Synthesis of Linear, Cyclic, Figure-Eight-Shaped, and Tadpole-Shaped Amphiphilic Block Copolyethers via t‑Bu‑P4‑Catalyzed Ring-Opening Polymerization of Hydrophilic and Hydrophobic Glycidyl Ethers

This paper describes the synthesis of systematic sets of figure-eight- and tadpole-shaped amphiphilic block copolyethers (BCPs) consisting of poly(decyl glycidyl ether) and poly[2-(2-(2-methoxyethoxy)ethoxy)ethyl glycidyl ether], together with the corresponding cyclic counterparts, via combination of the t-Bu-P4-catalyzed ring-opening polymerization (ROP) and click cyclization. The clickable linear BCP precursors, with precisely controlled azido and ethynyl group placements as well as a fixed molecular weight and monomer composition (degree of polymerization for each block was adjusted to be around 50), were prepared by the t-Bu-P4-catalyzed ROP with the aid of functional initiators and terminators. The click cyclization of the precursors under highly diluted conditions produced a series of cyclic, figure-eight-, and tadpole-shaped BCPs with narrow molecular weight distributions of less than 1.06. Preliminary studies of the BCPs self-assembly in water revealed the significant variation in their cloud points depending on the BCP architecture, though there were small architectural effects on their critical micelle concentration and morphology of the aggregates.