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Composite type proton conduction membrane material containing amino-sulfonic group and preparation thereof
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A proton-conducting membrane, sulfonic acid-based technology, used in solid electrolyte fuel cells, fuel cells, fuel cell components, etc., can solve the problems of high membrane swelling rate and poor mechanical properties, and achieve enhanced mechanical properties and reduced swelling. The effect of sex, good toughness
Inactive Publication Date: 2011-01-26
JILIN UNIV
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But no matter what kind of material, there are common shortcomings: when the degree of sulfonation is relatively high, although the proton conductivity is relatively high, the swelling rate of the membrane is also high, and the mechanical properties are very poor.
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Embodiment 1
[0028] Embodiment 1: the preparation (1) of the polyether ether naphthalone of aminobenzene side group
[0029] 2.0122 grams (0.01mol) of 4-aminophenylhydroquinone, 3.7236 grams (0.01mol) of 1,4-bis(4-fluorophenylcarbonyl)naphthalene and 1.6585 grams of anhydrous potassium carbonate, 25ml sulfolane, 25ml toluene Put it into a 100ml three-necked flask equipped with a water device, pass nitrogen, raise the temperature to reflux of toluene, stir and reflux for 1.5 to 2 hours, remove the toluene, raise the temperature to 180°C, continue to react at about 180°C for 4 to 5 hours, and polymerize The solution was precipitated in water, crushed, washed and dried to obtain a brown powder of polyether ether naphthalone with 4-aminophenyl structure. The glass transition temperature measured by DSC was 224°C. The molecular formula is as follows:
[0030]
Embodiment 2
[0031] Embodiment 2: the preparation (2) of the polyether ether naphthalone of aminobenzene side group
[0032] The method is the same as in Example 1, and the amount of monomers is enlarged tenfold for polymerization. 20.122 grams (0.1mol) of 4-aminophenylhydroquinone, 37.236 grams (0.1mol) of 1,4-two (4-fluorophenylcarbonyl) naphthalene and 16.585 grams of anhydrous potassium carbonate, 250ml sulfolane, and 60ml toluene Put it into a 500ml three-necked flask equipped with a water device, pass nitrogen, raise the temperature to reflux of toluene, stir and reflux for 3 to 4 hours, remove the toluene, raise the temperature to 190°C, continue to react at about 190°C for 7 to 9 hours, and dissolve the polymerization solution Precipitate in water, pulverize, wash and dry to obtain the same brown powder of polyether ether naphthalone with 4-aminophenyl structure as in Example 1.
Embodiment 3
[0033] Embodiment 3: the preparation (3) of the polyether ether naphthalone of aminobenzene side group
[0034] The solvent sulfolane in Example 1 or 2 is replaced by N-methylpyrrolidone, and the azeotropic dehydrating agent toluene is replaced by xylene to obtain polyether ether naphthone with a 4-aminophenyl structure. The effect is the same.
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Abstract
The invention relates to compound proton conduction membrane material containing amino-sulfonic group and a preparation method thereof, belonging to the technical field of high polymer material. The compound proton conduction membrane material consists of aminobenzene pendant group polyether-ether-naphthalenone and sulfonated polymer which preferably is sulfonated polyether-ether-ketone polymer containing fluorine. Polyether-ether-naphthalenones polymer which contains amino pendant group and has good performance is synthesized by utilizing nucleophilic polycondensation, and then is mixed withthe sulfonated polymer to obtain a proton conduction membrane used for a proton conduction membrane fuel cell. Due to the intermolecular force between amino-group and sulfonic group, the water absorption rate of the proton conduction membrane is reduced, thus reducing the swelling capacity of the membrane; meanwhile, as naphthalene nucleus structure is introduced, the mechanical property of the material is enhanced, and the material especially has good toughness when in a dry state; furthermore, the invention provides necessary foundation for preparing the proton conduction membrane under thecondition of high temperature and low humidity.
Description
technical field [0001] The invention belongs to the technical field of macromolecular materials, and in particular relates to proton conduction membranes in different proportions prepared from polyether ether naphthylone polymers containing aminobenzene side groups and fluorine-containing sulfonated polyether ether ketones and a preparation method thereof. Background technique [0002] Proton conduction membrane fuel cell (PEMFC) uses solid electrolyte polymer membrane as electrolyte, so it has the advantages of high energy conversion rate, low temperature start-up, no leakage of electrolytic cell, no corrosion, and long service life. Therefore, it is recognized as the most promising power source for aerospace, military, electric vehicles and regional power stations. As a key component of the proton-conducting membrane fuel cell, the proton-conducting membrane plays the role of isolating fuel and oxidant, and conducting protons, and its performance determines the performance...
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