KR101294270B1 - Hydrphobic chain of amphiphilic dendritic polymer self-assembled membrane for adsorption of metallic ion and method for preparation thereof - Google Patents

Abstract

The present invention is a metallic ion adsorption membrane comprising a metal ion adsorption membrane self-assembly hydrophobic chain of amphiphilic dendritic polymer, an amphiphilic dendritic polymer having a hydrophobic chain and a polymer for forming a membrane A method of preparing a metallic ion adsorption membrane in which a composition for coating and a metallic ion adsorption membrane coating composition is applied onto a support and poured into a hydrophilic coagulation liquid to self-assemble a hydrophobic chain of an amphiphilic dendritic polymer on the surface thereof and the metallic ion The present invention relates to a method for removing heavy metal ions in a solution using an adsorption membrane. According to the present invention, the metal ion adsorption membrane can be manufactured in a short time at low cost, the metal ion can be adsorbed with high efficiency, and it is economical because the metal ion adsorbed membrane can be removed and the metal ion adsorption membrane can be reused only by acid / base control. .

Description

Hydrphobic chain of amphiphilic dendritic polymer self-assembled membrane for adsorption of metallic ion and method for preparation of the amphiphilic chain of amphiphilic polymer

The present invention relates to a membrane for adsorption of metallic ions, a method for preparing the same, and a method for removing metallic ions in water using the same.

Heavy metal ions emitted from industrial wastewater, agricultural activities, and industrial waters pose a deadly danger to humans and ecosystems through various routes. Heavy metal ions inhibit or interfere with the essential chemical action of cells or biomolecules in the body, and pose a lethal danger to the biochemical function of biological species through the action of destroying the properties of the biomembrane in the body. It was found to give (Bayramoglu G, Arica MY, Bektas S. J. Appl . Polym . Sci . 2007 , 106 , 169). The risk of such heavy metals can be confirmed through the case of itai-itai disease caused by cadmium poisoning and Minamata disease caused by mercury poisoning.

Accordingly, the environmentally friendly method (LOHAS) and environmental pollution prevention technologies are attracting attention, and technologies for adsorbing or detecting various environmental pollution-causing substances including heavy metal ions have been actively studied. For example, the adsorption of heavy metal ions using an adsorbent has advantages in process convenience, economical efficiency, and high removal efficiency even at low concentrations of heavy metals, and performance of various materials as an adsorbent has been studied. In particular, it has been reported that carbon materials such as activated carbon and carbon nanotubes, which have excellent thermal stability and high chemical stability against acids and bases, may be used as adsorbents for heavy metal removal (Xiao B , Thomas KM. Langmuir 2005, 21 , 3892, Wang H, Zhou A, Peng F, Yu H, Yang J. J. Colloid . Interface . Sci . 2007, 316 , 277).

In addition, as a part of this, a method of removing heavy metals using a dendritic polymer has been used, but this requires a repeated step reaction to increase the number of generations of dendrimers. If the dendrimer alone is used, the removal and removal rate of harmful substances in the water can be increased, but the inefficiency of separating them and the loss of dendrimers occur, thus removing the existing hazardous substances in water (chemical precipitation method, evaporation method, liquid film method). , It is difficult to expect economic advantages compared to oxidation / reduction method, ion exchange method, reverse osmosis membrane method and electrolysis method.

Accordingly, the problem to be solved by the present inventors is to prepare a dendritic polymer that exhibits properties and functionality similar to dendrimers in a one-pot reaction rather than a complex and repetitive step reaction, and to fuse it to the membrane, low cost, It is to provide a metal ion adsorption membrane which can remove harmful substances with high efficiency.

In order to solve the above problems, in one aspect the present invention provides a metallic ion adsorption membrane is self-assembly (self-assembly) on the surface of the hydrophobic chain of the amphiphilic dendritic polymer.

