Metal‐free <scp>ATRP</scp> and <scp>ROP</scp> for graft copolymers: an orthogonal strategy for sequential and concurrent polymerizations at room temperature

Abstract Well‐defined poly[(methyl acrylate)‐ co ‐(hydroxyethyl acrylate)]‐ graft ‐ poly(ε‐caprolactone ) copolymers were synthesized using a completely metal‐free strategy by combining atom transfer radical polymerization (ATRP) and ring‐opening polymerization (ROP) at ambient temperature. These two orthogonal, metal‐free, controlled/living processes, tested in both simultaneous and sequential approaches, were employed to fine‐tune grafting density and efficiency by systematically varying monomer concentration and polymerization time. Spectroscopic and chromatographic characterizations confirmed that both ATRP and ROP proceeded in a controlled fashion, yielding graft copolymers with narrowly distributed molecular weights. © 2025 Society of Chemical Industry.