含全氟联苯结构的磺化聚二氮杂萘酮醚氧膦质子交换膜的制备与性能

Synthesis and Properties of Sulfonated Poly(phthalazinone ether phosphine oxide)s with Perfluorobiphenyl Moieties for Proton Exchange Membranes

将全氟联苯、二(4-氟苯基)苯基氧膦与4-(4′-羟基)苯基-2,3-二氮杂萘酮共聚,合成了含全氟联苯结构的聚二氮杂萘酮醚氧膦,再经磺化反应,制备了含全氟联苯结构的磺化聚二氮杂萘酮醚氧膦(sPEPOF-x,x为含氟重复单元的摩尔分数)质子交换膜.由于强疏水全氟联苯结构促进了聚合物膜的亲水/疏水微相分离,提高了质子电导率,降低了溶胀率,sPEPOF质子交换膜表现出优良的综合性能.在80℃下,sPEPOF-25质子交换膜的溶胀率仅为10%,约为Nafion 117的一半,而其电导率为0.099 S/cm,约为Nafion 117的1.2倍,且耐氧化稳定性好,热稳定性高,具有潜在的应用前景.

The poly(phthalazinone ether phosphine oxide)s with perfluorobiphenyl moieties were synthesized by copolycondensation of decafluorobiphenyl,bis(4-fluorophenyl)phenylphosphorus oxide,and 4-(4-hydrolphenyl)phthalazinone,which were then converted to the sulfonated poly(phthalazinone ether phosphine oxide)s with perfluorobiphenyl moieties(sPEPOF-x,x means the molar percentage of F-containing units)by sulfonation.The highly hydrophobic perfluorobiphenyl moieties facilitate to form the microphase seperation structures within polymer membranes,increasing the proton conductivity and decreasing the swelling ratio,thus the resultant membranes display superior comprehensive properties.At 80℃,the sPEPOF-25 membrane presents a swelling ratio of only 10%,about half that of Nafion 117 membrane,whereas its proton conductivity is 0.099 S/cm,which is 1.2 times that of Nafion 117 membrane.It also possesses excellent thermal stability and oxidation resistance,showing potential application prospect.