KR20130060737A - Porous separation membrane and preparation method thereof - Google Patents

Abstract

PURPOSE: A porous membrane and a manufacturing method thereof are provided to make a porous membrane with uniform pore distribution since a pore volume formed in a support is reduced by impregnating the support in an impregnation solution before coating the support with a polymer solution. CONSTITUTION: A manufacturing method of a porous membrane comprises the following steps: a polymer solution is prepared by dissolving a polymer resin in a solvent, and mixing with an additive; a porous support is impregnated into an impregnation solution; a polymer resin layer is formed by coating the polymer solution on the porous support which is impregnated in the impregnation solution; and the polymer resin layer is precipitated in a non-solvent. [Reference numerals] (AA) Polymer resin layer; (BB) Porous support

Description

Porous Separation Membrane and Preparation Method etc

The present invention relates to a porous membrane used for ultrafiltration or precision filtration and a method for manufacturing the same.

In the fields of medicine, semiconductors, batteries, biotechnology, dairy products, beverages and foods, and water treatment, polymer membranes are used to separate liquids or gases. The micropores of such polymer membranes are very important economically and technically in the material separation process.

Generally, polymer membranes are prepared by a phase-transfer process regardless of their structure and mass transfer properties. As a method of preparing a polymer membrane, a polymer solution is prepared by dissolving the polymer in a solvent, and then casting the polymer solution and exposing it to steam so that steam is absorbed on the surface of the membrane (vapor induction phase separation). Casting a solution and precipitating it in a non-solvent coagulation bath (Non-Solvent Induced Phase Separation) and lowering the solubility of the polymer by lowering the temperature of the heated polymer casting film.

Regarding the manufacturing method of such a polymer membrane, US 5,886,059 and US 6,056,903 have been proposed. Specifically, US 5,886,059 relates to a method for producing an asymmetric polyethersulfone polymer membrane, (1) mixing a polyether sulfone polymer and a solvent to prepare a polymer solution, and (2) adding a non-solvent to the polymer solution. Preparing a dispersion by uniformly mixing the mixture, (3) exposing the dispersion to a gaseous environment, and (4) precipitating the dispersion through the step of quenching liquid. It consists of the steps of preparing and separating the sulfone polymer membrane. However, US Pat. No. 5,886,059 is difficult to handle due to the low viscosity of the polymer solution and has a limitation in providing a polymer membrane having a uniform pore distribution.

On the other hand, US 6,056,903 relates to a method for producing a polyether sulfone membrane, (1) preparing a casting solution containing a polyether sulfone polymer, a solvent and a lower aliphatic glycol, (2) casting the support Coating with a solution, (3) exposing the coated support in an atmospheric condition, and (4) precipitating the coated support in a precipitation bath containing lower aliphatic glycol and water to produce a polyethersulfone membrane. And (5) washing and drying the polyether sulfone membrane. However, US Pat. No. 6,056,903 has a limitation in producing a polymer membrane having a uniform pore distribution on the surface of the support because the casting solution exits through pores formed in the support when the casting solution is coated on the support.

An object of the present invention is to provide a method for producing a porous separator that can have a uniform pore distribution and a constant thickness in order to solve the above problems and a porous separator prepared by the above method.

In order to achieve the above object, the present invention comprises the steps of: a) preparing a polymer solution by dissolving a polymer resin in a solvent and mixing an additive; b) impregnating the porous support into the impregnation solution; c) forming a polymer resin layer by applying the polymer solution on the porous support impregnated with the impregnation solution; d) provides a method for producing a porous membrane comprising the step of precipitating the polymer resin layer in a non-solvent.

Here, step b) may further include removing the impregnation solution present on the surface of the porous support.

In addition, the method may further include exposing the polymer resin layer formed in step c) to steam before precipitation in the non-solvent.

In addition, the impregnation solution is polyethylene glycol (polyethylen glycol), glycerol (glycerol), 1,3-butanediol (1,3-butanediol), 1,4-butanediol (1,4-butanediol), 1,5-pentanediol (1,5-pentanediol), methyl pyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide and sulfolane Can be selected.

The present invention also provides a porous separator prepared by the above method.

Since the present invention reduces the pore volume formed in the support by impregnating the support in the impregnation solution before applying the polymer solution to the support, it is possible to minimize the escape of the polymer solution through the pores formed in the support, thereby uniform pore distribution. It can be prepared having a porous separator.

