(苯胺齐聚物-b-聚乙二醇)_3星型刚柔嵌段共聚物的合成

Synthesis of( Aniline Oligomer-b-Polyethylene Glycol)_3 Star-shaped Rod-Coil Block Copolymer

采用3种合成策略来制备(苯胺齐聚物-b-聚乙二醇)3三臂星型刚柔嵌段共聚物,获得了预期的目标产物.对每一种合成策略中各阶段的产物进行了结构表征,分析讨论了氧化偶联策略A和"先臂后核"缩合策略B的优点以及存在的问题,最终发展了简单、高效的"先核后臂"缩合策略C,即从均苯三甲酰氯和氨基/羧基封端苯胺四聚体出发,通过酰基化反应得到单分散的苯胺四聚体星型中间体M03,然后以1-乙基-(3-二甲基氨基丙基)碳酰二亚胺盐酸盐(EDCI)和4-二甲氨基吡啶(DMAP)为催化剂,使星型中间体M03与聚乙二醇单甲醚(m-PEG 550)经过脱水缩合反应得到(苯胺四聚体-b-聚乙二醇)3星型刚柔嵌段共聚物,并用红外光谱、质谱、核磁氢谱等进行了表征,表明所获得的产物与预期结构一致.

An（ aniline oligomer-b-polyethylene glycol）3star-shaped rod-coil block copolymer was designed,in which aniline oligomer possesses electrochromic property and polyethylene glycol（ PEG） has ion conductive property. This star-shaped rod-coil block copolymer could be used in electrochromic devices,which would be much more compatible and processable compared with traditional electrochromic devices fabricated by polyaniline and PEG separately. Three synthetic strategies,that is,oxidative coupling strategy A,arm-first condensation strategy B,and core-first condensation strategy C,were designed to obtain（ aniline oligomer-bPEG）3star-shaped rod-coil block copolymer. All related products prepared by the three strategies were characterized using FTIR,1H-NMR and MALDI-MS. The advantage and disadvantage of strategies A and B were discussed as well. And it was found that strategy C was a simple and efficient method for synthesizing the ideal（ aniline oligomer-b-PEG）3star-shaped rod-coil block copolymer. In strategy C,trimesoyl chloride was firstly reacted with amino / carboxyl-capped tetraaniline via an acylation reaction to give mono-dispersed starshaped intermediate M03,which was then reacted with poly（ ethylene glycol methyl ether） via polycondensation to give（ tetraaniline-b-PEG）3star-shaped rod-coil block copolymer（ S03）. The results suggested that ideal（ tetraaniline-b-PEG）3product was synthesized successfully based on the synthetic strategy C.