CN109157991B - Monovalent selective cation exchange membrane with side-chain quaternized polyaniline and preparation method thereof - Google Patents
Monovalent selective cation exchange membrane with side-chain quaternized polyaniline and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 91
- 238000005341 cation exchange Methods 0.000 title claims abstract description 40
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 40
- 230000001590 oxidative effect Effects 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 11
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 11
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical group CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000008213 purified water Substances 0.000 claims description 4
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 150000001350 alkyl halides Chemical class 0.000 abstract 1
- 210000004379 membrane Anatomy 0.000 description 39
- 239000000243 solution Substances 0.000 description 22
- 150000002500 ions Chemical class 0.000 description 8
- 239000003011 anion exchange membrane Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000909 electrodialysis Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/422—Electrodialysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Urology & Nephrology (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a side-chain quaternized polyaniline monovalent selective cation exchange membrane and a preparation method thereof. In the invention, the compactness of the active layer is ensured by polyaniline, and the positive charge of the membrane is effectively improved by quaternization modification of alkyl halides with different carbon chain lengths. Thereby achieving the selective separation of monovalent cations.
Description
Technical Field
The invention belongs to the technical field of separation membrane materials, relates to the development of membrane materials applied to the field of water treatment, and particularly relates to a preparation method of a monovalent selective cation exchange membrane with a side chain quaternized polyaniline.
Background
With the development of economy, global resources are increasingly exhausted, the water resource crisis is particularly serious, and seawater desalination and sewage reuse become important subjects of worldwide research. With the development of scientific technology, membrane separation technology has been recognized as one of the most promising high technologies in the water treatment industry. Electrodialysis technology has been widely used in various fields as an important branch of membrane separation technology. However, the ion exchange membrane as a core component of electrodialysis still has certain disadvantages in the practical application process, such as the problem of permeation of multi-valence ions, which can cause the reduction of current efficiency and increase of energy consumption of the electrodialyzer, and even cause the membrane sintering phenomenon, and the monovalent selective cation exchange membrane can effectively solve the problem.
At present, the research work on the monovalent permselective ion exchange membrane mainly focuses on two aspects, namely, the surface charge of the membrane is changed, and the permeation of multivalent ions is inhibited through electrostatic repulsion; secondly, the structure of the membrane is more compact, and the permeability of multivalent ions is reduced by virtue of a 'sieving effect'.
The composite film prepared by polyether-ether-ketone, polyether-sulfone and the like has lower resistance and good unit price selection performance. And the modified organic-inorganic composite membrane is prepared by taking polyaniline as a functional material and is applied to a monovalent ion selective separation system, and the result shows that the mixed membrane Na+The effect of migration is not significant, but Zn2+、Al3+The retention rate of the catalyst is greatly improved. The method uses polyethyleneimine as a modifying substance, and prepares the monovalent selective ion exchange membrane by a leaching and electrodeposition method respectively, so that the separation effect of leaching modification is more obvious under low ion concentration. However, the above methods have more or less disadvantages, the selectivity is not very high when simply increasing the density, and the method is only suitable for separation at low ion concentration, and the modified layer is not stable enough and has a risk of falling off. And the surface charge property of the membrane is simply improved, the separation effect can be greatly influenced by pH, the selectivity fluctuation under different pH values is large, and the stability of the modified layer is poor.
Most of membranes prepared by the prior art can not simultaneously obtain good separation effect and stability, and have small application range.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a monovalent selective cation exchange membrane with quaternized polyaniline side chains and a preparation method thereof.
The monovalent selective cation exchange membrane with the quaternized polyaniline on the side chain is characterized by comprising a base membrane and an active layer positioned on the interface of the base membrane, wherein the interface is oxidized and polymerized by aniline and an oxidant, and the obtained polymer is reacted with a quaternization reagent to obtain the quaternized polyaniline which is the active layer; the structural general formula of the quaternizing agent is X- (CH)2)n-CH3X is Cl, Br or I, and n represents an integer of 0-18; the quaternising agent is preferably ethyl bromide, 1-bromopropane or 1-bromobutane.
