CN104877137A - Thiazole functionalized alkaline anion-exchange membrane and preparation method thereof - Google Patents
Thiazole functionalized alkaline anion-exchange membrane and preparation method thereof Download PDFInfo
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- CN104877137A CN104877137A CN201510214127.8A CN201510214127A CN104877137A CN 104877137 A CN104877137 A CN 104877137A CN 201510214127 A CN201510214127 A CN 201510214127A CN 104877137 A CN104877137 A CN 104877137A
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Abstract
The invention provides a thiazole functionalized alkaline anion-exchange membrane and a preparation method thereof. The preparation method comprises the following steps: firstly, performing chloromethylation modification on polyether sulfone, and then performing a nucleophilic substitution reaction on the chloromethyl and a thiazole compound, thereby obtaining the thiazole type group functionalized alkaline anion-exchange membrane. The prepared thiazole type group functionalized alkaline anion-exchange membrane has relatively high ionic conductance, appropriate water absorption, good mechanical properties, excellent chemical stability and the like, and has favorable application prospect in anion-exchange membranes for fuel cells.
Description
Technical field
The present invention relates to a kind of anion-exchange membrane and preparation method thereof, particularly relate to the anion-exchange membrane and preparation method thereof of thiazole type group as functionalization group.
Background technology
In many decades in the past, many scholars are devoted to the research of efficient generating apparatus, therefore high-energy-density, higher-energy transformation efficiency and the energy conversion technique compared with the discharge of low stain thing can be provided to become the focus of research, and fuel cell is constantly developed in the research of this technology.Fuel cell is a kind of device that the chemical energy in fuel can be become electric energy, owing to there is not combustion reactions, energy conversion process by the restriction of carnot's working cycle, the high and environmental friendliness of energy conversion efficiency.
Ion-exchange membrane is as the key component of fuel cell, and not only need to separate the fuel in negative and positive the two poles of the earth and oxygenant, the most important thing is as medium conducting ion, the selection of ion-exchange membrane directly affects energy conversion efficiency and the work-ing life of fuel cell simultaneously.Anion-exchange membrane and cationic exchange membrane can be divided into: cationic exchange membrane conduction H according to conducting ion difference
+, anion-exchange membrane conduction OH
-.Because alkaline environment anodic oxygen speed of reaction rate of permeation that is high, stock liquid is low, the advantages such as water management is relatively simple, alkaline anion-exchange membrane fuel cell is considered to a kind of novel power generation device being better than Proton Exchange Membrane Fuel Cells, and therefore anion-exchange membrane also becomes the focus of research.The preparation of conventional anion exchange membrane introduces ion-exchange group by quaterisation in chloromethylated polymer matrix.The selection of quaternizing agent determines electrochemical activity and the stability of quaternary ammonium group.
At present, the functionalization group that alkaline fuel cell anion-exchange membrane is conventional is that quaternary ammonium group is with quaternary phosphine group, but these cation groups can pass through hofmann elimination, ylide mechanism or SN2 bimolecular nucleophilic substitution generation DeR in the basic conditions, cause OH
-transmissibility decline rapidly, thus have impact on work-ing life and the performance of battery.
In order to improve the chemical stability of alkaline fuel cell anion-exchange membrane, imidazoles is grafted in alkaline membrane as functionalization group, because imidazol ion has the sterically hindered of conjugation five-membered ring structure and imidazole ring, make imidazoles have excellent chemical stability as alkaline membrane functionalization group, the research for alkaline fuel cell anion-exchange membrane provides new direction.
Summary of the invention
In order to make research further in functionalization group, the invention provides a kind of novel thiazole type group is grafted on alkaline anion-exchange membrane as functionalized reagent, its preparation method is simple, workable, anion-exchange membrane ionic conductance prepared by the method is higher, satisfactory mechanical property, has the potentiality of application in anion-exchange membrane.
