KR101759998B1 - Ion-exchange polymer containing catechol group, preparation method and application thereof - Google Patents
Ion-exchange polymer containing catechol group, preparation method and application thereof Download PDFInfo
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- KR101759998B1 KR101759998B1 KR1020150156833A KR20150156833A KR101759998B1 KR 101759998 B1 KR101759998 B1 KR 101759998B1 KR 1020150156833 A KR1020150156833 A KR 1020150156833A KR 20150156833 A KR20150156833 A KR 20150156833A KR 101759998 B1 KR101759998 B1 KR 101759998B1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The present invention relates to an ion exchange polymer having a catechol group, a method for producing the same, and an application thereof, and more particularly, to an ion exchange polymer having both an adhesive force and an ion exchange ability, and a method for producing the same.
According to the present invention, it is possible to provide an ion-exchange polymer having both an adhesive force and an ion-exchange capacity by polymerizing a monomer having a catechol (1,2-dihydroxybenzene) group and a monomer having an ion exchange ability. The ion exchange polymer according to the present invention includes catechol group as one component, and can improve the adhesion, desalination performance, and durability between the carbon electrode and the ion exchange polymer.
Further, by coating the ion exchange polymer with a carbon electrode such as (M) CDI or FCDI to integrate the ion exchange membrane and the electrode, or by manufacturing a flow electrode having a core shell structure, a carbon electrode having a low electric resistance and having ion- The cell assembly can be simplified, and unnecessary costs such as replacement of the ion exchange membrane can be reduced. In addition, the adsorption capacity and efficiency of the carbon electrode used for desalination or water treatment can be remarkably improved.
Description
The present invention relates to an ion exchange polymer having a catechol group, a method for producing the same, and an application thereof, and more particularly, to an ion exchange polymer having both an adhesive force and an ion exchange ability, and a method for producing the same.
Capacitive deionization (CDI) is a water treatment technology that is useful for securing water resources and manufacturing ultrapure water for the semiconductor industry. It utilizes the principle of adsorbing ions having charges opposite to the cathode and anode through electricity (Yoram Oren, Desalination, 2008, 228, 10-29 .; Marc A. Anderson, Ana L. Cudero, Jesus Palma, Electrochimica Acta, 2010, 55, 3845-3856.). Conventional CDI has a disadvantage in that the process and desalination efficiency is not high due to limited adsorption capacity and high internal resistance by using fixed electrode and ion exchange membrane respectively (S. Porada et al., Progress in Materials Science, 2013, 58, 1388- 1442).
The flow-electrode capacitive deionization (FCDI) using a flow electrode is a technique that improves the repetitive desorption process by the ion saturation adsorption of the carbon fixed electrode which is a conventional CDI problem. The FCDI unit cell is composed of a flow electrode of activated carbon slurry and an ion exchange membrane. It is a system in which salt ions flowing into a cathode current collector pass through an ion exchange membrane and then an electric double layer is formed in the flow electrode pore. The flow-electrode capacitive deionization (FCDI) using a flow electrode is a desalination technique using a carbon electrode in the fluid phase (S. Jeon et al, Energy Environmental Science, 2013, 6, 1471-1475) There has been a lack of a technique for improving the repetitive desorption process by the ion saturation adsorption of the fixed electrode and a method for improving the adsorption ability and efficiency of the carbon electrode.
The present invention provides an ion exchange polymer having a catechol group, which has both adhesive strength and ion exchange ability, and a method for producing the same. The present invention also provides an ion-exchange carbon electrode using the ion-exchange polymer, a method for producing the same, an ion-exchange membrane, and a method for producing the same.
The present invention relates to a method for producing a catechol compound, comprising the steps of: (a) synthesizing a third monomer having a catechol group by reacting a first monomer having a catechol group with a second monomer having at least one selected from an acrylic monomer or a methacrylic monomer, ; And a step (b) of reacting a third monomer having the catechol group with a monomer having an ion exchange capacity (step b).
Synthesizing a third monomer having a catechol group (step a)
The first monomer in step (a) is a monomer having a catechol structure with excellent adhesion, and catecholamines and benzoates may be suitable.
