Systematic Synthesis of Block Copolymers Consisting of Topological Amphiphilic Segment Pairs from - and -Telechelic PEO and Poly(THF).

A set of four types of block copolymers consisting of topological amphiphilic segment pairs was effectively synthesized via - (functionalized cyclic) and - (center-functionalized linear) telechelic poly(ethylene oxide) (PEO) and poly(tetrahydrofuran) (poly(THF)). Accordingly, - and -telechelic PEO with an ethynyl group was newly prepared from relevant linear PEO precursors with quinuclidinium end groups and an ethynyl-functionalized dicarboxylate counteranion by the electrostatic self-assembly and covalent fixation (ESA-CF) process. Similarly, - and -telechelic poly(THF) with an azido group was obtained. The PEO and poly(THF) telechelics were subjected to click chemistry to systematically produce amphiphilic block copolymers with two symmetric topological forms, that is, an "8" shape () and a four-armed star shape (), and two asymmetric topological forms, that is, twin-tailed tadpole shapes ( and ) with respect to the hydrophilic-hydrophobic plane.