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Photoinduced electron/energy transfer (PET)-reversible addition–fragmentation chain transfer polymerization (RAFT) and conventional photoinitiated RAFT were used to synthesize polymer networks. In this study, two different metal catalysts, namely, tris[2-phenylpyridinato-C2,N]iridium(III) (Ir(ppy)3) and zinc tetraphenylporphyrin (ZnTPP), were selected to generate two different catalytic pathways, one with Ir(ppy)3 proceeding through an energy-transfer pathway and one with ZnTPP proceeding through an electron-transfer pathway. These PET-RAFT systems were contrasted against a conventional photoinitated RAFT process. Mechanically robust materials were generated. Using bulk swelling ratios and degradable cross-linkers, the homogeneity of the networks was evaluated. Especially at high primary chain length and cross-link density, the PET-RAFT systems generated more uniform networks than those made by conventional RAFT, with the electron transfer-based ZnTPP giving superior results to those of Ir(ppy)3. The ability to deactivate radicals either by RAFT exchange or reversible coupling in PET RAFT was proposed as the mechanism that gave better control in PET-RAFT systems. 

The choice of chain transfer agent in reversible addition/fragmentation chain transfer polymerization has proven to be instrumental in modulating the dispersity of a certain polyphenyl vinyl ketone (PVK). The monomer, PVK, which can self-initiate when exposed to blue light, was used to synthesize homopolymers, block copolymers by extending with a different monomer and gradient polymers. Regardless of the polymer architecture or degree of polymerization, a consistent trend in polymer dispersity was quantified, with higher loadings of the less active chain transfer agent xanthate leading to higher dispersities. The dispersity could be further modulated by photodegradation of vinyl ketone polymers under UV irradiation.