The first monomer of step a is specifically selected from the group consisting of dopamine, epinephrine, norepinephrine, 1,2-dihydroxybenzoic acid and 3,4-dihydroxybenzoic acid (3,4 dihydroxybenzoic acid), and more preferably, it may be dopamine.
The catechol group is a functional group with high adhesion to fluorine-based polymers such as PTFE as well as metals. Ion exchange polymers, which contain catechol as a component, help improve adhesion, desalination and durability between carbon electrodes and ion-exchange polymers. .
The second monomer in step (a) may be an acrylic or methacrylic monomer. More preferably, acrylic or methacrylic monomers may be monomers in the form of anhydride or carboxylic acid. Specifically, the second monomer of step a is selected from the group consisting of methacrylic anhydride, crotonic anhydride, 4-pentenoic anhydride and 2-methylenesuccinic anhydride 2-methylenesuccinic anhydride, and more preferably methacrylic anhydride or crotonic anhydride.
The third monomer synthesized in step a may include one or more selected from acrylamide monomer having a catechol group or methacrylamide monomer having a catechol group.
The step (a) may be carried out by adding the second monomer solution to the first monomer solution and reacting the mixture at 0 to 50 ° C for 1 to 24 hours, more preferably at room temperature for 12 hours have.
The first monomer solution may be a basic aqueous solution.
The solution of the second monomer (acrylic or methacrylic monomer) is dissolved in tetrahydrofuran (THF), chloroform, acetone, ethyl acetate, dichloromethane and 1,4-
Reacting a third monomer having a catechol group with a monomer having ion exchange ability (step b)
The ion-exchangeable monomer may be a styrene-based monomer having an ammonium group or a vinyl-based monomer. The ammonium group may be a trimethylammonium group (-N (CH 3 ) 3 + ).
Specifically, the ion-exchangeable monomer is preferably selected from the group consisting of [2- (methacryloyloxy) ethyl] trimethylammonium chloride, (3-acrylamidopropyl) trimethylammonium chloride (3-acrylamidopropyl) trimethylammonium chloride, [2- (acryloyloxy) ethyl] trimethylammonium chloride, [3- (methacryloylamino) propyl] trimethyl Trimethylammonium chloride, (vinylbenzyl) trimethylammonium chloride and N - [(ω-methacryloyl) -octadecyl] trimethylammonium chloride (N - [(ω-methacryloyl) -octadecyl] trimethyl ammonium chloride, and more preferably (vinylbenzyl) trimethyl ammonium chloride.
The step (b) may be carried out by dissolving the monomer having ion exchange capacity with the third monomer in a solvent and reacting the mixture at 60 to 80 ° C for 3 to 36 hours, more preferably at 70 ° C for 24 hours .
The solvent may be selected from the group consisting of dimethylformamide (DMF), tetrahydrofuran, chloroform, ethylene glycol, 1,4-dioxane, 1,2-dimethoxyethane, A polar organic solvent such as hexamethylphosphoramide or an alcohol such as methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, 2-butanol and the like.
In step b, an initiator may be added. Initiators may be azo-based or peroxide-based. Specifically, the initiator may be at least one selected from the group consisting of 2,2'-azobisisobutyronitrile (AIBN), 1,1'-azobis (cyclohexanecarbonitrile) 4,4-azobis (4-cyanovaleric acid), tert-amyl peroxybenzoate, benzoyl peroxide (4-azobisisobutyronitrile) benzoyl peroxide, lauroyl peroxide, potassium persulfate, tert-butyl peroxide, and tert-butyl peracetate. , ≪ / RTI >
The ion-exchange polymer produced by the above method may be an ion-exchange polymer having a catechol structure, which has a repeating unit represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
R 1 and R 2 are each independently H or CH 3 ,
R 3 is CONH (CH 2 ) a Ph (OH) 2 or CO 2 (CH 2 ) b PH (OH) 2 ,
R 4 is (CH 2 ) c NR ' 3 + , R' is H or an alkyl group having 1 to 3 carbon atoms,
a and b are each 1 to 4, c is 0 to 2,
m is from 1 to 9, and n is from 9 to 1.
