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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 was revealed as an effective chain transfer agent in the synthesis of well-defined end-functionalized poly(acrylic acid)s (PAA). These macroRAFT 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 NMP polymerization of sodium 4-styrene sulfonate (SSNa) in water. The thermal activation of the surface alkoxyamine groups which had hitherto been dormant induced the formation of a double hydrophilic corona PAA-b-PSSNa and a sharp reorganization of latex particles.

Graphical abstract: Alkoxyamine-functionalized latex nanoparticles through RAFT polymerization-induced self-assembly in water

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