Synthesis and self-assembly of dendritic–linear block copolymers containing poly(mandelic acid) with discrete molecular weights and stereochemical structures

Abstract

In this work, we present the synthesis of uniform PMAs, where the number of repeat units and their stereochemical arrangement are precisely defined. Utilizing an iterative convergent approach with orthogonally protected dimandelic acid building blocks, we achieved high molecular weight PMAs with the desired number of repeat units, extending up to 144 mandelic acids. Additionally, stereochemically defined poly(L-mandelic acid)s with up to 32 repeat units were successfully synthesized. These uniform PMAs were subsequently coupled with uniform branched poly(ethylene glycol) blocks to create uniform dendritic–linear block copolymers. The self-assembly of these block copolymers in solution was systematically investigated. In solution self-assembly, the synthesized block copolymers showed multiple phases from cylinder to inverse cubic as the molecular weight of PMA increased. In the case of solvent diffusion-evaporation-mediated self-assembly, the block copolymers underwent a phase transition as the rate of water addition decreased.