Kinetic Characterization of Surface-Initiated Photoiniferter-Mediated Photopolymerization in Presence of Tetraethylthiuram Disulfide

Introduction. Modification of surfaces with covalently grafted polymer brushes is a widely used technique to tailor surface properties such as wettability, biocompatibility, corrosion resistance and lubricity. In the current work, surface-tethered poly(methyl methacrylate) (PMMA) layers were produced via surface-initiated photoiniferter-mediated photopolymerization (SI-PMP). Photoiniferters, based on dithiocarbamate chemistries are often utilized as photoinitiators for “living” radical polymerizations in bulk or solution. However; it has been found that, due to a low concentration of deactivating radicals, SIPMP of methyl methacrylate suffers from irreversible termination reactions, which lead to cessation of polymerization. Therefore, to suppress the extent of irreversible termination reaction, a source of deactivating dithiocarbamyl species, tetraethylthiuram disulfide (TED), was added to the reaction mixture. The presented work is focused on investigating the impact of TED on the surface-tethered chain growth and the ability of this strategy to preserve active ends during brush formation to allow creation of block copolymers.