CN101759864A - Method for preparing perfluorocarboxylic acid ion membranes by liquid surface tape casting method - Google Patents
Method for preparing perfluorocarboxylic acid ion membranes by liquid surface tape casting method Download PDFInfo
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- CN101759864A CN101759864A CN200810159980A CN200810159980A CN101759864A CN 101759864 A CN101759864 A CN 101759864A CN 200810159980 A CN200810159980 A CN 200810159980A CN 200810159980 A CN200810159980 A CN 200810159980A CN 101759864 A CN101759864 A CN 101759864A
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- liquid
- perfluorocarboxylic acid
- solution
- acid ion
- acid resin
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- 238000000034 method Methods 0.000 title claims abstract description 70
- 239000007788 liquid Substances 0.000 title claims abstract description 67
- 239000012528 membrane Substances 0.000 title claims abstract description 57
- 238000010345 tape casting Methods 0.000 title claims description 14
- 239000011347 resin Substances 0.000 claims abstract description 61
- 229920005989 resin Polymers 0.000 claims abstract description 61
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 55
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 238000002844 melting Methods 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 11
- 238000005266 casting Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 6
- -1 perfluorocarboxylic acid ion Chemical class 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 18
- 239000000956 alloy Substances 0.000 claims description 18
- 238000007766 curtain coating Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 8
- 229910000497 Amalgam Inorganic materials 0.000 claims description 7
- 230000004927 fusion Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910000648 terne Inorganic materials 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 2
- 239000011734 sodium Substances 0.000 abstract 2
- 239000002131 composite material Substances 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 10
- 229910052718 tin Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000000758 substrate Substances 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 239000010127 yangjing Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910001338 liquidmetal Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- RAYLUPYCGGKXQO-UHFFFAOYSA-N n,n-dimethylacetamide;hydrate Chemical compound O.CN(C)C(C)=O RAYLUPYCGGKXQO-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to a method for preparing perfluorocarboxylic acid ion membranes, which is characterized in that the method comprises the following steps: (1) dissolving perfluorocarboxylic acid resin into a solvent for forming a uniform perfluorocarboxylic acid resin solution A; (2) adding materials with low melting point and high density into a heatable container, heating the container for dissolving the materials, and forming uniform liquid B in the container; (3) preheating the perfluorocarboxylic acid resin solution A and pouring the perfluorocarboxylic acid resin solution A onto the surface of the liquid B protected by nitrogen gas so that a thin layer solution is formed on the surface of the liquid B through casting; (4) heating the liquid B, then carrying out program temperature reduction, and continuously introducing the nitrogen gas for protection in the whole process; and (5) evaporating most or all of the solvent in the perfluorocarboxylic acid resin solution A to obtain the perfluorocarboxylic acid ion membrane on the surface of the liquid B. The perfluorocarboxylic acid ion membrane prepared by the invention can be applied to composite layers of sodium hudroxide use ion membranes, and has the advantages of uniform thickness, difficult bubble generation and stable performance, and the invention provides reliable carboxylic acid layer ion membranes for producing the sodium hudroxide use ion membranes.
Description
Technical field
The present invention relates to a kind of method for preparing perfluorocarboxylic acid ion membranes, particularly a kind of method of preparing perfluorocarboxylic acid ion membranes by liquid surface tape casting method.
Background technology
The perfluorinated ionic membrane legal system is equipped with the revolution that the chlor-alkali technology is a chlorine industry, it is the chlor-alkali production technology that a kind of energy consumption is low, pollution-free, quality product is high, China has introduced the ionic membrane whole plant of the U.S. with nearly ten million ton in Japan in the time of more than ten years, improve the equipment of China's chlorine industry greatly, solved the difficult problem that China high quality caustic soda needs import.Along with the progress and the development of science and technology of society, mercury process caustic soda and part graphite anode diaphragm process caustic soda will be replaced by the ionic membrane method caustic soda fully.