To achieve these goals, the present invention is by the following technical solutions:
An anion-exchange membrane for thiazole type radical functino, the functionalization group of described exchange membrane has following structure:
The anionresin membrane preparation method of thiazole type radical functino, said method comprising the steps of:
Polyethersulfone is dissolved in the 98 ﹪ vitriol oils, adds chloromethylation Octyl Ether, react under stirring after dissolving completely; After reaction terminates, reactant is precipitated in water, then with deionized water, dehydrated alcohol by product cleaning to neutral, product dries through suction filtration, room temperature, obtains chloromethylation polyethersulfone; The skeleton symbol of chloromethylation polyethersulfone is as follows:
Chloromethylation polyethersulfone is dissolved in organic solvent and is mixed with solution;
Thiazole type group is put in above-mentioned solution, is 60-100 DEG C of amination treatment in temperature of reaction, reaction times is 6-48h, film-casting liquid is carried out reprecipitation process, and thiazole type group unnecessary in removing film-casting liquid, cleans mould material with dehydrated alcohol, use soaked in absolute ethyl alcohol again, product dries through suction filtration, room temperature, obtains the mould material of thiazole type radical functino, is finally dissolved in organic solvent by mould material and is made into film-casting liquid, casting film, obtains the anion-exchange membrane of thiazole type radical functino.
The skeleton symbol of thiazole type radical functino anion-exchange membrane is as follows:
According to the anionresin membrane preparation method of thiazole type radical functino, described organic solvent is N, N-N,N-DIMETHYLACETAMIDE, DMF, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, ethylene dichloride, tetrachloroethane, methylene dichloride, chloroform or mixing solutions.
According to the anionresin membrane preparation method of thiazole type radical functino, the polymer concentration that described thiazole type group carries out reaction kinetic is 2%, 3%, 4%, 5%, 6%, 7%, 8%.
The anionresin membrane preparation method of described thiazole type radical functino, the ratio that described thiazole type group carries out the chloromethane cardinal sum thiazolyl group of reaction kinetic is 1:1,1:1.5,1:2,1:3,1:5,1:8,1:10.
The anionresin membrane preparation method of described thiazole type radical functino, described thiazole type group carries out the temperature of reaction 60-100 DEG C of reaction kinetic, and the reaction times is 6-48h.
The anionresin membrane preparation method of described thiazole type radical functino, the baking film temperature of the anion-exchange membrane of described thiazole type radical functino is 40-80 DEG C, and drying the film time is 12-72h.
The anionresin membrane preparation method of described thiazole type radical functino, the precipitation agent of described reprecipitation is one or more the mixed solvent in water, methyl alcohol, ethanol, propyl alcohol, ether, tetrahydrofuran (THF), acetone, butanone, ethyl acetate.
Embodiment
Below by specific examples, the present invention is described in further detail.
Embodiment described is below only a part of the present invention, not all embodiment.Embodiment lists preparation process and the performance characterization of the anion-exchange membrane with new function group, and just the present invention will be described for these embodiments, do not belong within protection scope of the present invention.
Embodiment 1
In 150mL there-necked flask, add the 30mL vitriol oil, then add 3g polyethersulfone powder, be stirred to and dissolve completely.There-necked flask is placed in ice-water bath lower the temperature, adds 12mL chloromethyl Octyl Ether, now react beginning, stirring velocity 600r/m.After reaction 6h, reactant is precipitated in water, then with deionized water, dehydrated alcohol by product cleaning to neutral, product dries through suction filtration, room temperature, obtains the chloromethylation polyethersulfone that white is thread.