The molecular weight of the ion-exchange polymer may range from 1000 to 100,000.
Further, the present invention relates to a process for producing a catechol compound, which comprises reacting a third monomer having a catechol group synthesized by reacting a first monomer having a catechol group with a second monomer containing at least one selected from an acrylic monomer or a methacrylic monomer, Wherein the monomer having ion exchange ability is a styrene-based monomer having an ammonium group or a vinyl-based monomer. The concrete contents are the same as those described in the ion-exchange polymer production method described above and therefore will not be described here.
The present invention also provides an ion-exchange polymer having a catechol structure having a repeating unit represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
R 1 and R 2 are each independently H or CH 3 ,
R 3 is CONH (CH 2 ) a Ph (OH) 2 or CO 2 (CH 2 ) b PH (OH) 2 ,
R 4 is (CH 2 ) c NR ' 3 + , R' is H or an alkyl group having 1 to 3 carbon atoms,
a and b are each 1 to 4, c is 0 to 2,
m is from 1 to 9, and n is from 9 to 1.
The molecular weight of the ion-exchange polymer may range from 1000 to 100,000.
The present invention also provides a method for preparing an ion-exchange polymer, comprising: preparing an ion-exchange polymer having a repeating unit represented by Formula 1; And coating the surface of the activated carbon with the ion exchange polymer. The present invention also provides a method of manufacturing an ion exchange carbon electrode having a core shell structure. Here, the ion-exchange polymer may be prepared according to the ion-exchange polymer production method.
The coating may be performed by dissolving the ion-exchange polymer in a solution in which activated carbon is dispersed, and then maintaining the mixture at 20 to 80 ° C for 6 to 48 hours, preferably at 40 to 60 ° C for 12 to 36 hours, More preferably, the reaction can be carried out at 50 DEG C for 24 hours.
The present invention also relates to a method for producing a carbon nanotube; And an ion exchange layer coated on the surface of the activated carbon with an ion exchange polymer having a repeating unit represented by the formula (1). Here, the ion-exchange polymer may be prepared according to the ion-exchange polymer production method. The ion-exchange carbon electrode may be used as a fluidized-bed electrode (flow electrode), and may be specifically used for flow-electrode capacitive deionization (FCDI).
The present invention also provides a method for producing a porous support, comprising: hydrophilizing and drying the porous support surface; And coating the porous support with the ion exchange polymer prepared by the above method by supporting the porous support in a solution in which the ion exchange polymer having the repeating unit represented by the formula (1) is dissolved. do. Here, the ion exchange polymer may be prepared by the ion exchange polymer production method.
The coating step may be carried out by supporting the porous support at 20 to 80 ° C for 6 to 48 hours in a solution in which the ion-exchange polymer is dissolved, more preferably at 50 ° C for 24 hours .
The porous support may be an olefin based porous support.
The present invention also relates to a porous support; And an ion exchange layer coated on the surface of the porous support, wherein the ion exchange layer comprises an ion exchange polymer having a repeating unit represented by the formula (1).
According to the present invention, it is possible to provide an ion-exchange polymer having both an adhesive force and an ion-exchange capacity by polymerizing a monomer having a catechol (1,2-dihydroxybenzene) group and a monomer having an ion exchange ability. The ion exchange polymer according to the present invention includes catechol group as one component, and can improve the adhesion, desalination performance, and durability between the carbon electrode and the ion exchange polymer.
Further, the ion exchange polymer is coated on a carbon electrode such as (M) CDI (membrane) capacitive deionization or FCDI (flow-electrode capacitive deionization) to integrate the ion exchange membrane and the electrode or to manufacture a flow electrode having a core shell structure It is possible to manufacture a carbon electrode having an ion exchange ability with a low electric resistance, simplify cell assembly, and reduce unnecessary costs such as replacement of an ion exchange membrane. In addition, the adsorption capacity and efficiency of the carbon electrode used for desalination or water treatment can be remarkably improved.
