An eco-friendly pathway to thermosensitive micellar nanoobjects via photoRAFT PISA: the full guide to poly(N-acryloylpyrrolidin)-block-polystyrene diblock copolymers.

Spherical macromolecular assemblies, so-called latexes, consisting of polystyrene (PS) resemble a relevant class of synthetic polymers used for a plethora of applications ranging from coatings or lubricants to biomedical applications. Their synthesis is usually tailored to the respective application where emulsifiers, radical initiators, or other additives still play a major role in achieving the desired properties. Herein, we demonstrate an alternative based on the photoiniferter reversible addition-fragmentation chain transfer (RAFT) polymerization-induced self-assembly (PISA) of Poly(N-acryloylpyrrolidin)-block-polystyrene (PAPy-b-PS). This approach yields monodisperse nanospheres with tunable sizes based on an aqueous formulation with only two ingredients. These nanospheres are additionally thermosensitive, meaning that they change their hydrodynamic diameter linearly with the temperature in a broad range between 10 °C and 70 °C. Combined with the eco-friendly synthesis in pure water at 40 °C, the herein presented route constitutes an unprecedented pathway to thermosensitive diblock copolymer aggregates in short reaction times without any additives.