RAFT Polymerization of Semifluorinated Monomers Mediated by a NIR Fluorinated Photocatalyst

Near-infrared (NIR) light plays an increasingly important role in the field of photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization due to its unique properties. Yet, the NIR photocatalyst with good stability for PET-RAFT polymerization remains promising. Here, a strategy of NIR PET-RAFT polymerization of semifluorinated monomers using fluorophenyl bacteriochlorin as a photocatalyst with strong absorption at the NIR light region (710-780 nm) is reported. In which, the F atoms are used to modify reduced tetraphenylporphyrin structure with enhanced photostability of photocatalyst. Under the irradiation of NIR light (lambda(max) = 740 nm), the PET-RAFT polymerization of semifluorinated methylacrylic monomers presents living/control characteristics and temporal modulation. By the PET-RAFT polymerization-induced self-assembly (PISA) strategy, stable fluorine-containing micelles are constructed in various solvents. In addition, the fluorinated hydrophobic surface is fabricated via a surface-initiated PET-RAFT (SI-PET-RAFT) polymerization using silicon wafer bearing RAFT agents with tunable surface hydrophobicity. This strategy not only enlightens the application of further modified compounds based on porphyrin structure in photopolymerization, but also shows promising potential for the construction of well-defined functional fluoropolymers.

Automated summary

This study presents a strategy for near-infrared (NIR) photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization of semifluorinated monomers using a NIR photocatalyst called fluorophenyl bacteriochlorin. The strategy involves modifying a reduced tetraphenylporphyrin structure with F atoms to enhance the photostability of the photocatalyst. Under NIR light irradiation, the PET-RAFT polymerization exhibits living/control characteristics and temporal modulation. Stable fluorine-containing micelles and fluorinated hydrophobic surfaces are successfully constructed using this strategy.