KR20190000876A - Polymeric composition for hydrophilic separation membrane containing sulfonated inorganic particles - Google Patents

Abstract

The present invention relates to a polymer composition for manufacturing a hydrophilic separation membrane containing sulfonated inorganic particles, preferably sulfonated titanium dioxide, and a hydrophilic separation membrane manufactured therefrom. The hydrophilic separation membrane of the present invention has an excellent water flux and an excellent antifouling property.

Description

TECHNICAL FIELD The present invention relates to a polymer composition for preparing a hydrophilic separation membrane containing sulfonated inorganic particles and a hydrophilic separation membrane prepared by the same.

The present invention relates to an ultrafiltration membrane having excellent hydrophilicity, high porosity and excellent antifouling property, including sulfonated inorganic particles, preferably sulfonated titanium dioxide.

Recently, water treatment membranes have attracted attention as technologies for treating water in an environmentally friendly manner. Such membranes have been applied to various water treatment fields such as domestic wastewater treatment, factory wastewater treatment, ultrapure water production, and desalination of seawater. The water treatment membrane may be classified into a microfiltration membrane, an ultrafiltration membrane, a hollow fiber membrane, a nanofiltration membrane, or a reverse osmosis membrane depending on purposes, and may be used as a mixture thereof.

In the case of the water treatment separator, a separator using a cellulose-based hydrophilic polymer such as cellulose acetate or cellulose nitrate and a separator using polyethylene, polypropylene, polysulfone, polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene And the like.

In the case of a hydrophilic polymer, interaction with water molecules is activated due to hydrogen bonding or the like, and thus water easily permeates and water permeability is high. However, the hydrophilic polymer is sensitive to heat and chemicals, The polymer chains are easily separated by the polymer, and the membrane is destroyed.

Hydrophobic polymers are generally resistant to heat and chemicals and have excellent physical properties such as mechanical strength. However, their water permeability is remarkably low due to hydrophobicity, and they are more hydrophilic than hydrophilic polymers due to contaminants such as proteins. There is a problem that it is easily contaminated. In order to solve such a problem of the hydrophobic polymer, various methods have been proposed in order to solve the problems of the hydrophobic polymer, such as an inorganic particle such as titanium dioxide during the production of the separation membrane, a functional group such as a carboxyl group on the surface of the separation membrane or a hydrophilic polymer such as polyvinyl alcohol Method. However, even in these methods, the hydrophilicity of the separator is still relatively low, so that the water permeability is low and it is vulnerable to contamination.

Korean Patent No. 10-0994178 also discloses a polyethersulfone composite membrane containing titanium dioxide particles, but since the hydrophilicity of the composite membrane produced by mixing these titanium dioxide particles is only partially improved, There is a problem that water permeability is low for application.

Korean Patent No. 10-0994178

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and provide a polymer composition for producing a hydrophilic separation membrane having high hydrophilicity.

Another object of the present invention is to provide a polymer composition for producing a hydrophilic separation membrane having a high water permeability.

Still another object of the present invention is to provide a polymer composition for the production of a hydrophilic separation membrane excellent in antifouling property.

Still another object of the present invention is to provide a polymer composition for producing a hydrophilic separation membrane having a high porosity.

The polymer composition for producing a hydrophilic separation membrane of the present invention comprises sulfonated inorganic particles and a base resin.

The sulfonated inorganic particle according to an embodiment of the present invention may be a sulfonated titanium dioxide.

In the polymer composition for preparing a hydrophilic membrane according to an embodiment of the present invention, the sulfonated titanium dioxide particles may have an atomic ratio of sulfur atoms to titanium atoms on the surface of the particles of 10 to 40%.

In the polymer composition for preparing a hydrophilic separation membrane according to an embodiment of the present invention, the titanium dioxide particles may have an average particle diameter of 10 to 700 nm.

In the polymer composition for preparing a hydrophilic separation membrane according to an embodiment of the present invention, the base resin may be one or more selected from a polysulfone polymer, a halogenated polymer, a polyolefin polymer, a polyacrylonitrile polymer and a polyimine polymer .

