CN106519273A - Anionic membrane - Google Patents
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- CN106519273A CN106519273A CN201610952028.4A CN201610952028A CN106519273A CN 106519273 A CN106519273 A CN 106519273A CN 201610952028 A CN201610952028 A CN 201610952028A CN 106519273 A CN106519273 A CN 106519273A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2471/12—Polyphenylene oxides
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Abstract
The invention discloses an anionic membrane. A method for preparing the anionic membrane includes preparation and crosslinking of anionic membrane fluid, and finally the crosslinked anionic membrane fluid is coated onto a glass pane. The anionic membrane fluid is dried to form a membrane body at the room temperature, then the membrane body is placed into boiled water of 100 DEG C for soaking by 0.5-1h so that the anionic membrane can be obtained, and the ionic membrane obtained ultimately has the low swelling ratio and excellent electric conductivity.
Description
Technical field
Patent of the present invention is related to a kind of anionic membrane.
Background technology
Ionic membrane is a kind of polymeric membrane containing ionic group and to the ion in solution with selective penetrated property.In the past
In decades, ion exchange membrane serves more and more important in fields such as separation engineering, new forms of energy battery and biomedical engineerings
Effect.With the continuous expansion of its application, the demand of film function diversification is also grown with each passing day.According to ion-exchange group
Ion exchange membrane can be divided three classes by the difference of group：Cation exchange membrane, anion exchange membrane, amphoteric ion exchange membrane (bag
Include Bipolar Membrane).Ion-exchange group imparts membrane material differential permeability, you can selectively to control oozing for certain ion
Thoroughly.Film is then come by the concentration (ion exchange capacity of film) of fixed ion group for the selective power of different electriferous state ions
Determine.
Holland《Membrane science magazine》(J.MembraneScience, 2002,207,157-170) is reported polyvinyl alcohol
The cationic membrane containing sulfonic group with two kinds of different acidic-groups of carboxyl is prepared with the blending of polystyrolsulfon acid maleic acid,
For the recovery of molecular weight larger ion such as aminoacid.As which is organic membrane, temperature tolerance is poor, and using value is limited, difficult
To separate different kinds of ions and amphion material.
The present invention is to provide for a kind of relatively low swelling ratio and the ionic membrane with excellent conductivity.
The content of the invention
The purpose of patent of the present invention is to provide a kind of anionic membrane, it is characterised in that the preparation method bag of the anionic membrane
Include following steps：
The preparation of step one, cavity block liquid
It is Br by counter ion-Quaternized polyphenylene oxide 50 C heat 30min, be warming up to using the heating rate of 5-10 C/min
90 C heat 1-4h, are cooled to 75 C insulation 1h using the cooling rate of 12 C/min, then are soaked in 0.5 1mol/L
30min in NaOH solution, washes with water after taking-up until cleaning mixture in the environment of sealing is dried 10-18h, obtains in neutrality
First desciccate；First desciccate is placed in chloroform in the case of inflated with nitrogen, butter of tin and chloromethyl first is added
Ether, pours ethanol into after 60-65 C reaction 15-32h, will precipitation filtrate vacuum drying, obtain the second desciccate, described the
The mass ratio of one desciccate, chloroform, butter of tin and chloromethyl methyl ether is 1-2:2-10:0.002-0.08：0.2-3；
Second desciccate is dissolved in the first solvent, after stirring 30min under magnetic stirring, 70-75 C is warming up to, is protected
Warm 30-60min, had both obtained quaternized polyphenylene oxide cavity block liquid after filtration；
Step 2, prepares the cavity block liquid of Cross-linked
By the cavity block liquid obtained by step one, the first solution and cross-linking agent is added to carry out stirring 30min under cross-linking reaction, room temperature,
60 C stirring 10-30min are warming up to, and are cooled to 50 C and 45min are stirred under the protection of nitrogen, obtain second molten after being down to room temperature
Liquid, adds polyvinyl alcohol in second solution, and reaction temperature is 40-60 C, and the response time is 30-60h, obtains Cross-linked
Cavity block liquid, the mass ratio of the quaternized polyphenylene oxide cavity block liquid, the first solution and cross-linking agent is 1-3:2-3:0.1-0.2, second
The mass ratio of solution and polyvinyl alcohol is 1-5:0.5-0.7；
The preparation of step 3, anionic membrane
By the Cross-linked cavity block liquid film obtained by step 2 on a glass, film forming is dried at room temperature for, afterwards film is placed
0.5-1h immersions are carried out in 100 DEG C of boiled water had both obtained anionic membrane.
