Visible-Light Induced Photopolymerization Mediated by Mn₂(CO)₁₀ in a Continuous-Flow process

Dimanganese decacarbonyl (Mn₂(CO)₁₀) is used as a versatile and efficient visible-light photoinitiator for multiple polymerization techniques in different continuous-flow processes. The use of Mn₂(CO)₁₀ results in good photoinitiation of conventional radical polymerizations of both methyl acrylate and methyl methacrylate, as well as the cationic polymerisation of isobutyl vinyl ether (IBVE). In addition, the combination of Mn₂(CO)₁₀ with certain Cu(II) catalysts affords controlled radical polymerization, yielding well-defined polymers with tuneable molecular weights under mild conditions. Polymerizations were performed under blue-light irradiation (λ = 405 nm) in a Corning Advanced-Flow™ reactor (CAFR). Copper-mediated protocols were also carried out in a Vapourtec flow reactor coupled with inline benchtop 80 MHz ¹H nuclear magnetic spectroscopy (NMR) allowing for real-time reaction monitoring. Inline and offline analyses, including NMR spectroscopy and size exclusion chromatography (SEC), confirmed relatively high monomer conversions (up to 86%) and the preparation of polymers with narrow dispersities (Đ ≈ 1.09–1.15). The excellent photo reactivity of Mn₂(CO)₁₀, combined with the intrinsic advantages of continuous-flow processing, enables accurate regulation of residence time, light intensity, and initiator concentration. This work establishes a versatile platform for visible-light-mediated polymer synthesis, unifying conventional radical, controlled radical, and cationic processes within a single continuous-flow framework, and highlighting its potential for sustainable, scalable and environmentally benign manufacturing of advanced polymeric materials.

• Request a Brochure
• Request more Info
• Request a Quote