乔宗文,陈涛.化学通报,2019,82(5):457-462.
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 PolysulfoneProton Exchange Membranes
投稿时间:2018-08-05  修订日期:2018-11-12
DOI:
中文关键词:  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
英文关键词:Chloromethylated  polysulfone, naphthalenesulfonic  acid type, aliphaticSsulfoacid  type, benzene  sulfoacid type, side  chainsulfonated polysulfone, Micro-phase
基金项目: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)和陕西国防学院科学研究计划项目(Gfy18-04)
作者单位E-mail
乔宗文* 陕西国防工业职业技术学院协同创新中心 陕西西安 qiaozongwen@126.com 
陈涛 中北大学化学工程学院  
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中文摘要:
      以双酚A型聚砜(PS)为基础,以自制的1,4-二氯甲氧基丁烷为试剂制备氯甲基化聚砜(CPS),接着以2-萘酚-6,8-二磺酸钾(NSK)为试剂通过亲核取代反应制备萘磺酸型侧链磺化聚砜(PS-NS),在红外光谱和核磁氢谱充分表征的基础上采用溶液浇注法制备相应的质子交换膜,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)质子交换膜,研究侧链结构对质子交换膜的吸水率、吸水溶胀率和尺寸稳定性的影响关系,结果显示:与主链型芳香聚合物质子交换膜相比,3种侧链型磺化聚砜质子交换膜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,导致质子交换膜的尺寸稳定性增加,相应的质子传导率减小,PS-ES膜在25℃和85℃的质子传导率达到0.072S/cm和 0.141S/cm,PS-NS在25℃和85℃的尺寸溶胀性仅为21.8%和51.5%,性能十分接近商业化的Nafion115膜。
英文摘要:
      With1,4-bischloromethyoxyl butane(BCD) as reagent, the chloromethylated polysulfone (CPS) was obtained by introducing chloromethyl group onto main chain of PS on basis of bisphenol A type Polysulfones. 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 PEMs were fabricated by solution casting method after characterizing their structures by FT-IR and 1H-NMR. Based on the aliphaticSsulfoacid type side chain sulfonated polysulfone (PS-ES) and benzene sulfoacid type side chain sulfonated polysulfone in our previousSresearch, the effects of side chain structure on performance including wateruptaking, swelling ratio and proton conductivity of PEMs were explored. It showed that the three 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. Along with the increase of number of rigid benzene on side chains, the flexibility of the side chains weaken, it lead to the increase of dimensional stability and decrease of proton conductivity. The proton conductivity of PS-ES was up to 0.072S/cm at 25℃ and 0.141S/cm at 85℃. The the swelling ratio of PS-ES PEM was only only 21.8% at 25℃ and 51.5% at 85℃. The properties are closed to commercialized Nafion115 PEMs.
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