Photoinduced atom transfer radical polymerization of methyl methacrylate with conducting polymer nanostructures as photocatalyst

Light-mediated control/living radical polymerization (CLRP) provides a convenient method to synthesize polymers with controlled molecular weight and narrow molecular weight distribution. However, high-energy wavelengths (such as UV light) and blue light are needed to initiate the polymerization, leading to unwanted side reactions. To overcome these defects, the use of long-wavelength light for light-mediated CLRP is highly desirable. In this work, photoinduced atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was successfully carried out for the synthesis of polyMMA (PMMA) with predictable molecular weights (Mn,GPC) and narrow molecular weight distribution (Mw/Mn). This was achieved using one-dimensional nanopoly(diphenyl butadiyne) (nanoPDPB) as photocatalyst, which activated the dormant alkyl bromides initiator to reversibly produce propagating radicals at ambient temperature. Initiation and termination of polymerization were regulated by periods of light. The polymerization of MMA was accomplished by the radicals generated in the redox reaction of nanoPDPB with EBP. Both 1H nuclear magnetic resonance (1H NMR) spectroscopy and chain-end extension polymerization show highly preserved bromine chain-end functionality in the synthesized PMMA. nanoPDPB displays remarkable photophysical properties in the visible light region. The polymerization of MMA followed the first-order kinetics and the evolution of the Mn,GPC versus monomer conversion and Mw/Mn demonstrated the well-controlled polymerization process. The living character of heterogeneous photomediated ATRP with nanoPDPB as photocatalyst was successfully confirmed.