In the polymer composition for preparing a hydrophilic separation membrane according to an embodiment of the present invention, the base resin may be sulfonated.

In the polymer composition for preparing a hydrophilic separation membrane according to an embodiment of the present invention, the polysulfone-based polymer may be one or two or more selected from polyethersulfone and polysulfone.

The polymer composition for preparing a hydrophilic separation membrane according to an embodiment of the present invention may further include one or more additives selected from a water-soluble polymer and a water-soluble salt.

The polymer composition for preparing a hydrophilic separation membrane according to an embodiment of the present invention may contain 0.1 to 20% by weight of sulfonated inorganic particles, 5 to 40% by weight of a base resin, 0.1 to 15% by weight of an additive and a residual amount of a solvent.

The present invention also includes a hydrophilic separation membrane prepared from a polymer composition for producing a hydrophilic separation membrane according to an embodiment of the present invention.

The hydrophilic separation membrane according to one embodiment of the present invention can satisfy the following formula (1).

[Formula 1]

는 상기 친수성 분리막의 수투과도(L/㎡·h)이며,

는 술폰화되지 않은 이산화티탄을 포함하는 분리막의 수투과도(L/㎡·h)이다.In Equation 1,

Is the water permeability (L / m < 2 > h) of the hydrophilic separation membrane,

Is the water permeability (L / m < 2 > h) of the separation membrane containing non-sulfonated titanium dioxide.

The hydrophilic separation membrane according to an embodiment of the present invention may be an ultrafiltration membrane, a microfiltration membrane, a hollow fiber membrane, or a nanofiltration membrane.

When a hydrophilic separation membrane is produced using the polymer composition for producing a hydrophilic separation membrane of the present invention, it has a high hydrophilicity.

When a hydrophilic separation membrane is produced by using the polymer composition for producing a hydrophilic separation membrane of the present invention, water permeability is excellent.

When the hydrophilic separation membrane is produced by using the polymer composition for producing a hydrophilic separation membrane of the present invention, it has an excellent antifouling property.

The hydrophilic separation membrane prepared by using the polymer composition for producing a hydrophilic separation membrane of the present invention has a high porosity.

1 is a graph showing an analysis of a sulfonated titanium dioxide according to an embodiment of the present invention by X-ray photoelectron spectroscopy.
2 is a scanning electron microscope (SEM) image of a section of a hydrophilic separation membrane according to one embodiment of the present invention and a comparative example.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. The following drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. Therefore, the present invention is not limited to the following drawings, but may be embodied in other forms, and the following drawings may be exaggerated in order to clarify the spirit of the present invention. Hereinafter, the technical and scientific terms used herein will be understood by those skilled in the art without departing from the scope of the present invention. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.

When a polymer resin such as polyethersulfone or polyvinylidene fluoride is used for a high mechanical strength in a conventional water treatment separator, it is difficult to permeate water because of low hydrophilicity and easily contaminated by contaminants contained in the fluid to be treated There was a problem.

The applicant of the present invention has studied for a long period of time in order to prepare a separator for water treatment having high hydrophilicity and is not easily contaminated. As a result, when a separator is prepared by mixing sulfonated inorganic particles, preferably sulfonated titanium dioxide, But also has an effect of increasing the antifouling property. Thus, the present invention has been completed.

Accordingly, the present application relates to a polymer composition for producing a hydrophilic separation membrane containing sulfonated inorganic particles and a base resin.

When a hydrophilic separation membrane is produced by using the polymer composition for preparing a hydrophilic separation membrane according to the present invention, it is advantageous in that it has excellent hydrophilicity, high water permeability, excellent porosity, antifouling property, and stable separation membrane.

In the polymer composition for preparing a hydrophilic separation membrane according to an embodiment of the present invention, the inorganic particles may be one or two or more selected from titanium dioxide, zirconium dioxide, aluminum hydroxide, magnesium oxide, zinc oxide and silicon dioxide.