The physical and chemical performance of perfluorocarboxylic acid ion membranes and its production process are closely related.At present, perfluorinated carboxylic acid resin's extrusion by melting or solution casting method are mainly adopted in the preparation of perfluorocarboxylic acid ion membranes.Because under temperature is 250 ℃ or higher situation, have-COOH or-tangible decarboxylation thermolysis can take place in the perfluorinated carboxylic acid ion-exchange resin of COONa structural form, emit carbonic acid gas, and it is crosslinked that resin generation unsaturated double-bond is caused, thereby melt extrusion can't be carried out.General general-COOCH earlier
3The resin of type group carries out film extrusion, then the film of making is hydrolyzed in certain density alkaline solution, obtains perfluorocarboxylic acid ion membranes.This kind method program is too much, and complex operation is unfavorable for producing in enormous quantities.Also have the investigator will have-COOH and-perfluorinated carboxylic acid ion-exchange resin and the solvent of COONa structural form be prepared into solution, then with this solution casting film-forming on solid phase surface, in this casting method film process, the concentration of solution of carrying out curtain coating is higher, and certain viscosity is arranged, the parameter of solution is very big to the film forming result's influence of curtain coating, and the material of the substrate of curtain coating, planeness, thermal expansivity etc. all can influence all even stable performance of thickness of film.
Thereby exploitation thickness perfluorocarboxylic acid ion membranes even, stable performance has crucial meaning.
Summary of the invention
The object of the present invention is to provide a kind of perfluorinated carboxylic acid resin's solution film forming method, the perfluorocarboxylic acid ion membranes that prepare a kind of thin layer, has good uniformity, this carboxylic acid membrane can be used for preparing the carboxylic layer in the caustic soda usefulness ionic membrane.
The present invention adopts preparing perfluorocarboxylic acid ion membranes by liquid surface tape casting method, and curtain coating solution is sprawled in the curtain coating substrate, and perfluorocarboxylic acid ion membranes is to form in the solution surface curtain coating.Compare with traditional method, the present invention adopts low melting point high-density matter molten state as the curtain coating plane, has lot of advantages, strength of solution is not had harsh requirement, and the solution of nearly all concentration all can carry out casting film-forming, and molten state liquid level itself is a horizontal plane in addition, need not carry out the adjustment of the preceding horizontal plane of curtain coating, simplified the curtain coating operating process, and its molten state liquid can be directly to the heating of perfluorinated carboxylic acid resin's solution, homogeneous heating is controlled easily.Present method has been simplified the troublesome operation flow process in the solution film forming process, the perfluorocarboxylic acid ion membranes that can obtain having good uniformity.
The invention provides a kind of method for preparing perfluorocarboxylic acid ion membranes, may further comprise the steps:
1) preparation of perfluorinated carboxylic acid resin's solution A
1. take by weighing the perfluorinated carboxylic acid resin, put into autoclave, add the mixture of organic solvent, water or organic solvent and water;
2. heating high-pressure still, temperature programming, temperature is 30～250 ℃, and stirs, stir speed (S.S.) 1～3000rpm/ minute;
3. be incubated 0,1～24h, then cooling gradually;
4. take out that liquid filtering promptly gets perfluorinated carboxylic acid resin's solution A in the autoclave;
2) preparation of liquid B
1. in heatable container, add the low melting point high-density matter;
2. heating container forms the liquid B of homogeneous to the complete fusion of low melting point high-density matter;
3) solution casting
1. the perfluorinated carboxylic acid resin's solution A with preparation is preheated to 10～250 ℃;
2. perfluorinated carboxylic acid resin's solution A is put on the liquid B surface of gas C protection, made it form thin layer solution in liquid B surface curtain coating.
4) film forming
With liquid B temperature programming to 20～250 ℃, programmed cooling is then taken off from the liquid B surface and to be got the gained perfluorocarboxylic acid ion membranes, constantly feeds gas C in the whole process and protects;
Preferably, above-mentioned steps 1) in perfluorinated carboxylic acid resin's structure be:
M=0～3 wherein, n=2～4, x=1～10, y=1～3, Y is CO
2M, M are H, NH
2, Na, K, Li, Ca, basic metal or alkaline-earth metal such as Mg.
Preferably, the concentration of the described perfluor sulfoacid resin solution A of step 1) is 0.01-75%, mass percent concentration.