Since the dendritic polymer is fused to the metallic ion adsorption membrane, the characteristic exhibited by the dendritic polymer, in particular, prevents chain entanglement due to a high density branch structure, excellent molecular mobility, and enables internal capture of harmful substances in water such as heavy metals ( cavity), including a number of high-density functional groups at the inside and the end, molecular weight and structure prediction, and its controllability.

The dendritic polymer has both hydrophilic and hydrophobic moieties.

It is preferable that the hydrophilic portion of the dendritic polymer has a higher branched structure having a multi-functional bonding site and a plurality of functional groups capable of conjugating metallic ions. The functional group may be, for example, one or more functional groups selected from the group consisting of -CH _2- , -CONH-, and -NH _2- , but is not limited thereto. The functional group forms a non-covalent electron pair with the metal ion, thereby efficiently conjugating the metal ion in the solution. The functional group is a terminal of the dendritic polymer of higher order structure And inside.

The hydrophobic portion of the dendritic polymer consists of a hydrophobic chain, and the hydrophobic chain is not limited thereto, but preferably a substituted or unsubstituted alkyl chain having 5 to 18 carbon atoms. The hydrophobic chain may include about 3 to about 12 per dendritic polymer, but is not limited thereto. The hydrophobic chain of the dendritic polymer is self-assembly at the membrane surface, and the dendritic polymer is fused to the membrane. The phenomenon of forming a higher order structure.

The monomer of the dendritic polymer may be, for example, an organic molecular sieve including at least one functional group selected from the group consisting of -CO-, -COO-, -CONH-, and -NH _2- , but is not limited thereto. Do not.

In addition, the molecular weight of the dendritic polymer may have a 3000 to 15000 gmol ^-1 , but is not limited thereto.

In another aspect, the present invention provides a metal ion adsorption membrane coating composition comprising an amphiphilic dendritic polymer having a hydrophobic chain and a polymer for forming a membrane.

The film forming polymer may be at least one selected from the group consisting of polysulfone, polyimide, polyamideimide, polyamide, polyacrylonitrile, and polyvinylidene fluoride, but is not limited thereto.

The metal ion adsorption membrane coating composition may further include an organic solvent or an additive in addition to the amphiphilic dendritic polymer and the membrane-forming polymer. Examples of the organic solvent include, but are not limited to, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone, and cyclohexa Paddy rice, 3-hexanone, 3-heptanone, 3-octanone, and mixtures thereof, and the like, including but not limited to water; One alcohol selected from the group consisting of methanol, ethanol, 2-methyl-1-butanol, 2-methyl-2-butanol, glycerol, ethylene glycol, diethylene glycol and propylene glycol; One ketone selected from the group consisting of acetone and methyl ethyl ketone; One polymer compound selected from the group consisting of polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyethylene glycol, polypropylene glycol, chitosan, chitin, dextran and polyvinylpyrrolidone; One salt selected from the group consisting of lithium chloride, sodium chloride, calcium chloride, lithium acetate, sodium sulfate and sodium hydroxide; Tetrahydrofuran; Trichloroethane; And it may be one selected from the group consisting of a mixture thereof.

The metal ion adsorption membrane coating composition preferably comprises 10 to 20% by weight of the membrane-forming polymer, 1 to 10% by weight of the dendritic polymer, 60 to 85% by weight of the organic solvent and 2 to 20% by weight of the additive, This is not restrictive.

The shape of the metallic ion adsorption membrane according to the present invention may be any type of metal oxide adsorption, but is not limited thereto, but may be, for example, in the form of a flat membrane or a hollow fiber membrane.

In another aspect, the present invention is applied to the composition for coating the metal ion adsorption membrane according to the present invention on a support, and put into a hydrophilic coagulating liquid, the metal ion in which the hydrophobic chain of the amphiphilic dendritic polymer self-assembled on the surface It provides a method for producing an adsorption membrane.

