• aggregation;
  • block copolymers;
  • cationic poly­merization;
  • miscibility;
  • vesicles
Thumbnail image of graphical abstract

A series of well-defined poly(α-methylstyrene)-block-poly(isobutyl vinyl ether) (PMS-b-PIBVE) diblock copolymers of varying compositions is synthesized via sequential cationic polymerization using an FeCl3-based initiating system at 0 °C. The copolymers exhibit a single glass transition temperature (Tg). The Tg vs. composition relationships for the copolymers show positive deviation from a linear relationship, which is explained by the Kwei equation. The copolymer (PMS35-b-PIBVE145 and PMS60-b-PIBVE128) molecules self-aggregate to form vesicles in organic solvents. However, the copolymers (PMS83-b-PIBVE94, PMS107-b-PIBVE52, and PMS129-b-PIBVE32) with higher rigid PMS contents do not form vesicles. PMS35-b-PIBVE145 vesicles can encapsulate hydrophobic and hydrophilic fluorescent macromolecules.