Preferably, above-mentioned steps 1) used organic solvent is selected from methyl alcohol, ethanol, Virahol, propyl alcohol, N in, dinethylformamide, N, wherein one or more of N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), pyrrolidone are preferred, step 2) the low melting point high-density matter described in, be fusing point-100～350 ℃, molten state density is greater than the material of 2.0g/cm3, the mixture of one or more materials in preferred Hg, Sn, In, terne metal, bismuth-base alloy, indium-base alloy, the amalgam.The low melting point high-density matter as curtain coating substrate select for use.
Preferably, the Heating temperature of melt liquid B is 20～250 ℃ step 2).
Preferably, perfluor sulfoacid resin solution A preheating temperature is 50～140 ℃ in the step 3).
Preferably, the method that step 4) is carried out temperature programming to liquid B is 0.1～30 ℃/minute, and the programmed cooling method is 0.1～60 ℃/minute.
Preferred, after step 4) is carried out temperature programming to liquid B, be incubated 0.1～10 hour.
Preferably, the gas C step 3) and 4) is N
2, CO
2, among He, Ne, Ar, Kr, Xe, the Rn one or more.
The present invention does not have particular requirement to perfluorinated carboxylic acid resin's strength of solution and viscosity, and homogeneous, stable solution can both prolong film forming at fusion liquid level upper reaches.
The present invention becomes embrane method to compare with existing perfluorinated carboxylic acid resin's solution casting to have the following advantages:
(1) the concentration range broad of perfluorinated carboxylic acid resin's resin solution of using of curtain coating does not have harsh requirement to the concentration of solution, and the viscosity of solution does not have particular requirement yet, has simplified the step of solution concentration in the general casting method.
(2) because the curtain coating substrate is a horizontal liquid level, compare, need not carry out horizontal adjustment, simplified the leveling process substrate with the solid phase plane.
The method of the substrate solution heating of (3) adopting has guaranteed the homogeneity and the stability that heat.
(4) Zhi Bei perfluorocarboxylic acid ion membranes thickness evenness increases substantially, and the film thickness error is less than 1%.
The present invention and existing perfluorocarboxylic acid-COOCH
3The type resin melt extrudes film forming and compares and have the following advantages:
(1) have-COOH or-perfluorinated carboxylic acid ion-exchange resin's of COONa structural form decomposition temperature is lower, extrusion by melting must make the perfluorinated carboxylic acid resin become molten state, perfluorinated carboxylic acid resin's fluxing point and decomposition point are approaching, thereby the perfluorinated carboxylic acid resin is decomposed, film-forming temperature can not produce resin resolution problem in the film process far below perfluorinated carboxylic acid resin's decomposition temperature in present method.
(2) have-COOCH
3After the perfluorinated carboxylic acid ion-exchange resin of type group melt extrudes film forming, also need film is hydrolyzed the present invention's step that need not be hydrolyzed.
(3) melt extrude film forming and be easy to generate bubble or needle pore defect, bubble is overflowed from the surface easily in present method, and heating uniformity is better, is difficult for producing defective.
(4) the present invention is at the fused solution surface filming, and resulting film surface finish and slickness all are better than scorification.
Embodiment:
The invention will be further described below by embodiment.
Table 1 is a perfluorocarboxylic acid ion membranes thickness measuring data sheet of the present invention, test membrane is a rectangle, respectively test center point and four edge thickness, thickness average value is the thickness of perfluorocarboxylic acid ion membranes, error is that mean thickness and mean thickness differ the difference between the test value of maximum.
Embodiment 1
Perfluorinated carboxylic acid resin and ethanol are placed autoclave by mass ratio at 3: 97, be heated to 160 ℃ by 10 ℃/minute speed, be incubated 20 hours, by 5 ℃/minute speed cooling, it is standby that the perfluorinated carboxylic acid resin's solution that obtains filters the back.Can heat in the stainless steel tank one that to add fusing point be 180 ℃ terne metal, heating is with its fusion.The perfluorinated carboxylic acid resin's solution that obtains previously is preheated to 120 ℃, join the surface of molten alloy liquid then, treat that perfluorinated carboxylic acid resin's solution heats alloy solution after molten state alloy liquid level curtain coating balance, 10 ℃/minute of heating rate, temperature stops heating when reaching 200 ℃, be incubated 10 minutes, cool then to 185 ℃.Feed N in this process always
2Protect.Take off from the alloy liquid level and to get institute's film forming, promptly get perfluorocarboxylic acid ion membranes.