Preferably, the polymer composition for producing a hydrophilic separation membrane of the present invention may be a sulfonated TiO ₂ . In the case of containing sulfonated titanium dioxide particles, hydrophilic separation can be remarkably improved by the sulfonation treatment, and a hydrophilic separation membrane having excellent antifouling property can be produced. In addition, adhesion with a base resin described later can be improved, Can be formed. Specifically, when the hydrophilic property is high in the separating membrane, the water permeability of the prepared separating membrane is remarkably increased, and the problem of low water permeability, which is a problem of the conventional separating membrane, can be solved. In addition, when the hydrophilic separation membrane of the present invention is applied to an actual water treatment facility with excellent antifouling property, cleaning is facilitated and the replacement cycle is lengthened, thereby reducing the maintenance cost. In addition, there is an advantage in that the adhesion with the base resin described later can be improved by the sulfonation treatment, thereby preventing the problem of elution of the titanium dioxide particles at the time of using the separation membrane, and producing a stable hydrophilic separation membrane for a long period of time.

The sulfonated titanium dioxide according to one embodiment of the present invention may have an atomic ratio of sulfur atoms to titanium atoms of 10 to 40% at the surface of titanium dioxide particles. When the titanium dioxide is sulphonated in the above range, not only the hydrophilicity of the separation membrane produced by hydrophilizing the titanium dioxide can be improved but also the sulfone group is stably present on the titanium surface.

The sulfonated inorganic particle according to an embodiment of the present invention is not limited as long as it is produced by a method of sulfonating an inorganic particle. Specifically, a method of treating an inorganic particle with an aqueous sulfuric acid solution can be used . More specifically, the inorganic particles may be mixed with an aqueous solution of sulfuric acid in an amount of 10 to 100 times by volume based on the volume of the inorganic particles. The concentration of the aqueous sulfuric acid solution may be 0.1 to 1 M, but is not limited thereto. The size of the inorganic particles according to an embodiment of the present invention is not limited as long as it is in a range capable of forming a hydrophilic separation membrane by mixing with a polymer described later. Specifically, the average particle size may be 10 to 700 nm, More specifically, the average particle diameter may be 10 to 500 nm.

The sulfonated inorganic particles according to an exemplary embodiment of the present invention may be contained in an amount of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the total weight of the polymer composition for producing a hydrophilic separation membrane. When the sulfonated inorganic particles are contained within the above-mentioned range, there are few sulfonated inorganic particles that can not adhere to the base resin in the prepared separation membrane, and the sulfonated inorganic particles are sufficiently contained on the prepared separation membrane, Hydrophilicity and antifouling property can be secured.

In the polymer composition for preparing a hydrophilic separation membrane according to an embodiment of the present invention, the base resin is usually used in a separation membrane, and there is no limitation in the case of the polymer resin capable of adhering the sulfonated inorganic particles. Specifically, the base resin may be one or more selected from a polysulfone-based polymer, a halogenated polymer, a polyolefin-based polymer, a polyacrylonitrile-based polymer, and a polyimine-based polymer, and more specifically may be a polysulfone-based polymer. When the polysulfone-based polymer is used as the base resin, the dispersibility of the sulfonated inorganic particles in the polymer composition for producing a hydrophilic separation membrane is remarkably improved owing to the high interaction with the sulfonated inorganic particles, Is uniformly dispersed in the prepared separation membrane, and the stability of the membrane is excellent because the sulfonated inorganic particles are not easily separated after the production of the membrane. In addition, this uniform dispersion has an advantage that the water permeability and stain resistance of the entire membrane are improved.

