Preparation and Application of Side Chain Sulfonated Polyimide Bridged by Quinoxaline Group
A technology of sulfonated polyimide and quinoxaline group is applied in the preparation of proton exchange membrane and the preparation of side chain sulfonated polyimide, which can solve the synthesis of side chain sulfonated diamine monomer The problems of complex process, low yield and complex polymerization process can achieve the effects of excellent mechanical properties and thermal stability, high proton conductivity and broad application prospects.
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[0049] The present invention also proposes a preparation method of side chain type sulfonated polyimide bridged by quinoxaline groups, including the preparation method of sulfonated polyimide homopolymer and sulfonated polyimide copolymer, wherein The preparation method of the sulfonated polyimide homopolymer (y=1) with general formula (I or II) comprises the following steps:
[0050] Under nitrogen protection, dissolve 4,4'-bis(4-amino-phenoxy)benzil in an organic solvent, and then add 4,4'-bis(4-amino-phenoxy)benzil Acyl equimolar dianhydride monomer and a certain amount of organic weak acid, react the reaction system at 50-120°C for 1-8h, then react at 140-220°C for 8-24h, then cool the system to 70-100°C, and then add With 4,4'-bis(4-amino-phenoxy)benzil equimolar sulfonated diamine and a certain amount of organic weak base, react for 2-4 hours, after the reaction, pour it into methanol to obtain a filamentous The product is dried under vacuum after repeated washing to ob...
Embodiment 1
[0060] Example 1: Synthesis of a side-chain sulfonated polyimide homopolymer bridged by quinoxaline groups and preparation of a proton exchange membrane:
[0061] Under nitrogen protection and mechanical stirring, add 4,4'-bis(4-amino-phenoxy)benzil 4.24g (10mmol) and m-cresol 50-130mL into a dry 250mL three-necked flask, After complete dissolution, add 2.68g (10mmol) of 1,4,5,8-naphthalene tetracarboxylic dianhydride and 1.22-3.66g (10-30mmol) of benzoic acid. Preferably, the optimal addition amount of m-cresol in the present embodiment is 70mL, and benzoic acid is 2.44g (20mmol). First react the reaction system at 50-120°C for 1-8h, then react at 140-220°C for 8-24h, then cool the system down to 70-100°C, then add 4-(3,4-diamino-phenoxy )-1,3-benzenedisulfonic acid 3.60g (10mmol) and triethylamine 2.02-4.04g (20-40mmol), react for 2-4h, preferably, the three temperatures in this embodiment are 100°C, At 180°C and 80°C, the three times are 4h, 20h, and 4h respectively, and ...
Embodiment 2
[0063] Example 2: Synthesis of a side-chain sulfonated polyimide copolymer bridged by quinoxaline groups and preparation of a proton exchange membrane:
[0064] Under the protection of nitrogen and mechanical stirring, add 4.24g (10mmol) of 4,4'-bis(4-amino-phenoxy)benzil and 65mL of m-cresol to a dry 250mL three-necked flask, and wait for complete After dissolution, 2.68 g (10 mmol) of 1,4,5,8-naphthalene tetracarboxylic dianhydride and 3.05 g (25 mmol) of benzoic acid were added. First react the reaction system at 100°C for 4h, then react at 180°C for 20h, then cool the system down to 80°C, then add 4-(3,4-diamino-phenoxy)-1,3-benzenedisulfonic acid 1.80g (5mmol) and triethylamine 1.52g (15mmol), reacted for 4h. All the other experimental procedures were the same as in Example 1.
[0065] The preparation method of the proton exchange membrane is the same as in Example 1.
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