Conventional dendritic polymer production methods include, for example, divergent synthesis and convergent synthesis. Divergent synthesis is a synthetic method that grows the outer structure by activating and growing step by step from one central molecule. It is a method of synthesizing repeatedly by activation and growth from the outermost terminal group of the dendrimer to the center direction (P. Hodgem, Nature, 362, 18 (1993), CJ Hawker and JMJ Frechet, J. Am. Chem. Soc. , 112, 7638 (1990).). For example, poly (amido amine (PAMAM)) dendrimers used molecules such as ammonia, ethylenediamine (EDA), and propyldiamine as their central molecules, and then reacted with methyl acrylate and Michael , Michael was synthesized by repeating amidation with EDA and Michael addition reaction (DA Tomalia, AM Naylor, and WA Goddard III, Angew. Chem. Int. Ed. Engl., 29, 138 (1990)).

This method takes a lot of time and money, the present inventors have developed a method for producing an amphiphilic dendritic polymer in the following manner. Specifically, the amphiphilic dendritic polymer is prepared by dissolving an ester compound in a solvent; Reacting amine compounds; And reacting with a hydrophobic compound after dissolving the reactant. More specifically, according to the target molecular weight of the mixture of esters and amines, the ratio is adjusted to 1: 4 to 10 (esters: amines) to perform the reaction under argon environmental conditions at 50 to 140 ° C for 12 to 48 hours. At this time, the reaction may be carried out while adding an amine compound to the ester compound to obtain a hydrophilic portion of the dendritic polymer and react with the hydrophobic compound to obtain an amphiphilic dendritic polymer. According to a specific embodiment of the present invention, methyl acrylate (methyl acrylate) ester compound in methanol and dissolved for 30 minutes while maintaining 0 ~ 5 ° C, amine compound ethylenediamine (ethylenediamine) was added for 2 hours After carrying out the reaction and raising the temperature to 23 ° C. and further reacted for 24 hours; Additional ethylenediamine was added to carry out the synthesis under argon at a temperature of 50 ° C. for 24 hours. Then, in order to prepare to have a hydrophobic chain, the previously obtained preparation was dissolved in chloroform, triethylamine was added together to dissolve together, and a palmitoyl chloride solution dissolved in chloroform was added to the container. After dropping slowly, the reforming reaction was carried out for 24 hours, and precipitated in methanol to obtain a final product through filtration (Example 1). According to this method, an amphiphilic dendritic polymer can be easily produced in a one-pot reaction easily and within a short time.

In order to manufacture a metallic ion adsorption membrane, the composition for applying a metallic ion adsorption membrane according to the present invention comprising an amphiphilic dendritic polymer prepared by the above method is applied on a support, but the support is not limited thereto. For example, it may be a glass plate, a polyester film, a nonwoven-polysulfone porous support or a nonwoven-polyvinylidene fluoride porous support.

The method of applying the composition for applying the metallic ion adsorption membrane on the support is in accordance with methods known in the art, for example, by spinning or casting, according to a specific embodiment of the present invention a film applicator It was applied using.

In the next step, the support on which the composition for coating the metal ion adsorption membrane is applied is introduced into a hydrophilic coagulation liquid. By the addition, the hydrophilic portion of the amphiphilic dendritic polymer in the composition for applying the metallic ion adsorption membrane is aligned toward the hydrophilic coagulating liquid portion and the hydrophobic chain is solidified by self-assembly on the membrane surface. . In a specific embodiment of the present invention as a hydrophilic coagulant, a mixture of water and NMP mixed at 95: 5 was used, but is not limited thereto.

Additionally, the method may further include washing the solidified metallic ion adsorption membrane with a washing solution and then drying the hydrophilic coagulating solution.

The metal ion adsorption membrane according to the present invention is economical because it is possible to adsorb the metal ions with high efficiency, remove the adsorbed metal ions only by controlling the acid group and reuse the metal ion adsorption membrane.

Therefore, in another aspect, the present invention is a step of adsorbing a metal ion adsorption membrane self-assembled hydrophobic chain of amphiphilic dendritic polymer in a solution containing heavy metal ions on the surface to adsorb heavy metal ions in the solution, and the adsorbed heavy metal It provides a method for removing heavy metal ions in a solution, comprising the step of washing ions through acid group control.

