ATRP法制备侧链型聚醚醚酮阴离子交换膜  

Synthesis and Properties of Side-chain-type PEEK-g-DMAEMA Anion Exchange Membranes via ATRP

作　　者：黄雪红[1] 宋勋[1] 谢文梅 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：《高分子学报》2014年第9期1212-1218,共7页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号61250016;60976019);福建省自然科学基金(基金号2013J01172;2014J01030);福建省教育厅项目(项目号JB12042;JK2013009)资助

摘　　要：以二氟二苯甲酮、双酚A和邻甲基氢醌单体缩聚合成聚醚醚酮(PEEK)作为基膜材料.PEEK经修饰改性合成带有异丙基溴端基PEEK,以此为原子转移自由基聚合(ATRP)大分子引发剂,通过ATRP法在PEEK主链上接枝引入聚甲基丙烯酸二甲基胺基乙酯(DMAEMA)侧链,得到梳状PEEK接枝聚合物(PEEK-gDMAEMA).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)等方法对PEEK-g-DMAEMA的结构进行表征.实验结果表明,甲基丙烯酸二甲基胺基乙酯被成功地接枝在聚醚醚酮主链上,PEEK-g-DMAEMA膜具有明显的亲水疏水微相分离形貌,叔胺基团相互聚集成形成离子通道.接枝聚合反应10 h,PEEK-g-DMAEMA膜的离子交换容量为2.07 mmol·g-1,以此膜为电解槽隔膜,2 h的OH-离子透过率达0.15 mol·L-1,说明PEEK-g-DMAEMA膜具有良好的离子交换能力.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 NBS, hydroxylation with dimethylol propionate sodium and esterification reaction with bromo-2-methylpropionyl bromide. Comb-like PEEK-g-DMAEMA （poly （2-（dimethylamino） ethyl methacrylate）） was successfully synthesized via atom transfer radical polymerization （ATRP） using double-arm PEEK as the macroinitiator. The membranes of PEEK-g-DMAEMA were prepared by solution cast. The mixture solvent of water and NMP was used to design the membrane morphology. The structure and morphology of PEEK-g-DMAEMA membranes were characterized by FTIR, 1H-NMR, TG and scanning electron microscopy （SEM）. The synthesized PEEK-g-DMAEMA is found to improve hydrophilic/hydrophobic phase separation. The weight loss of PEEK-g-DMAEMA membranes occurs at 230 ~C due to tertiary amine group decomposition. IR results showed that new absorption band at 1728 cm-1 was assigned to the stretching vibration of carbonyl （ C = O） groups. The band at 2770 cm-l was ascribed to the --N--C stretching of tertiary amino groups linkage compared to original PEEK. With the increase in the DMAEMA grafting degree, the ion exchange capacity （IEC） and water content increase from 1.49 to 2.07 mmol · g-1 and 46.91% to 84. 19% , respectively. The OH- permeability of copolymer membranes enhances with the increase of IEC, reaching a value of 0.15 mol/L at 2 h. They display reasonably high OH- permeability due to the abundant DMAEMA side chains and the large interchain space,which is available for water occupation.

关 键 词：原子转移自由基聚合(ATRP) 聚醚醚酮 甲基丙烯酸二甲基胺基乙酯 阴离子交换膜 

分 类 号：TQ316.322[化学工程—高聚物工业]