The use of a new symmetrical trithiocarbonate holding two alkoxyamine moieties (I), was explored in surfactant-free emulsion polymerization of styrene or n-butyl acrylate through reversible addition-fragmentation chain transfer (RAFT). I revealed as an effective chain transfer agent in the synthesis of well-defined end-functionalized poly(acrylic acid)s (PAA). These macro RAFT agents were further used in water for the preparation of amphiphilic triblock copolymers by polymerization induced self-assembly (PISA). The corresponding final latex particles decorated with alkoxyamine moieties were used to trigger out NMP polymerization of sodium 4-styrene sulfonate (SSNa) in water. The thermal activation of the surface alkoxyamines groups which had hitherto been dormant induced the formation of a double hydrophilic corona PAA-b-PSSNa and a sharp reorganization of latex particles.

Dual RDRP agents provide access to new polymeric materials by combining ATRP, NMP, and RAFT polymerization without end group transformations.

A new strategy for synthesizing multiblock copolymers comprising polystyrene, polyacrylates, poly(N-isopropylacrylamide), etc. is described.