原子转移自由基聚合法制备侧链型磺化聚醚醚酮阳离子交换膜

doi:10.3724/SP.J.1095.2014.30400

摘要/Abstract

摘要： 以二氟二苯甲酮、双酚A和邻甲基氢醌为单体先经缩聚反应生成聚醚醚酮(PEEK),PEEK经修饰合成含有溴异丙基侧基的聚醚醚酮，以此为原子转移自由基聚合(ATRP)大分子引发剂，通过ATRP法聚合，在PEEK主链上接枝引入聚苯乙烯磺酸钠侧链，得到侧链型PEEK接枝聚合物(PEEK-g-StSO3Na)。用傅里叶变换红外(FTIR) 光谱、核磁共振氢谱(1H NMR)、热重分析(TG)和扫描电子显微镜(SEM)等技术手段对PEEK-g-StSO3Na的结构进行表征。结果表明，苯乙烯磺酸钠成功的被接枝到聚醚醚酮主链上，PEEK-g-StSO3Na膜具有明显的亲水疏水微相分离结构，磺酸基团相互聚集形成离子通道，离子交换容量为2.034 mmol/g的PEEK-g-StSO3Na膜的电导率为8.34×10-2 S/cm，膜的尺寸稳定性优于Nafion 117。

关键词: 原子转移自由基聚合, 聚醚醚酮, 阳离子交换膜, 苯乙烯磺酸钠

Abstract: Poly(ether ether ketone)(PEEK) was synthesized by the aromatic nucleophilic polycondensation reaction of 4,4′-difluorobenzophenone, bisphenol A and 2-methylhydroquinone. Double-arm PEEK macroinitiator containing isopropyl bromide end groups was obtained by bromination with N-bromosuccinimide(NBS), hydroxylation with dimethylol propionate sodium and esterification reaction with bromo-2-methylpropionyl bromide. The membranes of PEEK-g-StSO3Na were prepared by solution casting. A mixed solvent of water and N-methyl-2-pyrrolidone(NMP) was used to design the membrane morphology. The structure and morphology of PEEK-g-StSO3Na membranes were characterized by FT-IR, 1H NMR, TGA and SEM. The synthesized PEEK-g-StSO3Na was found to improve hydrophilic/hydrophobic phase separation. With the increase of the grafting density of StSO3Na, the ion exchange capacity(IEC) increases from 0.643 to 2.034 mmol/g and the conductivities of the membrane is 8.34×10-2 S/cm. The PEEK-g-StSO3Na membranes have higher proton conductivities and lower swelling ratio than Nafion 117.

Key words: atom transfer radical polymerization, poly(ether ether ketone), cation exchange membrane, sodium p-styrenesulfonate

中图分类号:

O631

黄雪红, 林娟, 郑榕学, 林艺凤, 丁富传, 凌启淡. 原子转移自由基聚合法制备侧链型磺化聚醚醚酮阳离子交换膜[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30400.

HUANG Xuehong, LIN Juan, ZHENG Ronxue, LIN Yifeng, DING Fuchuan*, LING Qidan*. Synthesis of Side-chain-sulfonated Poly(ether ether ketone) as Cation Exchange Membranes by Atom Transfer Radical Polymerization[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30400.

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