KR20170020104A - Anti-fouling water treatment membrane surface-modifide with positive charge, negative charge or neutral particles and method for manufacturing the same - Google Patents
Anti-fouling water treatment membrane surface-modifide with positive charge, negative charge or neutral particles and method for manufacturing the same Download PDFInfo
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- KR20170020104A KR20170020104A KR1020150114841A KR20150114841A KR20170020104A KR 20170020104 A KR20170020104 A KR 20170020104A KR 1020150114841 A KR1020150114841 A KR 1020150114841A KR 20150114841 A KR20150114841 A KR 20150114841A KR 20170020104 A KR20170020104 A KR 20170020104A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
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- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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Abstract
Description
The present invention relates to an anti-fouling water treatment separation membrane which is surface-modified with positive charge, negative charge or neutral particle and a production method thereof, and more particularly to a fouling separation membrane having a positive charge, a negative charge or a neutrality, which improves fouling by underwater charge or neutral pollutants The present invention relates to a water-repellent water-treatment separation membrane that is surface-modified with particles and a method for producing the same.
The water treatment method using a membrane has advantages of less installation space, excellent processing capacity, and low operating cost compared with the existing technologies. Recently, it has been applied to various water treatment fields such as sewage treatment, seawater desalination treatment, home use, medical use and industrial use .
These are divided into microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), and reverse osmosis (RO) membranes depending on pore sizes, The kinds of substances that are different.
Among them, Microfitration (MF) and Ultrafiltration (UF) membranes, which can be driven at low pressure, can effectively remove contaminants such as colloid particles or microorganisms, and are excellent in physical properties and heat resistance , Polyvinylidene fluoride (PVDF), polysulfone (PSF), polyethersulfone (PES), polyacrylonitrile (PAN) and the like having high chemical resistance are used.
However, these materials have an interaction between the hydrophobic organic contaminants and the surface of the separation membrane, thereby accelerating the contamination. As a result, deterioration of membrane performance such as decrease in water permeability occurs.
In addition, many contaminants in sewage have electric charges, so that various methods such as hydrophilic polymer coating, blending, modification or coating of chargeable material on the surface of the separation membrane have been tried to reduce the contamination of the separation membrane.
However, the method of introducing the surface hydrophilic property and the electric characteristic of the membrane by coating and blending has the effect of reducing the contamination in a short time use, but the effect is inferior in long time use.
Further, in the case of grafting modification using membrane surface hydrophilic monomers or monomers having charge characteristics, although the decontamination effect lasts for a long time, harsh conditions such as high reaction temperature and extreme pH conditions are required, There is a problem that the water permeability decreases due to the reduction of the membrane pore size due to the polymerization, so that the technical development is still required.
SUMMARY OF THE INVENTION The present invention provides a water-repellent, water-repellent, water-repellent, or water-repellent, water-repellent, water-repellent, water-repellent membrane that can sustain long-term contamination-reducing effects even under mild conditions.
Other objects and advantages of the present invention will become apparent from the following description. It is also to be easily understood that the objects and advantages of the present invention can be realized by a means or a method described in the claims and a combination thereof.
In order to solve the above problems, according to one aspect of the present invention, there is provided a polymer electrolyte membrane comprising a separation membrane substrate having a first functional group on at least one surface thereof, a higher order branched polymer having a second functional group, a first functional group of the separation membrane substrate, There is provided an anti-fouling water treatment separation membrane which is surface-modified with positive charge, negative charge or neutral particles each containing a crosslinking agent chemically bonded to a bifunctional group.
The higher order polymer may be neutral, negative negative charged at the end, or positively charged at the terminal.
The neutral higher order polymer is hyperbranched polyglycerol (HPG), and the positive or negative higher order polymer may be a higher order polyglycerol derivative having a positive charge or negative charge at the terminal.
The crosslinking agent may include at least one selected from cyanuric chloride, and an isocyanate-based compound.
The separator substrate may be formed of a material selected from the group consisting of polyvinylidene fluoride (PVDF), polysulfone (PSF), polyethersulfone (PES), polyacrylonitrile (PAN), polycarbonate And may include at least one member selected from the group consisting of polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), cellulose, and cellulose acetate have.
The separator substrate may include a surface layer having a pore size of 0.001 to 1 mu m and an inner support layer having a thickness of 10 to 500 mu m.