Perfluorocarboxylic acid ion membranes thickness measuring data of the present invention are as table 1a.
Embodiment 2
Perfluorinated carboxylic acid resin and dimethyl sulfoxide (DMSO) are placed autoclave by mass ratio at 35: 65, be heated to 170 ℃, be incubated 18 hours, in heating and insulating process, keep stirring stir speed (S.S.) 60rpm/ minute by 10 ℃/minute speed.By 5 ℃/minute speed cooling, it is standby that the solution that obtains filters the back.Can heat in the stainless steel tank one that to add fusing point be 180 ℃ bismuth-base alloy, heating is with its fusion.The perfluorinated carboxylic acid resin's solution that obtains previously is preheated to 120 ℃, join the surface of molten alloy liquid then, treat that perfluorinated carboxylic acid resin's solution heats alloy solution after molten state alloy liquid level curtain coating balance, 10 ℃/minute of heating rate, temperature stops heating when reaching 240 ℃, be incubated 10 minutes.Cool then to 185 ℃.Feed He in this process protects always.Take off from the alloy liquid level and to get institute's film forming, promptly get perfluorocarboxylic acid ion membranes.
Perfluorocarboxylic acid ion membranes thickness measuring data of the present invention are as table 1b.
Embodiment 3
With perfluorinated carboxylic acid resin and N, dinethylformamide places autoclave by mass ratio at 50: 50, is heated to 220 ℃ by 5 ℃/minute speed, is incubated 24 hours, keeps stirring stir speed (S.S.) 2000rpm/ minute in heating and insulating process.By 2 ℃/minute speed cooling, it is standby that the solution that obtains filters the back.Can heat in the stainless steel tank one that to add fusing point be 160 ℃ indium-base alloy, heating is with its fusion.The perfluorinated carboxylic acid resin's solution that obtains previously is preheated to 110 ℃, join the surface of molten alloy liquid then, treat that perfluorinated carboxylic acid resin's solution heats alloy solution after molten state alloy liquid level curtain coating balance, 10 ℃/minute of heating rate, temperature stops heating when reaching 195 ℃, be incubated 10 minutes.Cool then to 175 ℃.Feed Ne in this process protects always.Take off from the alloy liquid level and to get institute's film forming, promptly get perfluorocarboxylic acid ion membranes.
Perfluorocarboxylic acid ion membranes thickness measuring data of the present invention are as table 1c.
Embodiment 4
Perfluorinated carboxylic acid resin and Virahol are placed autoclave by mass ratio at 13: 87, be heated to 205 ℃, be incubated 10 hours, in heating and insulating process, keep stirring stir speed (S.S.) 180rpm/ minute by 15 ℃/minute speed.By 5 ℃/minute speed cooling, it is standby that the solution that obtains filters the back.Can heat in the stainless steel tank one and to add metallic tin, be heated to 240 ℃ its fusion.The perfluorinated carboxylic acid resin's solution that obtains previously is preheated to 50 ℃, join the surface of liquid tin then, treat that perfluorinated carboxylic acid resin's solution liquid towards tin after liquid tin curtain coating balance heats 10 ℃/minute of heating rate, temperature stops heating when reaching 245 ℃, be incubated 10 minutes.Cool then to 240 ℃.Feed Ar in this process protects always.Take off from the liquid tin surface and to get institute's film forming, promptly get perfluorocarboxylic acid ion membranes.
Perfluorocarboxylic acid ion membranes thickness measuring data of the present invention are as table 1d.
Embodiment 5
With perfluorinated carboxylic acid resin, water and N, dinethylformamide places autoclave by mass ratio at 10: 40: 50, is heated to 200 ℃ by 5 ℃/minute speed, is incubated 24 hours, keeps stirring stir speed (S.S.) 300rpm/ minute in heating and insulating process.By 5 ℃/minute speed cooling, it is standby that the solution that obtains filters the back.Can heat the liquid Hg of adding in the stainless steel tank one.The perfluorinated carboxylic acid resin's solution that obtains previously is preheated to 110 ℃, join the surface of liquid Hg then, treat that perfluorinated carboxylic acid resin's solution heats 10 ℃/minute of heating rate at weighing apparatus back, liquid Hg surface current Yangjing liquid towards Hg, temperature stops heating when reaching 180 ℃, be incubated 10 minutes.Cool then to 140 ℃.Feed Kr in this process protects always.Take off from liquid Hg surface and to get institute's film forming, promptly get perfluorocarboxylic acid matter ionic membrane.