1 shows the results of 1 H-NMR analysis of an ion-exchange polymer having a catechol group (m = 1 and n = 9 in the formula of FIG. 1), according to an embodiment of the present invention.
Figure 2 shows FT-IR analysis results of an ion exchange polymer having a catechol group, according to an embodiment of the present invention. 2, the PDA is poly (dopamine methacrylamide-co-benzyltrimethylammonium), wherein the molar ratio of dopamine methacrylamide to benzyltrimethylammonium is 2: 8. DMA is dopamine methacrylamide, VBTMA is vinylbenzyltrimetylammonium, and DA is dopamine hydrochloride.
3 is a graph showing the results of UV absorption analysis of an ion exchange polymer having a catechol group, according to an embodiment of the present invention. In Figure 3, DA is dopamine hydrochloride and PDA is poly (dopamine methacrylamide-co-benzyltrimethylammonium).
4 is a graph showing the result of thermogravimetric analysis of an ion exchange polymer having a catechol group according to an embodiment of the present invention.
5 is a photograph showing an ion exchange membrane according to Example 3 (left) and Example 4 (right).
Hereinafter, the present invention will be described in more detail with reference to examples. The objects, features and advantages of the present invention can be easily understood through the following embodiments. It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. Therefore, the scope of the present invention should not be limited by the following examples.
Example 1: Preparation of ion-exchange polymer
1) Synthesis of methacrylamide monomer having catechol group (a)
Sodium borate and sodium bicarbonate were dissolved in distilled water (100 mL) to adjust the pH to 8 and purged with nitrogen for 1 hour. Dopamine (0.03 mol) was dissolved in this solution, and methacrylic anhydride (0.03 mol) dissolved in tetrahydrofuran (THF, 25 mL) was slowly injected. The reaction was carried out at room temperature for 12 hours while maintaining the pH of 8 in a nitrogen atmosphere. The reaction was extracted with ethylacetate and the pH of the water layer was lowered to 2 with 1N HCl (aq). Then, the mixture was extracted with ethyl acetate, and the aqueous layer was again adjusted to pH 7 with sodium bicarbonate (aq), and the organic layer was extracted once more with ethyl acetate. The supernatant was treated with NaCl (aq) and anhydrous MgSO 4 powder was added to remove water from the organic layer and then filtered.
2) Synthesis of acrylamide monomers having a catechol group (b)
Dopamine (1 mol) was dissolved in a solution of sodium borate and sodium bicarbonate after nitrogen bubbling. Crotonic anhydride (1 mol) and triethylamine (1 mol) were dissolved in THF and reacted at 4 ° C in an aqueous solution of dopamine. The pH of the water layer was lowered to 2 with 1N HCl (aq). Then, the mixture was extracted with ethyl acetate, and the aqueous layer was again adjusted to pH 7 with sodium bicarbonate (aq), and the organic layer was extracted once more with ethyl acetate. The supernatant was treated with NaCl (aq) and anhydrous MgSO 4 powder was added to remove water from the organic layer and then filtered.
3) Synthesis of polymer having trimethylammonium group (c)
(Vinylbenzyl) trimethylammonium chloride (0.9 mol) and initiator AIBN ([M] / [I] = 100) prepared in the above manner were dissolved in anhydrous DMF, The reaction was allowed to proceed at 70 DEG C for 24 hours. Precipitated in methanol and then dried.
Example 2: Preparation of ion-exchange carbon electrode
Activated carbon (1 g) was dispersed in sodium borate / sodium bicarbonate solution (100 mL, pH 8), washed with ultrasonic wave for 10 minutes, and then filtered. After dispersing in sodium borate / sodium bicarbonate solution (100 mL, pH 8), 0.5 g of synthesized polymer (C) was added and dissolved. The polymer was coated on the surface of activated carbon by stirring at 50 DEG C for 24 hours.