The chloromethylation polyethersulfone of the 6h of drying is dissolved in N, in N-N,N-DIMETHYLACETAMIDE, be mixed with the polymers soln that mass percentage is 5%, chloromethane radix and thiazole feed intake in the ratio of 1:3, 12h is reacted at 60 DEG C, by reaction solution Precipitation in ethanol, to remove unnecessary thiazole, with dehydrated alcohol, the mould material obtained is cleaned 3 times, use soaked in absolute ethyl alcohol 12h again, eventually pass suction filtration, room temperature is dried, obtain the mould material powder of pure thiazole functionalization, again above-mentioned mould material powder is dissolved in N, the film-casting liquid that mass percent is 5% is mixed with in N-N,N-DIMETHYLACETAMIDE, baking oven film-casting liquid being put into 50 DEG C dries film, film is taken off after solvent all volatilizees, film is put in the NaOH solution of 1mol/L and soak 48h, soak with the deionized water boiled again, until become neutrality, just obtain the hydroxide ion exchange membrane of thiazole functionalization.The loading capacity of this hydroxide ion exchange membrane is 0.61mmol/g, and water-intake rate is 12.1%, and the ionic conductance under normal temperature is 7.7mS/cm.
Embodiment 2
The preparation of chloromethylation polyethersulfone is with described in example one, the chloromethylation polyethersulfone of the 6h of drying is dissolved in N, in N-N,N-DIMETHYLACETAMIDE, be mixed with the polymers soln that mass percentage is 7%, chloromethane radix and thiazole feed intake in the ratio of 1:5, 12h is reacted at 80 DEG C, by reaction solution Precipitation in ethanol, to remove unnecessary thiazole, with dehydrated alcohol, the mould material obtained is cleaned 3 times, use soaked in absolute ethyl alcohol 12h again, eventually pass suction filtration, room temperature is dried, obtain the mould material powder of pure thiazole functionalization, again above-mentioned mould material powder is dissolved in N, the film-casting liquid that mass percent is 5% is mixed with in N-N,N-DIMETHYLACETAMIDE, baking oven film-casting liquid being put into 50 DEG C dries film, film is taken off after solvent all volatilizees, film is put in the NaOH solution of 1mol/L and soak 48h, soak with the deionized water boiled again, until become neutrality, just obtain the hydroxide ion exchange membrane of thiazole functionalization.The loading capacity of this hydroxide ion exchange membrane is 1.24mmol/g, and water-intake rate is 30.6%, and the ionic conductance under normal temperature is 14.4mS/cm.
Embodiment 3
The preparation of chloromethylation polyethersulfone is with described in example one, the chloromethylation polyethersulfone of the 6h of drying is dissolved in N, in N-N,N-DIMETHYLACETAMIDE, be mixed with the polymers soln that mass percentage is 8%, chloromethane radix and 2-methylthiazol feed intake in the ratio of 1:10, 6h is reacted at 100 DEG C, by reaction solution Precipitation in ethanol, to remove unnecessary 2-methylthiazol, with dehydrated alcohol, the mould material obtained is cleaned 3 times, use soaked in absolute ethyl alcohol 12h again, eventually pass suction filtration, room temperature is dried, obtain the mould material powder of pure 2-methylthiazol functionalization, again above-mentioned mould material powder is dissolved in N, the film-casting liquid that mass percent is 5% is mixed with in N-N,N-DIMETHYLACETAMIDE, baking oven film-casting liquid being put into 50 DEG C dries film, film is taken off after solvent all volatilizees, film is put in the NaOH solution of 1mol/L and soak 48h, soak with the deionized water boiled again, until become neutrality, just obtain the hydroxide ion exchange membrane of 2-methylthiazol functionalization.The loading capacity of this hydroxide ion exchange membrane is 2.24mmol/g, and water-intake rate is 85.6%, and the ionic conductance under normal temperature is 19.1mS/cm.
