KR101425373B1 - Asymmetric composite membrane of silicone polymer and preparing method of the same - Google Patents

Abstract

The present invention relates to a method for preparing a polymer solution, comprising: applying a solution of a polymer comprising a silicone polymer and a pore-forming agent on a support; And forming an asymmetric composite membrane by impregnating the support with a non-solvent to cause phase transformation, thereby providing a method for producing a silicon polymer asymmetric composite membrane and a silicon polymer asymmetric composite membrane. Since the process for producing a silicon polymer asymmetric composite membrane of the present invention proceeds by a simple phase transfer method, it is excellent in production efficiency, and has excellent properties of an inorganic film by using a silicone polymer and is excellent in heat resistance and strength, Field.

Description

Technical Field [0001] The present invention relates to a polymeric asymmetric composite membrane and a method for manufacturing the same.

The present invention relates to a silicon polymer asymmetric composite membrane and a method of manufacturing the same, and more particularly, to a silicon polymer asymmetric composite membrane comprising a silicon polymer, particularly a ladder polysilsesquioxane, using a phase transfer method, .

The water industry is developing as a new growth engine as the explosion of population and the rapid pollution caused by industrialization have become serious and the importance of water has been recognized. Such market trends require high quality water supply, efficient treatment of industrial wastewater, and desalination of seawater. Among them, researches are actively conducted to improve the water treatment process using the most efficient membrane for energy saving.

The characteristics required for the separation membrane used in the water treatment process include high water permeation characteristics, high exclusion characteristics for specific materials, mechanical strength and chemical resistance. Particularly, inorganic separators are excellent in terms of mechanical strength and chemical resistance, but most of them are polysulfone-based, cellulose-based, polyamide-based and fluorinated polyaliphatic polymer membranes which are inexpensive.

  Such a polymer membrane is susceptible to physical properties such as chemical resistance, heat resistance and stain resistance, microorganisms and the like. Above all, since the hydrolysis is rapidly performed by a basic chemical used for regenerating the membrane, there is a problem in life. Therefore, in order to solve the above-mentioned problems, development of an excellent separation membrane material such as an inorganic membrane has been demanded.

In general, inorganic membranes are prepared by sintering alumina powder, which is used as a support having micropores of fine filtration level and coating the support with a sol to reduce pores. The separator thus prepared can be usefully used under conditions of a high temperature or an organic solvent which can not be treated as a general polymer separator. These inorganic membranes are characterized by high manufacturing cost, low production rate, and very thick inorganic membrane support. The thickness of the inorganic film is a crucial factor that determines the characteristics of the separator. An inorganic film support has been produced by an extruder method using a water-soluble polymer. However, since the inorganic film prepared by the extruder method using the water- It is difficult to reduce the entire cross-sectional area of the support, so that there is a great difficulty in improving the performance of the support.

In order to reduce the cross-sectional area of the membrane, a phase-inversion method can be used. By using this method, it is possible to form a desired pore, to easily control the length and size of the pore, And it is possible to manufacture a separator easily and inexpensively. However, inorganic films prepared by the phase transformation method have not been reported to date.

Patent Application No. 10-2003-0094657 discloses a method for producing a porous ceramic hollow fiber inorganic membrane support using a phase transfer method. Specifically, it is a method of producing a porous hollow inorganic membrane support which is made by carbonizing a polymer at 600 ° C using aluminum powder and polysulfone (PSf) and sintering at 1300 ° C to maintain the strength. However, this prior invention discloses a method for producing a support using an inorganic membrane, and a separation membrane having excellent water permeability characteristics of the inorganic membrane itself has not been studied so far.

Patent Application No. 10-2003-0094657

In order to solve the above-mentioned problems, the present invention provides a method for producing an asymmetric silicon polymer composite membrane formed by a phase transfer method using a silicon polymer, and has an inorganic film characteristic, excellent heat resistance and strength, The present invention also provides an asymmetric silicon polymer composite membrane which can be used for a semiconductor device.