2nd, a kind of anionic membrane as claimed in claim 1, it is characterised in that the second desciccate described in step one
Mass ratio with the first solvent is 1-10：5-20；First solvent is by N, N- dimethylaminomethyl ethyl acrylate, benzene second
Alkene, dimethylformamide, dimethyl sulfoxide and methanol composition, the N, N- dimethylaminomethyl ethyl acrylate, styrene,
The mol ratio of dimethylformamide, dimethyl sulfoxide and methanol is 1-5:2-4:5-8:17-22:10-30；
3rd, a kind of anionic membrane as claimed in claim 1, it is characterised in that the first solution is by N described in step 2（C
H3）2-（CH2）N- N（CH3）2（n=1-5）Constitute with N-Methyl pyrrolidone, the N（CH3）2-（CH2
）N- N（CH3）2（n=1-5）Mol ratio with N-Methyl pyrrolidone is 1-5：2-3, cross-linking agent are amine propyl triethoxy
Silane.
4th, a kind of anionic membrane as claimed in claim 1, it is characterised in that the anionic membrane obtained by the step 5
Thickness be 30-50 μm.
Beneficial effect：
1st, counter ion is Br-Ammonium polyphenylene oxide（QPPO-Br）30min is heated in 50 C, using the intensification speed of 5-10 C/min
Rate is warming up to 90 C heating 1-4h, is cooled to 75 C insulation 1-3h using the cooling rate of 12 C/min, and the step is using different
Heating rate carry out rising it is gentle lower the temperature, and heated at different temperature, wherein most critical the step of for rising first
Temperature to 90 C carries out being cooled to 75 C insulations using the rate of temperature fall of 12 C/min, finds through substantial amounts of experiment, cooling
Speed it is too fast and behind all causing slowly excessively, it is impossible to form ionic bond, or only forming part ionic bond, the drop of 12 C/min
Warm speed is optimal, and the discovery of the invention in addition can effectively strengthen ionic bond using the step of cooling after intensification
Formation, through lot of experiments find, using cooling step formed anionic membrane ionic bond, compared to be provided without cooling step
The ionic bond of the anionic membrane for being formed suddenly many 25%, and be cooled to 75 C and effectively effectively can subtract in heating 1h
It is the time being immersed in the drying in NaOH and sealed environment less, effectively cost-effective；
2nd, step is added " the first desciccate to be placed in chloroform in the case of inflated with nitrogen, butter of tin is added in step one
And chloromethyl methyl ether, ethanol is poured into after 60-65 C reaction 15-32h, precipitation filtrate is vacuum dried, the second drying is obtained
Product, the mass ratio of first desciccate, chloroform, butter of tin and chloromethyl methyl ether is 1-2:2-10:0.002-0.08：
Through substantial amounts of experiment, 0.2-3 " learns that adding the step can effectively strengthen the conductivity of the ionic membrane.
3rd, the composition of the first solvent described herein and proportioning are that the substantial amounts of experiment of applicant is obtained, prior art
In generally adopt single solvent, the present invention to carry out relaxing strict items proportioning and employ magnetic force using multi-solvents and stir
Mix, enabling form more stable quaternized polyphenylene oxide cavity block liquid, and be easy to the Cross-linked in later stage to react.
4th, in step 2, cross-linking agent and creative is added in cross-linking reaction and adds the first solution, first solution
For homemade solution, and there is during stirring a temperature-fall period, and the process in cooling collects and adds nitrogen
Protection, is learnt through substantial amounts of experiment, can effectively be strengthened the stability of the cavity block liquid of Cross-linked using step 2 of the present invention,
So as to promote the stability of anionic membrane, and service life, and compared to not containing anionic membrane obtained by above-mentioned steps
Service life increases 30-45%.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.
