Emulsion-Directed Synthesis of Poly-Porphyrin Nanoparticles as Heterogeneous Photocatalysts for PET-RAFT Polymerization

Heterogeneous photocatalysts have attracted extensive attention in photo-induced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization due to their remarkable advantages such as easy preparation, tunable photoelectric properties, and recyclability. In this study, zinc (II) 5,10,15,20-tetrakis(4-aminophenyl)porphyrin (ZnTAPP)-based poly-porphyrin nanoparticles (PTAPP-Zn) are constructed by an emulsion-directed approach. It is investigated as a heterogeneous photocatalyst for PET-RAFT polymerization of various methacrylate monomers under visible light exposure, and the reactions show refined polymerization control with high monomer conversions. Furthermore, it is demonstrated that the PTAPP-Zn nanoparticles with the larger pore size enhance photocatalytic activity in PET-RAFT polymerization. In addition, the capabilities of oxygen tolerance and temporal control are demonstrated and PTAPP-Zn particles can be easily recycled and reused without an obvious decrease in catalytic efficiency. Poly-porphyrin nanoparticles (PTAPP-Zn) are synthesized and employed as photoredox catalysts for the well-controlled photo-induced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization under visible light radiation.image