기를 포함하는 고분자 화합물인 경우 제한이 없으며, 구체적으로 폴리술폰 또는 폴리에테르술폰 등 일 수 있다. 또한, 본 발명의 일 실시예에 의한 친수성 분리막 제조용 고분자 조성물에서 상기 할로겐화 중합체라 함은, 고분자 조성물의 단위체 중 수소 원자 대신 할로겐 원자가 하나 이상 치환된 단위체를 포함하는 고분자 화합물을 의미한다. 일 예로, 폴리비닐리덴플로라이드, 폴리테트라플루오로에틸렌 또는 폴리비닐클로라이드 등이 있으나 이에 한정되는 것은 아니다. 이에 더하여, 본 발명의 일 실시예에 의한 친수성 분리막 제조용 고분자 조성물에서 폴리올레핀은 올레핀계 화합물을 중합하여 제조된 고분자 조성물인 경우 제한이 없으나, 구체적으로 폴리에틸렌 또는 폴리프로필렌일 수 있다. 또한 본 발명의 일 실시예에 의한 폴리아크릴로니트릴계 중합체는 아크릴로니트릴 또는 아크릴로니트릴 유도체를 단위체로 포함하는 조성물 또는 공중합체인 경우 제한이 없으나, 구체적으로는 아크릴로니트릴 단일중합체 또는 아크릴로니트릴이 30 중량%이상 포함된 공중합체일 수 있다. 이에 더하여, 본 발명의 일 실시예에 의한 폴리이민계 중합체는 이민기를 단위체로 포함하는 고분자 조성물인 경우 제한이 없으나, 상세하게는 폴리알킬렌이민일 수 있으며, 이때 알킬렌은 탄소수 1 내지 5의 알킬렌기일 수 있다.In the polymer composition for producing a hydrophilic separation membrane according to an embodiment of the present invention,

Group is not limited, and specifically, it may be polysulfone, polyethersulfone, or the like. In the polymer composition for preparing a hydrophilic separation membrane according to an embodiment of the present invention, the halogenated polymer refers to a polymer compound comprising a unit in which at least one halogen atom is substituted for a hydrogen atom in the unit composition of the polymer composition. Examples include, but are not limited to, polyvinylidene fluoride, polytetrafluoroethylene, or polyvinyl chloride. In addition, in the polymer composition for producing a hydrophilic separation membrane according to an embodiment of the present invention, the polyolefin may be a polymer composition prepared by polymerizing an olefin compound, but may be polyethylene or polypropylene. In addition, the polyacrylonitrile-based polymer according to one embodiment of the present invention is not limited as long as it is a composition or a copolymer containing acrylonitrile or acrylonitrile derivative as a unit, but specific examples thereof include acrylonitrile homopolymer or acrylonitrile May be a copolymer containing not less than 30% by weight. In addition, the polyimine-based polymer according to one embodiment of the present invention is not limited as long as it is a polymer composition containing an imine group as a unit, and more specifically, may be a polyalkyleneimine, wherein the alkylene is an alkyl having 1 to 5 carbon atoms It can be a ring.

In the polymer composition for producing a hydrophilic separation membrane according to an embodiment of the present invention, the base resin may be sulfonated. Specifically, the resin used for the separator may be a sulfonated resin, and more specifically, a sulfonated polysulfone-based polymer, a sulfonated halogenated polymer, and a sulfonated polyolefin-based polymer. Preferably, a base resin that does not contain sulfone groups may be included in the monomer unit by sulfonation treatment. When the above-mentioned base resin is sulfonated and then a separator is produced, the dispersibility is improved due to the high interaction between the sulfonated base resin and the sulfonated inorganic particles, and the sulfonated inorganic particles are uniformly dispersed in the membrane And the water permeability is remarkably improved as compared with the case of using a base resin which is dispersed and not sulfonated.

At this time, the sulfonation of the base resin is not particularly limited as long as it is a method used for sulfonating the polymer, but a method of treating the base resin with sulfuric acid at room temperature can be used. More specifically, a high concentration sulfuric acid having a weight of 0.5 to 4 times the weight of the base resin and the base resin is mixed with the sulfuric acid and the base resin in an amount of 95 to 99% Or more.

In the polymer composition for preparing a hydrophilic separation membrane according to an embodiment of the present invention, the above-mentioned base resin may be contained in an amount of 5 to 40% by weight, preferably 10 to 25% by weight. When the ratio of the base resin is the same as above, there is an advantage that the porosity is remarkably improved due to bonding with the sulfonated inorganic particles as described above, and the surface area is widened, and the phase transition is easily performed in the step of preparing the membrane, There is an advantage that a separation membrane can be formed.