According to an aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: applying a polymer solution including a silicon polymer and a pore-forming agent on a support; And

And impregnating the support with a non-solvent to form an asymmetric composite film by phase transitions, thereby providing a method of manufacturing a composite asymmetric silicon polymer membrane.

In one embodiment of the present invention, the method may further comprise removing the pore-forming agent from the asymmetric composite membrane.

In one embodiment of the present invention, the silicon polymer may be ladder polysilsesquioxane.

In one embodiment of the present invention, the ladder-type polysilsesquioxane may be represented by the following general formula (1).

[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently selected from the group consisting of an aryl group, an alkyl group, an allyl group, a vinyl group, an epoxy group, an amine group, a halogen, an alkylhalogen, a methacrylic group, an azide group, Is a single functional group selected from the group consisting of < RTI ID = 0.0 >

m and n are each independently an integer selected from 1 to 40,000)

In one embodiment of the present invention, the ladder-type polysilsesquioxane may have a molecular weight of 10,000 to 800,000.

In one embodiment of the present invention, the ladder-type polysilsesquioxane may be an aryl group, an alkyl group, an allyl group, a vinyl group, an epoxy group, an amine group, a halogen, an alkylhalogen, a methacrylic group, A silyl group, and an acryl group.

In one embodiment of the present invention, the ladder-type polysilsesquioxane may have at least one terminal group of a phenyl group and a methyl methacrylate group.

In one embodiment of the present invention, when the terminal groups of the ladder-type polysilsesquioxane are different, the molar ratio of the functional groups may be 6: 4 to 4: 6.

In one embodiment of the present invention, the solvent of the silicone polymer solution is selected from the group consisting of N, N -dimethylformamide (DMF), dimethylacetamide (DMAc), N-methyl- (DMSO). ≪ / RTI >

In one embodiment of the present invention, the pore former is selected from the group consisting of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyethylene glycol (PEO), polyvinyl alcohol (PVA) ), Sodium chloride (NaCl), magnesium chloride (MgCl ₂ ), potassium chloride (KCl), calcium chloride (CaCl ₂ ) and zinc chloride (ZnCl ₂ ).

In one embodiment of the present invention, the silicone polymer may be contained in the polymer solution in an amount of 1 to 45% by weight based on the solvent.

In one embodiment of the present invention, the pore-forming agent may be contained in an amount of 1 to 30% by weight based on the silicon polymer.

In one embodiment of the present invention, the support may be at least one selected from the group consisting of plastic, glass, and polymer scaffolds.

In one embodiment of the present invention, the non-solvent may be at least one selected from the group consisting of water alone, alcohol alone, aqueous alcohol solution and aqueous solution containing an organic solvent.

In an embodiment of the present invention, the non-solvent temperature may be 20 to 80 ° C.

In one embodiment of the present invention, the asymmetric composite membrane may be one having a sponge or a surface having a uniform finger shape.

The present invention also provides a polymeric asymmetric composite membrane having uniform sponges or fingers formed by phase transition of a polymer solution containing a silicone polymer and a pore-forming agent and a non-solvent.

Since the process for producing a silicon polymer asymmetric composite membrane of the present invention proceeds by a simple phase transfer method, it is excellent in production efficiency, and has excellent properties of an inorganic film by using a silicone polymer and is excellent in heat resistance and strength, Field.

FIG. 1 is a cross-sectional SEM photograph of a silicon polymer asymmetric composite membrane according to a comparative example of a silicon polymer according to the present invention.
2 and 3 are cross-sectional SEM images of a silicon polymer asymmetric composite membrane according to an embodiment of the present invention, according to the content of pore-forming agent.
4 is a SEM photograph of a silicon polymer asymmetric composite film applied on a PET support according to an embodiment of the present invention.
FIG. 5 is a result of thermogravimetric analysis of ladder-type polysilsesquioxane used in a silicon polymer asymmetric composite membrane according to an embodiment of the present invention.
FIG. 6 shows the results of tensile strength and tensile strain of a silicon polymer asymmetric composite membrane according to an embodiment of the present invention.
7 and 8 are graphs showing the water permeability of a silicon polymer asymmetric composite membrane according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail in order to facilitate the present invention by those skilled in the art.