The cross-linked quaternized polyaniline monovalent selective cation exchange membrane is characterized in that an oxidant is ferric chloride, ammonium persulfate or potassium dichromate.
The preparation method of the monovalent selective cation exchange membrane with the side-chain quaternized polyaniline is characterized in that a quaternizing agent is dissolved in an organic solvent to be used as a quaternary ammonium solution, and the cation exchange membrane is used as a base membrane; soaking the base membrane in aniline monomer solution, taking out, sucking the aniline monomer solution on the surface of the base membrane by using filter paper, soaking the base membrane in oxidant solution for oxidative polymerization reaction, allowing the aniline monomer and the oxidant to perform oxidative polymerization reaction on the surface of the base membrane to generate a polyaniline active layer, taking out the base membrane, drying, soaking in quaternary ammonium solution for reaction, taking out the base membrane from the quaternary ammonium solution, and repeatedly washing with purified water to obtain the side-chain quaternized polyaniline monovalent selective cation exchange membrane.
The preparation method of the monovalent selective cation exchange membrane with the side chain quaternized polyaniline is characterized in that an oxidant is ferric chloride, ammonium persulfate or potassium dichromate.
The preparation method of the monovalent selective cation exchange membrane with the side chain quaternized polyaniline is characterized in that in the oxidant solution, the solvent is water, the concentration of the oxidant is 0.1-10 mol/L, and the oxidant is ferric chloride.
The preparation method of the monovalent selective cation exchange membrane with the side chain quaternized polyaniline is characterized in that the base membrane is soaked in aniline monomer solution for 5-300 min; in the aniline monomer solution, the solvent is ethanol, and the concentration of the aniline monomer is 0.1-10 mol/L.
The preparation method of the monovalent selective cation exchange membrane with the side-chain quaternized polyaniline is characterized in that in a quaternary ammonium solution, the mass concentration of a quaternizing agent is 0.1-100 g/L, and an organic solvent is ethanol.
The preparation method of the monovalent selective cation exchange membrane with the side chain quaternized polyaniline is characterized in that the base membrane is placed in a quaternary ammonium solution for soaking reaction for 1-50 hours.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
(1) the side chain quaternized polyaniline monovalent selective cation exchange membrane is prepared by using a quaternized polyaniline active layer which is generated by oxidizing polymerization of aniline and an oxidizing agent and then reaction of the oxidized polymerization and a quaternization reagent on the surface of a base membrane, the property of selectively separating single and polyvalent cations is realized by ingeniously utilizing the compactness of polyaniline and the charge property after quaternization modification, and the good water stability of the polyaniline and the electrostatic interaction with the base membrane after quaternization modification ensure the good stability of the active layer.
(2) In the preparation process of the side chain quaternized polyaniline monovalent selective cation exchange membrane, the thickness density and the quaternization degree (the quaternization degree is the surface charge property) of the active layer can be effectively regulated and controlled by regulating the reaction conditions in the preparation step, such as the concentration of aniline monomer component feed liquid, the operation time, the operation temperature and the like, so that the obtained monovalent cation selective separation membrane has the performance of selectively separating single polyvalent cations.
Drawings
FIG. 1 is a scanning electron microscope image of the surface of the monovalent selective cation exchange membrane of side-chain quaternized polyaniline obtained in example 1;
FIG. 2 is a sectional scanning electron micrograph of the monovalent selective cation membrane obtained in example 1;
FIG. 3 is a schematic structural diagram of a testing apparatus according to the present invention;
in the figure: 1-a first electrode chamber, 2-a dilute chamber, 3-a dense chamber, 4-a second electrode chamber, 5-a first anion exchange membrane, 6-a monovalent selective cation exchange membrane, 7-a second anion exchange membrane, 8-an anode, 9-a cathode, and 10-a feed liquid port.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1:
as the base membrane, a commercial cation exchange membrane, which is available from Deshan Cauda, Japan, model number CM-1, was used.
