• atom transfer radical polymerization (ATRP);
  • click chemistry;
  • diblock copolymers;
  • hetero Diels–Alder cycloaddition;
  • reversible addition fragmentation chain transfer (RAFT)


Thumbnail image of graphical abstract

The use of the reversible addition fragmentation chain transfer—hetero Diels–Alder (RAFT-HDA) click reaction for the modular construction of block copolymers is extended to the generation of high molecular weight materials. Cyclopentadienyl end-functionalized polystyrene (PS-Cp) prepared via both atom transfer radical polymerization (ATRP) and the RAFT process are conjugated to poly(isobornyl acrylate) (PiBoA) (also prepared via RAFT polymerization) to achieve well-defined block copolymers with molecular weights ranging from 34 000 to over 100 000 g · mol−1 and with small polydispersities (PDI < 1.2). The conjugation reactions proceeded in a very rapid fashion (less than 10 min in the majority of cases) under ambient conditions of temperature and atmosphere. The present study demonstrates—for the first time—that RAFT-HDA click chemistry can provide access to high molecular weight block copolymers in a simple and straight-forward fashion.