Impact of Added Tetraethylthiuram Disulfide Deactivator on the Kinetics of Growth and Reinitiation of Poly(methyl methacrylate) Brushes Made by Surface-Initiated Photoiniferter-Mediated Photopolymerization

Without intervention, it has been found that surface-initiated photoiniferter-mediated photopolymerization (SI-PMP) of methyl methacrylate suffers from irreversible termination, which leads to cessation of polymerization. These irreversible termination reactions were successfully reduced by preaddition of tetraethylthiuram disulfide (TED). The poly(methyl methacrylate) layers were also reinitiated using styrene as a monomer to investigate the effect of TED concentration on the extent of irreversible termination. The reinitiation efficiency increased as [TED] was increased, indicating that extent of irreversible termination reactions can be reduced by increasing [TED]. It was also observed that dithiocarbamyl radicals generated from TED can initiate polymerization in solution, resulting in significant monomer consumption.