Perfluorocarboxylic acid ion membranes thickness measuring data of the present invention are as table 1e.
Embodiment 6
Perfluorinated carboxylic acid resin, water and N,N-dimethylacetamide are placed autoclave by mass ratio at 35: 30: 35, be heated to 145 ℃, be incubated 18 hours, in heating and insulating process, keep stirring stir speed (S.S.) 160rpm/ minute by 10 ℃/minute speed.By 15 ℃/minute speed cooling, it is standby that the solution that obtains filters the back.Can heat the liquid Hg of adding in the stainless steel tank one.The perfluorinated carboxylic acid resin's solution that obtains previously is preheated to 170 ℃, join the surface of liquid Hg then, treat that perfluorinated carboxylic acid resin's solution heats 1 ℃/minute of heating rate at weighing apparatus back, liquid Hg surface current Yangjing liquid towards Hg, temperature stops heating when reaching 180 ℃, be incubated 10 minutes.Cool then to 125 ℃.Feed Xe in this process protects always.Take off from liquid Hg surface and to get institute's film forming, promptly get perfluorocarboxylic acid ion membranes.
Perfluorocarboxylic acid ion membranes thickness measuring data of the present invention are as table 1f.
Embodiment 7
With perfluorinated carboxylic acid resin, ethanol, Virahol and N, dinethylformamide was by mass ratio 10: 20: 20: 50 place autoclave, are heated to 190 ℃ by 10 ℃/minute speed, are incubated 24 hours, in heating and insulating process, keep stirring stir speed (S.S.) 300rpm/ minute.By 5 ℃/minute speed cooling, it is standby that the solution that obtains filters the back.Can heat in the stainless steel tank one and to add tin amalgam, it is molten state to add thermic.The perfluorinated carboxylic acid resin's solution that obtains previously is preheated to 130 ℃, join the surface of tin amalgam then, treat that perfluorinated carboxylic acid resin's solution heats tin amalgam in weighing apparatus back, surface current Yangjing of tin amalgam, 10 ℃/minute of heating rate, temperature stops heating when reaching 245 ℃, be cooled to 210 ℃ then.Feed Rn in this process protects always.Take off from the tin amalgam surface and to get institute's film forming, promptly get perfluorocarboxylic acid ion membranes.
Perfluorocarboxylic acid ion membranes thickness measuring data of the present invention are as table 1g.
Embodiment 8
With perfluorinated carboxylic acid resin, ethanol, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO) and water were by mass ratio 5: 20: 20: place autoclave at 20: 35, be heated to 200 ℃ by 10 ℃/minute speed, be incubated 20 hours, in heating and insulating process, keep stirring stir speed (S.S.) 100rpm/ minute.By 10 ℃/minute speed cooling, it is standby that the solution that obtains filters the back.Can heat in the stainless steel tank one and to add metal In, be heated to 170 ℃ and cause it and be molten state.The perfluorinated carboxylic acid resin's solution that obtains previously is preheated to 140 ℃, join the surface of liquid metal In then, treat that perfluorinated carboxylic acid resin's solution heats in weighing apparatus back, surface current Yangjing of liquid metal In liquid towards metal In, 30 ℃/minute of heating rate, temperature stops heating when reaching 205 ℃, be incubated 10 minutes.Be cooled to 180 ℃ then.Feed CO in this process always
2Protect.Take off from the surface of liquid metal In and to get institute's film forming, promptly get perfluorocarboxylic acid ion membranes.
