AGET ATRP of Poly[poly(ethylene glycol) methyl ether methacrylate] Catalyzed by Hydrophobic Iron(III)–Porphyrins

Commercially available hydrophobic porphyrins are investigated as an environmentally friendly catalytic system for iron‐mediated atom transfer radical polymerization (ATRP) of poly(ethylene glycol) monomethyl ether methacrylate (PEGMA). Polymerizations in organic solvent are optimized using activators generated by electron transfer (AGET ATRP), based on iron(III)–porphyrin complexes, and tin(II) 2‐ethyl hexanoate or ascorbic acid as a reducing agent. Copper‐free PPEGMA macromolecules are obtained with high conversion, controlled molecular weight, and polydispersity index compared with standard copper‐based ATRP. The facile preparation and availability of the catalyst, together with its expected low toxicity, represent clear advantages for the synthesis of PPEGMA‐based materials for biomedical use.