The impact of conditions was investigated on a model photoinduced electron/energy transfer reversible addition−fragmentation chain transfer (PET-RAFT) polymerization. Within the cylindrical geometries studied, with relatively small changes in path length, the impact of reaction vessel dimensions and dilution was relatively small on the polymerization kinetics and control of the polymerization. This suggests that PET-RAFT can be relatively insensitive to small changes in reactor geometry and reaction volume when cylindrical systems are used. The intensity of the photoreactor was a key factor in determining reaction rate, with an approximate 1/2 order scaling of the apparent rate with intensity. Reactant concentration ratios were also important, with an approximate 1/2 order of the apparent rate with the photocatalyst loading and an approximate −1/2 order scaling apparent polymerization rate coefficient with the RAFT agent concentration. However, there is a limit to rate increases with higher Ir catalyst loadings due to the optical density.

Photolabile amine protecting groups are combined with RAFT polymerization to create well-defined amine containing polymers, which is typically a challenge for RAFT polymerization.