The heavy metal ions include, but are not limited to, copper (Cu (II)), nickel (Ni (II)), zinc (Zn (II), lead (Pb (II), cadmium (Cd (II)), and mercury ( Hg (II)) may be one or more heavy metal ions selected from the group consisting of.

In addition, when the concentration of the heavy metal ions in the solution is 1 ~ 1000 ppm the method according to the present invention can be applied effectively, but is not limited to this can also be used to remove other harmful substances other than heavy metal ions.

In addition, since the heavy metal ions adsorbed can be easily separated and removed only by adjusting the acid base, the washing solution can be continuously used, but the washing solution is not limited thereto. For example, pH 6 or less, such as hydrochloric acid, nitric acid, and sulfuric acid solutions Acid solutions can be used.

In addition, the use of the metal ion adsorption membrane according to the present invention has been described a method for removing heavy metal ions in solution, but is not limited to this exemplary use can be applied and applied to a variety of future applications, these uses of the scope of the present invention It doesn't go away.

By using the metal ion adsorption membrane according to the present invention, it is possible to effectively remove harmful substances such as heavy metal ions in the water and to reduce membrane fouling due to the hydrophilic portion of the dendritic polymer as well as acid ㆍ It is possible to reuse the membrane because it can easily separate and remove the harmful substances collected by controlling base condition.

1 is a schematic diagram showing an amphiphilic dendritic polymer.
2 is a schematic diagram showing a membrane structure according to the present invention.
3 is a schematic diagram of a mechanism for removing harmful substances in water such as heavy metals according to the present invention.
4 is a schematic view showing a film production method according to the present invention.
5 is an infrared spectroscopic analysis (FT-) of a hydrophilic dendritic polymer (HYPAM) produced according to Example 1 (a) and an amphiphilic dendritic polymer (a-HYPAM) produced according to Example 1 (b). IR) spectrum is shown.
Figure 6 shows the nuclear magnetic resonance spectroscopy (Quantitative ¹³ C NMR) spectrum of the hydrophilic dendritic polymer produced according to Example 1 (a).
7 shows nuclear magnetic resonance spectroscopy ( ¹ H NMR) spectra of a hydrophilic dendritic polymer produced according to Example 1 (a) and an amphiphilic dendritic polymer produced according to Example 1 (b). .
FIG. 8 shows attenuated total reflection infrared spectroscopy (ATR-FTIR) spectra for the film (a) prepared according to Example 3 (a) and the film (b) prepared according to Example 3 (b).
FIG. 9 shows X-ray photoelectron spectroscopy (XPS) spectra of a polysulfone film (film (a)) and a polysulfone film (film (b)) having an amphiphilic dendritic polymer attached thereto.
10 shows the results of thermogravimetric analysis of the membranes (a) and (b).
FIG. 11 is a graph showing the amount of cadmium trapped in the cadmium trapping test performed in Example 5 with respect to the cadmium.

Hereinafter, embodiments of the present invention will be described in detail to facilitate understanding of the present invention. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the following embodiments. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.

< Example  1> hydrophobic Alkyl  Chains and hydrophilic polymer chains Dendritic  Synthesis of polymer

< Example  1 (a)> containing hydrophilic polymer chains Dendritic  Synthesis of polymer

30 mL of methanol is added to a 250 mL three-necked flask, and 8.61 g (100 mmol) of methyl acrylate, an ester substance having a carbon-carbon double bond, is added. Place the container in an ice bath and stir for 30 minutes while maintaining 0-5 ° C to dissolve well. 1.50 g (25 mmol) of amine-based ethylenediamine is slowly dropped into the vessel, followed by a 2 hour synthetic reaction, followed by further reaction for 24 hours. After removal of the solvent and the unreacted substance through a rotary evaporator, 10.52 g (175 mmol) of ethylenediamine is added to carry out the synthesis reaction under an argon environment at a temperature of 50 ° C for 24 hours. The product was obtained by performing a further reaction for 1 hour at 60 ° C, 2 hours at 100 ° C, 2 hours at 120 ° C, 2 hours at 140 ° C using a rotary concentrator, respectively.