The polymer composition for preparing a hydrophilic separation membrane according to an embodiment of the present invention may include one or more additives selected from water-soluble polymers and water-soluble salts. In detail, the water-soluble polymer may be polyvinylpyrrolidone, polyethylene glycol or polyethyleneimine, but there is no limitation on the water-soluble polymer composition. In the case of a water-soluble salt, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, lithium bromide , Sodium bromide, potassium bromide, and the like. However, polyvinylpyrrolidone as a water-soluble polymer or lithium chloride as a water-soluble salt may be preferably used as an additive.

When the water-soluble polymer or the water-soluble salt as described above is contained, the polymer composition for the production of a hydrophilic separation membrane according to an embodiment of the present invention is used to form a separation membrane having a higher porosity and water permeability There is an advantage to be able to do. In addition, when a water-soluble polymer is used as an additive, there is an advantage that pores are uniformly formed on a separation membrane produced by interaction with a sulfonated inorganic particle.

In the polymer composition for preparing a hydrophilic separation membrane according to an embodiment of the present invention, the above-mentioned additives may be contained in an amount of 0.1 to 15% by weight, preferably 0.1 to 10% by weight. When the additive is included in the above range, it is possible to secure sufficient pores in the separator to be produced later, and the additive remains in the separator, thereby minimizing the influence on the characteristics of the separator such as hydrophilicity and water permeability.

The polymer composition for production of hydrophilic separation according to an embodiment of the present invention may further include a solvent. The solvent is not limited as long as it is a polar aprotic solvent, but specifically includes N-methylpyrrolidone, dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, ethyl acetate, Acetone and acetonitrile, and more particularly, one or more selected from N-methylpyrrolidone, dimethylacetamide and N, N-dimethylformamide. Such a solvent may be present in a residual amount on the polymer composition for producing a hydrophilic separation membrane when the sulfonated inorganic particles and the base resin are added in the above-mentioned range. Specifically, it may include 55 to 90% by weight, and more specifically 70 to 90% by weight, of the polymer composition for manufacturing an overall hydrophilic separation membrane. When the solvent is included in the above-mentioned range, there is an advantage that the separation membrane can be stably manufactured later while dispersing the base resin and the sulfonated inorganic particles evenly.

The separation membrane using the polymer composition for producing a hydrophilic separation membrane according to an embodiment of the present invention is not particularly limited as long as the method used for the preparation of the separation membrane is generally used. Specifically, the separation membrane can be prepared using the phase transfer method . More specifically, a solvent-nonmetal phase transfer method, a thermal induction phase transfer method, or a steam-induced phase transfer method can be used. More specifically, a solvent-nonmetal phase transfer method can be used. When the solvent-free mass transfer method is used, the sulfonated inorganic particles There is an advantage that a separation membrane having uniform water permeability and antifouling property can be produced. In this case, the non-solvent used in the solvent-non-solvent phase transfer method is not limited as long as it is a polar protic solvent, but may be water in detail.

The separation membrane prepared by using the polymer composition for preparing a hydrophilic separation membrane according to an embodiment of the present invention has an advantage of being excellent in hydrophilicity, high in water permeability and excellent in antifouling property. In detail, the water permeability of the membrane prepared using only the base water may be higher than 1.8 times, and the water permeability of the membrane containing non-sulfonated inorganic particles may be higher than 1.3 times.

Specifically, the hydrophilic separation membrane according to one embodiment of the present invention can satisfy the following expression (1).

[Formula 1]

는 본 발명의 일 실시예에 의한 친수성 분리막의 수투과도(L/㎡·h)이며,

는 술폰화되지 않은 이산화티탄을 포함하는 분리막의 수투과도(L/㎡·h)이다.In Equation 1,

Is the water permeability (L / m < 2 > h) of the hydrophilic separation membrane according to an embodiment of the present invention,

Is the water permeability (L / m < 2 > h) of the separation membrane containing non-sulfonated titanium dioxide.

That is, the hydrophilic separation membrane containing the sulfonated inorganic particles can improve the water permeability of the separation membrane containing the same amount of non-sulfonated inorganic particles by at least 1.3 times and up to 5 times. The remarkable improvement of the water permeability is advantageous in that the treatment capacity can be remarkably improved when utilized in water treatment using an actual separation membrane.