The first functional group of the separator substrate may include at least one selected from the group consisting of OH, -NH 2, -CN, -CO- , -COOH, and -CONH-.
According to another aspect of the present invention, there is provided a method for producing a polymer electrolyte membrane, comprising: reacting a core material having a second functional group with a protecting group-containing compound to thereby bond a protecting group to the second functional group; , Removing the protecting group bonded to the second functional group of the higher order branched polymer, and separating the second functional group of the higher order branched polymer having at least one surface with the first functional group and the second functional group of the higher order branched polymer by using a crosslinking agent A method of producing a water-repellent, water-repellent, or neutral-surface-modified water-repellent, water-repellent, water-treating separator.
The core material may be selected from the group consisting of ethanolamine, 3-amino-1,2-propanediol, and tris (hydroxylmethyl) aminomethane. And at least one member selected from the group consisting of
The protecting group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.
The higher order polymer may be hyperbranched polyglycerol (HPG).
The monomer may be glycidol.
The method may further include the step of introducing a positive charge or a negative charge to the terminal of the higher order branched polymer before or after removing the protecting group of the higher order polymer.
The step of introducing the positive charge may include a step of replacing the terminal of the higher order branched polymer with at least one of a quaternary ammonium group, a phosphonium group and a sulfonium group.
The step of introducing the negative charge may include the step of replacing the terminal of the higher order oligomer by a sulfonic group or a phosphoric acid group.
The separation membrane base material having the first functional group may be formed by at least one of ultraviolet irradiation, electron beam irradiation, plasma irradiation and acidic or basic solution treatment on at least one surface of the separation membrane substrate.
The step of bonding using the crosslinking agent comprises the steps of: preparing a separating membrane substrate having a crosslinking agent bonded thereto by reacting the separating membrane substrate having the first functional group with a crosslinking agent; And
And reacting the separating membrane substrate to which the crosslinking agent is bound with a second functional group of the higher order branched polymer.
According to another aspect of the present invention, there is provided a method of manufacturing a water treatment separation membrane that is surface-modified with positive charge, negative charge, or neutral particles produced by the above-described method.
The present invention has the advantage of preventing hydrophobic contaminants from adhering to the surface of a separation membrane and preventing bonding between hydrophobic contaminants by introducing a hydrophilic neutral polymer to the surface of the water treatment separation membrane.
Further, the present invention has an advantage that the stain resistance can be improved by introducing a positive or negative polymer having the same charge as the contaminant to the surface of the water treatment separator, due to the electric mutual repulsion force.
BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and, together with the description of the invention, It is not interpreted.
Fig. 1 and Fig. 2 are graphs showing the results of the stain resistance evaluation test of Example 1. Fig.
Hereinafter, the present invention will be described in detail. The terms or words used in the present specification and claims should not be construed in a conventional or dictionary sense and the inventor shall appropriately define the concept of the term in order to explain its invention in the best way The present invention should be construed in accordance with the meaning and concept consistent with the technical idea of the present invention. Therefore, the embodiments described in the present specification and the configurations shown in the drawings are only the most preferred embodiments of the present invention, and not all of the technical ideas of the present invention are described. Therefore, at the time of the present application, It should be understood that various equivalents and modifications are possible.
A water treatment separation membrane according to a preferred embodiment of the present invention comprises a separation membrane substrate having a first functional group on at least one surface thereof, a high-order branched polymer having a second functional group, and a first functional group of the separation membrane substrate and a second functional group of the high- There is provided an antifouling water treatment separation membrane surface-modified with positive charge, negative charge or neutral particles each containing a cross-linking agent chemically bonded to each other.
The separator substrate applicable to the present invention may be any material chemically stable in the art without limitation, and preferably includes polyvinylidenefluoride (PVDF), polysulfone (PSF), polyethersulfone Polyethersulfone (PES), Polyacrylonitrile (PAN), Polycarbonate (PC), Polyethylene (PE), Polypropylene (PP), Polyvinyl chloride Cellulose, cellulose acetate and cellulose acetate, or a mixture thereof.
The separator substrate may have a single layer structure or a multi-layer structure including a surface layer and an inner support layer.
The surface layer may have a porous structure including pores, and the pores may have a diameter ranging from 0.001 to 1 占 퐉. Pores having diameters of various sizes may be mixed to form a uniform diameter May be mixed and formed.
