基于自交联杂萘联苯聚芳醚阴离子交换膜制备及其物理化学性质

Preparation and Physicochemical Property of Self-Crosslinked Poly(phthalazinone ether ketone) Anion-Exchange Membranes

以氯甲基杂环聚醚酮(CMPPEK)为原料,加入三乙胺进行铵化,并分别加入二乙烯三胺(DETA)和二乙胺(DEA),生成的仲胺基(或叔胺基)与邻近分子链氯甲基团进行自交联.经过制膜和离子交换反应,制备了DETA自交联杂萘联苯聚芳醚阴离子交换膜(DETA-QPPEK-OH)和DEA自交联杂萘联苯聚芳醚阴离子交换膜(DEA-QPPEK-OH).采用傅里叶变换红外(FTIR)光谱对制备自交联膜的化学结构进行表征.研究了DETA-QPPEK-OH和DEA-QPPEK-OH膜的理化性质,结果表明前者具有较低吸水率和更低溶胀度.通过研究DETAQPPEK-OH和DEA-QPPEK-OH膜的离子传导率随温度的变化规律,结果表明在80°C时其离子传导率分别达到0.060和0.028 S cm-1,表明本文制备的自交联膜具有较高离子传导率.此外还通过热重分析(TGA)对两类自交联膜的热稳定性进行了研究.

Self-crosslinked poly（phthalazinone ether ketone） anion-exchange membranes （AEMs） were successfully fabricated from chloromethylated poly（phthalazinone ether ketone） （CMPPEK） by amination, membrane casting, and OH-exchange reaction steps. Triethylamine （TEA） was used as an ammonium agent, and diethylenetriamine （DETA） and diethylamine （DEA） were used as self-crosslinking agents in the quaternary reaction of CMPPEK, resulting in DETA-QPPEK-OH and DEA-QPPEK-OH AEMs, respectively. The chemical structures of DETA-QPPEK-OH and DEA-QPPEK-OH were characterized using Fourier transform infrared （FTIR） spectroscopy. The physicochemical properties of these AEMs were investigated including ion-exchange capacity （IEC）, swelling ratios, water uptake, and ionic conductivities at 30 ~C. The results showed that the swelling ratio of the DETA-crosslinked AEM was lower than that of the DEA- crosslinked AEM. This could be attributed to multi-crosslinking of multi-amino groups in the DETA structure. The temperature dependences of the ionic conductivities of the AEMs were measured from 30 to 80 ~C. The ionic conductivities of the DEA-crosslinked and DETA-crosslinked AEMs were 0.060 and 0.028 S~ cm-~ at 80 ~C, respectively. The thermal stabilities of the resulting DETA-QPPEK-OH and DEA- QPPEK-OH membranes were investigated using thermogravimetric analysis （TGA）, under a nitrogen atmosphere. The obtained membranes have high dimensional stabilities and are very promising for potential applications in anion-exchange membrane fuel cells （AEMFCs）.