In addition, the separator manufactured by using the polymer composition for preparing a hydrophilic membrane according to an embodiment of the present invention has an excellent antifouling property. In detail, the separation membrane containing the sulfonated base resin and the sulfonated inorganic particles showed excellent antifouling property (93%). In particular, the antifouling property of the separator prepared by using the base resin is more than 20% to 32%, and the antifouling property of the separator containing the non-sulfonated inorganic particles can be improved by 13% or more. Such an improvement of the antifouling property is advantageous in that it is easy to clean when applied to actual water treatment equipment, and the maintenance period is longened by reducing the maintenance cost.

Hereinafter, the present invention will be described in detail with reference to examples. It is to be understood that the embodiments described below are only for the understanding of the present invention, and the present invention is not limited to the embodiments described below.

1 g of titanium dioxide (US Research nanomaterial, Inc. TiO ₂ anatase 99 +%, Size 10-25 nm, US3490, CAS No. 13463-67-7), 20 ml of methanol and 15 ml of 0.5 M sulfuric acid aqueous solution were mixed, Was irradiated with ultrasound for 1 hour to prepare sulfonated titanium dioxide.

2 g of the prepared sulfonated titanium dioxide, 15 g of polyethersulfone, 1 g of PVP and 84 g of N-methylpyrrolidone were mixed to prepare a mixed solution, which was stirred for 48 hours or more to be dispersed evenly.

The prepared mixed solution was allowed to stand at room temperature for more than 9 hours to remove bubbles, cast the solution on a glass plate, cast the solution on a glass plate with a thickness of 150 to 250 μm using a knife, and immersed in a coagulation bath comprising 15 to 25 ° C water . The immersed membrane was washed with water at 50 DEG C for 30 minutes to prepare a hydrophilic membrane (PES-STiO2).

A hydrophilic separation membrane (SPES-STiO ₂ ) was produced in the same manner as in Example 1 except that an equivalent amount of sulfonated polyether sulfone was used instead of polyethersulfone. At this time, sulfonation treatment of polyethersulfone was carried out by mixing 100 ml of sulfuric acid (98%) and 10 g of polyethersulfone and stirring at room temperature for 1 hour or more. Sulfonated base resin (S-PES) is precipitated with ice-cold de-ionized water under rapid agitation, and the resulting precipitate is recovered by filtration and washed repeatedly with deionized water two to three times Followed by washing.

7.5 g of polyethersulfone, 7.5 g of sulfonated polyethersulfone, 1 g of polyvinylpyrrolidone and 84 g of N-methylpyrrolidone were mixed to prepare a mixed solution, and then water To prepare a separation membrane.

[Comparative Example 1]

15 g of polyethersulfone, 1 g of polyvinylpyrrolidone and 84 g of N-methylpyrrolidone were mixed to prepare a mixed solution, and then the membrane was immersed in water in the same manner as in Example 1 to prepare a separation membrane (PES) .

[Comparative Example 2]

A hydrophilic separation membrane (PES-TiO ₂ ) was prepared by the same method as in Example 1 except that the untreated titanium dioxide was mixed in the same amount.

[Comparative Example 3]

A hydrophilic separation membrane (SPES-TiO ₂ ) was prepared by the same method as in Example 2 except that the untreated titanium dioxide was mixed in the same amount.

[Confirmation of sulfonation of titanium dioxide]

The sulphonated titanium dioxide prepared in Example 1 was confirmed by X-ray photoelectron spectroscopy and the degree of sulphonation was shown in Fig.

- Experimental instrument: K-Alpha, Thermo Scientific, UK

- Analytical method: An aluminum Kα line was used as an X-ray source, and energy of 30 eV was irradiated.

- Analysis software: Thermo Scientific Avantage software, ver 5.932

Referring to FIG. 1, it can be seen that a peak indicating S2p bonding is generated near 170 eV, and it can be confirmed that titanium dioxide is sulfonated based on this peak.

