CN103242552B - Preparation method of quaternized amphoteric ion exchange membrane - Google Patents
Preparation method of quaternized amphoteric ion exchange membrane Download PDFInfo
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Abstract
The invention discloses a preparation method of a quaternized amphoteric ion exchange member and in particular relates to a preparation method of an amphoteric ion exchange membrane in ion exchange, sterilization and other fields. The preparation method comprises the following steps of: preparing a binary monomer grafting solution; carrying out irradiation grafting on a commercialized polymeric membrane and introducing a sulfonic acid group and a quaternization group which have a cation exchange function; and putting the membrane material into a hydrochloric acid water solution to carry out a protonation reaction to generate sulfoacid ions with a cation exchange function and quaternary ammonium ions with an anion exchange function so as to obtain the amphoteric ion exchange membrane. The preparation method is simple and convenient to operate; and meanwhile, the problems of damages to grafting chains in the sulfonation process and environment pollution caused by the damages to the grafting chains as well as the fussy problem that two steps are generally needed in the quaternization reaction are solved.
Description
Technical field
The present invention relates to functional polymer technology field of membrane materials, be specifically related to a kind of low cost, low environment pollutes the method preparing amphoteric ion exchange membrane.
Background technology
Ion-exchange membrane a kind ofly ion in solution is had to the polymeric membrane of selective penetrated property containing ionic group.In the past few decades, ion-exchange membrane serves more and more important effect in fields such as separation engineering, new forms of energy battery and biomedical engineerings.Along with the continuous expansion of its Application Areas, the demand of film function diversification is also grown with each passing day.According to the difference of ion-exchange group, ion-exchange membrane can be divided three classes: cationic exchange membrane, anion-exchange membrane, amphoteric ion exchange membrane (comprising Bipolar Membrane).Ion-exchange group imparts mould material selective permeability, namely can control the infiltration of certain ion selectively.And due to electrostatic repulsion, electronegative chemical group is (as-SO
3 -with-COO
-) can cation exchange capacity (CEC) be provided, and the group of positive charge is (as-NH
3 +,-NRH
2 +,-NR
2h
+with-NR
3 +) then can give film and exchange the character of negatively charged ion.Film is then decided by the concentration (loading capacity of film) of non diffusible ion group for the selective power of different band electricity condition ion.
The character of ion-exchange membrane depends on the character of functional monomer and the size of grafting amount.The monomer of grafting can be divided into two classes: functional monomer, as vinylformic acid, methacrylic acid (J.Membr.Sci.2003 (219): 1-13); Non-functional monomer, as (J.Appl.Polym.Sci.2000 (78): 2443-2453) such as vinylbenzene, N-vinyl pyridine and 1-chloro-4-methyl-benzenes.Grafting functional monomer can directly give polymeric substrate with ion-exchange capacity, and grafting non-functional monomer such as vinylbenzene then needs to obtain ion-exchange capacity by further reaction kinetic, and wherein the most frequently used is sulfonation and quaternized.The former introduces anionic group and obtains cationic exchange membrane, and the latter then introduces cation group and obtains anion-exchange membrane.But sulfonation reaction itself not only needs to use strong sulfonated reagent (as chlorsulfonic acid etc.) and this kind of reagent environment being produced to severe contamination of stable organic solvent (as methylene dichloride etc.), and also round Realization (J.Membr.Sci.2009 (339): 115-119) is difficult to for the control (if each phenyl ring is by the upper sulfonic acid group of modification) of complete sulfonation reaction.And for quaterisation, be also generally use the aminocompound of halogenated alkyl hydrocarbon to grafted chain to react.Therefore preparing on amphoteric ion exchange membrane material, usually needing to use too much step to carry out the modification of graft copolymer membrane.But quaternary ammonium-sulfonic acid type amphoteric ion exchange membrane material not only has two-way ion exchanging function, and quaternizing unit also has sterilization effect, this is that this mould material provides possibility (Macromol.Biosci.2007 (7): 1149-1159) in the application of different field.Therefore, exploitation has the ion-exchange film system of special construction and new preparation technology, and to advancing, the commercialized development of amphoteric ion exchange membrane is significant.
Summary of the invention
The object of this invention is to provide a kind of low cost, the simple and convenient process for preparing of amphoteric ion exchange membrane that low environment pollutes.
