交联结构磺化聚醚醚酮质子交换膜的制备与性能

Preparation and Properties of Sulfonated Poly (ether ether ketone) Crosslinked Proton Exchange Membranes

采用3种具有不同链段长度、分子结构的硅氧烷二胺与磺化聚醚醚酮(SPEEK)反应,制备了3种具有不同交联结构的磺化聚醚醚酮质子交换膜。通过傅里叶变换红外光谱证实了交联结构的存在。通过热重分析仪、万能材料试验机和电化学综合站,研究了不同硅氧烷交联结构对质子交换膜的力学性能、热稳定性、水中尺寸稳定性、甲醇渗透率、可交换阳离子容量和质子传导率等性能的影响。结果表明,交联改性可大幅度提高SPEEK膜的力学性能、阻醇性能以及尺寸稳定性。使用含苯环结构的硅氧烷二胺(PMS)制备的交联结构质子交换膜具有最好的综合性能。相较于SPEEK纯膜,SPEEK/PMS交联质子膜的甲醇渗透系数由2.28×10^(-6) cm^2/s减小到1.89×10^(-7) cm^2/s,有效选择性是纯膜的5.6倍,溶胀比降低了59.7%。

Three different kinds of crosslinked proton exchange membranes were prepared based on sulfonated poly （ether ether ketone） （SPEEK） and three types siloxane diamine. The crosslinked structure was confirmed by Fourier transform infrared spectroscopy. Mechanical properties, thermal stability, and proton conductivity of the crosslinked proton exchange membranes were conducted by universal material testing machine, thermogravimetric analyzer （TG）, and electrochemical workstation. Dimensional stability in water, methanol resistance performance, water uptake and ion exchange capacity were studied in detail. The results show that mechanical properties, methanol resistance performance and dimensional stability of proton exchange membranes are enhanced obviously due to crosslinking modification. The crosslinked proton membranes prepared with phenyl containing siloxane diamine （PMS） have better comprehensive performance compared to SPEEK. The methanol permeability of SPEEK modified with PMS is 1.89 × 10-7 cm2/s, which is much lower than that of SPEEK 2.28×10-6 cm2/s. Moreover, the effective selectivity of SPEEK/PMS crosslinked proton exchange membrane is 5.6 times of that of SPEEK and the swelling ratio decreases by 59.7 %.