[Observation of cross-section of the prepared separation membrane]

Sectional views of the separation membranes of Example 1, Comparative Example 1 and Comparative Example 2 were observed through a scanning electron microscope and shown in Fig. CSPM 5500 manufactured by AFM Co., Ltd. was used. In Comparative Example 1, a, Comparative Example 2, and Example 1 were represented by c and c, respectively.

[Water flux experiment]

The water permeability of each of Examples 1 to 2 and Comparative Examples 1 to 3 was measured using a self-produced cross-flow filtration reactor. The cross - filtration reactor used had an internal diameter of 6 ㎝ and an internal effective area of 28.26 ㎠. The membrane was mounted on a water permeability device and operated at a pressure of 0.15 MPa. The permeation amount per time and area of each membrane was measured and shown in Table 1.

Referring to the results shown in Table 1 below, it can be seen that the water permeability of Examples 1 and 2 in which titanium dioxide was subjected to sulfonation treatment is significantly higher than that in Examples 2 and 3, and the water permeability 2.68 times higher than that of the previous year.

Membrane Water permeability (L / m < 2 > h) Example 1 755 Example 2 940 Comparative Example 1 350 Comparative Example 2 560 Comparative Example 3 670

[Antifouling Experiment]

The antifouling effect of each membrane was divided into three stages. Each membrane was mounted on a cross-flow filter, and water permeability was measured (first water permeability) while distilled water was permeated for 30 minutes. Thereafter, 0.5 g / l BSA (Bovine Serum Albumin) solution was permeated through each membrane for 30 minutes, and then the water permeability of each membrane was measured for distilled water for 30 minutes (second water permeability). On the basis of the measured results, the antifouling properties of Examples 1 to 2 and Comparative Examples 1 to 3 were calculated using the following Formula 2 and shown in Table 2.

Referring to Table 2, when the hydrophilic separation membrane including the sulfonated titanium dioxide is produced, the water permeability is maintained at a high level even through the permeation of the contaminant, and it can be confirmed that the antifouling property is high.

[Formula 2]

Membrane Antifouling (%) Example 1 83% Example 2 93% Comparative Example 1 61% Comparative Example 2 70% Comparative Example 3 79%

Claims (12)

And a base resin, wherein the sulfonated inorganic particles and the base resin are prepared by mixing an aqueous sulfuric acid solution. The method according to claim 1,
Wherein the inorganic particles are sulfonated titanium dioxide. 3. The method of claim 2,
Wherein the titanium dioxide has an atomic ratio of sulfur atoms to titanium atoms on the surface of the particles of 10 to 40%. The method according to claim 1,
Wherein the inorganic particles have an average particle diameter of 10 to 700 nm. The method according to claim 1,
Wherein the base resin comprises any one or two or more selected from a polysulfone-based polymer, a halogenated polymer, a polyolefin-based polymer, a polyacrylonitrile-based polymer, and a polyimine-based polymer. 6. The method of claim 5,
Wherein the base resin is sulfonated. 6. The method of claim 5,
Wherein the polysulfone-based polymer comprises any one or two or more selected from polyether sulfone and polysulfone. The method according to claim 1,
Wherein the polymer composition for preparing a hydrophilic separation membrane further comprises any one or two or more additives selected from a water-soluble polymer and a water-soluble salt. 9. The method of claim 8,
0.1 to 20% by weight of the inorganic particles, 5 to 40% by weight of the base resin, 0.1 to 15% by weight of the additive and a residual solvent. A hydrophilic separation membrane produced by the polymer composition for producing a hydrophilic separation membrane according to any one of claims 1 to 9. 11. The method of claim 10,
(1).
[Formula 1]

(In the above formula 1,

Is the water permeability (L / m < 2 > h) of the hydrophilic separation membrane,

Is the water permeability (L / m < 2 > h) of the separation membrane containing un-sulfonated titanium dioxide. 11. The method of claim 10,
A hydrophilic membrane that is an ultrafiltration membrane, a microfiltration membrane, a hollow fiber membrane, or a nanofiltration membrane.

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