利用亲核缩聚方法合成出带有氨基的磺化度可控的磺化聚芳醚酮砜共聚物(Am-SPAEKS),并在180 ℃下制备了C-Am-SPAEKS交联膜.红外和氢核磁图表明氨基已被引入到SPAEKS共聚物中,而且Am-SPAEKS聚合物中的磺酸基团与氨基反应生成磺酰胺键而形成共价交联.通过对C-Am-SPAEKS膜性能测试发现,氨基与磺酸基团之间发生的共价交联反应使交联膜的致密性增加,从而使膜的甲醇渗透系数显著降低,膜的溶胀性、热稳定性和膜的保水能力都得到了提高.在120 ℃时C-Am-SPAEKS膜的质子传导率达到了0.0883 S/cm,而其甲醇渗透系数在25 ℃时为 0.5×10-7cm2/s,明显低于SPAEKS膜的8.9×10-7 cm2/s和Nafion膜的2×10-6 cm2/s.实验结果表明,C-Am-SPAEKS膜能够满足质子交换膜燃料电池(PEMFC)的使用要求,有望在中高温和直接甲醇燃料电池中得以应用.
The sulfonated poly (aryl ether ketone sulfone) copolymers bearing pendant amino groups were synthesized by nucleophilic polycondensation method in this paper.The C-Am-SPAEKS crosslinked membrane was obtained by a heating reaction at 180 ℃.The FTIR spectrum and1H-NMR spectrum showed that the amino group had been introduced into the SPAEKS copolymer and the amide bond between the amino and the sulfonic acid groups was formed.The results indicated that the covalent crosslinking between the amino and the sulfonic acid groups decreased the methanol permeability and the swelling ratio,improved the thermal stability and water retention capacity of the C-Am-SPAEKS crosslinked membrane.The proton conductivity of the C-Am-SPAEKS crosslinked membrane reached 0.0883 S/cm at 120 ℃ which is able to meet the requirements of proton exchange membrane fuel cells.The methanol permeability of the C-Am-SPAEKS crosslinked membrane was only 0.5×10-7cm2/s at 25℃,which was much lower than that of SPAEKS membrane (8.9×10-7 cm2/s) and Nafion (2×10-6 cm2/s) under the same test conditions.All the results indicate that the C-Am-SPAEKS crosslinked membrane is promising as proton exchange membranes for middle-high temperature proton exchange membrane fuel cells applications and direct methanol fuel cells.