The present invention relates to a method for preparing a polymer solution, comprising: applying a solution of a polymer comprising a silicone polymer and a pore-forming agent on a support; And forming an asymmetric composite film by impregnating the support with the non-solvent to effect phase transformation, thereby providing a method for manufacturing a composite asymmetric silicon polymer membrane.

The method may further include removing the pore-forming agent from the asymmetric composite membrane.

Hereinafter, a method of manufacturing the asymmetric composite membrane of the present invention will be described in more detail.

First, a step of applying a polymer solution containing a silicone polymer and a pore-forming agent on a support is performed.

In the present invention, the silicone polymer is not particularly limited as long as it is a polymer containing silicon, but may preferably be ladder polysilsesquioxane. Compared with conventional polysilsesquioxane, the ladder-type polysilsesquioxane has a low -OH content and does not undergo condensation, so that not only the dimensional stability due to heat is high but also the thermal stability is very high. In addition, since the solubility in an organic solvent is very high, there is an advantage that a free-standing film can be produced using various solvents.

In the present invention, the ladder-type polysilsesquioxane may have a molecular weight of 10,000 to 800,000. Preferably 100,000 to 400,000. When the molecular weight is less than 10,000, uniform pores can not be formed. When the molecular weight is more than 800,000, the viscosity of the solution is too high, which makes it difficult to cast the film.

Wherein the ladder-type polysilsesquioxane is selected from the group consisting of an aryl group, an alkyl group, an allyl group, a vinyl group, an epoxy group, an amine group, a halogen, an alkylhalogen, a methacrylic group, an azide group, a sulfone group, Lt; RTI ID = 0.0 > termini. ≪ / RTI > That is, the terminal groups may be the same or different.

Preferably, the ladder-type polysilsesquioxane may have at least one terminal group of a phenyl group and a methyl methacrylate group.

In the present invention, the "aryl group" is also represented by -Ar, obtained by subtracting one hydrogen atom from a vacancy-derived hydrocarbon, and includes a phenyl group, an anthryl group, a phenanthryl group and the like.

In the present invention, the 'alkyl group' is a branched or branched alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a t- And a cycloalkyl group having 3 to 10 carbon atoms such as a pentyl group and a cyclohexyl group.

In the present invention, the 'allyl group' is a functional group represented by H ₂ C═CH-CH ₂ - and includes allyl alcohol, allyl ether, and the like.

In the present invention, the 'vinyl group' is a functional group represented by CH ₂ = CH- and includes vinyl chloride, vinyl acetate, acrylic acid, styrene and the like.

In the present invention, an 'acryl group' is an ester containing a vinyl group, that is, a functional group in which two carbon atoms are double bonds and a carbonyl group is directly bonded to one of the carbon atoms (alpha carbon) -COOR) -. ≪ / RTI >

When the terminal groups of the ladder-type polysilsesquioxane are different, the molar ratio of the respective functional groups may be 6: 4 to 4: 6. When one type of functional group is contained in a larger amount than the above range, specifically, when the number of phenyl groups is large, the film is brittle, and if the methyl methacrylic group is large, the polymer may be in a liquid phase, making it difficult to produce an asymmetric composite film.

In the present invention, the ladder-type polysilsesquioxane may be represented by the following general formula (1).

[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently selected from the group consisting of an aryl group, an alkyl group, an allyl group, a vinyl group, an epoxy group, an amine group, a halogen, an alkylhalogen, a methacrylic group, an azide group, Is a single functional group selected from the group consisting of < RTI ID = 0.0 >

m and n are each independently an integer selected from 1 to 40,000)

In the above formula, R ₁ and R ₂ may be the same or different. The ratio of m and n may be from 10: 0 to 0:10, but is preferably from 6: 4 to 4: 6.

