to 35, and the number average molecular weight of the block copolymer is 3,500 to 7,000 Daltons. delete The method of claim 1, a) preparing an aqueous solution by mixing PEO-PLGA-PEO block copolymer represented by Chemical Formula 1 with distilled water, alcohol and acid; b) reacting the organic-silica precursor mixed with the aqueous solution; c) hydrothermally reacting the material obtained in step b); And d) filtering and washing the material obtained in step c) to remove the block copolymer and to dry the final material; Including; Wherein the organo-silica precursor is at least one material selected from the group consisting of materials represented by Formula 2 and materials represented by Formula 3: <Formula 2> R ¹ _i R ² _j MO _4-ij <Formula 3> R ¹ _k R ² _l O _3-kl MSMO _3-kl R ¹ _k R ² _l In which R ¹ And Each R ² is independently an alkyl group having 1 to 10 carbon atoms; O is an alkoxy group having 1 to 5 carbon atoms; M is Si or Ti atom; S is an alkylene group having 1 to 15 carbon atoms, or a thiophene group having 5 to 40 carbon atoms, an alkylthiophene group, a phenylene group, an alkylphenylene group, an arylphenylene group, an arylene group, an alkylarylene group or an arylalkylene group; i and j are each independently integers of 0 to 3 satisfying 0 ≦ i + j ≦ 3, and k and l are each independently integers of 0 to 2 satisfying 0 ≦ k + l ≦ 2. The method of claim 3, wherein The unit number of blocks of the block copolymer x is 16, y is an integer of 3 to 7, z is an integer of 25 to 35, the number average molecular weight is a triblock copolymer and the molecular weight and block specified as 3,500 ~ 7,000 Daltons When the relative ratio falls within the above range, in addition to the PEO-PLGA-PEO block copolymer represented by the formula (1), a PLGA-PEO diblock copolymer or a triblock copolymer of the PLGA-PEO-PLGA type different in physical form from the formula (1) Method usable as structural derivatives. The method of claim 3, wherein The aqueous solution prepared in step a) is characterized in that it comprises 2 to 2.5% by weight of PEO-PLGA-PEO block copolymer, 0.3 to 7.4% by weight acid and 0 to 6.7% by weight alcohol. delete The method of claim 3, wherein The organo-silica precursor is mixed in the range of 15 to 100 moles based on 1 mole of PEO-PLGA-PEO block copolymer. The method of claim 3, wherein The reaction of step b) is carried out by vigorously stirring for 0.5 to 2 hours at a temperature of 30 ~ 50 ℃. The method of claim 3, wherein The hydrothermal reaction of step c) is carried out by standing for 20 to 24 hours at a temperature of 80 ~ 100 ℃. The method of claim 9, Allowing the evaporation of the reaction vessel and controlling the rate of evaporation to obtain a membrane as final material. The method of claim 3, wherein The filtration of step d) is carried out by a filtration device including a suction flask, and the washing is performed by sequentially passing 100 to 500 mL of ethanol, distilled water and acetone into the filtration device for 20 to 30 minutes or 250 to 1 g of precipitate. Using 300 mL of ethanol and 5-15 g of 36% aqueous hydrochloric acid solution by stirring for 7-10 hours. The method of claim 1, Wherein said organo-silica material is an organo-silica powder or an organo-silica membrane. delete

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