Example 3: Preparation of ion exchange membrane
The porous support (polypropylene) is immersed in 0.1 M HCl solution to hydrophilize the surface. Washed three times with distilled water and dried. 1 g of the polymer (C) prepared by the above method was dissolved in sodium borate / sodium bicarbonate (100 mL, pH 8) and then supported on a dried porous support. The polymer (c) was coated on the porous support by holding at 50 DEG C for 24 hours, sufficiently washed with distilled water, and dried to prepare an ion exchange membrane having a film thickness of 0.055 mm.
Example 4: Preparation of ion exchange membrane
An ion-exchange membrane having a membrane thickness of 0.170 mm was prepared in the same manner as in Example 3 except that the polymer (1 g) was made different from the porous support (nonwoven fabric).
Experimental Example 1: Characterization of ion-exchange polymer
In order to confirm the synthesis of the ion-exchange polymer (PDA, poly (dopamine methacrylamide-co-benzyltrimethylammonium) and poly (dopamine methacrylamide-co-benzyltrimetylammonium)) prepared according to Example 1, the physical properties of the ion- The results are shown in Figs. 1 to 4.
One H-NMR analysis
The 1 H-NMR analysis for the structure determination of the ion-exchange polymer used D 2 O as a solvent, and the following peaks were confirmed: -CON-H; 8.02 ppm, -CONH-CH 2 - ; 4.10ppm, - catechol benzene (catechol benzene); 6.70 ppm, - benzyl; 7.29 ppm, - trimethyl ammonium; 3.05 ppm.
FR-IR analysis
The results of FT-IR analysis for identifying the functional groups of the ion-exchange polymer are shown in FIG. The following characteristic peaks were confirmed in the ion-exchange polymer according to Example 1, and it was found that ion-exchange molecules having both adhesive strength and ion-exchange capacity were successfully produced: Triethylammonium group 1340-1330 cm -1, an aromatic ring of benzyltrimethylammonium 800-850 cm -1 , and a catechol OH r group 3300-3500 cm -1 . In FIG. 2, the PDA is made of poly (dopamine methacrylamide-co-benzyltrimethylammonium), DMA is dopamine methacrylamide, VBTMA is vinylbenzyltrimetylammonium, DA is dopamine hydrochloride.
UV absorbance analysis
The UV absorbance was measured for the concentration of catechol contained in the ion-exchange polymer (PDA) according to Example 1, and the results are shown in FIG. After measuring the absorbance of dopamine hydrochloride (DA), the catechol concentration in the PDA polymer was measured according to Lambert Beer's law. As a result, it was found that the catechol group contained 35% (w / w) Respectively. In Figure 3, DA is dopamine hydrochloride and PDA is poly (dopamine methacrylamide-co-benzyltrimethylammonium).
Thermogravimetric analysis (TGA) analysis
Trimethylammonium groups were identified by thermogravimetric analysis of the ion-exchange polymer (PDA) according to Example 1. It was confirmed that trimethylamine was decomposed by primary thermal decomposition at around 240 ° C. and benzyltrimethylammonium was decomposed by secondary thermal decomposition at about 320 to 440 ° C.
Experimental Example 2: Resistance Analysis of Ion Exchange Membrane
Ion-exchange membranes of 0.055 mm and 0.170 mm in film thickness were prepared according to Examples 3 and 4, respectively, and their appearance was observed. Also, the film resistance was analyzed using this. As shown in FIG. 5, it was confirmed that the difference in the color of the ion exchange membrane was apparent depending on the content of the ion exchange polymer. The resistance of the ion exchange membrane was measured by using an LCR meter after swelling the ion exchange membrane in a 0.5 M NaCl solution for 24 hours. The difference of the resistance value according to the film thickness was shown. In the case of the film thickness 0.055 mm, the film resistance value was 0.7? Cm 2 , And the membrane resistance value of 2.3 Ωcm 2 at a film thickness of 0.170 mm. If the membrane resistance is low, the resistance to the whole system is reduced. Therefore, it is advantageous that the membrane resistance is low in the case of the storage desalination and the salinity generation.