A kind of anionic membrane, it is characterised in that the preparation method of the anionic membrane is comprised the following steps：
The preparation of step one, cavity block liquid
It is Br by counter ion-Quaternized polyphenylene oxide 50 C heat 30min, be warming up to using the heating rate of 5-10 C/min
90 C heat 1-4h, are cooled to 75 C insulation 1h using the cooling rate of 12 C/min, then are soaked in 0.5 1mol/L
30min in NaOH solution, washes with water after taking-up until cleaning mixture in the environment of sealing is dried 10-18h, obtains in neutrality
First desciccate；First desciccate is placed in chloroform in the case of inflated with nitrogen, butter of tin and chloromethyl first is added
Ether, pours ethanol into after 60-65 C reaction 15-32h, will precipitation filtrate vacuum drying, obtain the second desciccate, described the
The mass ratio of one desciccate, chloroform, butter of tin and chloromethyl methyl ether is 1-2:2-10:0.002-0.08：0.2-3；
Second desciccate is dissolved in the first solvent, after stirring 30min under magnetic stirring, 70-75 C is warming up to, is protected
Warm 30-60min, had both obtained quaternized polyphenylene oxide cavity block liquid after filtration；
Step 2, prepares the cavity block liquid of Cross-linked
By the cavity block liquid obtained by step one, the first solution and cross-linking agent is added to carry out stirring 30min under cross-linking reaction, room temperature,
60 C stirring 10-30min are warming up to, and are cooled to 50 C and 45min are stirred under the protection of nitrogen, obtain second molten after being down to room temperature
Liquid, adds polyvinyl alcohol in second solution, and reaction temperature is 40-60 C, and the response time is 30-60h, obtains Cross-linked
Cavity block liquid, the mass ratio of the quaternized polyphenylene oxide cavity block liquid, the first solution and cross-linking agent is 1-3:2-3:0.1-0.2, second
The mass ratio of solution and polyvinyl alcohol is 1-5:0.5-0.7；
The preparation of step 3, anionic membrane
By the Cross-linked cavity block liquid film obtained by step 2 on a glass, film forming is dried at room temperature for, afterwards film is placed
0.5-1h immersions are carried out in 100 DEG C of boiled water had both obtained anionic membrane.
The mass ratio of the second desciccate and the first solvent described in step one is 1-10：5-20；First solvent
It is by N, N- dimethylaminomethyl ethyl acrylate, styrene, dimethylformamide, dimethyl sulfoxide and methanol composition, described
The mol ratio of N, N- dimethylaminomethyl ethyl acrylate, styrene, dimethylformamide, dimethyl sulfoxide and methanol is 1-
5:2-4:5-8:17-22:10-30；
Described in step 2, the first solution is by N（CH3）2-（CH2）N- N（CH3）2（n=1-5）With N- methylpyrroles
Alkanone is constituted, the N（CH3）2-（CH2）N- N（CH3）2（n=1-5）Mol ratio with N-Methyl pyrrolidone is
1-5：2-3, cross-linking agent are amine propyl-triethoxysilicane.
The thickness of the anionic membrane obtained by the step 5 is 30-50 μm.
Heat stability be 190-246 C, preferably 220 C, more preferably 246 C；
Moisture content is 37-47%；
Tensile strength is 30-50 MPa
Water absorption rate test：One piece of diaphragm of shearing, record weight is m1, soaking at room temperature 48h in distilled water, takes out surface after taking-up
Moisture, it is heavy to obtain m2, obtain moisture content=（m2-m1）/m1 .
The swelling test of water resistant：One piece of diaphragm of clip, is immersed in 200h in the water of 65 C, dries the water on surface, weighs weight in wet base
For m1.Wet sample is dried to constant weight in 85 C, it is m to weigh dry weight again2.Calculate sample swellbility be（m1 – m2）×100%/
m2.Swellbility is obtained for 69-85%.
Electrical conductivity (σ) is determined：Proton conductivity (σ) is using four probes electrochemical impedance instrument (Hioki3552), in frequency
Measure under conditions of 100Hz to 100KHz.One ionic membrane and two pairs of black coating platinum electrodes are arranged in politef battery.
Battery is placed in high purity water to measure the electrical conductivity in water.Electrical conductivity can be calculated by following formula：σ=D/ (LBR),
Wherein, D is the distance between two electrodes, and L and B is the thickness and width of PEM respectively, and R is then the impedance for measuring
Value.When testing in 40 DEG C of high purity water, need to be calculated using the size of fully water suction state lower film.Obtaining electrical conductivity is
0.16-0.18（s/cm）.
It should be understood that these embodiments are only illustrative of the invention and is not intended to limit the scope of the invention.In addition, it is to be understood that
After the content for having read instruction of the present invention, those skilled in the art can be made various changes or modifications to the present invention, these
The equivalent form of value equally falls within the application appended claims limited range.
