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  

Synthesis of Side-chain-sulfonated Poly(ether ether ketone) as Cation Exchange Membranes by Atom Transfer Radical Polymerization

作　　者：黄雪红[1] 林娟[1] 郑榕学 林艺凤[1] 丁富传[1] 凌启淡[1] 

机构地区：[1]福建师范大学材料科学与工程学院、福建省高分子材料重点实验室,福州350007

出　　处：《应用化学》2014年第8期878-884,共7页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金资助项目(61250016,60976019);福建省自然科学基金(2013J01172);福建省教育厅项目(JB12042,JK2013009)~~

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8.34×10-2S/cm,膜的尺寸稳定性优于Nafion 117。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-StSO3 Na 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-StSO3 Na was found to improve hydrophilic/hydrophobic phase separation. With the increase of the grafting density of StSO3 Na, 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 Nation 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 

分 类 号：O631[理学—高分子化学]