In addition, due to the affinity of the impregnating solution in which the polymer solution and the support are impregnated, the pore formation of the surface may be increased and the thickness of the porous separator may be adjusted, thereby providing a porous separator having a constant thickness.

1a to 1d are photographs of the porous separator according to Example 1 of the present invention observed with an electron microscope.
2a and 2b are photographs of the porous separator according to Example 2 of the present invention observed with an electron microscope.
3A and 3B are photographs of the porous separator according to Example 3 of the present invention under an electron microscope.
4A and 4B are photographs of the porous separator according to Example 4 of the present invention under an electron microscope.
Figure 5 is a photograph of the porous separator according to Example 5 of the present invention with an electron microscope.
Figure 6 is a photograph of the porous separator according to Example 6 of the present invention with an electron microscope.
7A and 7B are photographs of the porous separator according to Example 7 of the present invention under an electron microscope.
8a and 8b are photographs of the porous separator according to Example 8 of the present invention observed with an electron microscope.
9A and 9B are photographs of the porous separator according to Example 9 of the present invention under an electron microscope.
10a and 10b are photographs of the porous separator according to Example 10 of the present invention under an electron microscope.
11A and 11B are photographs of the porous separator according to Example 11 of the present invention under an electron microscope.
12a to 12d are photographs of the porous separator according to Comparative Example 1 of the present invention observed with an electron microscope.
13a and 13b are photographs of the porous separator according to Comparative Example 2 of the present invention observed with an electron microscope.
14a and 14b are photographs of the porous separator according to Comparative Example 3 of the present invention observed with an electron microscope.
15a and 15b are photographs of the porous separator according to Comparative Example 4 of the present invention observed with an electron microscope.

Hereinafter, the present invention will be described in detail.

In the method for preparing a porous membrane according to the present invention, in applying the polymer solution on the porous support, the uniform pore distribution and uniform thickness on the porous support are minimized by minimizing the passage of the polymer solution between the pores formed in the porous support. It is a characteristic to form the polymeric resin layer which has a. Such a method for producing a porous separator according to the present invention is as follows.

a) polymer solution preparation

The polymer resin is prepared by dissolving the polymer resin in a solvent and mixing the additives. At this time, the polymer resin that can be used is not particularly limited, but polyethersulfone, polysulfone, polyetherketone, polyetheretherketone, sulfonated polystyrene, sulfo Sulfonated Polysulfone, Sulfonated Polyethersulfone, Sulfonated Polyimide, Sulfonated Polyetherketone, Polyvinylidenefluoride, It is preferably selected from the group consisting of polytetrafluoroethylene, polyvinylchloride and polyvinylidenechloride.

The solvent that can be used to dissolve the polymer resin is not particularly limited as long as it can dissolve the polymer resin, but non-limiting examples include methyl pyrrolidone, dimethylacetamide, and dimethylformamide. , Dimethylsulfoxide and sulfolane may be used.

The additive mixed in the polymer solution is to form pores in the polymer resin layer formed by drying the polymer solution. Specifically, as the mixed additive is removed, pores are formed on the surface and the inside of the polymer resin layer. At this time, the additive used serves to form pores or remain in the polymer resin layer to hydrophilize the polymer resin layer. Such additives are not particularly limited as long as they do not react with the polymer resin and are well mixed with a solvent for dissolving the polymer resin, but are not limited to polyethylene glycol, methyl cellosolve, glycerol, and the like. Glycols, polyvinylpyrrolidone, acetone, propionic acid, acetic acid, silica (SiO ₂ ), titanium dioxide, pyridine and It is preferable that at least one selected from the group consisting of polyvinylpyridine.

Meanwhile, the polymer resin, the solvent, and the additive mixed in the polymer solution are 1-50% by weight of the polymer resin and 1-80% of the solvent, based on 100% by weight of the polymer solution, in consideration of the physical properties and pore distribution of the polymer resin layer to be formed. It is preferable to mix with% and 0.01-90 weight% of additives. In addition, the polymer solution may be further mixed with additives known in the art within a range that does not affect the physical properties of the polymer resin layer.

b) porous support Impregnation

The porous support is impregnated into the impregnation solution to reduce the pore volume of the porous support. Here, the porous support is a non-woven fabric, and the usable material is not particularly limited, but polypropylene, polyester, polyethylene terephthalate, polyvinylacetate, ethylenevinylacetate, polyamide, polysulfone, polyester sulfone, and the like Can be mentioned.