The amphoteric ion exchange membrane for ion-exchange, sterilization and other field prepared by the present invention, its chemical structure is such as formula shown in I:
In formula I, R
1can be methyl or ethyl; Number of repeat unit p can be 1,2 or 3; M, n, o represent the different grafting unit polymerization degree respectively; Membrane is the base material film with different polymer architecture.
The preparation method of amphoteric ion exchange membrane provided by the present invention, comprising: preparation dibasic monomer graft copolymer solution; Irradiation grafting is carried out to commercialization polymeric membrane, introduces sulfonic acid group and the quaternized ammonium groups with cationic exchange function; This mould material is put into aqueous hydrochloric acid and carries out protonation reaction, produce and there is the sulfonate ion of cationic exchange function and there is the quaternary ammonium radical ion of anionresin function, obtain amphoteric ion exchange membrane.Concrete technical scheme is as follows:
A preparation method for amphoteric ion exchange membrane, comprises the steps:
1) following method is adopted a) or b) to carry out irradiation grafting to polymeric film:
A) adopt the method for co-irradiation grafting, concrete steps are join in irradiation tube by the solvent of polymeric film, reaction monomers, participation graft reaction, logical nitrogen (N
2) seal afterwards, then use
60co gamma-rays or electron beam at room temperature carry out co-irradiation grafting reaction;
B) adopt the method for pre-irradiation grafting, concrete steps are the environment first polymeric film being placed in aerobic or anaerobic, use
60co gamma-rays or electron beam irradiation, then react the polymeric film after irradiation and the graft copolymer solution mix and blend containing reaction monomers;
Wherein, described polymeric film is the one in polyvinylidene difluoride (PVDF) (PVDF) film, fluorinated ethylene propylene (PVF) film, ethylene-tetrafluoroethylene copolymer (ETFE) film, polyethylene (PE) film, polypropylene (PP) film and polyethylene terephthalate (PET) film; Described reaction monomers is made up of monomer I and monomer II, monomer I is sodium p styrene sulfonate and/or p styrene sulfonic acid potassium, and monomer II is one or more in dimethylaminoethyl methyl esters, dimethylaminoethyl methacrylate, dimethylaminoethyl propyl ester; The solvent of described participation graft reaction is dimethyl sulfoxide (DMSO) and/or diethyl sulfoxide; The described graft copolymer solution containing reaction monomers is the solution that described reaction monomers is dissolved in described solvent (i.e. dimethyl sulfoxide (DMSO) and/or diethyl sulfoxide) and obtains;
2) after completion of the reaction, take out the film after irradiation grafting, clean homopolymer and the complete monomer of unreacted with deionized water; Then this mould material is put into aqueous hydrochloric acid and carry out protonation reaction, obtain the amphoteric ion exchange membrane with sulfonate ion and quaternary ammonium radical ion.
Above-mentioned steps 1) in, method a) co-irradiation grafting reaction absorption dose be preferably 5 ~ 100kGy; Method b) 5 ~ 100kGy is preferably to the dosage that polymeric film carries out irradiation, the polymeric film after irradiation can be preserved under low temperature (being generally-20 DEG C); Polymeric film after irradiation and the mixed temperature of reaction of graft copolymer solution are preferably 40 ~ 80 DEG C, and the reaction times is 1 ~ 6h preferably.
Preferably, step 1)
60co gamma-ray irradiation dose rate is 20 ~ 100Gy/min, and electron beam irradiation dose rate is 10 ~ 100Gy/s.
Preferably, step 1) described in the thickness of polymeric film material be 25 ~ 50 μm.
Preferably, in step 1) reaction soln in, total volumetric molar concentration of monomer I and monomer II is 0.1mol/L ~ 2mol/L, and the mol ratio of monomer I and monomer II is 3: 1 ~ 1: 3.Above-mentioned steps 2) in protonation reaction process be preferably: mould material is immersed in aqueous hydrochloric acid and stirs 10 ~ 24 hours in the temperature range of room temperature to 70 DEG C.Wherein, described aqueous hydrochloric acid concentration is 1 ~ 3mol/L.
Further, in step 2) after, obtained amphoteric ion exchange membrane is immersed self-assembly in polyelectrolyte solution and be prepared into bilayer or multilayer ion-exchange membrane.
