含磺化芴基侧基的聚芳醚氧膦质子交换膜的合成与表征  

Synthesis and Characterization of Poly(arylene ether phosphine oxide)s with Pendent Sulfonated Fluorenyl as Proton Exchange Membranes

作　　者：付志男 谈云龙 肖谷雨[1] 颜德岳[1] FU Zhinan;TAN Yunlong;XAIO Guyu;YAN Deyue(School of Chemistry and Chemical Engineering,Shanghai Jiao Tong University,Shanghai 200240,China)

机构地区：[1]上海交通大学化学化工学院,上海200240

出　　处：《功能高分子学报》2022年第1期36-43,共8页Journal of Functional Polymers

基　　金：国家自然科学基金(21774073);广东省科技专项资金项目(190805155540379)。

摘　　要：将9,9-二(4-羟苯基)芴(BHPF)与二(4-氟苯基)苯基氧膦(BFPPO)聚合,合成了含芴基侧基的聚芳醚氧膦(PAEPO),并采用后磺化法,制备了侧链型磺化聚芳醚氧膦(sPAEPO)质子交换膜。通过核磁与红外确定了聚合物的化学结构,用原子力显微镜对sPAEPO的微观结构进行了表征,同时对sPAEPO质子交换膜的尺寸稳定性和质子电导率进行了测试。结果表明,侧基苯环上的磺酸基促使聚合物膜形成亲水相连通性好的微相分离结构,有利于提高质子电导率,并保持低溶胀率,综合性能优良。所得质子交换膜在80°C下的溶胀率为30%,低于绝大多数非氟质子交换膜的溶胀率,质子电导率为0.075 S/cm,与Nafion 117的质子电导率接近,并且热稳定性与耐氧化性优良。The preparation of non-fluorinated proton exchange membranes(PEMs) includes post-sulfonation and direct polycondensation methods. The latter method involves the synthesis of sulfonated monomers, but the purification of sulfonated monomers is generally time-consuming. Herein, poly(arylene ether phosphine oxide)s(PAEPO) with pendant fluorenyl groups are synthesized by polycondensation of 9,9-bis(4-hydroxyphenyl) fluorene and bis(4-fluorophenyl) phenyl phosphine oxide, then the side-chain type sulfonated poly(arylene ether phosphine oxide)s(sPAEPO) are prepared by postsulfonation as proton exchange membranes. NMR and FT-IR are used to determine the chemical structure of PAEPO and sPAEPO, and AFM is employed to characterize the microstructure of the sPAEPO PEMs. The dimensional stability and proton conductivity of the sPAEPO PEMs are also investigated. The results illustrate that the sulfonic acid groups in the side benzene rings facilitate the resultant membranes to form the microphase separation structures with well-connected hydrophilic phases, achieving high proton conductivity, low swelling, and excellent overall properties. At 80 °C, the as-made PEMs exhibit a swelling of 30%, less than that of most non-fluorinated PEMs, whereas their proton conductivity is 0.075 S/cm,close to that of Nafion 117. Besides, they also display excellent thermal stability and oxidation resistance. Therefore, the as-made PEMs show promising application prospects.

关 键 词：质子交换膜 磺化 聚芳醚氧膦 芴基 

分 类 号：O631[理学—高分子化学]