The production method of the ladder-type polysilsesquioxane represented by the above-mentioned formula (1) is not particularly limited, but the synthesis method disclosed in "Polymer Chemistry, Synthesis and Characterization of UV-Curable Ladder-Like Polysilsesquioxane, Seung-Sock Choi" It may be manufactured.

Specifically, for example, the ladder-type polysilsesquioxane in which R ₁ and R ₂ are each a phenyl group and a methyl methacrylate group may be represented by the following formula (2).

(2)

In the present invention, the solvent used in the polymer solution is not limited as long as it is a solvent in which the silicone polymer is dissolved, but preferably N, N -dimethylformamide (DMF), dimethylacetamide (DMAc) May be at least one selected from the group consisting of 2-pyrrolidone (NMP) and dimethylsulfoxide (DMSO), more preferably dimethylacetamide (DMAc). Dimethylacetamide (DMAc) has the property of improving the phase transition rate.

In the preparation of the polymer solution, the polymer solution preferably contains 1 to 50% by weight, more preferably 30 to 50% by weight, of the silicone polymer based on the total weight of the polymer solution. When the content of the silicone polymer is less than 1% by weight, the viscosity of the separator is too low to manufacture the separator. When the content of the silicone polymer is more than 50% by weight, the content of the solid content is too large.

In the present invention, the pore-forming agent is not limited to any one as long as it can be dissolved in the solvent, that is, the solvent in which the silicone polymer is dissolved, but it should not be mixed with the silicone polymer. Preferably a polymer including polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyethylene glycol (PEO), polyvinyl alcohol (PVA), lithium chloride (LiCl), sodium chloride (NaCl) magnesium (MgCl _2), potassium chloride (KCl), calcium chloride (CaCl _2), and zinc chloride, and a number greater than that (ZnCl ₂₎ selected from the group consisting of inorganic salts, including, more preferably, polyvinyl pyrrolidone (PVP ). In the present invention, in addition to the pore forming function, the pore forming agent also acts to reduce the solids content of the silicone polymer solution and increase the viscosity.

It is preferable that the pore-forming agent has a large molecular weight. Specifically, the molecular weight of polyvinyl pyrrolidone (PVP) is preferably 300 or more, more preferably 360 or more.

It is impossible to obtain an asymmetric separator having a sponge structure or finger-shaped uniform pores without using a pore-forming agent. In addition, uniform pores enable superior water permeability and rejection characteristics when applied to membranes.

delete

In addition, the content of the solvent used in the polymer solution is preferably 50 to 70% by weight, more preferably 50 to 60% by weight based on the total solution.

The polymer solution thus prepared is applied on various supports and cast. In the present invention, the support may be any one or more selected from the group consisting of plastic, glass, and polymer scaffolds, though not limited thereto. More preferably a PET support, and the PET support has the property that it can analyze the membrane properties immediately after production. The coating method is not particularly limited as long as it is generally used.

Next, a step of forming an asymmetric composite film by impregnating the support on which the polymer solution is applied with impregnation and phase transitions is performed.

In the present invention, the non-solvent may be any solvent in which the silicone polymer is not dissolved, but is preferably at least one selected from the group consisting of water alone, alcohol alone, aqueous alcohol solution and aqueous solution containing an organic solvent, . The organic solvent in an aqueous solution containing an organic solvent is not particularly limited as an organic solvent generally used.

At this time, the temperature of the non-solvent is preferably 20 to 80 캜, more preferably 20 to 40 캜. If the temperature of the non-solvent is lower than 20 캜, the phase transition between the solvent and the non-solvent is not easy, and if the temperature is higher than 80 캜, the phase transition is too fast to form the separator properly.

