Polymerization-induced self-assembly: the effect of end group and initiator concentration on morphology of nanoparticles prepared via RAFT aqueous emulsion polymerization

Polymerization-induced self-assembly (PISA) is a widely used technique for the synthesis of nanoparticles with various morphologies including spheres, worms, and vesicles. The development of a PISA formulation based on reversible addition fragmentation chain transfer (RAFT) aqueous emulsion polymerization offers considerable advantages such as enhanced rate of polymerization, high conversion and environmentally friendly conditions. However, this formulation has typically produced spheres as opposed to worms and vesicles. Herein, we report the formation of vesicle morphology by increasing the RAFT end-group hydrophobicity of the macromolecular chain transfer agent or manipulating the radical initiator concentration used in the aqueous emulsion polymerization PISA formulation. Additionally, decreasing the molecular weight of the hydrophobic polystyrene domain in these vesicles leads to the formation of worms. This work demonstrates that RAFT end-group hydrophobicity and radical initiator concentration are key parameters which can be exploited to enable access to sphere, worm, and vesicle morphologies via the RAFT aqueous emulsion polymerization