Reversible addition-fragmentation chain transfer (RAFT) is a living polymerization technique that offers low molar mass dispersity and highly precise molecular weight polymers. In this study, Photoinduced electron/energy transfer (PET)- reversible addition-fragmentation chain transfer polymerization (RAFT) and conventional photoinitiated RAFT were used to prepare polymer networks. Ir(ppy)<sub>3</sub> and ZnTPP were used as photocatalysts to generate two different catalytic pathways, an energy transfer pathway and an electron transfer pathway respectively. These two PET RAFT systems were compared against a conventional photoinitated RAFT process. The homogeneity of the polymer networks was evaluated using swelling ratios and utilizing cleavable disulfide crosslinker. PET-RAFT systems generate more homogeneous networks compared to conventional RAFT method at higher primary chain length and crosslink density. The electron transfer based ZnTPP demonstrated superior results to those of Ir(ppy)<sub>3</sub> in terms of primary chain uniformity and network swelling. The combination of RAFT exchange and reversible coupling in PET RAFT was proposed as the mechanism that gave better control in PET-RAFT systems.

PET-RAFT increases uniformity in polymer networks

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