When the supporter coated with the polymer solution is impregnated with the non-solvent, a phase-inversion phenomenon occurs. Specifically, as the solvent and the non-volatile phase transition occur, the solvent and the pore-forming agent rapidly transfer to the non-solvent. At this time, uniform pores are formed. In addition, one surface of the sponge or finger shape is uniformly formed by the pore-forming agent.

Finally, the step of removing the pore-former from the asymmetric composite membrane can be further roughened.

For example, the pore-forming agent can be removed by sufficiently impregnating the asymmetric composite membrane with distilled water. The water can be dried at room temperature and completely dried in a vacuum oven at 50 ° C to be used as a separator. Through this process, the asymmetric composite membrane is solidified.

The asymmetric composite membrane produced by the manufacturing method according to the present invention shows a weight reduction of less than 2% at 400 ° C or less. This can be confirmed in Test Example 2 to be described later. Specifically, it exhibits a weight reduction of less than 2%, i.e. 0.001 to 1.99%.

Also, the asymmetric composite membrane produced by the method of the present invention may have a tensile strength of 7 MPa or more and a tensile strain of 30% or more. This can be confirmed in Test Example 3 to be described later. Specifically, the tensile strength may be 7 to 10 MPa, and the tensile strain may be 30 to 50%.

The present invention also provides a polymeric asymmetric composite membrane having uniform sponges or fingers formed by phase transition of a polymer solution containing a silicone polymer and a pore-forming agent and a non-solvent. Since the silicon polymer asymmetric composite membrane according to the production method of the present invention proceeds by a simple phase transfer method, it is excellent in production efficiency, and is excellent in heat resistance and strength due to the characteristics of an inorganic film using a silicone polymer, And can be applied to various fields.

The present invention will be described in more detail through the following examples. However, the examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

[Comparative Example 1] Fabrication of asymmetric composite membrane using ladder-type polysilsesquioxane

8 g of ladder-type polysilsesquioxane was dissolved in 12 g of dimethylacetamide (DMAc) to prepare a 40% by weight polymer solution. Before the asymmetric separation membrane was prepared, ultrasonic treatment was performed to remove bubbles in the polymer solution to remove air bubbles.

After the glass plate was hydrophilized by UVO treatment, each prepared polymer solution was poured on a glass plate. The polymer solution was cast on a glass plate using a duct knife having a thickness of 200 μm, and then the glass plate was impregnated with water at 25 ° C. to prepare a phase-separated membrane. After 30 minutes, it was separated from the glass plate, immersed in clean distilled water to solidify it, and dried at room temperature to prepare a ladder-type polysilsesquioxane asymmetric composite membrane.

[Comparative Examples 2 and 3] Production of asymmetric composite membrane according to content of ladder-type polysilsesquioxane

A ladder-type polysilsesquioxane asymmetric composite membrane was prepared in the same manner as in Comparative Example 1 except that 10 g and 12 g of ladder-type polysilsesquioxane were dissolved. Each was made of a polymer solution of 50% by weight and 60% by weight, which were designated Comparative Examples 2 and 3.

 [Example 1] Production of asymmetric composite membrane using ladder-type polysilsesquioxane and pore-forming agent

6.4 g of ladder-type polysilsesquioxane and 1.6 g of polyvinylpyrrolidone (PVP, 360 kDa) as a pore-forming agent were dissolved in 12 g of dimethylacetamide (DMAc) to prepare a 40% by weight polymer solution.

The glass plate was hydrophilized by UVO treatment and the prepared polymer solution was poured on a glass plate. The polymer solution was cast on a glass plate using a duct knife having a thickness of 200 μm, and then the glass plate was impregnated with water at 25 ° C. to prepare a phase-separated membrane. After 30 minutes, it was separated from the glass plate, immersed in clean distilled water to solidify it, and dried at room temperature to prepare a ladder-type polysilsesquioxane asymmetric composite membrane.