Also, the inner supporting layer may be a porous structure including pores, and may preferably have a finger-like or sponge-like pore structure, Lt; / RTI >
In addition, the separator substrate may include a first functional group on one surface or both surfaces, wherein the first functional group serves to connect the separator substrate with the crosslinking agent, and the material capable of forming a stable chemical bond with the crosslinking agent is not limited -OH, -NH 2 , -CN, -CO-, -COOH, and -CONH-, or a mixture thereof, more preferably -COOH, -OH, - NH 2 can be used.
The higher-order polymer having the second functional group may include one functional group capable of binding to the crosslinking agent at the end of the polymer, and when the functional group includes two or more second functional groups, the higher- It is ideal to have a single second functional group because the features of the multi-branched structure disappear.
The second functional group applicable to the present invention may be any one of an amine group and a thiol group, and preferably an amine group.
The higher order polymer may be either neutral in itself, negative in which a negative charge is introduced at the terminal, or positive in which a positive charge is introduced at the terminal .
By modifying the surface of the membrane substrate with such a neutral, negative, or positive polymer, it is possible to improve the fouling caused by contaminants that have underwater charges. Specifically, by introducing a neutral polymer having hydrophilicity into the surface of the water treatment separation membrane, It is possible to prevent the substance from adhering to the separator surface and to prevent the bonding between the hydrophobic contaminants.
In addition, the membrane substrate is modified so as to have the same charge as the contaminant, and the contaminants are prevented from adhering to the separator due to the electrical repulsive force, thereby improving the stain resistance.
Further, when the higher order polymer is used, the charge density becomes higher, and the above-mentioned effect can be maximized.
The neutral higher order polymer according to an embodiment of the present invention may be hyperbranched polyglycerol (HPG).
In addition, according to a preferred embodiment, the positive high order polymer is a higher order polyglycerol derivative having a positive charge at the terminal.
At this time, the positive charge can be chemically stable and positively charged in the art without limitation, and can be, for example, any one of quaternary ammonium, phosphonium group, and sulfonium group, or a mixture thereof.
In addition, according to a preferred embodiment, the high-order-of-charge polymer is a higher order polyglycerol derivative having a negative charge at the terminal.
At this time, the negative charge can be chemically stable and negatively charged in the art without limitation, and examples thereof include any one of a sulfonic group and a phosphoric group, or a mixture thereof.
The cross-linking agent is a substance that is chemically bonded to the first functional group of the separator base material and the second functional group of the high-order polymer to bridge the cross-linking so that the high-order polymer can be introduced to the surface of the separator. . Preferably, the crosslinking agent may be any one of cyanuric chloride and isocyanate compounds or a mixture thereof.
Hereinafter, the same components as those of the above-described water treatment separation membrane in the description of the method for producing a water treatment separation membrane to be described later will be described in detail if the repetition of the description is determined to unnecessarily obscure the essential matter, to be.
A method for producing a water-repellent, water-repellent, water-treating separation membrane that is surface-modified with positive, negative, or neutral particles according to a preferred embodiment of the present invention comprises reacting a core material having a second functional group with a protecting group- Polymerizing the core material and the monomer to form a higher order polymer, removing the protecting group bonded to the second functional group of the higher order polymer, and removing at least a first functional group And a second functional group of the higher order branched polymer, using a crosslinking agent.
The step of bonding the protecting group to the second functional group is a step of protecting the second functional group by reacting the protecting group with the core material having the second functional group to prevent polymerization reaction of the second functional group having high reactivity with the monomer .
Core materials that can be applied to the present invention include ethanol amine, 3-amino-1,2-propanediol, tris (hydroxylmethyl) aminomethane (Tris (hydroxylmethyl) aminomethane), or a mixture thereof, preferably, tris (hydroxylmethyl) aminomethane.
The protecting groups applicable to the present invention may be applied differently depending on the second functional group. Non-limiting examples of the protective group include any one of aromatic hydrocarbon groups and aliphatic hydrocarbon groups, or a mixture thereof. .
