PET-RAFT Increases Uniformity in Polymer Networks.

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.