The impregnation solution used to impregnate the porous support is not particularly limited, but has affinity with the polymer solution, and may be polyethylene glycol, glycerol, 1,3-butanediol (1). , 3-butanediol), 1,4-butanediol, 1,5-pentanediol, 1,5-pentanediol, methyl pyrrolidone, dimethylacetamide, dimethyl It is preferable that at least one selected from the group consisting of formamide, dimethylsulfoxide, and sulfolane. Among these, it is more preferable to use a mixed solution of glycerol and methylpyrrolidone, a mixed solution of glycerol and dimethylacetamide, and a mixed solution of polyethylene glycol and methylpyrrolidone.

Conventionally, as the porous support is used without any pretreatment process, it is difficult to manufacture a polymer resin layer having a uniform pore distribution and a constant thickness due to a high rate of the polymer solution exiting through the pores of the porous support. However, the present invention reduces the pore volume of the porous support to minimize the rate at which the polymer solution escapes through the pores of the support (when the impregnation solution is 100% impregnated into the pores of the porous support, the polymer solution may be completely blocked from escaping). ) A polymer resin layer having a uniform pore distribution and a constant thickness can be formed.

In addition, the adhesion between the polymer resin layer and the porous support may be determined by the viscosity of the impregnation solution and / or the affinity between the polymer solution and the impregnation solution (which exhibits affinity when the solvent dissolving the polymer resin has a polarity similar or equivalent to that of the impregnation solution). It can be increased (a part of the polymer resin is impregnated in the porous support), it is possible to control the thickness of the polymer resin layer and to form pores having a uniform distribution on the surface and inside of the polymer resin layer.

Here, the impregnation solution may exist on the surface of the porous support by impregnating the porous support with the impregnation solution, and it is preferable to add a process of removing the impregnation solution. This is because the polymer resin layer formed as the impregnation solution existing on the surface of the porous support is removed or the porous support and the polymer resin layer can be prevented from being easily peeled off. In this case, the method of removing the impregnation solution existing on the surface of the porous support is not particularly limited, but a method of scraping off with a casting knife may be applied. In addition, the time and temperature which impregnate a porous support in an impregnation solution are not specifically limited, According to manufacturing process conditions, it can change suitably and apply.

On the other hand, the process of preparing the polymer solution (a) step and the step of impregnating the porous support (b) step is not a constraint of time and time relationship, may be made at the same time.

c) polymer resin layer formation

When the porous support impregnated with the polymer solution and the impregnation solution is prepared, the polymer solution is coated on the porous support to form a polymer resin layer in which no pores are formed. In this case, a line spray casting knife coating apparatus may be used so that the polymer solution may be applied to the porous support with a uniform thickness.

d) non-solvent precipitation (nonsolvent - induced phase separation , NIPS )

Through the above process, the porous support on which the polymer resin layer is formed is precipitated in the non-solvent. This is for forming pores in the polymer resin layer (mainly inside the polymer resin layer). When the polymer resin layer precipitates in the non-solvent, the precipitant present in the polymer resin layer reacts with the non-solvent to form pores. Here, the non-solvent may be defined as not dissolving the polymer resin, and the usable material is not particularly limited as long as it does not dissolve the polymer resin, but an organic solvent, water, or glycols may be used. Among these, it is preferable that a nonsolvent is water. On the other hand, the temperature of the non-solvent in which the polymer resin layer is precipitated is 0 to 90 ° C, preferably 4 to 70 ° C, and the time for precipitation is 1 to 24 hours.

Meanwhile, the present invention may further include exposing the polymer resin layer to vapor (vapor-induced phase separation, VIPS) after forming the polymer resin layer on the porous support and before depositing the non-solvent. This is to form pores on the surface of the polymer resin layer. When the polymer resin layer is exposed to steam, the precipitant and vapor react with each other to form surface pores. Here, the vapor is defined as a gas generated while the solvent (liquid) is evaporated, and the material usable as a solvent for generating steam is not particularly limited, but an organic solvent, water, or glycols may be used. Among these, the solvent for generating steam is preferably water. As the polymer resin layer is exposed to steam and then precipitated in the non-solvent, uniform pores can be formed on the surface of the polymer resin layer, and the non-solvent can easily penetrate into the polymer resin layer through the formed pores. The pore formation rate inside a resin layer can also be raised.