The step of preparing the higher-order polymer may include the step of polymerizing the monomer and the core material to which the protecting group is bonded to the second functional group. The higher-order polymer may have a degree of polymerization of 5 to 300, And may have a degree of polymerization of 10 to 50. [
The monomer that can be used in the present invention can be polymerized with the core material to form a polymer, and a substance containing a functional group capable of being substituted with a negative charge or a positive charge can be applied in various ways. Preferably, the monomer is selected from the group consisting of glycidol, to be.
In addition, the higher order polymer prepared by the above-mentioned method can be variously manufactured according to the core material and the monomer material used in the reaction, and a non-limiting example is hyperbranched polyglycerol (HPG).
The step of removing the protecting group bonded to the second functional group of the higher order polymer differs depending on the second functional group and the bonded protecting group but does not chemically react with the higher order polymer in addition to the second functional group, The method of removing the protecting group may be applied without limitation.
The method may further include a step of introducing a positive charge or a negative charge to the terminal of the higher order branched polymer before or after removing the protecting group of the higher order branched polymer.
The positive charge can be introduced by reacting with glycidyl trimethyl ammonium chloride.
The negative charge can be introduced by reacting a high-order polymer terminal with a sulfur trioxide pyridine complex.
The step of introducing a positive charge at the terminal of the higher order polymer can be applied to water treatment of a water containing a large amount of positively charged contaminants and a positive charge at the terminal of the higher order polymer and a positive charge of the contaminant generate mutual electrical repulsion It is possible to prevent the contaminants from adhering to the separator surface.
The positive charge that can be applied to the present invention may be chemically stable and positively charged without limitation, and may be any one of quaternary ammonium, phosphonium group, and sulfonium group, ≪ / RTI >
In the same principle, the step of introducing a negative charge at the terminal of the higher order polymer can be applied to water treatment of water containing a large amount of contaminants having a negative charge, and the negative charge at the terminal of the higher order polymer and the negative charge of the contaminant are electrically It is possible to prevent the contaminants from adhering to the surface of the separator by generating repulsive force.
At this time, the negative charge can be chemically stable and negatively charged in the art without limitation, and examples thereof include any one of a sulfonic group and a phosphoric group, or a mixture thereof.
The positive charge introducing step or negative charge introducing step may be selectively applied according to an embodiment of the present invention. In order to manufacture a water treatment separator including a neutral higher order polymer, the positive and negative charge introducing steps are omitted .
And combining the separation membrane substrate having the first functional group on at least one surface with the second functional group of the higher order polymer using a crosslinking agent.
At this time, the separation membrane base material having the first functional group can be prepared by introducing functional groups into one or both surfaces of the separation membrane base material through ultraviolet irradiation, electron beam irradiation, plasma treatment, acidic or basic solution treatment, To form a functional group.
Besides the separation membrane surface treatment, materials having specific functional groups such as -COOH, -NH 2 , -NH 2 , and -OH can be mixed with a separation membrane material to prepare a separation membrane having a functional group introduced into its surface.
The step of bonding using a crosslinking agent may include a step of preparing a separating membrane having a crosslinking agent bonded thereto by reacting the separating membrane substrate having the functional group with a crosslinking agent, and a step of reacting the separating membrane substrate having the crosslinking agent bonded thereto with the high order branched polymer can do.
According to another embodiment of the present invention, there is provided a water treatment separation membrane in which an antifouling function is expressed by surface modification produced by the above-described method.
Hereinafter, the present invention will be described in detail with reference to the following examples. However, the embodiments according to the present invention can be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to provide a more complete understanding of the present invention to those skilled in the art.
[Example 1]
One of the amine groups present in the core material was protected with benzyl bromide to activate the three hydroxyl groups present in the core material and catalyzed by the epoxy ring opening reaction of the core material with monomer glycidol at 100 ° C Neutral HPG was prepared by anionic polymerization. Then, a positive charge-introduced HPG is prepared through epoxy ring-opening reaction of glycidyl trimethylammonium chloride molecules including terminal group-activated HPG and positively charged quaternary ammonium groups at 0 ° C with sodium hydroxide solution. Negative charge introduction HPG was prepared by reacting hydroxyl group of HPG dissolved in dimethylformamide with sulfur trioxide pyridine complex and sulfonation reaction. After the preparation, the charge-introduced HPG was dissolved in a solvent mixed with ethanol or distilled water and ethanol at a ratio of 1: 1. Hydrogenolysis was carried out by blowing hydrogen gas at 60 ° C and 1 atm for 15 hours or more, One HPG was prepared.