< Example  1 (b)> hydrophobic Alkyl  Chain Amphibian Dendritic  Synthesis of polymer

In order to obtain an amphiphilic dendritic polymer, the product obtained above is dissolved in chloroform and 4.25 g of triethylamine is added to dissolve together. A solution of 5.77 g of palmitoyl chloride, previously dissolved in chloroform, was slowly dropped into the vessel, reformed for 24 hours, and precipitated in methanol to obtain a final product through filtration.

< Example  2> manufactured Dendritic  Structural Analysis of Polymers

Qualitative evaluation of the synthesis of dendritic polymer prepared according to Example 1 was analyzed using infrared spectroscopy (FT-IR). In addition, quantitative structural analysis and degree of substitution of terminal amino groups were evaluated using nuclear magnetic resonance spectroscopy ( ¹³ C NMR, ¹ H NMR).

From these results, it can be seen that the dendritic polymer obtained according to the preparation method is composed of a hydrophobic group composed of an alkyl chain and a hydrophilic group having a plurality of functional groups and cavities capable of trapping harmful substances in water.

(1) infrared spectroscopy FT - IR )

5 is a qualitative analysis of the hydrophilic dendritic polymer (HYPAM) synthesized in Example 1 (a) and the amphiphilic dendritic polymer (a-HYPAM) prepared in Example 1 (b) using infrared spectroscopy. The result is. Hydrophilic dendritic polymer has characteristic peaks (peak) is the stretch (stretch) and the bend (bend) of each terminal amino group (NH) in about 3600 ~ 3200 cm ^-1 and 1555 cm ^-1 appears, 3100 ~ 2900 cm ^-1 in the CH stretch appears and 1640 cm ^{- 1,} it was confirmed that the fine composite appears as a stretching of the amide group (C = O). Modification of the terminal amino group to palmitol chloride with a long aliphatic chain results in a strong absorption peak of NH stretch at 3300 cm ⁻¹ and a strong absorption peak of CH stretch due to long aliphatic chain at 3100-2900 cm ⁻¹ . It was confirmed that the modified amphiphilic polymer.

(2) nuclear magnetic resonance spectroscopy ( ¹³ C NMR , ^One H NMR )

FIG. 6 shows the results of quantitative structural analysis (HYPAM) of the hydrophilic dendritic polymer synthesized in Example 1 (a) using Quantitative ¹³ C NMR. First, 0.058 g (0.64 mmol) of tetramethylammonium hydroxide ((CH ₃ ) ₄ NOH) was used as a reference material, and 0.14 g of dendritic polymer was dissolved in D ₂ O substituted with deuterium, followed by analysis. . The characteristic peaks of each carbon are shown from a to i, and the abundance ratio of each carbon and the amount of functional groups were obtained from the integral ratio with the reference material. The primary amine in the dendritic polymer was 5.03 mmolg ^-1 , the third amine was 3.43 mmolg ^-1 , the amide was 6.22 mmolg ^-1 , and the ester was 1.19 mmolg ^-1 . The number of functional groups per molecule was determined by calculating the weight average molecular weight (3600 gmol ^-1 ) of the dendritic polymer determined by the multi-angle light scattering (MALS) analysis. As a result, 18.1 primary amines, 12.4 tertiary amines, 22.4 amides, and 4.28 esters were found.

7 is a result of confirming the degree of substitution of the amphiphilic dendritic polymer (a-HYPAM) prepared in Example 1 (b) using ¹ H NMR. Each material was analyzed by dissolving in chloroform (CDCl ₃ - d ) substituted with deuterium. It was confirmed that the characteristic peak of each material appeared from 1 to 12, and that the modified peak was confirmed by confirming that the peaks of 9 to 12, which are characteristic peaks of palmitole chloride, appeared in the spectrum of amphiphilic dendritic polymer. It was confirmed that 8.67 primary amine groups were substituted with hydrophobic groups by determining the integral ratio between peaks 1 and 11 corresponding to the primary amine.

