摘要
制备了萘磺酸型和芘磺酸型磺化聚砜(PSf NS和PSf TS)质子交换膜(PEM),探讨了在相同的磺酸基团含量下,亲水链段结构对PEM的吸水率、吸水溶胀率、质子传导率和抗氧化稳定性等的影响.结果显示,由于亲水基团远离聚合物主链,能够在纳米水平形成类似于Nafion膜的相分离结构,PSf NS和PSf TS PEM在高磺化度下能保持良好的尺寸稳定性.在相同的磺酸含量下,PSf TS由于亲水链段少,吸水效率更高,亲水链段的磺酸基团数目多,有利于吸收水分的聚集,相分离结构更明显,PSf TS在高吸水率下的尺寸稳定性、抗氧化稳定性和阻醇性能更好.其中PSf TS 3膜在25和85℃的溶胀率仅为20.3%和48.1%,室温时的甲醇扩散系数(DK)仅为7.54×10^-7 cm^2/s,优于商业化Nafion115膜在相同条件下的性能(16.8×10^-7 cm^2/s),有望应用于燃料电池.
Based on the preparation of chloromethylated polysulfone(CMPSf),two kinds of side chain type sulfonated polysulfone,naphthalenesulfonic acid type polysulfone(PSf NS)and pyrenesulfonic acid type polysulfone(PSf TS)with different hydrophilic chain segments were successfully prepared via nulecophilic substitution with 2-naphthol-6,8-disulfonic acid dipotassium(NS)and 8-hydroxy-1,3,6-pyrene trisulfonic acid sodium(TS)as reagents,respectively.After characterizing their structure by the FTIR and 1H NMR,the corresponding PSf NS and PSf TS PEMs were obtained by solution casting method.The effect of hydrophilic segment structure on performance including water sorption,size stability and proton conductivity of PEMs at the same bonding amount of sulfonic group were explored.The result put up PSf NS and PSf TS PEMs keep excellent size stability,antioxidative stability and anti-methanol permeability at high water sorption because they could form micro-phase separation structure similar to Nafion membrane due to the hydrophilic sulfonic acid group far away from hydrophobic polysulfone main chain.With the same bonding amount of sulfonic acid,PSf TS has a higher water absorption efficiency due to less hydrophilic chain segment and a larger number of sulfonic acid group PSf in the hydrophilic chain segment,which is conducive to the aggregation of absorbed water and the more obvious phase separation structure.It leads to the PSf TS present better size stability and anti-oxidative at high water sorption.The swelling ratio of PSf TS 3 PEM was only 20.3%and 48.1%at 25 and 85℃respectively.Meanwhile,the methanol permeability was only 7.54×10^-7 cm^2/s at room temperature,much lower than commercialization Nafion115 PEM(16.8×10^-7 cm^2/s at room temperature)at the same condition.The PEM is expected to be used in the practical application of fuel cell.The research results are of great significance for the design and preparation of high-performance membrane materials.
作者
乔宗文
QIAO Zongwen(Department of Chemical Engineering,Shaanxi Institute of Technology,Xi’an 710300,China)
出处
《膜科学与技术》
CAS
CSCD
北大核心
2020年第4期49-54,共6页
Membrane Science and Technology
基金
陕西省自然科学基金项目(2019JQ-927)
陕西省教育厅自然科学研究计划项目(18JK0069)
陕西国防学院自然科学研究计划项目(Gfy18-04)。
关键词
聚砜
萘磺酸
芘磺酸
相分离
尺寸稳定性
polysulfone
naphthalenesulfonic acid type
pyrenesulfonic type
phase separation
size stabil-ity
