Exploring the impact of process parameters on the metal-free light-catalyzed ATRP polymerization of PVDF-based block copolymers

The synthesis of well-defined poly(vinylidene fluoride) (PVDF)-based block copolymers has been an important topic in recent years to accurately modify its properties and to achieve high-quality composites. Atom transfer radical polymerization (ATRP) proved itself to be a viable technique for the controlled synthesis of PVDF-based block copolymers. Recently, organic photoredox catalysts (OPRCs) have been reported as effective photocatalysts in light-catalyzed ATRP. Here, we use three OPRs (perylene, 10-methylphenotiazine, 10-phenylphenotiazine) for the ATRP of methylmethacrylate using telechelic PVDF as macroinitiators. We explore the impact of three process parameters: the end group on the polymer chain, the concentration of MMA, and the concentration of the OPRC in solution. First, three different telechelic PVDF were tested under the same monomer and OPRC concentrations to select the best macroinitiator for this system. Then, the effects on the overall control and on the conversion when the concentration of monomer or OPRC is varied were evaluated.