Claims (21)
Reacting a third monomer having the catechol group with a monomer having ion exchange capability (step b), the method comprising the steps of:
Wherein the ion-exchange polymer has a repeating unit represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
R 1 and R 2 are each independently H or CH 3 ,
R 3 is CONH (CH 2 ) a Ph (OH) 2 or CO 2 (CH 2 ) b PH (OH) 2 ,
R 4 is (CH 2 ) c NR ' 3 + , R' is H or an alkyl group having 1 to 3 carbon atoms,
a and b are each 1 to 4, c is 0 to 2,
m is from 1 to 9, and n is from 9 to 1.
Wherein the first monomer of step a) comprises at least one member selected from the group consisting of dopamine, epinephrine, norepinephrine, 1,2-dihydroxybenzoic acid and 3,4-dihydroxybenzoic acid Lt; RTI ID = 0.0 > (I) < / RTI >
The second monomer of step (a)
Wherein the catechol compound is a compound containing at least one member selected from the group consisting of methacrylic anhydride, crotonic anhydride, 4-pentenoic anhydride and 2-methylenesuccinic anhydride. Method of making polymer.
Wherein the third monomer synthesized in step (a) comprises at least one selected from acrylamide monomer having a catechol group or methacrylamide monomer having a catechol group, and a method for producing an ion-exchange polymer having a catechol group .
Wherein the step (a) comprises adding a second monomer solution to the first monomer solution and reacting the mixture at 0 to 50 ° C for 1 to 24 hours.
The monomer having ion exchange ability is at least one selected from the group consisting of [2- (methacryloyloxy) ethyl] trimethylammonium chloride, (3-acrylamidopropyl) trimethylammonium chloride, [2- (acryloyloxy) ethyl] trimethylammonium (Vinylbenzyl) trimethylammonium chloride, and N - [(omega -methacryloyl) -octadecyl] trimethylammonium chloride, in the presence of at least one compound selected from the group consisting of Wherein the catechol group comprises at least one catechol group.
Wherein the step (b) comprises dissolving the monomer having ion exchange capacity with the third monomer in a solvent, and then reacting the mixture at 60 to 80 ° C for 3 to 36 hours.
The solvent may be selected from the group consisting of dimethylformamide, tetrahydrofuran, chloroform, ethylene glycol, 1,4-dioxane, 1,2-dimethoxyethane, hexamethylphosphoramide, methanol, ethanol, 1-propanol, isopropyl alcohol, -Butanol and 2-butanol. 3. The process for producing an ion-exchange polymer according to claim 1, wherein the catechol group is selected from the group consisting of butanol and 2-butanol.
Wherein the initiator is added to the step (b).
The initiator may be selected from the group consisting of 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexanecarbonitrile), 4,4-azobis (4-cyanovaleric acid) Wherein the catechol group comprises at least one member selected from the group consisting of benzoyl peroxide, oxybenzoate, benzoyl peroxide, lauroyl peroxide, potassium persulfate, tertiary-butyl peroxide and tertiary-butyl peracetate. / RTI >
Wherein the ion-exchange polymer has a molecular weight of 1000 to 100,000.
[Chemical Formula 1]
In Formula 1,
R 1 and R 2 are each independently H or CH 3 ,
R 3 is CONH (CH 2 ) a Ph (OH) 2 or CO 2 (CH 2 ) b PH (OH) 2 ,
R 4 is (CH 2 ) c NR ' 3 + , R' is H or an alkyl group having 1 to 3 carbon atoms,
a and b are each 1 to 4, c is 0 to 2,
m is from 1 to 9, and n is from 9 to 1.
Wherein the ion-exchange polymer has a molecular weight of 1000 to 100,000.
And coating the surface of the activated carbon with the ion-exchange polymer.
[Chemical Formula 1]
In Formula 1,
R 1 and R 2 are each independently H or CH 3 ,
R 3 is CONH (CH 2 ) a Ph (OH) 2 or CO 2 (CH 2 ) b PH (OH) 2 ,
R 4 is (CH 2 ) c NR ' 3 + , R' is H or an alkyl group having 1 to 3 carbon atoms,
a and b are each 1 to 4, c is 0 to 2,
m is from 1 to 9, and n is from 9 to 1.
