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侧链结构对侧链型磺化聚砜质子交换膜性能的影响

Effect of Side Chain Structure on Properties of Side Chain Type Sulfonated Polysulfone Proton Exchange Membranes
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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.
作者 乔宗文 陈涛 Qiao Zongwen;Chen Tao(Collaborative Innovation Center of Department of Chemical Engineering,Shaanxi Institute of Technology,Xi'an 710300;Department of Chemical Engineering,North University of China,Taiyuan 030051)
出处 《化学通报》 CAS CSCD 北大核心 2019年第5期457-462,共6页 Chemistry
基金 陕西省教育厅科学研究计划项目(18JK0069) 2018年西安市科协青年人才托举计划项目(201809) 陕西国防学院自然科学项目(Gfy18-04)资助.
关键词 氯甲基化聚砜 萘磺酸型 脂肪磺酸型 苯磺酸型 侧链磺化聚砜 微相分离 Chloromethylated polysulfone Naphthalenesulfonic acid type Aliphatic sulfoacid type Benzene sulfoacid type Side chainsulfonated polysulfone Micro-phase separation
作者简介 乔宗文,男,博士生,主要从事功能高分子的合成与性能研究。E-mail:qiaozongwen@126.com
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