磺化聚苯乙烯/侧链交联型磺化聚芳醚酮砜复合质子交换膜的制备与性能  

Preparation and Properties of Sulfonated Polystyrene/Sulfonated Poly(aryl ether ketone sulfone)Copolymer with Pendant Crosslinked Structure Composite Proton Exchange Membranes

作　　者：程海龙 韩康辉 李奥 陶璐静 易飞扬 孙娇娇 CHENG Hailong;HAN Kanghui;LI Ao;TAO Lujing;YI Feiyang;SUN Jiaojiao(School of Materials Science and Engineering,Jilin Institute of Chemical Technology,Jilin 132022,China)

机构地区：[1]吉林化工学院材料科学与工程学院,吉林132022

出　　处：《高等学校化学学报》2024年第8期129-139,共11页Chemical Journal of Chinese Universities

基　　金：吉林省教育厅科学技术研究项目(批准号:JJKH20220238KJ);吉林省自然科学基金(批准号:YDZJ202301ZYTS299)资助.

摘　　要：如何平衡质子交换膜(PEM)的吸水性与尺寸稳定性及质子传导与甲醇渗透之间的关系一直是PEM材料的研究热点.本文通过直接缩聚法合成了含有丙烯基的聚芳醚酮砜共聚物(PAEKS),利用自由基接枝反应将磺化聚苯乙烯(SPS)和苯乙烯磺酸钠通过丙烯基引入到PAEKS中,制备了一系列磺化聚苯乙烯/侧链交联型磺化聚芳醚酮砜交联复合膜cr-SPAEKS-x(其中x代表复合膜中磺酸基团的含量),利用核磁共振波谱及红外光谱对其进行了表征.由扫描电子显微镜照片可见,SPS和苯乙烯磺酸钠在交联复合膜中分布非常均匀,没有发生任何分相现象.交联网络结构的形成提高了膜的热稳定性、氧化稳定性及力学性能.同时其独特的亲/疏水相分离结构和交联网络结构也有效提高了交联复合膜的尺寸稳定性和阻醇性能,80℃时磺酸基团含量最高的cr-SPAEKS-120%膜在高达63.5%的吸水率下溶胀率仅为20.1%,甲醇渗透系数最高为3.47×10^(-7) cm^(2)/s,远低于Nafion117的23.80×10^(-7) cm^(2)/s.独特的链结构形成的亲/疏水相分离结构使得该系列膜具有较好的质子传导性能,cr-SPAEKS-120%膜在20和80℃下的质子传导率分别达到0.043和0.113 S/cm,可见该系列交联复合膜在直接甲醇燃料电池中具有良好的应用前景.Balancing water absorption and dimensional stability,along with optimizing proton conduction and minimizing methanol permeation in proton exchange membranes(PEMs),has been a focal point in PEM research.In pursuit of this objective,a poly(aryl ether ketone sulfone)containing allyl group(PAEKS)was synthesized through the direct condensation polymerization.Subsequently,a series of sulfonated polystyrene/crosslinked sulfonated poly(aryl ether ketone sulfone)(cr-SPAEKS-x,x stands for the content of sulfonic acid group)composite proton exchange membranes were prepared by grafting sulfonated polystyrene(SPS)and sodium styrene sulfonate onto the allyl groups in PAEKS through a radical reaction.The crosslinked composite membranes were characterized using 1H nuclear magnetic resonance(^(1)H NMR)and Fourier transform infrared spectroscopy(FTIR).The scanning electronic microscopy(SEM)image showed that SPS and sodium styrene sulfonate distributed uniformly in the cross-linked composite membranes without any phase separation phenomenon.The crosslinked network structure enhanced the thermal stability,oxidation stability,and mechanical properties of the membranes.Simultaneously,the unique hydrophilic/hydrophobic phase separation structure and crosslinked network also effectively improve the dimensional stability and methanol resistance of the crosslinked composite membranes.At 80℃,the swelling rate of the cr-SPAEKS-120%membrane with the highest content of sulfonic acid group was only 20.1% with a water uptake of 63.5%.The highest methanol permeability coefficient of the crosslinked composite membrane was only 3.47×10^(-7) cm^(2)/s,significantly lower than that of Nafion117(23.80×10^(-7) cm^(2)/s).The hydrophilic/hydrophobic phase separation structure created by the unique chain structure also imparted excellent proton conductivity to the series of mem-branes.Specifically,the proton conductivity of cr-SPAEKS-120% achieved 0.043 S/cm and 0.113 S/cm at 20 and 80℃,respectively.As a result,these series of crosslinked composite

关 键 词：磺化聚苯乙烯 侧链交联型磺化聚芳醚酮砜 尺寸稳定性 阻醇性能 交联复合质子交换膜 

分 类 号：O631.1[理学—高分子化学]