Wherein the coating step is performed by dissolving the ion-exchange polymer in a solution in which activated carbon is dispersed, and then holding the ion-exchange polymer at 40 to 60 ° C for 12 to 36 hours.
And an ion exchange layer coated with an ion exchange polymer having a repeating unit represented by the following formula (1) on the surface of the activated carbon.
[Chemical Formula 1]
In Formula 1,
R 1 and R 2 are each independently H or CH 3 ,
R 3 is CONH (CH 2 ) a Ph (OH) 2 or CO 2 (CH 2 ) b PH (OH) 2 ,
R 4 is (CH 2 ) c NR ' 3 + , R' is H or an alkyl group having 1 to 3 carbon atoms,
a and b are each 1 to 4, c is 0 to 2,
m is from 1 to 9, and n is from 9 to 1.
1. A method for preparing an ion exchange membrane, comprising: supporting the porous support in a solution containing an ion exchange polymer having a repeating unit represented by the following formula (1), and coating the porous support with an ion exchange polymer.
[Chemical Formula 1]
In Formula 1,
R 1 and R 2 are each independently H or CH 3 ,
R 3 is CONH (CH 2 ) a Ph (OH) 2 or CO 2 (CH 2 ) b PH (OH) 2 ,
R 4 is (CH 2 ) c NR ' 3 + , R' is H or an alkyl group having 1 to 3 carbon atoms,
a and b are each 1 to 4, c is 0 to 2,
m is from 1 to 9, and n is from 9 to 1.
Wherein the coating step is carried out by supporting the porous support at 20 to 80 DEG C for 6 to 48 hours in a solution in which the ion exchange polymer having the repeating unit represented by the formula (1) is dissolved.
And an ion exchange layer coated on the surface of the porous support,
Wherein the ion exchange layer comprises an ion exchange polymer having a repeating unit represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
R 1 and R 2 are each independently H or CH 3 ,
R 3 is CONH (CH 2 ) a Ph (OH) 2 or CO 2 (CH 2 ) b PH (OH) 2 ,
R 4 is (CH 2 ) c NR ' 3 + , R' is H or an alkyl group having 1 to 3 carbon atoms,
a and b are each 1 to 4, c is 0 to 2,
m is from 1 to 9, and n is from 9 to 1.
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| KR101981980B1 (en) * | 2016-11-11 | 2019-05-27 | 한국에너지기술연구원 | Ion exchange membrane using catechol-amine bond and method for manufacturing the same |
| KR102093967B1 (en) * | 2016-11-28 | 2020-03-26 | 주식회사 엘지화학 | Adsorption film of polysulfide, separator comprising the same, lithium-sulfur battery and manufacturing method thereof |
| CN113024739B (en) * | 2019-12-09 | 2022-03-22 | 南京理工大学 | Preparation method of catechol-based fluorescent micelle for iron ion detection |
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| US20120157602A1 (en) | 2006-11-21 | 2012-06-21 | Abbott Laboratories | Copolymers having zwitterionic moieties and dihdroxyphenyl moieties and medical devices coated with the copolymers |
| JP2014012858A (en) * | 2006-08-04 | 2014-01-23 | Knc Ner Acquisition Sub Inc | Biomimetic compounds and synthetic methods therefor |
| KR101388916B1 (en) | 2012-11-01 | 2014-04-25 | 충남대학교산학협력단 | Preparation of highly porous adsorptive ball particle for the adsorption of lithium using carbonization process |
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| JP2014012858A (en) * | 2006-08-04 | 2014-01-23 | Knc Ner Acquisition Sub Inc | Biomimetic compounds and synthetic methods therefor |
| US20120157602A1 (en) | 2006-11-21 | 2012-06-21 | Abbott Laboratories | Copolymers having zwitterionic moieties and dihdroxyphenyl moieties and medical devices coated with the copolymers |
| KR101388916B1 (en) | 2012-11-01 | 2014-04-25 | 충남대학교산학협력단 | Preparation of highly porous adsorptive ball particle for the adsorption of lithium using carbonization process |
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| JOURNAL OF MEMBRANE SCIENCE (2009), 327, pp.244-253* |
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