模型支化共聚物的合成及其受限状态下的自组装

Graft copolymers with full regularity are excellent for studying the relation between the structure and properties of branched copolymer as well as the ordered supermolecular structure of polymer. Up till now, graft-from, graft-onto and macromonomer are the common methods used in the synthesis of graft copolymer and it is difficulty to get fully regular graft copolymer in the most cases. In this project, the macomonomers of polystyrene, polytetrahydrofunan and poly(ethylene oxide) with thienyl end group have been prepared through anionic and cationic polymerization with functional initiators or terminator. Therefore, graft copolymers with rigid polythiophene backbone and homodispersed graft chain as well as block copolymers from 2-thienyl-capped macromonomer were obtained. 1,1-dichloromethylethylene was synthesized and was used to initiate ATRP of styrene to result in a macromonomers with the polymerizable group in the center of chain. With the help of Si-H addition reaction, poly(dimethylsiloxane-g-styrene)s with two graft chain at each branch point were obtained. Moreover, 1,1-dichloromethylethylene was used to couple the living anionic chains with two center in order to get poly(styrene-g-vinyl ether), but failed due to the low .initiation ability of the left ethylenyl group. Polystyrenes with a-holoalkyl group in the phenyl ring were successfully synthesized through group transition reactions and the functionality can reach a high value while no side reaction happened. Therefore poly(styrene-g-butylacrylate)s with homodispersed main chain and side chains were obtained.

采用活性或可控聚合方法制备出结构不同的模型支化共聚物，包括刚性主链接枝共聚物和完全规整的接枝共聚物。通过调节模型支化共聚物的结构和使用多种实验手段，研究它们溶液中的胶束行为和固态自组装行为，并进行计算机模拟，揭示链段运动受限状态与结构规整共聚物超分子结构的关系，加深对聚合物自组装行为的理解，丰富聚合物聚集态研究内容。