Two series of disulfonated iptycene-based poly(arylene ether sulfone) random copolymers, i.e., TRP-BP (triptycene-based) and PENT-BP (pentiptycene-based), were synthesized via condensation polymerization from disulfonated monomer and comonomers to prepare proton exchange membranes (PEMs) for potential applications in electrochemical devices such as fuel cell. To investigate the effect of iptycene units on membrane performance, these copolymers were systematically varied in composition (i.e., iptycene content) and the degree of sulfonation (i.e., 30–50%), which were characterized comprehensively in terms of water uptake, swelling ratio, oxidative stability, thermal and mechanical properties, and proton conductivity at various temperatures. Comparing to copolymers without iptycene units, TRP-BP and PENT-BP ionomers showed greatly enhanced thermal and oxidative stabilities due to strong intra- and inter-molecular supramolecular interactions induced by hierarchical iptycene units. In addition, the introduction of iptycene units in general provides PEMs with exceptional dimensional stability of low volume swelling ratio at high water uptakes, which is ascribed to the supramolecularly interlocked structure as well as high fractional free volume of iptycene-based polymers. It is demonstrated that the combination of high proton conductivity and good membrane dimension stability is the result of the synergistic effects of multiple factors including free volume (iptycene content), sulfonation degree, hydrophobicity, and swelling behavior (supramolecular interactions).

由二磺化单体和共聚单体通过缩聚反应合成了TRP-BP（三萜烯基）和PENT-BP（戊四烯基）两类二苯乙烯基的聚二甲苯基无规共聚物。膜（PEM）在电化学装置（例如燃料电池）中的潜在应用。为了研究iptycene单元对膜性能的影响，对这些共聚物的组成（iptycene含量）和磺化度（30％至50％）进行了系统地改变，并根据吸水率，溶胀率进行了全面表征，在各种温度下的氧化稳定性，热和机械性能以及质子传导性。与不含茂金属单元的共聚物相比，TRP-BP和PENT-BP离聚物显示出极大的增强的热稳定性和氧化稳定性，这是由于分级的并茂单元引起的强烈的分子内和分子间超分子相互作用。另外，一般引入茂茂单元为PEM提供了优异的尺寸稳定性，即在高吸水率下具有低体积溶胀率，这归因于超分子互锁结构以及高比例的基于茂茂的聚合物。结果表明，高质子传导率和良好的膜尺寸稳定性的结合是多种因素协同作用的结果，这些因素包括自由体积（并茂含量），磺化度，疏水性和溶胀行为（超分子相互作用）。