Synthesis and characterization of glycidylpolymer- based poly(ionic liquid)s: highly designable polyelectrolytes with a poly(ethylene glycol) main chain
Synthesis and characterization of glycidylpolymer- based poly(ionic liquid)s: highly designable polyelectrolytes with a poly(ethylene glycol) main chain
复制标题
缩水甘油基聚合物基聚（离子液体）的合成和表征：具有聚（乙二醇）主链的高度可设计的聚电解质
DOI：
10.1039/c5ra17609c
复制
发表时间：
2015
期刊：
影响因子：
3.9
通讯作者：
Satoshi Moriyama. Jedeok Kim
中科院分区：
文献类型：
--
作者：
Taichi Ikeda;Ikuhiro Nagao;Satoshi Moriyama. Jedeok Kim
通过缩水甘油叠氮聚合物与离子液体的炔烃衍生物的点击官能化反应，合成了一系列缩水甘油基聚离子液体S(阳离子GTP)。考察了三种阳离子基团(咪唑、吡啶和吡咯烷)以及1，2，3-三氮唑与阳离子基团之间的两种间隔基(C4H8烷链(C4)和四(乙二醇基)(EG4))。用核磁共振、红外光谱、差示扫描量热法、热重分析和交流阻抗谱对阳离子GTP进行了表征。通过对模型聚合物的凝胶渗透色谱分析，估算出阳离子GTP的重均相对分子质量为0.8-100万Da。部分分解聚合物的~1H核磁共振分析证实，阳离子GTP与C4间隔基的热分解始于阳离子部分的脱离。与C4基团相比，EG4基团降低了玻璃化转变温度，提高了离子电导率。具有EG4间隔基、吡咯烷阳离子部分和双(三氟甲磺酰亚胺)反阴离子的阳离子GTP具有最高的无水离子电导率(30℃时为1 1×10−5 S cm−1，12 0℃时为1 1×10−3 S cm−1)。通过电极极化分析估算了导电离子的浓度和迁移率。咪唑基团与Tf2N反阴离子的结合能较低，因而具有较高的导电离子浓度。与其他GTP相比，吡啶GTP的导电离子迁移率具有更强的温度依赖性。
A series of glycidyl-polymer-based poly(ionic liquid)s (cationic GTPs) was synthesized via the click functionalization of a glycidyl azide polymer with alkyne derivatives of ionic liquids. Three types of cationic moieties (imidazolium, pyridinium and pyrrolidinium) and two types of spacers between the 1,2,3-triazole and cationic moiety (C4H8 alkyl chain (C4) and tetra(ethylene glycol) (EG4)) were examined. The cationic GTPs were characterized by NMR, IR, differential scanning calorimetry, thermogravimetric analysis and impedance spectroscopy. From the gel permeation chromatography analysis of the model polymer, the weight-average molecular weights of cationic GTPs were estimated to be 0.8–1.0 million Da. 1H NMR analysis of the partially decomposed polymer confirmed that the thermal decomposition of the cationic GTPs with the C4 spacer begins with the detachment of the cationic moiety. Compared with the C4 spacer, the EG4 spacer decreases the glass transition temperature and increases the ionic conductivity. The cationic GTP with the EG4 spacer, pyrrolidinium cationic moiety and bis(trifluoromethanesulfonyl)imide (Tf2N) counter anion exhibited the highest anhydrous ionic conductivity (1.1 × 10−5 S cm−1 at 30 °C and 1.1 × 10−3 S cm−1 at 120 °C). The conducting ion concentration and mobility were estimated by electrode polarization analysis. The imidazolium moiety gives a relatively higher conducting ion concentration because of the lower binding energy with the Tf2N counter anion. Compared with other GTPs, the pyridinium GTPs showed greater temperature dependences of their conducting ion mobilities.