Preferably, described polyelectrolyte solution is one or more in Nafion solution, poly (sodium 4-styrenesulfonate) solution, quaternized polystyrene solution and quaternized polyaryletherketone solution.
Advantage of the present invention and useful effect are:
1. the present invention passes through radiation graft polymerization, the macromolecular grafted chain containing negatively charged ion and cation exchange group is being introduced with the form of covalent linkage without on the polymer base material of ion exchanging function, and the present invention is using cheap commercialization fluoro containing polymers film, polyethylene, polypropylene and polyethylene terephthalate film as starting material, can prepare cheap new type amphoteric ion-exchange membrane.
2. the present invention regulates and controls the performance such as ion capacity, proton conduction of ion-exchange membrane easily by change radiation absorber amount, monomer concentration and proportioning and grafting solvent.
3. the present invention adopts the monomer with cation and anion exchange effect to carry out graft copolymerization, then obtains amphoteric ion exchange membrane through protonated.Compared to the method for conventional synthesis amphoteric ion exchange membrane, novel method one-step synthesis, method is simple, avoids sulfonation process, reduces environmental pollution.
4. the present invention adopts water-soluble monomer to carry out graft copolymerization, compared to the method for conventional synthesis amphoteric ion exchange membrane, avoids the use of other organic solvents in subsequent operations, method safety environmental protection.
5. the present invention adopts in dimethyl sulfoxide (DMSO) and/or diethyl sulfoxide to carry out graft copolymer solution preparation as solvent, and after irradiation, grafted chain directly quaterisation occurs.Compared to the synthetic method of the protonated formation quaternized ammonium groups of tradition, the quaternized ammonium groups chemical structure of the inventive method is more stable, is not easily destroyed.
Accompanying drawing explanation
Fig. 1 is the process route chart that embodiment 1 prepares amphoteric ion exchange membrane.
Fig. 2 is the amphoteric ion exchange membrane specific conductivity (σ) prepared of embodiment 1 and water retention (Water uptake) and percentage of grafting (DOG) graph of a relation.
Fig. 3 is the section SEM picture of amphoteric ion exchange membrane prepared by embodiment 1.
Embodiment
Illustrate the present invention by embodiment below, but these embodiments should not be interpreted as limitation of the present invention.
Embodiment 1
Prepare the synthetic route of amphoteric ion exchange membrane as shown in Figure 1, be that 50 μm of polyvinylidene difluoride (PVDF) (PVDF) films are immersed in the dimethyl sulphoxide solution (i.e. grafting liquid) of sodium p styrene sulfonate (SSS) that reaction monomers total concn is 1mol/L and dimethylaminoethyl methacrylate (DMAEMA) by film thickness, then use
60co gamma-rays at room temperature carries out irradiation, and dose rate is 100Gy/min, and absorption dose is 40kGy, and wherein the mol ratio of sodium p styrene sulfonate (SSS) and dimethylaminoethyl methacrylate (DMAEMA) is 2: 1.After irradiation, wash away homopolymer with deionized water and the complete monomer post-drying of unreacted is stand-by.Immersed by gained graft copolymer membrane in the aqueous hydrochloric acid of 1mol/L protonated, room temperature reaction 24h, obtains amphoteric ion exchange membrane.
Amphoteric ion exchange membrane specific conductivity (σ) adopts AC impedence method to measure, water retention (Water uptake) is obtained by the change of measuring deionized water saturated front and back film quality, result as shown in Figure 2, as can be seen from the figure specific conductivity and water retention all increase with the increase of percentage of grafting, therefore effectively can regulate specific conductivity and the water retention of required amphoteric ion exchange membrane by controlling percentage of grafting.
As shown in Figure 3, the surface of film and inside successfully realize graft reaction to the cross-section morphology of amphoteric ion exchange membrane as we know from the figure.
Embodiment 2
Be 50 μm of polyvinylidene difluoride (PVDF) (PVDF) film Vacuum Package by film thickness, carry out electron beam irradiation, dose rate is 100Gy/s, and absorption dose is 100kGy ,-20 DEG C of preservations after irradiation.Irradiated film is immersed in the dimethyl sulphoxide solution of sodium p styrene sulfonate (SSS) that reaction monomers total concn is 1mol/L and dimethylaminoethyl methacrylate (DMAEMA), then stirring reaction at 60 DEG C, wherein the mol ratio of sodium p styrene sulfonate (SSS) and dimethylaminoethyl methacrylate (DMAEMA) is 2: 1.After irradiation, wash away homopolymer with deionized water and the complete monomer post-drying of unreacted is stand-by.
