Construction of PIB-b-PDEAEMA well-defined amphiphilic diblock copolymers via sequential living carbocationic and RAFT polymerization

ABSTRACT A series of well‐defined amphiphilic diblock copolymers consisting of hydrophobic polyisobutylene (PIB) and hydrophilic poly(2‐(diethylamino)ethyl methacrylate) (PDEAEMA) segments was synthesized via the combination of living carbocationic polymerization and reversible addition fragmentation chain transfer (RAFT) polymerization. Living carbocationic polymerization of isobutylene followed by end‐capping with 1,3‐butadiene was first performed at −70 °C to give a well‐defined allyl‐Cl‐terminated PIB with a low polydispersity (Mw/Mn =1.29). This end‐functionalized PIB was further converted to a macromolecular chain transfer agent for mediating RAFT block copolymerization of 2‐(diethylamino)ethyl methacrylate at 60 °C in tetrahydrofuran to afford the target well‐defined PIB‐b‐PDEAEMA diblock copolymers with narrow molecular weight distributions (Mw/Mn ≤1.22). The self‐assembly behavior of these amphiphilic diblock copolymers in aqueous media was investigated by fluorescence spectroscopy and transmission electron microscope, and furthermore, their pH‐responsive behavior was studied by UV‐vis and dynamic light scattering. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1478–1486 The synthesis of polyisobutylene‐b‐poly(2‐(diethylamino)ethyl methacrylate) well‐defined amphiphilic pH‐responsive diblock copolymers via the combination of living carbocationic polymerization and RAFT polymerization is reported.