Soaking a base membrane in 1 mol/L aniline monomer solution for 60min (the solvent of the aniline monomer solution is ethanol), taking out the base membrane, drying redundant solution on the surface of the base membrane by using filter paper, soaking the base membrane in 1 mol/L ferric chloride aqueous solution for 60min, carrying out oxidation polymerization reaction on the surface of the base membrane by using aniline monomer under the action of ferric chloride to generate a polyaniline active layer, then placing the base membrane on a heater at 60 ℃ for drying, then placing the base membrane in 5g/L bromoethane solution for soaking reaction for 6 h (the solvent of the bromoethane solution is ethanol), finally taking out the base membrane from the bromoethane solution, repeatedly washing the base membrane with purified water to obtain a side chain quaternized monovalent selective cation exchange membrane, and placing the obtained product in purified water for storage.
In the embodiment, a surface scanning electron microscope image and a cross-section scanning electron microscope image of the monovalent selective cation exchange membrane prepared by the side chain quaternized polyaniline are respectively shown in fig. 1 and fig. 2, an aniline monomer is subjected to oxidative polymerization reaction on the surface of a base membrane under the action of an oxidant to generate spherical polyaniline which is mutually stacked, and then a thin and compact active skin layer is formed through quaternization modification.
And carrying out a single-multivalent cation selective electrodialysis experiment on the obtained polyaniline monovalent selective cation exchange membrane product with quaternized side chains, wherein the testing device of the electrodialysis experiment is structurally shown in fig. 3 and comprises an electrode chamber, the left end and the right end of the electrode chamber are respectively provided with an anode 8 and a cathode 9, a first anion exchange membrane 5, a monovalent selective cation exchange membrane 6 and a second anion exchange membrane 7 are arranged in the electrode chamber and divide the electrode chamber into a first electrode chamber 1, a fade chamber 2, a dense chamber 3 and a second electrode chamber 4, and the tops of the first electrode chamber 1, the fade chamber 2, the dense chamber 3 and the second electrode chamber 4 are respectively provided with a liquid feeding port 10. The first anion exchange membrane 5 and the second anion exchange membrane 7 are both available from Deshan Caoda, Japan, and have the model number CM-1. The monovalent selective cation exchange membrane 6 is a product of the side-chain quaternized polyaniline monovalent selective cation exchange membrane prepared in the embodiment.
The test procedure was as follows: experiment with Na+/Mg2+The aqueous solution is used as a test system, and Na is added+/Mg2+Adding the aqueous solution into a dilute chamber 2 and a concentrated chamber 3 (Na) respectively+/Mg2+In aqueous solution, Na+And Mg2+Initial concentration is 0.05 mol/L), 0.05 mol/L of Na is respectively added into the first electrode chamber 1 and the first electrode chamber 42SO4Adding 0.1A constant current DC to the anode 8 and cathode 9 to dilute Na in the chamber 2+、Mg2+Will penetrate monovalent selective cation exchange membrane 6 and enter dense chamber 3 under the effect of electric field force, and its flux will be less than monovalent ion flux due to the blocking effect of monovalent selective cation exchange membrane on multivalent ion, and one hour later, the solution of taking out and diluting chamber 2 utilizes ion chromatography to analyze Na+And Mg2+And calculating Na+、Mg2+Flux of (A), (B)
Wherein JiIs flux, C0As initial concentration, C1At final concentration, t is time), and Na+Relative to Mg2+A selective transmission value of (
Wherein S is the permselectivity value, JNaIs Na+Flux of (A), JMgIs Mg2+Flux of (c).
The calculation results are as follows: byIn the figures 1 and 2, a quaternized polyaniline active skin layer is successfully attached to the surface of the original basement membrane through the experimental operation, the active skin layer effectively blocks the passage of divalent magnesium ions,
the permselectivity of this membrane increased to 2.47 compared to the original base membrane (permselectivity of less than 1.0), i.e. the permselectivity of monovalent selective cation exchange membrane 6 increased to 2.47 compared to first anion exchange membrane 5.
Example 2
The procedure in example 1 above was unchanged, changing the ethyl bromide solution to a 1-bromobutane solution. Testing the separation performance, calculated
The permselectivity of this film increased to 2.65 compared to the original base film (permselectivity of less than 1.0).