[Comparative Examples 4 and 5] Production of asymmetric composite membranes according to the molecular weight of polyvinylpyrrolidone

A ladder-type polysilsesquioxane asymmetric composite membrane was prepared in the same manner as in Example 1, except that the types of polyvinylpyrrolidone used as the pore-forming agent were 40 kDa and 10 kDa. 40 kDa and 10 kDa were respectively designated as Comparative Examples 2 and 3.

[Comparative Example 6]

A ladder-type polysilsesquioxane asymmetric composite membrane was prepared in the same manner as in Example 1 except that the content of polyvinylpyrrolidone (PVP, 360 kDa) used as a pore-forming agent was changed to 0.8 g.

[Example 2]

A ladder-type polysilsesquioxane asymmetric composite membrane was prepared in the same manner as in Example 1, except that a PET support was used instead of a glass plate as a support in the production of the ladder-type polysilsesquioxane asymmetric composite membrane.

[Test Example 1] Measurement by Scanning Electron Microscopy (SEM)

A scanning electron microscope was used to measure the cross-sectional photographs of the asymmetric composite membrane according to Example 1 and Comparative Examples 1-4. The results are shown in Table 1 ((a), (b), (c) and (c) 1) and FIG. 4, respectively.

The SEM cross-sectional photographs shown in FIG. 1 were obtained by observing the phase transition depending on the concentration by setting the content of ladder-type polysilsesquioxane to 40, 50, and 60 wt%, respectively. As can be seen from FIG. 1, although the phase transition phenomenon occurs, it can be seen that the pore size and structure are generally uneven.

2 is a cross-sectional photograph of an asymmetric separator prepared by mixing 20 wt% of polyvinylpyrrolidone (PVP, 10 kDa) as a pore-forming agent. The molecular weight of the polyvinylpyrrolidone is low and thus no normal phase transition phenomenon is observed. However, as compared with FIG. 1, it can be seen that more uniform pores are formed.

3 is a cross-sectional photograph of an asymmetric separator prepared using polyvinylpyrrolidone of 40 kDa (Comparative Example 2) having a larger molecular weight and 360 kDa (Example 1). As can be seen from Fig. 3, when polyvinylpyrrolidone of 360 kDa (Example 1) was used, the upper layer (surface) became a dense selective layer and the lower layer became a porous support.

FIG. 4 is a cross-sectional photograph showing the production of an asymmetric separation membrane containing 10% by weight and 20% by weight of polyvinylpyrrolidone having a molecular weight of 360 kDa. As can be seen from FIG. 4, the structure of the finger was 10% by weight and the structure of the sponge was 20% by weight. It is considered that the different structures are affected by the content of polyvinylpyrrolidone.

[Test Example 2] Thermogravimetric analysis (TGA) measurement

In order to examine the heat resistance characteristics of Example 1, weight change with temperature was measured with a thermogravimetric analyzer, and the results are shown in FIG. As can be seen in Fig. 5, the asymmetric composite membrane showed a weight reduction of less than 2% up to 400 DEG C, indicating that it was very stable.

[Test Example 3] Universal testing machine (UTM) measurement

In order to measure the mechanical strength of the asymmetric composite membrane according to Example 1, tensile strength and tensile strain were measured, and the results are shown in FIG. As can be seen from FIG. 6, the asymmetric composite membrane has a tensile strength of 7 MPa or more and a tensile strain of 30% or more, which is excellent in mechanical strength.

[Test Example 4] Measurement of water permeability

In order to measure the water permeability of the asymmetric composite membrane according to Examples 1 and 2, a flat membrane evaluation cell capable of measuring by applying a horizontal pressure was used. The area of the composite membrane used as the sample was 18.24 cm ² and the applied pressure was 1 bar and all measurements were made at 25 ° C. The water permeation characteristics are generally expressed in units of LMH (L / m ² h), which means a large area and a permeability (L) obtained per hour.