By protonation reaction 24h under room temperature in the aqueous hydrochloric acid of gained graft copolymer membrane immersion 1mol/L, obtain amphoteric ion exchange membrane.
Embodiment 3
Prepare amphoteric ion exchange membrane by the method identical with embodiment 1, subsequently film is immersed 24h in the Nafion solution of 5%, after oven dry, obtain compound amphoteric ion exchange membrane.
Embodiment 4
By the method identical with embodiment 1, be 20kGy unlike absorption dose in irradiation grafting reaction.
Embodiment 5
By the method identical with embodiment 1, be 0.5mol/L unlike the total concn of monomer in irradiation grafting reaction.
Embodiment 6
By the method identical with embodiment 1, be 1: 3 unlike the mol ratio of sodium p styrene sulfonate and dimethylaminoethyl methacrylate in irradiation grafting reaction.
Embodiment 7
By the method identical with embodiment 1, be 1: 2 unlike the mol ratio of sodium p styrene sulfonate and dimethylaminoethyl methacrylate in irradiation grafting reaction.
Embodiment 8
By the method identical with embodiment 1, be 1: 1 unlike the mol ratio of sodium p styrene sulfonate and dimethylaminoethyl methacrylate in irradiation grafting reaction.
Embodiment 9
By the method identical with embodiment 1, be 3: 1 unlike the mol ratio of sodium p styrene sulfonate and dimethylaminoethyl methacrylate in irradiation grafting reaction.
Embodiment 10
By the method identical with embodiment 1, be base material unlike taking thickness as the pvf film of 25 μm.
Embodiment 11
By the method identical with embodiment 1, unlike being that the ethylene-tetrafluoroethylene copolymer film of 50 μm is for base material with thickness.
Embodiment 12
By the method identical with embodiment 1, be base material unlike taking thickness as the polyethylene film of 50 μm.
Embodiment 13
By the method identical with embodiment 1, be base material unlike taking thickness as the polypropylene screen of 50 μm.
Embodiment 14
By the method identical with embodiment 1, unlike being that the polyethylene terephthalate film of 50 μm is for base material with thickness.
Embodiment 15
By the method identical with embodiment 1, be p styrene sulfonic acid potassium and dimethylaminoethyl methacrylate unlike grafted monomer.
Embodiment 16
By the method identical with embodiment 1, be diethyl sulfoxide unlike grafting solvent.
Embodiment 17
By the method identical with embodiment 1, be sodium p styrene sulfonate and dimethylaminoethyl methyl esters unlike grafted monomer.
Embodiment 18
By the method identical with embodiment 1, be sodium p styrene sulfonate and dimethylaminoethyl propyl ester unlike grafted monomer.
Embodiment 19
By the method identical with embodiment 1, it is 70 DEG C unlike protonated temperature.
Claims (10)
1. a preparation method for amphoteric ion exchange membrane, comprises the steps:
1) following method is adopted a) or b) to carry out irradiation grafting to polymeric film:
A) adopt the method for co-irradiation grafting: join in irradiation tube by the solvent of polymeric film, reaction monomers, participation graft reaction, seal after logical nitrogen, then use
60co gamma-rays or electron beam at room temperature carry out co-irradiation grafting reaction;
B) method of pre-irradiation grafting is adopted: first used by polymeric film
60co gamma-rays or electron beam irradiation, then mix the polymeric film after irradiation with the graft copolymer solution containing reaction monomers, stirring reaction;
Wherein, described polymeric film is the one in polyvinylidene fluoride film, pvf film, ethylene-tetrafluoroethylene copolymer film, polyethylene film, polypropylene screen and polyethylene terephthalate film; Described reaction monomers is made up of monomer I and monomer II, monomer I is sodium p styrene sulfonate and/or p styrene sulfonic acid potassium, and monomer II is one or more in dimethylaminoethyl methyl esters, dimethylaminoethyl methacrylate, dimethylaminoethyl propyl ester; The solvent of described participation graft reaction is dimethyl sulfoxide (DMSO) and/or diethyl sulfoxide; The described graft copolymer solution containing reaction monomers described reaction monomers is dissolved in the solution that dimethyl sulfoxide (DMSO) and/or diethyl sulfoxide obtain;
2) step 1) after completion of the reaction, take out the film after irradiation grafting, clean homopolymer and the complete monomer of unreacted with deionized water; Then this mould material is put into aqueous hydrochloric acid and carry out protonation reaction, obtain the amphoteric ion exchange membrane with sulfonate ion and quaternary ammonium radical ion.