< Example  3> Dendritic  Polymer end  Attached Water Treatment Membrane Manufacturing

Amphiphilic dendritic prepared in Example 1 to capture polysulfone as a polymer for film formation, N-methyl-2-pyrrolidone (NMP) as a solvent, and harmful substances in water The membrane was prepared using the polymer as an additive. According to the composition shown in Table 1 below, each component was mixed to prepare a uniform dope solution.

division Sample name Polysulfone NMP Amphiphilic dendritic polymer Remarks Example 3 (a) Membrane (a) 0.75 4.25 Control group Example 3 (b) Membrane (b) 0.26

 (Unit: g)

The prepared dope solution was applied to a glass plate using a film applicator, and then put into a coagulation bath containing a hydrophilic coagulant (water: NMP = 95: 5 (w / w)) for 24 hours. Keep it. The prepared membrane was washed with distilled water at room temperature for 24 hours and then dried in a convection oven at 50 ° C. for 24 hours.

< Example  4> Dendritic  Polymer end  Structural Analysis of Attached Membranes

Attenuated total reflection infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) were used for surface analysis of the film prepared in Example 3. In addition, the amount of adhesion was measured through thermogravimetric analysis (TGA).

(One) Total attenuation  Infrared spectroscopy ATR - FTIR )

The chemical structure was analyzed by confirming the characteristic functional groups on the membrane surface prepared in Example 3, and the presence or absence of adhesion of the dendritic polymer was confirmed. 8 is a qualitative analysis result of two films prepared in Example 3 using attenuated total reflection infrared spectroscopy. Example 3 (a) Referring to the film characteristic peak appears and manufactured by the CH stretch at approximately 3100 ~ 2800 cm ^-1 1585 cm ^- confirmed to appear a strong absorption peak of the aromatic C = C stretch at ¹ and 1488 cm ^-1 At 1150 cm ^-1 , strong absorption peaks of S = O stretch were observed. This was all confirmed to be due to the chemical structure of the polysulfone. The membrane of Example 3 (b) also confirmed the same absorption peak at the same wavenumber, and additionally a strong absorption peak corresponding to an NH stretch at 3299 cm ⁻¹ and an amide C═O stretch at 1640 cm ⁻¹ . Confirmed. This is the same peak found in the chemical structure of the dendritic polymer attached to the membrane confirmed that it was successfully attached.

(2) X-ray photoelectron spectroscopy ( XPS )

The chemical structure was analyzed by surface element analysis of the two membranes prepared in Example 3, and the presence or absence of adhesion of the dendritic polymer was confirmed. 9 shows elemental analysis results of two films prepared in Example 3 using X-ray photoelectron spectroscopy. The film prepared in Example 3 (a) did not show a characteristic peak at N _1s and the binding energy (binding energy) at O _1s was confirmed to appear a characteristic peak due to O = S = O at 533 eV. On the other hand, in the case of the membrane prepared in Example 3 (b), it was confirmed that a strong peak due to amino (-NH-) and amide (-NHCO-) at 399 eV at N _1s and O = S at O _1s Not only the peak of = O but also the peak attributable to C = O of the amide at 532 eV appeared. From these characteristic peaks, it was confirmed that the dendritic polymer was well attached.

(3) thermogravimetric analysis TGA )

10 is a graph showing the weight loss according to the temperature of the membrane prepared in Example 3 using thermogravimetric analysis. Looking at the weight loss of the membrane prepared in Example 3 (a) it can be seen that the decrease began at a slight decrease at about 480 ° C and rapidly decreases at 500 ~ 550 ° C. This is because polysulfone, which is a support, causes a transition, and its onset temperature is 500 ° C. The film prepared in Example 3 (b) began to gradually decrease in weight at about 250 ° C., and then rapidly decreased at 280 ~ 350 ° C. and then rapidly decreased in the 500 ~ 550 ° C section. Through this, it was confirmed that the transition start temperature of the dendritic polymer was 280 ° C, and the decrease in width up to 500 ° C was confirmed to be attached to the membrane by 25.02wt% of the total weight of the membrane.