The measurement results are shown in Figs. 7 and 8, respectively.

As can be seen from FIG. 7, it was found that the higher the content of the ladder polysilsesquioxane was, the lower the water permeability was, and the water permeability was increased according to the water permeation pressure irrespective of the content. As can be seen from the cross-sectional structure shown in FIG. 1, it seems that the asymmetric separator was not formed and exhibited a very low water permeation characteristic of less than 15 LMH / bar.

8 is a graph showing the results of measurement of water permeation by preparing an asymmetric separator on a PET support according to the second embodiment. As can be seen from FIG. 8, as the content of polyvinylpyrrolidone increases, the water permeability also increases, which indicates that the water permeation property of the sponge structure is better than that of the finger-shaped structure. An asymmetric separator having an ultrafiltration membrane having a water permeability of 400 to 700 LMH / bar was prepared.

Claims (19)

Applying a polymeric solution comprising a silicone polymer and a pore-forming agent on a support; And
And forming an asymmetric composite film by impregnating the support with a non-solvent to induce phase transformation, thereby forming an asymmetric composite film. The method according to claim 1,
Wherein the method further comprises removing the pore-former from the asymmetric composite membrane. The method according to claim 1,
Wherein the silicon polymer is a ladder-type polysilsesquioxane. The method of claim 3,
Wherein the ladder-type polysilsesquioxane is represented by the following general formula (1).
[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently selected from the group consisting of an aryl group, an alkyl group, an allyl group, a vinyl group, an epoxy group, an amine group, a halogen, an alkylhalogen, a methacrylic group, an azide group, Is a single functional group selected from the group consisting of < RTI ID = 0.0 >
m and n are each independently an integer selected from 1 to 40,000) delete The method of claim 3,
Wherein the ladder-type polysilsesquioxane is selected from the group consisting of an aryl group, an alkyl group, an allyl group, a vinyl group, an epoxy group, an amine group, a halogen, an alkylhalogen, a methacrylic group, an azide group, a sulfone group, Lt; RTI ID = 0.0 > 1, < / RTI > The method of claim 3,
Wherein the ladder-type polysilsesquioxane has at least one terminal group of a phenyl group and a methyl methacrylate group. delete The method according to claim 1,
Wherein the solvent of the silicone polymer solution is selected from the group consisting of N, N -dimethylformamide (DMF), dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP) and dimethylsulfoxide Gt; The method according to claim 1,
The pore former may be selected from the group consisting of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyethylene glycol (PEO), polyvinyl alcohol (PVA), lithium chloride (LiCl), sodium chloride (MgCl ₂ ), potassium chloride (KCl), calcium chloride (CaCl ₂ ) and zinc chloride (ZnCl ₂ ). The method according to claim 1,
Wherein the silicon polymer is contained in the polymer solution in an amount of 1 to 45% by weight based on the total weight of the polymer solution. delete The method according to claim 1,
Wherein the support is at least one selected from the group consisting of plastic, glass and polymeric support. The method according to claim 1,
Wherein the non-solvent is at least one selected from the group consisting of water alone, alcohol alone, aqueous alcohol solution and aqueous solution containing an organic solvent. The method according to claim 1,
Wherein the non-solvent temperature is 20 to 80 占 폚. The method according to claim 1,
Wherein the asymmetric composite membrane has a sponge or a surface having a uniform finger shape. 17. The method of claim 16,
Wherein the asymmetric composite membrane has a weight loss of less than 2% at < RTI ID = 0.0 > 400 C < / RTI > 17. The method of claim 16,
Wherein the asymmetric composite membrane has a tensile strength of 7 MPa or more and a tensile strain of 30% or more. A process for the preparation of a compound according to any one of claims 1 to 4, 6, 7, 9 to 11 and 13 to 18,
A polymeric asymmetric composite membrane having uniform sponges or fingers formed by phase transition of a polymeric solution comprising a silicone polymer and a pore-forming agent.

Images