Claims (4)
1. a kind of anionic membrane, it is characterised in that the preparation method of the anionic membrane is comprised the following steps：
The preparation of step one, cavity block liquid
It is Br by counter ion-Quaternized polyphenylene oxide 50 C heat 30min, be warming up to using the heating rate of 5-10 C/min
90 C heat 1-4h, are cooled to 75 C insulation 1h using the cooling rate of 12 C/min, then are soaked in 0.5 1mol/L
30min in NaOH solution, washes with water after taking-up until cleaning mixture in the environment of sealing is dried 10-18h, obtains in neutrality
First desciccate；First desciccate is placed in chloroform in the case of inflated with nitrogen, butter of tin and chloromethyl first is added
Ether, pours ethanol into after 60-65 C reaction 15-32h, will precipitation filtrate vacuum drying, obtain the second desciccate, described the
The mass ratio of one desciccate, chloroform, butter of tin and chloromethyl methyl ether is 1-2:2-10:0.002-0.08：0.2-3；
Second desciccate is dissolved in the first solvent, after stirring 30min under magnetic stirring, 70-75 C is warming up to, is protected
Warm 30-60min, had both obtained quaternized polyphenylene oxide cavity block liquid after filtration；
Step 2, prepares the cavity block liquid of Cross-linked
By the cavity block liquid obtained by step one, the first solution and cross-linking agent is added to carry out stirring 30min under cross-linking reaction, room temperature,
60 C stirring 10-30min are warming up to, and are cooled to 50 C and 45min are stirred under the protection of nitrogen, obtain second molten after being down to room temperature
Liquid, adds polyvinyl alcohol in second solution, and reaction temperature is 40-60 C, and the response time is 30-60h, obtains Cross-linked
Cavity block liquid, the mass ratio of the quaternized polyphenylene oxide cavity block liquid, the first solution and cross-linking agent is 1-3:2-3:0.1-0.2, second
The mass ratio of solution and polyvinyl alcohol is 1-5:0.5-0.7；
The preparation of step 3, anionic membrane
By the Cross-linked cavity block liquid film obtained by step 2 on a glass, film forming is dried at room temperature for, afterwards film is placed
0.5-1h immersions are carried out in 100 DEG C of boiled water had both obtained anionic membrane.
2. a kind of anionic membrane as claimed in claim 1, it is characterised in that the second desciccate described in step one and the
The mass ratio of one solvent is 1-10：5-20；First solvent by N, N- dimethylaminomethyl ethyl acrylate, styrene,
Dimethylformamide, dimethyl sulfoxide and methanol composition, the N, N- dimethylaminomethyl ethyl acrylate, styrene, two
The mol ratio of methylformamide, dimethyl sulfoxide and methanol is 1-5:2-4:5-8:17-22:10-30.
3. a kind of anionic membrane as claimed in claim 1, it is characterised in that the first solution is by N described in step 2（C
H3）2-（CH2）N- N（CH3）2（n=1-5）Constitute with N-Methyl pyrrolidone, the N（CH3）2-（CH2
）N- N（CH3）2（n=1-5）Mol ratio with N-Methyl pyrrolidone is 1-5：2-3, cross-linking agent are amine propyl triethoxy
Silane.
4. a kind of anionic membrane as claimed in claim 1, it is characterised in that the thickness of the anionic membrane obtained by the step 5
Spend for 30-50 μm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115926425A (en) * | 2022-12-14 | 2023-04-07 | 武汉轻工大学 | Cross-linked anion exchange membrane and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775202A (en) * | 2010-02-05 | 2010-07-14 | 山东天维膜技术有限公司 | Method based on sulfonated polyphenylene oxide for preparing organic-inorganic hybrid cation-exchange membranes |
| CN103372381A (en) * | 2012-04-19 | 2013-10-30 | 中国科学技术大学 | Anion-exchange film, preparation method thereof and fuel cell |
| CN104437145A (en) * | 2014-11-12 | 2015-03-25 | 盐城师范学院 | Method for preparing zwitterion membrane by use of alkaline anion exchange membrane solution and acid cation exchange membrane solution |
-
2016
- 2016-10-27 CN CN201610952028.4A patent/CN106519273A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775202A (en) * | 2010-02-05 | 2010-07-14 | 山东天维膜技术有限公司 | Method based on sulfonated polyphenylene oxide for preparing organic-inorganic hybrid cation-exchange membranes |
| CN103372381A (en) * | 2012-04-19 | 2013-10-30 | 中国科学技术大学 | Anion-exchange film, preparation method thereof and fuel cell |
| CN104437145A (en) * | 2014-11-12 | 2015-03-25 | 盐城师范学院 | Method for preparing zwitterion membrane by use of alkaline anion exchange membrane solution and acid cation exchange membrane solution |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115926425A (en) * | 2022-12-14 | 2023-04-07 | 武汉轻工大学 | Cross-linked anion exchange membrane and preparation method thereof |
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Application publication date: 20170322 |