On the other hand, the polymer resin layer is preferably exposed to steam at 10 to 100% relative humidity, 0 to 300 ℃ and 0.1 seconds to 10 minutes of exposure conditions, 50 to 100% relative humidity, 0 to 50 ℃ and 5 More preferably exposed to steam in minutes.

The polymer resin layer that has undergone the above process is in a gel state, and then, after the washing process, the solvent (the solvent in which the polymer resin is dissolved, an additive, and an impregnation solution, etc.) is removed and dried to solidify. The porous membrane of the invention can be prepared. At this time, the porous separator may be washed with acetone, methanol, ethanol or water to remove the used solvent, and it is preferable to use water of 20 to 90 ° C. On the other hand, the temperature for drying the washed porous separator is 20 ~ 200 ℃ (preferably 40 ~ 100 ℃).

The porous membrane of the present invention prepared as described above comprises a polymer resin layer in which pores having a diameter of 0.1 nm to 10 μm, preferably less than 1 μm, more preferably less than 0.5 μm are uniformly formed.

Hereinafter, the present invention will be described in detail with reference to examples. However, these examples are for illustrating the present invention specifically, and the scope of the present invention is not limited to these examples.

[ Example  One]

1) Polymer solution preparation

A polymer solution was prepared by using 10% by weight of polyethersulfone as a polymer resin, 65% by weight of N-methyl-2-pyrrolidone (NMP) as a solvent, 10% by weight of glycerol as an additive, and 15% by weight of polyethylene glycol having a molecular weight of 20000. It was.

2) porous support Impregnation

After immersing the polyester support in a container containing glycerol as an impregnation solution at room temperature (25 ° C) within 1 minute, the glycerol present on the surface was removed with a casting knife.

3) Porous Membrane Manufacturing

The thickness of the casting knife was adjusted to 150 μm to cast the polymer solution prepared on the impregnated polyester support while maintaining the temperature at 30 ° C. to form a polymer resin layer. Thereafter, the relative humidity of 90%, 20 ℃, was exposed to water vapor for 1 minute and then precipitated in non-solvent water (20 ℃) for 12 hours. Next, the mixture was washed with 70 ° C. water (distilled water) for 3 hours and then dried at a temperature of 70 ° C. in a dry oven for 24 hours to prepare a porous separator.

In order to confirm the pore shape and distribution of the prepared porous membrane, observation was carried out using an electron microscope (SEM), and the results are shown in FIGS. 1A to 1D.

[ Example  2]

Example 1, except that a polymer solution mixed with 10% by weight of polyether sulfone as a polymer resin, 65% by weight of N-methyl-2-pyrrolidone (NMP) as a solvent and 25% by weight of glycerol as an additive was used. In the same manner as the porous separator was prepared.

In order to confirm the pore shape and distribution of the prepared porous membrane, observation was performed using an electron microscope (SEM), and the results are shown in FIGS. 2A and 2B.

[ Example  3]

Polymer solution mixed with 10% by weight of polyethersulfone as polymer resin, 65% by weight of N-methyl-2-pyrrolidone (NMP) as solvent, 22% by weight of glycerol as additive and 3% by weight of polyethylene glycol having molecular weight of 20000 A porous separator was manufactured in the same manner as in Example 1, except that.

In order to confirm the pore shape and the distribution of the prepared porous membrane, observation was carried out using an electron microscope (SEM), and the results are shown in FIGS. 3A and 3B.

[ Example  4]

Polymer solution mixed with 10% by weight of polyethersulfone as polymer resin, 65% by weight of N-methyl-2-pyrrolidone (NMP) as solvent, 15% by weight of glycerol as additive and 10% by weight of polyethylene glycol having molecular weight of 20000 A porous separator was manufactured in the same manner as in Example 1, except that.

In order to confirm the pore shape and distribution of the prepared porous membrane, observation was performed using an electron microscope (SEM), and the results are shown in FIGS. 4A and 4B.

[ Example  5]

A porous separator was prepared in the same manner as in Example 2, except that the prepared polymer solution was cast on the impregnated polyester support and then exposed to water vapor for 3 minutes.

In order to confirm the pore shape and distribution of the prepared porous membrane, observation was carried out using an electron microscope (SEM), and the results are shown in FIG. 5 (pore formation of 0.1 to 10 μm).

