Transition metal catalyzed atom Transfer Radical Polymerization (ATRP): from heterogeneous to homogeneous catalysis using 1,10‐phenantroline and its derivatives as new copper(I) ligands

Atom Transfer Radical Polymerization (ATRP) of styrene is investigated in both heterogeneous and homogeneous media using 1‐phenylethyl chloride (1‐PECl)/CuCl/1,10‐phenantroline and derivatives as initiating systems. Using a 1‐PECl/CuCl/4,7‐diphenyl‐1,10‐phenantroline system in 1,2‐dimethoxybenzene as a solvent at 130°C, homogeneous ATRP of styrene leads to polymers with polydispersities down to 1,1. These new systems are compared with previously described 4,4′‐disubstituted 2,2′‐bipyridine‐based systems in terms of kinetics and quality of control.