Example 3
The procedure in example 1 above was unchanged, changing the bromoethane solution to a 1-bromohexane solution. Testing the separation performance, calculated
The permselectivity of this film increased to 2.84 compared to the original base film (permselectivity of less than 1.0).
The description is given for the sole purpose of illustrating embodiments of the inventive concept and should not be taken as limiting the scope of the invention to the particular forms set forth in the embodiments, but rather as being limited only to the equivalents thereof as may be contemplated by those skilled in the art based on the teachings herein.
Claims (6)
1. A monovalent selective cation exchange membrane of side-chain quaternized polyaniline is characterized by comprising a base membrane and an active layer positioned on the interface of the base membrane, wherein the interface is oxidized and polymerized by aniline and an oxidant, and the obtained polymer is reacted with a quaternization agent to prepare the quaternized polyaniline which is the active layer;
the structural general formula of the quaternizing agent is X- (CH)2)n-CH3X is Cl, Br or I, and n represents an integer of 1-18; the quaternizing agent is ethyl bromide, 1-bromopropane or 1-bromobutane; meanwhile, the side chain quaternized polyaniline monovalent selective cation exchange membrane is used for Na+And Mg2+The separation between them;
the preparation method of the side-chain quaternized polyaniline monovalent selective cation exchange membrane comprises the following steps: dissolving a quaternizing agent in an organic solvent to be used as a quaternary ammonium solution, and using a cation exchange membrane as a base membrane; soaking the base membrane in aniline monomer solution, taking out, sucking the aniline monomer solution on the surface of the base membrane by using filter paper, soaking the base membrane in oxidant solution for oxidative polymerization reaction, allowing the aniline monomer and the oxidant to perform oxidative polymerization reaction on the surface of the base membrane to generate a polyaniline active layer, taking out the base membrane, drying, soaking in quaternary ammonium solution for reaction, taking out the base membrane from the quaternary ammonium solution, and repeatedly washing with purified water to obtain the side-chain quaternized polyaniline monovalent selective cation exchange membrane.
2. The monovalent selective cation exchange membrane according to claim 1, wherein the oxidant is ferric chloride, ammonium persulfate or potassium dichromate.
3. The monovalent selective cation exchange membrane with quaternized polyaniline on side chain according to claim 1, wherein in the oxidant solution, the solvent is water, the concentration of the oxidant is 0.1-10 mol/L, and the oxidant is ferric chloride.
4. The monovalent selective cation exchange membrane with quaternized polyaniline on side chain according to claim 1, wherein the time for soaking the base membrane in aniline monomer solution is 5-300 min; in the aniline monomer solution, the solvent is ethanol, and the concentration of the aniline monomer is 0.1-10 mol/L.
5. The monovalent selective cation exchange membrane with the quaternized polyaniline with a side chain as claimed in claim 1, wherein the mass concentration of the quaternizing agent in the quaternary ammonium solution is 0.1-100 g/L, and the organic solvent is ethanol.
6. The monovalent selective cation exchange membrane with quaternized polyaniline on side chain according to claim 1, wherein the time for soaking the base membrane in quaternary ammonium solution is 1-50 h.
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| WO2003072854A3 (en) * | 2002-02-28 | 2004-01-15 | Univ Stuttgart | Composites and composite membranes |
| CN102935389A (en) * | 2012-10-30 | 2013-02-20 | 中国海洋大学 | Method for preparing cation exchange membrane with monovalent preferential separation function |
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| WO2003072854A3 (en) * | 2002-02-28 | 2004-01-15 | Univ Stuttgart | Composites and composite membranes |
| CN102935389A (en) * | 2012-10-30 | 2013-02-20 | 中国海洋大学 | Method for preparing cation exchange membrane with monovalent preferential separation function |
Non-Patent Citations (2)
| Title |
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| Chemical Modification of the Surface of a Sulfonated Membrane by Formation of a Sulfonamide Bond;Gwenae¨l Chamoulaud等;《Langmuir》;20040504;第4989-4995页 * |
| Chemical Polymerization of Aniline on a Poly(styrene sulfonic acid) Membrane: Controlling the Polymerization Site Using Different Oxidants;Sophie Tan等;《J. Phys. Chem. B》;20050702;第14085-14092页 * |
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