Biobased Amphiphilic Block Copolymers by RAFT‐Mediated PISA in Green Solvent.

Biobased amphiphilic diblock copolymers are prepared thanks to the combination of reversible addition–fragmentation transfer (RAFT) polymerization and polymerization‐induced self‐assembly (PISA) in an eco‐friendly solvent mixture. First, the formation of a poly(acrylic acid) macroRAFT agent (PAA‐TTC) is performed in water at 70 °C. Then, in a series of experiments, the PAA‐TTC macroRAFT agent is used directly, without purification, as both chain transfer agent and stabilizing agent in the RAFT‐PISA of menthyl acrylate (MnA) in dispersion in an ethanol/water mixture. The polymerizations of MnA are fast with high final conversions and well‐controlled amphiphilic diblock copolymers are synthesized. Stable, sub‐micrometric spherical particles composed of the diblock copolymers are formed. The influence of the monomer concentration and the length of the solvophobic block on the diameter of the self‐assemblies is studied by means of dynamic light scattering and cryogenic transmission electron‐microscopy. [ABSTRACT FROM AUTHOR]