< Example  5> Dendritic  Polymer end  Heavy metals on attached membrane Capture  And membranes through recovery Recovery rate  evaluation

In order to evaluate the recovery rate through the heavy metal collection and recovery of the membrane prepared in Example 3, the experiment was performed under the conditions described in Table 2. Evaluation was carried out by attaching membranes prepared using a stirred cell, and the effective area of the membranes used was 13.4 cm ² .

division
Capture
collection
flux
Total measurement time
Remarks
heavy metal Measuring interval Membrane (a) 25 ppmCd (II) Every 30 minutes
0.1 MHCl
0.1 mL / min 180 minutes Control group Membrane (b)

11 is a result showing the accumulated amount after measuring the cadmium concentration of the sample under the above conditions using inductively coupled plasma atomic emission spectrometry (ICP-AES). The total amount of cadmium ions added was 450.7 μg , and among the membranes (a) prepared in Example 3 (a), the cumulative collection amount was 5.1 μg, which was very low. In contrast to the third embodiment with (b) an den result 197.5 μ g which showed a high absorption capacity to 228.6 μ g for laundry tick the film (b) is attached to a polymer recovering cadmium in the acid treatment solution prepared from a 86.7% It showed a high membrane recovery rate.

Claims (13)

A metal ion adsorption membrane for removing heavy metal ions in a solution in which a hydrophobic chain of an amphiphilic dendritic polymer is self-assembled on a surface thereof. The metallic ion adsorption membrane of claim 1, wherein the dendritic polymer has a plurality of functional groups capable of conjugating metallic ions. The metal ion adsorption membrane of claim 2, wherein the functional group is at least one functional group selected from the group consisting of -CH _2- , -CONH-, and -NH _2- . The metal ion adsorption membrane of claim 1, wherein the hydrophobic chain is a substituted or unsubstituted alkyl chain having 5 to 18 carbon atoms. The metal ion adsorption membrane of claim 1, wherein the hydrophobic chain comprises 3 to 12 per dendritic polymer. The composition for coating a metal ion adsorption membrane comprising an amphiphilic dendritic polymer having a hydrophobic chain and a membrane-forming polymer is coated on a support, and then injected into a hydrophilic coagulating solution, so that the hydrophobic chain of the amphiphilic dendritic polymer is coated on the surface. A method for preparing a metallic ion adsorption membrane for removing heavy metal ions in a self-assembled solution. The method of claim 6, wherein the film-forming polymer is at least one selected from the group consisting of polysulfone, polyimide, polyamideimide, polyamide, polyacrylonitrile, and polyvinylidene fluoride. The method of claim 6, wherein the metallic ion adsorption membrane coating composition further comprises an organic solvent or an additive. The method of claim 8, wherein the metallic ion adsorption membrane coating composition comprises 10 to 20% by weight of the membrane-forming polymer, 1 to 10% by weight dendritic polymer, 60 to 85% by weight of the organic solvent and 2 to 20% by weight of the additive Characterized in that it comprises a method. delete The method of claim 6, wherein the amphiphilic dendritic polymer in the composition for applying the metallic ion adsorption membrane is a step of dissolving an ester compound in a solvent; Reacting amine compounds; And reacting with a hydrophobic compound after dissolving the reactant. Adsorbing heavy metal ions in the solution by introducing a self-assembled metallic ion adsorption membrane onto the surface of a hydrophobic chain of amphiphilic dendritic polymer in a solution containing heavy metal ions, and adjusting the adsorbed heavy metal ions through acid / base control A method of removing heavy metal ions in a solution, comprising the step of washing. The method of claim 1, wherein the amphiphilic dendritic polymer molecular weight is characterized in that the 3000 to 15000 gmol ^-1 , the metal ion adsorption membrane for removing heavy metal ions in the solution.

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