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 <i>N</i>,<i>N</i>-dimethylacrylamide (DMA), benzyl acrylate (BnA), <i>n</i>-butyl acrylate (<i>n</i>-BA), and <i>t</i>-butyl acrylate (<i>t</i>-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.