Claims (6)
1. an anion-exchange membrane for thiazole type radical functino, is characterized in that, the structure of thiazole type radical functino polyethersulfone is as follows:
2. the anion-exchange membrane of a kind of thiazole type radical functino according to claim 1, it is characterized in that, the structure of functionalization group is as follows:
3. the preparation method of the anion-exchange membrane of the thiazole type radical functino described in claim 1 or 2, is characterized in that following steps: polyethersulfone is dissolved in the 98 ﹪ vitriol oils, adds chloromethylation Octyl Ether, react under stirring after dissolving completely; After reaction terminates, reactant is precipitated in water, then with deionized water, dehydrated alcohol by product cleaning to neutral, product dries through suction filtration, room temperature, obtains chloromethylation polyethersulfone;
The skeleton symbol of chloromethylation polyethersulfone is as follows:
Chloromethylation polyethersulfone is dissolved in organic solvent and is mixed with solution;
Thiazole type group is put in above-mentioned solution, be 60-100 DEG C of amination treatment in temperature of reaction, the reaction times is 6-48h, and film-casting liquid is carried out reprecipitation process, thiazole type group unnecessary in removing film-casting liquid, cleaned by mould material with dehydrated alcohol, then use soaked in absolute ethyl alcohol, product dries through suction filtration, room temperature, obtain the mould material of thiazole type radical functino, finally mould material is dissolved in organic solvent and is made into film-casting liquid, casting film, obtain the anion-exchange membrane of thiazole type radical functino.
4. the preparation method of the anion-exchange membrane of thiazole type radical functino according to claim 3, it is characterized in that, described organic solvent is N, N-N,N-DIMETHYLACETAMIDE, DMF, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, ethylene dichloride, tetrachloroethane, methylene dichloride, chloroform or mixing solutions.
5. the preparation method of the anion-exchange membrane of thiazole type radical functino according to claim 3, it is characterized in that, the precipitation agent of described reprecipitation is one or more the mixed solvent in water, methyl alcohol, ethanol, propyl alcohol, ether, tetrahydrofuran (THF), acetone, butanone, ethyl acetate.
6. the anionresin membrane preparation method of thiazole type radical functino according to claim 4, it is characterized in that, the precipitation agent of described reprecipitation is one or more the mixed solvent in water, methyl alcohol, ethanol, propyl alcohol, ether, tetrahydrofuran (THF), acetone, butanone, ethyl acetate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106040318A (en) * | 2016-06-03 | 2016-10-26 | 合肥工业大学 | Anion exchange membrane material on basis of pyrazole onium salt, method for preparing anion exchange membrane material and application thereof |
| CN113856502A (en) * | 2021-10-18 | 2021-12-31 | 大连理工大学 | Quaternary amine type anion exchange membrane for reverse electrodialysis technology, preparation method and application thereof |
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| CN101628979A (en) * | 2009-07-03 | 2010-01-20 | 中山大学 | Sulfonated fluorene-containing polyether sulphone for proton exchange membrane of all-vanadium flow battery and preparation method and application thereof |
| US20100055534A1 (en) * | 2008-09-02 | 2010-03-04 | General Electric Company | Electrolyte membrane, methods of manufacture thereof and articles comprising the same |
| CN102728237A (en) * | 2012-06-20 | 2012-10-17 | 中国科学技术大学 | Homogeneous anion exchange membrane and preparation method thereof |
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| US20100055534A1 (en) * | 2008-09-02 | 2010-03-04 | General Electric Company | Electrolyte membrane, methods of manufacture thereof and articles comprising the same |
| CN101628979A (en) * | 2009-07-03 | 2010-01-20 | 中山大学 | Sulfonated fluorene-containing polyether sulphone for proton exchange membrane of all-vanadium flow battery and preparation method and application thereof |
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| CN106040318A (en) * | 2016-06-03 | 2016-10-26 | 合肥工业大学 | Anion exchange membrane material on basis of pyrazole onium salt, method for preparing anion exchange membrane material and application thereof |
| CN106040318B (en) * | 2016-06-03 | 2018-06-15 | 合肥工业大学 | Anion exchange membrane material based on pyrazoles salt and its preparation method and application |
| CN113856502A (en) * | 2021-10-18 | 2021-12-31 | 大连理工大学 | Quaternary amine type anion exchange membrane for reverse electrodialysis technology, preparation method and application thereof |
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