Narducci Riccardo, Ercolani Gianfranco, Becerra-Arciniegas Raul Andres, Pasquini Luca, Knauth Philippe, Di Vona Maria Luisa
Dep. Industrial Engineering, and International Associated Laboratory: Ionomer Materials for Energy, University of Rome Tor Vergata, 00133 Roma, Italy.
Dep. Chemical Sciences and Technologies, University of Rome Tor Vergata, 00133 Roma, Italy.
Membranes (Basel). 2019 Apr 29;9(5):57. doi: 10.3390/membranes9050057.
We synthesized anion exchange polymers by a reaction of chloromethylated poly(2,6-dimethyl-1,4-phenylene)oxide (PPO) with strongly basic 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). TBD contains secondary and tertiary amine groups in the guanidine portion. To favor the functionalization with the secondary amine, TBD was activated with butyl lithium. The yield of amine formation via the reaction of the benzyl chloride moiety with TBD was 85%. Furthermore, we prepared polymers with quaternary ammonium groups by the reaction of PPO-TBD with CHI. The synthesis pathways and ionomer structure were investigated by NMR spectroscopy. The thermal decomposition of both ionomers, studied by thermogravimetry, started above 200 °C, corresponding to the loss of the basic group. The ion exchange capacities, water uptake and volumetric swelling are also reported. The "intrinsic" anion conductivity of PPO-TBD due to the dissociation of grafted TBD was in the order of 1 mS/cm (Cl form). The quaternized ionomer (PPO-TBD-Me) showed an even larger ionic conductivity, above 10 mS/cm at 80 °C in fully humidified conditions.
我们通过氯甲基化聚（2,6 - 二甲基 - 1,4 - 亚苯基）氧化物（PPO）与强碱性1,5,7 - 三氮杂双环[4.4.0]癸 - 5 - 烯（TBD）反应合成了阴离子交换聚合物。TBD在胍部分含有仲胺和叔胺基团。为了有利于仲胺的官能化，TBD用丁基锂活化。苄基氯部分与TBD反应生成胺的产率为85%。此外，我们通过PPO - TBD与CHI反应制备了带有季铵基团的聚合物。通过核磁共振光谱研究了合成途径和离聚物结构。通过热重分析研究的两种离聚物的热分解在200℃以上开始，这对应于碱性基团的损失。还报道了离子交换容量、吸水率和体积溶胀情况。由于接枝的TBD解离，PPO - TBD的“本征”阴离子电导率约为1 mS/cm（Cl形式）。季铵化离聚物（PPO - TBD - Me）在完全湿润条件下于80℃时表现出甚至更大的离子电导率，高于10 mS/cm。
