以氨基封端的苯胺四聚体为基础, 通过将端氨基取代为不同数量的羧基, 得到了一系列连接臂数不同的苯胺四聚体-聚乙二醇共聚物, 对反应历程中的各阶段产物进行了结构表征, 并对苯胺四聚体及最终产物进行了电化学性能测试. 结构表征证明反应按照设计路线成功进行并得到了理想的产物; 循环伏安特性曲线表明, 共聚物基本保留了苯胺四聚体的电化学性能, 可以发生从还原态到中间态再到氧化态的转变.

In this paper, three block or star-shaped tetraaniline-polyethylene glycol copolymers were obtained using a series of methylbenzenesulfonyl chloride homologous compounds as intermediates. To achieve this goal, firstly, tetraaniline was synthesised by 4-aminodiphenyamine through redox reaction in an acidic acetone solution; tetraaniline was then reacted with 4-toluene sulfonyl chloride, 2,5-dimethylbenzenesulfonyl chloride and 2-mesitylenesulfonyl chloride, respectively, to give a series of sulfamide intermediate products with different amounts of capped methyl groups on the benzene ring. These sulfamide intermediate products were oxidized by potassium permanganate, to turn the capped methyl groups equally into carboxyl groups. At last, methoxy polyethylene glycol (PEG) was reacted with these carboxyl groups through esterification reaction to give the tetraaniline-polyethylene glycol copolymers, in which the number of PEG chains was determined by the number of methyl groups on the intermediate products mentioned above. Structure characterization of all related products within the routes, as well as electrical chemical property test of tetraaniline and final products, was carried out using FT-IR, ¹H NMR, UV-Vis, GPC and electrochemical workstation. The results of structure characterization suggested that ideal products were synthesized successfully through designed routes, the cyclic voltammogram and conductivity data suggested that the electrical chemical property of these copolymers was similar with that of tetraaniline, possessing the typical change of oxidation-reduction states. As polyaniline is a typical electrochromism material, whose electrochromism capability is majorly succeeded by tetraaniline, these copolymers could be used in an electrochromism device, in which tetraaniline acts as electrochromism material, while polyethylene glycol acts as ion conducting material. Compared with electrochromism devices formed by polyaniline and polyethylene glycol separately, the ones formed by these copolymers would be much more compatible and processible. Furthermore, the micro structure of an electrochromism device could be formed through copolymers' self-assembly, and the micro phase morphology of the structure could be modified by adjusting the molecular weight of each segment, as well as the number of polyethylene glycol chains.