具有高效长侧链的芘磺酸型磺化聚砜阳离子交换膜的性能

doi:10.19894/j.issn.1000-0518.200264

摘要/Abstract

摘要： 以双酚A型聚砜和无致癌毒性的溴甲基化试剂1,4-二溴丁烷为原料,通过烷基化反应在聚砜分子上引入可交换溴原子制备溴代聚砜(BPSF),将BPSF与8-羟基-1,3,6-芘三磺酸钠(TS)试剂通过亲核取代反应制备一种磺酸基团远离聚合物主链的芘磺酸型磺化聚砜(PS-TS)。采用溶液流延法制备PS-TS阳离子交换膜,通过控制亲核取代反应的时间制备了一系列磺酸基团含量不同的磺化聚砜膜PS-TS-n(PSF-TS-1(0.79 mmol/g)、PSF-TS-2(1.01 mmol/g)、PSF-TS-3(1.28 mmol/g))。结果表明,由于亲疏水区域距离较远,形成的相分离程度明显,PSF-TS膜在高吸水率下仍能保持很好的尺寸稳定性,随着磺酸基团含量增多,相分离程度增强,其中磺酸基团含量为1.32 mmol/g的PSF-TS-3膜在25和85 ℃的溶胀率仅为22.9%和51.3%,相应的质子传导率达到了0.088和0.149 S/cm,尺寸稳定性超过了商业化Nafion115膜在相同条件下的性能,有望用于燃料电池的实际应用。

关键词: 聚砜, 芘磺酸, 尺寸稳定性, 吸水率, 甲醇渗透率

Abstract: Bisphenol A type polysulfone (PSF) and 1, 4-dibromobutane bromide without carcinogenic toxicity were used as raw materials. Brominated polysulfone (BPSF) was obtained by introducing exchangeable bromine atoms onto polysulfone molecules through the alkylation reaction. Subsequently, a kind of pyrenesulfonic type side chain sulfonated polysulfone(PS-TS) was obtained by locating sulfonic group far away from main chain of polymers via nucleophilic substitution reaction with 8-hydroxy-1,3,6-pyrene trisulfonic acid sodium (TS) as the nucleophilic reagent. The PS-TS cation exchange membrane was prepared by solution casting method. A series of PS-TS-n membranes with different bonding amounts of sulfonic acid group, PS-TS-1(0.79 mmo/g), PS-TS-2(1.01 mmo/g) and PS-TS-3(1.28 mmo/g) was prepared by controlling the flnucleophilic substitution reaction time. The result show that PS-TS proton exchange membranes keep outstanding size stability at high water sorption because they could form obvious micro-phase separation structure by locating the hydrophilic region far from the hydrophobic region. With the bonding amount of sulfonic acid group increases, the degree of micro-phase strengthens. The swelling ratio of PS-TS-3 cation exchange membrane, whose bonding amount of sulfonic group is 1.32 mmol/g, is only 22.9% and 51.3% at room temperature and 85 ℃, respectively. The corresponding proton conductivities are up to 0.088 S/cm and 0.149 S/cm, respectively. The size stability is better than that of commercialized Nafion115 at the same condition. It is expected to be used in practical applications for fuel cells.

Key words: Polysulfone, Pyrenesulfonic type, Dimensional stability, Water uptake, Methanol permeability

中图分类号:

O631

乔宗文, 陈涛. 具有高效长侧链的芘磺酸型磺化聚砜阳离子交换膜的性能[J]. 应用化学, 2021, 38(6): 668-674.

QIAO Zong-Wen, CHEN Tao. Properties of Pyrenesulfonic Type Sulfonated Polysulfone Cation Exchange Membrane with High Performance Long Side Chain[J]. Chinese Journal of Applied Chemistry, 2021, 38(6): 668-674.

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