The surface of the pure PVDF membrane having chemical resistance was irradiated with a plasma of 13.56 MHz and 100 W for 4 minutes in an atmosphere of an argon (Ar) gas of 8 cm 3 / min and an oxygen gas of 20 cm 3 / min to form a functional group shown in FIG. After the reaction, toluene was impregnated with toluene solution of phenlylene diisocyanate (PDC) and catalyst for 3 hours to react the isocyanate group of the crosslinking agent with the functional group on the surface of the separating membrane to prepare a polymer membrane modified with a crosslinking agent. In order to covalently bond the charge-introduced HPG having a stain resistance to the polymer separator, a polymer membrane modified with a cross-linking agent was impregnated into the solution containing the charge-introduced HPG, and then stirred at room temperature for 24 hours to prepare a charge-
Evaluation of contamination resistance
In order to evaluate the stain resistance of the water treatment membrane prepared in Example 1, a water solution prepared by dissolving a typical lysozyme (LYZ: 0.5 g / L) protein as a positively charged organic substance and a representative bovine serum protein (BSA: 0.5 g / L) Pollutants.
In the first experiment, the membrane permeated by ethanol was permeated by distilled water for 10 minutes, permeability was confirmed, permeation of LYZ water was permeated for 1 hour, permeability reduction was analyzed, membrane backwashing was conducted to measure the degree of recovery of the membrane, In order to confirm the degree of recovery, the distilled water was passed through again and the experiment was carried out for three cycles in order to evaluate reuse.
As shown in FIG. 1, in the case of the pure PVDF membrane, the decrease in water permeability was the largest in the case of LYZ permeation as a contaminant, and the water permeability recovery by backwashing was the smallest. However, It was confirmed that the transmittance was higher than that. In the case of negatively charged HPG modified membranes, the decrease in permeability was the largest among the modified membranes due to the electrostatic attraction, the intermediate value in the case of the neutral HPG modified membranes, and the permeability decreased due to the electrical repulsive force with the lysozyme in the positively charged HPG modified membranes And it is confirmed that the most efficient for permeation of contaminated water having a positive charge is.
In the second experiment, the stain resistance was evaluated by the same procedure as the first experiment using BSA solution, which is a negative charge contaminant. In the case of the pure PVDF membrane having a similar zeta potential value (negative value) in FIG. 2, the permeability reduction width was larger than that of the hydrophilic HPG modified membrane having hydrophobicity. However, In the case of the positive charge HPG modified membranes, the adsorption due to the electric attractive force occurred and the decrease in the permeability was the greatest. As a result, it was confirmed that the negative charge HPG modified membrane had the highest stain resistance due to the increase in hydrophilicity and the electric repulsive force when the contaminated water having a negative charge was treated.
Claims (18)
A higher order polymer having a second functional group; And
And a cross-linking agent chemically bonded to the first functional group of the separator substrate and the second functional group of the high-order branched polymer, respectively.
The higher order polymer is neutral. Wherein the negative charge is a negative charge introduced at the end or a positive charge is introduced at the end, wherein the positive charge, the negative charge or the neutral particle is surface-modified.
Wherein said neutral higher order polymer is hyperbranched polyglycerol (HPG), and said positive or negative higher order polymer is a hyperglycidyl polyglycerol derivative having a positive or negative charge at the terminal. Contaminated water treatment membrane modified with neutral particles.
Wherein the cross-linking agent comprises at least one selected from cyanuric chloride and an isocyanate-based compound, wherein the cross-linking agent is surface-modified with positive charge, negatively charged or neutral particles.
The separator substrate may be formed of a material selected from the group consisting of polyvinylidene fluoride (PVDF), polysulfone (PSF), polyethersulfone (PES), polyacrylonitrile (PAN), polycarbonate And those containing at least one member selected from the group consisting of polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), cellulose and cellulosic acetate Characterized by a positive charge, a negative charge, or a neutral particle.
Wherein the separation membrane substrate comprises a surface layer having a pore size of from 0.001 to 1 m and an inner support layer having a thickness of from 10 to 500 m.
The first functional group of the membrane substrate is a positively charged, negatively charged or neutral particles, characterized in that it comprises at least one selected from the group consisting of OH, -NH 2, -CN, -CO- , -COOH, -CONH- and Surface modified water repellent water treatment membrane.