Perfluorocarboxylic acid ion membranes thickness measuring data of the present invention are as table 1h
Table 1 perfluorocarboxylic acid ion membranes thickness measuring
| Kind | ??a | ??b | ??c | ??d | ??e | ??f | ??g | ??h |
| Thickness/μ m | ??15.4 | ??16.6 | ??33.8 | ??16.2 | ??20.2 | ??40.4 | ??25.6 | ??21.4 |
| Error/μ m | ??±0.1 | ??±0.1 | ??±0.3 | ??±0.1 | ??±0.2 | ??±0.5 | ??±0.3 | ??±0.2 |
Claims (10)
1. the method for a preparing perfluorocarboxylic acid ion membranes by liquid surface tape casting method, its preparation method comprises following steps:
1) preparation of perfluorinated carboxylic acid resin's solution A
1. take by weighing the perfluorinated carboxylic acid resin, put into autoclave, add the mixture of organic solvent, water or organic solvent and water;
2. heating high-pressure still, temperature programming, temperature is 30～250 ℃, and stirs, stir speed (S.S.) 1～3000rpm/ minute;
3. be incubated 0.1～24h, gradually cooling;
4. take out that liquid filtering promptly gets perfluorinated carboxylic acid resin's solution A in the autoclave;
2) preparation of liquid B
1. in heatable container, add the low melting point high-density matter;
2. heating container forms the liquid B of homogeneous to the complete fusion of low melting point high-density matter;
3) solution casting
1. the perfluorinated carboxylic acid resin's solution A with preparation is preheated to 10～250 ℃;
2. perfluorinated carboxylic acid resin's solution A is put on the liquid B surface of gas C protection, made it form thin layer solution in liquid B surface curtain coating;
4) film forming
With liquid B temperature programming to 20～250 ℃, programmed cooling is then taken off from the liquid B surface and to be got the gained perfluorocarboxylic acid ion membranes, constantly feeds gas C in the whole process and protects.
2. the method for a kind of preparing perfluorocarboxylic acid ion membranes by liquid surface tape casting method as claimed in claim 1 is characterized in that the described perfluorinated carboxylic acid resin's of step 1) structure is:
M=0～3 wherein, n=2～4, x=1～10, y=1～3, Y is CO
2M, M are H, NH
2, Na, K, Li, Ca, basic metal or alkaline-earth metal such as Mg.
3. the method for a kind of preparing perfluorocarboxylic acid ion membranes by liquid surface tape casting method as claimed in claim 1 is characterized in that, the mass percent concentration of perfluorinated carboxylic acid resin's solution A is 0.01～75% in the step 1).
4. the method for a kind of preparing perfluorocarboxylic acid ion membranes by liquid surface tape casting method as claimed in claim 1, it is characterized in that, used organic solvent is selected from methyl alcohol, ethanol, Virahol, propyl alcohol, N in the step 1), wherein one or more of dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), pyrrolidone.
5. the method for a kind of preparing perfluorocarboxylic acid ion membranes by liquid surface tape casting method as claimed in claim 1, it is characterized in that, step 2) the low melting point high-density matter described in is the mixture of one or more materials in Hg, Sn, In, terne metal, bismuth-base alloy, indium-base alloy, the amalgam.
6. the method for a kind of preparing perfluorocarboxylic acid ion membranes by liquid surface tape casting method as claimed in claim 1 is characterized in that step 2) in the Heating temperature of melt liquid B be 20～250 ℃.
7. the method for a kind of preparing perfluorocarboxylic acid ion membranes by liquid surface tape casting method as claimed in claim 1 is characterized in that, perfluorinated carboxylic acid resin's solution A preheating temperature is 50～140 ℃ in the step 3).
8. the method for a kind of preparing perfluorocarboxylic acid ion membranes by liquid surface tape casting method as claimed in claim 1 is characterized in that, the method that step 4) is carried out temperature programming to liquid B is 0.1～30 ℃/minute, and the programmed cooling method is 0.1～60 ℃/minute.
9. the method for a kind of preparing perfluorocarboxylic acid ion membranes by liquid surface tape casting method as claimed in claim 1 is characterized in that, after step 4) is carried out temperature programming to liquid B, is incubated 0.1～10 hour.
10. the method for a kind of preparing perfluorocarboxylic acid ion membranes by liquid surface tape casting method as claimed in claim 1 is characterized in that, step 3) and 4) in gas C be N
2, CO
2, among He, Ne, Ar, Kr, Xe, the Rn one or more.
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