首先,将9,9-二(3,5-二甲基-4-羟基苯基)芴(DMBHF)、9,9-双(4-羟苯基)芴(BHF)和4,4’-二氟二苯甲酮(DFB)在高温下缩聚,得到聚芴醚酮(PFEK-x)(x=30、40、50,x为DMBHF含量,以DFB的物质的量计,下同);接着,利用溴代反应将PFEK-x的甲基功能化...首先,将9,9-二(3,5-二甲基-4-羟基苯基)芴(DMBHF)、9,9-双(4-羟苯基)芴(BHF)和4,4’-二氟二苯甲酮(DFB)在高温下缩聚,得到聚芴醚酮(PFEK-x)(x=30、40、50,x为DMBHF含量,以DFB的物质的量计,下同);接着,利用溴代反应将PFEK-x的甲基功能化为溴甲基;然后,通过4-羟基苯磺酸钠的SN2亲核取代制得具有不同离子交换容量的磺化聚芴醚酮(SPFEK-x);最后,通过溶液浇铸法成膜并酸化,制得新型低成本质子交换膜(PEMs)。采用^(1)HNMR、FTIR、TGA对其进行了表征,并对其性能进行了测试。结果表明,SPFEK-40膜具有较高的质子传导率及离子选择性、较低的钒离子渗透率及面电阻,综合性能优异。以SPFEK-40膜组装的全钒液流电池(VRFB)在电流密度为80 m A/cm^(2)时的能量效率为88.2%,高于以Nafion 212膜组装的VRFB的84.8%。此外,以SPFEK-40膜组装的VRFB在30次循环后放电容量保持率为84.3%,远高于以Nafion 212膜组装的VRFB(66.1%)。该合成路线的原料来源广泛,价格低廉,不涉及危险的磺化反应,易于工业放大。制得的SPFEK-x均具有良好的机械性能和氧化稳定性。展开更多
Six highly fluorinated poly(arylene ether)s were prepared by using a nucleophilic polycondensationreaction and their sulfonation selectivity was investigated.Single site of each repeated unit on pendant phenylgroup co...Six highly fluorinated poly(arylene ether)s were prepared by using a nucleophilic polycondensationreaction and their sulfonation selectivity was investigated.Single site of each repeated unit on pendant phenylgroup could be obtainedviathe postsulfonation approach under mild reaction conditions.Phenylated fluorina-ted poly(arylene ether)(Ph-FPAE) showed more excellent controllability over substituted sites and sulfonationdegree when chlorosulfonic acid was used as sulfonation reagent.The resulting sulfonated Ph-FPAE(Ph-SF-PAE) exhibited good thermal stability,solubility and hot-water dimensional stability,and also had a protonconductivity of 0.10 S/cm at 100℃.The results showed that Ph-SFPAE might be a candidate material forproton exchange membrane in fuel cell applications.展开更多
文摘首先,将9,9-二(3,5-二甲基-4-羟基苯基)芴(DMBHF)、9,9-双(4-羟苯基)芴(BHF)和4,4’-二氟二苯甲酮(DFB)在高温下缩聚,得到聚芴醚酮(PFEK-x)(x=30、40、50,x为DMBHF含量,以DFB的物质的量计,下同);接着,利用溴代反应将PFEK-x的甲基功能化为溴甲基;然后,通过4-羟基苯磺酸钠的SN2亲核取代制得具有不同离子交换容量的磺化聚芴醚酮(SPFEK-x);最后,通过溶液浇铸法成膜并酸化,制得新型低成本质子交换膜(PEMs)。采用^(1)HNMR、FTIR、TGA对其进行了表征,并对其性能进行了测试。结果表明,SPFEK-40膜具有较高的质子传导率及离子选择性、较低的钒离子渗透率及面电阻,综合性能优异。以SPFEK-40膜组装的全钒液流电池(VRFB)在电流密度为80 m A/cm^(2)时的能量效率为88.2%,高于以Nafion 212膜组装的VRFB的84.8%。此外,以SPFEK-40膜组装的VRFB在30次循环后放电容量保持率为84.3%,远高于以Nafion 212膜组装的VRFB(66.1%)。该合成路线的原料来源广泛,价格低廉,不涉及危险的磺化反应,易于工业放大。制得的SPFEK-x均具有良好的机械性能和氧化稳定性。
文摘Six highly fluorinated poly(arylene ether)s were prepared by using a nucleophilic polycondensationreaction and their sulfonation selectivity was investigated.Single site of each repeated unit on pendant phenylgroup could be obtainedviathe postsulfonation approach under mild reaction conditions.Phenylated fluorina-ted poly(arylene ether)(Ph-FPAE) showed more excellent controllability over substituted sites and sulfonationdegree when chlorosulfonic acid was used as sulfonation reagent.The resulting sulfonated Ph-FPAE(Ph-SF-PAE) exhibited good thermal stability,solubility and hot-water dimensional stability,and also had a protonconductivity of 0.10 S/cm at 100℃.The results showed that Ph-SFPAE might be a candidate material forproton exchange membrane in fuel cell applications.