[ Example  6]

A polymer solution was mixed with 10% by weight of polyethersulfone as a polymer resin, 65% by weight of N-methyl-2-pyrrolidone (NMP) as a solvent, 20% by weight of glycerol as a pore-forming agent and 5% by weight of polyethylene glycol having a molecular weight of 20000. A porous separator was prepared in the same manner as in Example 1, except that after casting on the impregnated polyester support, water vapor was exposed for 3 minutes.

In order to confirm the pore shape and distribution of the prepared porous membrane, observation was performed using an electron microscope (SEM), and the results are shown in FIG. 6 (pore formation of 0.1 to 5 μm).

[ Example  7]

A porous membrane was prepared in the same manner as in Example 4, except that the prepared polymer solution was cast on the impregnated polyester support and then exposed to water vapor for 3 minutes.

In order to confirm the pore shape and distribution of the prepared porous membrane, observation was performed by electron microscopy (SEM), and the results are shown in FIGS. 7A and 7B (pore formation of 0.1 to 2 μm).

[ Example  8]

A porous separator was prepared in the same manner as in Example 1, except that the prepared polymer solution was cast on the impregnated polyester support and then exposed to water vapor for 3 minutes.

In order to confirm the pore shape and distribution of the prepared porous membrane, observation was carried out by electron microscopy (SEM), and the results are shown in FIGS. 8A and 8B (pore formation of 0.1 to 10 μm).

[ Example  9]

16% by weight of polyethersulfone as polymer resin, 34% by weight of N-dimethyl acetamide (DMAc) as solvent, 40% by weight of methyl cellosolve, and 10% by weight of polyvinylpyrrolidone having molecular weight of 24000 as additive The porous membrane was prepared in the same manner as in Example 1 except that after casting on the impregnated polyester support was exposed to water vapor for 15 seconds.

In order to confirm the pore shape and distribution of the prepared porous membrane, observation was carried out using an electron microscope (SEM), and the results are shown in FIGS. 9A and 9B (pore formation of 0.1 to 1 μm).

[ Example  10]

Polyester support impregnated with a polymer solution mixed with 15% by weight of polyethersulfone as a polymer resin, 55% by weight of N-dimethyl acetamide (DMAc) as a solvent, 15% by weight of glycerol as an additive and 15% by weight of polyethylene glycol having a molecular weight of 1000 A porous separator was prepared in the same manner as in Example 1, except that after casting on water, the film was exposed to water vapor for 15 seconds.

In order to confirm the pore shape and distribution of the prepared porous separator, electron microscopy (SEM) was observed, and the results are shown in FIGS. 10A and 10B (pore formation and transmittance (LMH) 738 of 0.1 to 1.5 μm).

[ Example  11]

A porous separator was manufactured in the same manner as in Example 10, except that the polyester support was impregnated with 1,3-butanediol as an impregnation solution.

In order to confirm the pore shape and distribution of the prepared porous membrane, the electron microscope (SEM) was observed, and the results are shown in FIGS. 11A and 11B (pore formation and permeability (LMH) 705 of 0.1 to 1 μm).

[ Comparative example  One]

A porous separator was manufactured in the same manner as in Example 1, except that the polyether support was not impregnated with the impregnation solution. In order to confirm the pore shape and distribution of the prepared porous membrane, the electron microscope (SEM) was observed, and the results are shown in FIGS. 12A to 12D.

[ Comparative example  2]

A porous separator was manufactured in the same manner as in Example 2, except that the polyether support was not impregnated with the impregnation solution. In order to confirm the pore shape and distribution of the prepared porous membrane, observation was performed using an electron microscope (SEM), and the results are shown in FIGS. 13A and 13B.

[ Comparative example  3]

A porous separator was manufactured in the same manner as in Example 3, except that the polyether support was not impregnated with the impregnation solution. In order to confirm the pore shape and distribution of the prepared porous membrane, observation was carried out using an electron microscope (SEM), and the results are shown in FIGS. 14A and 14B.

[ Comparative example  4]

A porous separator was manufactured in the same manner as in Example 4, except that the polyether support was not impregnated with the impregnation solution. In order to confirm the pore shape and distribution of the prepared porous membrane, observation was carried out using an electron microscope (SEM), and the results are shown in FIGS. 15A and 15B.

