Iron-initiated radical polymerization of acrylate monomers

In this study, we present a novel Fe-H initiated radical polymerization method for various acrylate monomers, using commercially available iron(III) acetylacetonate as a catalyst and tetramethyldisiloxane (TMDSi) as a reducing agent, under mild conditions. Methyl acrylate (MA) polymerization at 40 °C resulted in monomer conversion up to 65%, and significant molecular weights up to 400 kg mol–1 and unimodal dispersity. Rheological and mechanical studies revealed that the polymer exhibits strong viscoelastic properties and high elasticity, influenced primarily by the molecular weight. The polymerization of N,N-dimethylacrylamide (DMA), benzyl acrylate (BnA), n-butyl acrylate (n-BA), and t-butyl acrylate (t-BA) demonstrated similar control, with molecular weights ranging from around 200 to 700 kg mol–1 and conversions between 20% and 50%. The findings highlight the potential of Fe-H initiated polymerization as a sustainable and efficient alternative to conventional radical polymerization methods, offering advantages in scalability, control, and material properties.