Multiblock copolymer nanoparticles RAFT emulsion polymerization: incorporation of a fluorine-containing functional monomer

Abstract

Multiblock copolymers provide a versatile platform for tailoring nanoscale organization and combining functional properties that are difficult to achieve with conventional polymer architectures. Here, we report the synthesis of fluorine-rich multiblock copolymer nanoparticles via one-pot surfactant-free RAFT emulsion polymerization in water using an amphiphilic macroRAFT agent. Sequential monomer additions enabled efficient chain extension and formation of well-defined multiblock architectures comprising n-butyl methacrylate (nBMA) and fluorinated statistical blocks of 2,2,3,4,4,4-hexafluorobutyl methacrylate (HFMA) and benzyl methacrylate (BzMA) in a one-pot system. Multiblock copolymer nanoparticles with high molecular weight were obtained with high monomer conversion in each polymerization cycle, controlled molecular weight distributions, and progressive particle growth without evidence of secondary nucleation. Cryogenic TEM confirmed controlled nanoparticle growth, while EDX-STEM elemental mapping verified successful incorporation of fluorinated segments within the nanoparticles. These results demonstrate that aqueous RAFT emulsion polymerization provides a robust and scalable route to fluorinated multiblock nanoparticles, enabling nanoscale confinement of highly incompatible fluorinated domains and opening opportunities for advanced functional materials.