Referring to the electron micrographs of the porous separators of Examples 1 to 4 and Comparative Examples 1 to 4, the porous separator according to Examples 1 to 4 of the present invention prepared using the support impregnated with the impregnation solution was Comparative Example 1 It was confirmed that the pore distribution is more uniform than the porous separator according to the to 4 and the polymer resin layer has a constant thickness. In addition, in the porous separators of Examples 1 to 4 according to the present invention, the support was not exposed on the surface of the polymer resin layer (compared to FIGS. 1B and 12B), and it was confirmed that much uniform pores were generated.

In addition, in the porous membrane of FIG. 1C corresponding to the present invention, the polymer resin is not penetrated into the inside (lower layer) of the porous support, and the polymer resin layer is mainly formed on the surface of the porous support. It was confirmed that the polymer resin penetrated inside (lower layer). This supports the fact that the polymer solution can be prevented from coming out by impregnating the porous support with the impregnation solution as in the present invention.

On the other hand, to confirm the permeation performance and pore size of the porous membrane prepared by the production method of the present invention was carried out the following experiment using the porous membrane prepared in Examples 5 to 8, the results are shown in Table 1 Indicated.

[ Experimental Example ]

1. Pore size measurement

The pore size was measured using an Auto Firm-Porometer (CFP-1200AEL) using the bubble point method.

2. Measurement of permeability

The average value of the pure water permeability of the sample was measured under a vacuum condition of 0.1 bar using a circular porous plate having a diameter of 40 mm.

Average pore size
(μm) Bubble point
Pore Size (μm) Maximum distribution
Pore size
(μm) Permeability
(LMH) Example 5 0.408 0.638 0.201 179 Example 6 1.775 8.419 0.902 2003 Example 7 0.207 0.538 0.207 115 Example 8 0.841 3.636 0.199 603

Referring to Table 1, the porous separator prepared by the production method of the present invention has a maximum distribution pore size in the range of 0.15 ~ 0.95㎛, according to the size of the powder to be filtered can be applied accordingly. In addition, it was confirmed that the permeability and regeneration ability is superior to the separator used in the conventional precision filtration (generally, showing a transmittance (LMH) of about 80 to 170 at 0.1 bar basis).

Claims (9)

a) dissolving the polymer resin in a solvent and mixing the additives to prepare a polymer solution;
b) impregnating the porous support into the impregnation solution;
c) forming a polymer resin layer by applying the polymer solution on the porous support impregnated with the impregnation solution; And
d) a method of manufacturing a porous separator comprising the step of precipitating the polymer resin layer in a non-solvent. The method of claim 1,
The step b) further comprises the step of removing the impregnation solution present on the surface of the porous support. The method of claim 1,
Method for producing a porous membrane, characterized in that further comprising the step of exposing the polymer resin layer formed in step c) to steam. The method of claim 1,
The impregnation solution is polyethylene glycol (polyethylen glycol), glycerol (glycerol), 1,3-butanediol (1,3-butanediol), 1,4-butanediol (1,4-butanediol), 1,5-pentanediol (1 At least one selected from the group consisting of 5-pentanediol, methyl pyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide and sulfolane Method for producing a porous membrane, characterized in that. The method of claim 1,
The polymer resin is polyehtersulfone, polysulfone, polyetherketone, polyetheretherketone, sulfonated polystyrene, sulfonated polysulfone , Sulfonated polyethersulfone, sulfonated polyimide, sulfonated polyetherketone, polyvinylidenefluoride, polytetrafluoroethylene, Polyvinyl chloride (polyvinylchloride) and polyvinylidene chloride (Polyvinylidene chloride) method for producing a porous separator, characterized in that selected from the group consisting of. The method of claim 1,
The additives include polyethylene glycol, methyl cellosolve, glycerol, polyvinylpyrrolidone, acetone, propionic acid, acetic acid, Silica (SiO ₂ ), titanium dioxide (titanium dioxide), pyridine (pyridine) and polyvinylpyridine (polyvinylpyridine) a method for producing a porous membrane, characterized in that at least one selected from the group consisting of. The method of claim 1,
The polymer solution, based on 100% by weight of the polymer solution, 1 to 50% by weight of the polymer resin, 1 to 80% by weight of the solvent and 0.01 to 90% by weight of the additive method for producing a porous separator, characterized in that . A porous separator prepared by the method of any one of claims 1 to 7. 9. The method of claim 8,
Porous separator, characterized in that the pores of 0.1nm ~ 10㎛ diameter formed.

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