侧链结构对侧链型磺化聚砜质子交换膜性能的影响
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摘要
以双酚A型聚砜(PS)为基础,与自制的1,4-二氯甲氧基丁烷反应制备氯甲基化聚砜(CPS),接着与2-萘酚-6,8-二磺酸钾(NSK)进行亲核取代反应制备萘磺酸型侧链磺化聚砜(PS-NS)。采用溶液浇注法制备相应的质子交换膜(PEMs),结合前期研究的脂肪磺酸型侧链磺化聚砜(PS-ES)和苯磺酸型侧链磺化聚砜(PS-BS) PEMs,考察侧链结构对PEMs的吸水率、吸水溶胀率和尺寸稳定性的影响关系。结果表明,与主链型芳香聚合物PEMs相比,3种侧链型磺化聚砜PEMs由于亲水基团远离疏水主链,能够形成类似于Nafion膜的相分离结构,在高吸水率下保持更好的尺寸稳定性;在相同的离子交换膜容量(IEC)下,PS-ES、PS-BS和PS-NS膜随着侧链刚性苯环数目的增加,侧链的运动能力减弱,导致PEMs的尺寸稳定性增加,相应的质子传导率减小; PS-ES膜在25℃和85℃的质子传导率分别达到0. 072和0. 141 S/cm,PS-NS在25℃和85℃的尺寸溶胀性仅为21. 8%和51. 5%,性能与商业化的Nafion115膜十分接近。
The chloromethylated polysulfone( CPS) was obtained by introducing chloromethyl group onto the main chain of PS with 1,4-bischloromethoxyl butane( BCD) as reagent. Subsequently naphthalenesulfonic acid type side chain polysulfone( PS-NS) was prepared via nucleophilic substitution with 2-naphthol-6,8-disulfonic acid dipotassium as nucleophilic reagent. The corresponding proton exchange membranes( PEMs) were fabricated by solution casting method after characterizing their structures by FT-IR and1 H NMR. Based on the aliphatic sulfoacid type side chain sulfonated polysulfone( PS-ES) and benzene sulfoacid type side chain sulfonated polysulfone( PSBS) in our previous research,the effects of side chain structure on performance including wateruptaking,swelling ratio and proton conductivity of PEMs were explored. The results showed that the three kind of PEMs keep better size stability at high wateruptaking compared with the main chain type aromatic PEMs because they could form micro-phase separation by locating the hydrophilic sulfonic acid group far away from hydrophobic polysulfone main chain. As the number of rigid benzene rings in the side chain increases,the flexibility of the side chains weakens,resulting in increased dimensional stability of the PEMs and a corresponding decrease in proton conductivity. The proton conductivity of PS-ES was up to 0. 072 S/cm at 25℃ and 0. 141 S/cm at 85℃. The swelling ratio of PS-NS PEM was only 21. 8% at 25℃ and 51. 5% at 85℃. The performance is close to commercialized Nafion115 PEMs.
The chloromethylated polysulfone( CPS) was obtained by introducing chloromethyl group onto the main chain of PS with 1,4-bischloromethoxyl butane( BCD) as reagent. Subsequently naphthalenesulfonic acid type side chain polysulfone( PS-NS) was prepared via nucleophilic substitution with 2-naphthol-6,8-disulfonic acid dipotassium as nucleophilic reagent. The corresponding proton exchange membranes( PEMs) were fabricated by solution casting method after characterizing their structures by FT-IR and1 H NMR. Based on the aliphatic sulfoacid type side chain sulfonated polysulfone( PS-ES) and benzene sulfoacid type side chain sulfonated polysulfone( PSBS) in our previous research,the effects of side chain structure on performance including wateruptaking,swelling ratio and proton conductivity of PEMs were explored. The results showed that the three kind of PEMs keep better size stability at high wateruptaking compared with the main chain type aromatic PEMs because they could form micro-phase separation by locating the hydrophilic sulfonic acid group far away from hydrophobic polysulfone main chain. As the number of rigid benzene rings in the side chain increases,the flexibility of the side chains weakens,resulting in increased dimensional stability of the PEMs and a corresponding decrease in proton conductivity. The proton conductivity of PS-ES was up to 0. 072 S/cm at 25℃ and 0. 141 S/cm at 85℃. The swelling ratio of PS-NS PEM was only 21. 8% at 25℃ and 51. 5% at 85℃. The performance is close to commercialized Nafion115 PEMs.
引文
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[3]宫飞祥,齐永红,薛群翔.高等学校化学学报,2014,35(2):433~439.
[4]M M Han,G Zhang,M Y Li et al.J.Power Sources,2011,196:9916~9923.
[5]J S Yang,Q F Li,J O Jensen et al.J.Power Sources,2012,205:114~121.
[6]P Kumar,K Dutta,S Das et al.Appl.Energy,2014,123:66~74.
[7]荣倩,顾爽,贺高红等.高分子材料科学与工程,2009,8:126~129.
[8]A K Mishra,S Bose,T Kuila et al.Prog.Polym.Sci.,2012,37:842~869.
[9]张振鹏,王岩,张静静等.高等学校化学学报,2014,6:1343~1347.
[10]S G Feng,Y M Shang,X F Xie et al.J.Membrane Sci.,2009,35:13~20.
[11]陶丹,向雄志,王雷.高分子学报,2014,3:326~332.
[12]T Kobayashi,M Rilukawa,K Sanui et al.Solid State Ionic,1998,106:219~225.
[13]Y Zhang,Y Wan,C J Zhao et al.Polymer,2009,50:4471~4478.
[14]J H Pang,K Z Shen,S N Feng et al.J.Power Sources,2014,263:59~65.
[15]乔宗文,高保娇,陈涛.高分子学报,2015,(5):571~580.
[16]Y Q Zhu,A Manthiram.J.Power Sources,2011,196:7481~7487.
[17]J C Tsai,C K Lin.J.Power Sources,2011,196:9308~9316.
[18]J F Zheng,Q Y He,N Gao et al.J.Power Sources,2014,261:38~45.
[19]J K Deuk,J J Min,Y N Sang.J.Ind.Eng.Chem.,2015,21:36~52.
[20]K D Kreuer.J.Membrane Sci.,2011,185:29~39.
[21]G G Wang,Y M Weng,D Chu et al.J.Membrane Sci.,2009,332:63~68.