2. preparation method as claimed in claim 1, is characterized in that, step 1) the absorption dose of method a) co-irradiation grafting reaction be 5 ~ 100kGy.
3. preparation method as claimed in claim 1, is characterized in that, step 1) method b) dosage that carries out irradiation to polymeric film is 5 ~ 100kGy.
4. preparation method as claimed in claim 1, is characterized in that, step 1) method b) in, the polymeric film after irradiation and the mixed temperature of reaction of monomer solution are 40 ~ 80 DEG C, and the reaction times is 1 ~ 6h.
5. preparation method as claimed in claim 1, is characterized in that, step 1) in
60co gamma-ray irradiation dose rate is 20 ~ 100Gy/min, and electron beam irradiation dose rate is 10 ~ 100Gy/s.
6. preparation method as claimed in claim 1, is characterized in that, step 1) described in the thickness of polymeric film be 25-50 μm.
7. preparation method as claimed in claim 1, is characterized in that, in step 1) reaction soln in, monomer I and the total volumetric molar concentration of monomer II are 0.1mol/L ~ 2mol/L, and wherein the mol ratio of monomer I and monomer II is 3: 1 ~ 1: 3.
8. preparation method as claimed in claim 1, is characterized in that, step 2) described in protonation reaction be mould material is immersed in aqueous hydrochloric acid to stir 10 ~ 24 hours at room temperature to 70 DEG C, wherein, described aqueous hydrochloric acid concentration is 1 ~ 3mol/L.
9. preparation method as claimed in claim 1, is characterized in that, in step 2) after, obtained amphoteric ion exchange membrane is immersed self-assembly in polyelectrolyte solution, is prepared into bilayer or multilayer ion-exchange membrane.
10. preparation method as claimed in claim 9, is characterized in that, described polyelectrolyte solution is one or more in Nafion solution, poly (sodium 4-styrenesulfonate) solution, quaternized polystyrene solution and quaternized polyaryletherketone solution.
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| WO2016205973A1 (en) * | 2015-06-24 | 2016-12-29 | 清华大学 | Partiallyfluorinated poly(fluorenyl ether oxadiazole) amphoteric ion exchange membrane and preparation method thereof |
| WO2016205972A1 (en) * | 2015-06-24 | 2016-12-29 | 清华大学 | Poly(oxadiazole aryl ether-co-bisphenol fluorine) proton exchange membrane and preparation method thereof |
| CN105037781A (en) * | 2015-07-09 | 2015-11-11 | 江苏华晖环保科技有限公司 | Method for preparing novel ion exchange membrane |
| CN106348405A (en) * | 2016-09-06 | 2017-01-25 | 深圳市君想环境科技有限公司 | Novel preparation method of homogenous film material for electric desalting and electrophoresis |
| CN111318191A (en) * | 2018-12-14 | 2020-06-23 | 有研工程技术研究院有限公司 | Preparation method of ion exchange membrane |
| CN109994763B (en) * | 2019-01-09 | 2021-11-02 | 华中科技大学 | Preparation method of all-vanadium redox flow battery diaphragm |
| CN112898491B (en) * | 2021-02-03 | 2023-03-14 | 陕西福天宝环保科技有限公司 | Amphoteric ion exchange membrane and preparation method thereof |
| CN115160476B (en) * | 2022-06-20 | 2023-12-01 | 大连融科储能技术发展有限公司 | Cross-linked amphoteric ion exchange membrane and preparation method and application thereof |
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| CN1299811C (en) * | 2004-11-03 | 2007-02-14 | 上海大学 | Method for preparing cation exchange membrane with high content of sodium sulfonate group |
| CN102181069B (en) * | 2011-04-12 | 2012-11-21 | 北京大学 | Preparation method of amphoteric ion exchange membrane |
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