Polymerizing the core material with the protecting group to produce a higher order polymer;
Removing the protecting group bound to the second functional group of the higher order polymer; And
A method for producing a water-repellent, water-repellent, or neutral-particle-modified, water-repellent, water-repellent, water-treating separator comprising a separating membrane substrate having a first functional group on at least one surface thereof and a second functional group of the higher order branched polymer using a crosslinking agent .
The core material may be selected from the group consisting of ethanolamine, 3-amino-1,2-propanediol, and tris (hydroxylmethyl) aminomethane. Wherein the water-repellent, water-repellent or neutral-particle surface-modified water-repellent separator comprises at least one selected from the group consisting of water,
Wherein the protecting group is an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and wherein the protecting group is an aromatic hydrocarbon group or an aliphatic hydrocarbon group.
Wherein the high order polymer is a hyperbranched polyglycerol (HPG). The method of claim 1, wherein the high-order polymer is hyperbranched polyglycerol (HPG).
Wherein the monomer is surface-modified with positively charged, negatively charged or neutral particles characterized by glycidol.
Further comprising the step of introducing a positive charge or a negative charge to the terminal of the higher order branched polymer before or after removing the protecting group of the higher order branched polymer. Gt;
Wherein the step of introducing the positive charge comprises a step of replacing the terminal of the higher order branched polymer with at least one of a quaternary ammonium group, a phosphonium group and a sulfonium group. (2).
Wherein the step of introducing the negative charge comprises a step of replacing the terminal of the higher order oligomer by a sulfonic group or a phosphoric acid group.
The separation membrane base material having the first functional group is characterized in that a functional group is formed on at least one surface of the separation membrane substrate by at least one of ultraviolet irradiation, electron beam irradiation, plasma irradiation and acidic or basic solution treatment. Wherein the water-repellent water-treating separator has a surface modified with water.
The step of bonding using the crosslinking agent comprises the steps of: preparing a separating membrane substrate having a crosslinking agent bonded thereto by reacting the separating membrane substrate having the first functional group with a crosslinking agent; And
And reacting the separating membrane substrate to which the crosslinking agent is bound with a second functional group of the higher order branched polymer, wherein the crosslinking agent is reacted with the second functional group of the higher order branched polymer.
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| CN112808033A (en) * | 2021-01-14 | 2021-05-18 | 浙江大学 | Method for preparing antibacterial anti-pollution filter membrane based on charge regulation and control |
| CN115400604A (en) * | 2022-09-06 | 2022-11-29 | 西北工业大学 | Positive charge nanofiltration membrane coating for magnesium-lithium separation and preparation method thereof |
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| CN100337727C (en) * | 2005-10-31 | 2007-09-19 | 浙江大学 | Microporous polymer film containing cross-linked super branched molecule and its prepn |
| KR101361704B1 (en) | 2012-03-08 | 2014-02-11 | 한국과학기술연구원 | Membrane for water-filtering and fabricating method thereof |
| CN103263858B (en) | 2013-05-15 | 2015-05-27 | 北京工业大学 | Cross-linking hyperbranched polymer composite nano filtration membrane prepared by one step method in water phase, preparation method and application |
| KR101394872B1 (en) | 2014-03-06 | 2014-05-13 | (주)엠비티 | Flat-membrane cartridge for filtration and flat-membrane filtration module |
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2015
- 2015-08-13 KR KR1020150114841A patent/KR101826340B1/en active IP Right Grant
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| CN112808033A (en) * | 2021-01-14 | 2021-05-18 | 浙江大学 | Method for preparing antibacterial anti-pollution filter membrane based on charge regulation and control |
| CN112808033B (en) * | 2021-01-14 | 2022-05-10 | 浙江大学 | Method for preparing antibacterial anti-pollution filter membrane based on charge regulation and control |
| CN115400604A (en) * | 2022-09-06 | 2022-11-29 | 西北工业大学 | Positive charge nanofiltration membrane coating for magnesium-lithium separation and preparation method thereof |
| CN115400604B (en) * | 2022-09-06 | 2023-08-18 | 西北工业大学 | Positive charge nanofiltration membrane coating for magnesium-lithium separation and preparation method thereof |
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