用于燃料电池质子交换膜的含萘及氮杂环结构的新型磺化聚酰亚胺的合成及性能

将自制的4,4'-二氨基二苯醚-2,2'-二磺酸基(ODADS)、 含氮杂环芳香二胺1,2-二氢-2-(4-氨基苯基)-4-[4-(4-氨基苯氧基)-苯基]-二氮杂萘-1-酮(DHPZ-DA)和1,4,5,8-萘四甲酸二酐(NTDA)进行直接缩合聚合反应, 通过改变磺化二胺单体的含量来改变聚合物的磺化度, 成功地合成了一系列高分子量的不同磺化度的六元环聚酰亚胺(SPIs), 其特性粘度在0.55-1.47 dL/g. 采用FTIR和 1H NMR技术表征了聚合物的结构. 研究了经溶液浇铸成磺化聚合物膜的理化性质. 结果表明, 随着聚合物磺化度的增大, 膜的含水率和离子交换能力增大, 尺寸稳定性、 对水的稳定性以及抗氧化性降低.

Synthesis and Partial Properties of Naphthalene and Phthalazinone-based Sulfonated Copolyimides for Proton Exchange Membrane in Fuel Cells

A new sulfonated copolyimides(SPIs) containing both of naphthalene and phthalazinone moieties in polymer's main chain were successfully synthesized from 4,4'-diaminophenyl ether-2,2' disulfonic acid(ODADS), 1,2-dihydro-2-(4-aminophenyl)-4-[4-(4-aminophenoxy)phenyl]-phthalazin-1-one(DHPZ-DA) and 1,4,5,8-naphthalenetetracarboxylic dianhydride(NTDA) via direct polymerization, which are potentially utilized in proton exchange membrane in PEMFC. The obtained sulfonated polymers(SPIs) have a molecular weight with the inherent viscosity range from 0.55 to 1.47 dL/g. The chemical structure of the SPIs was carefully characterized by FTIR and 1H NMR. The yellow transparent and tough membranes cast from m-cresol solution of SPIs were obtained, which were utilized to investigate the physicochemical properties of new copolymers. The data demonstrate that the membrane's water uptake, swelling ratio, ion exchange capacities(IEC), as well as the resistance to both of water and oxidation varied accordingly with the increase of sulfonation degree of the new SPIs. The introduction of DHPZ-DA improved the SPIs' solubility. Meanwhile, the thermic stability of copolymers by TGA was also investigated.