SI-PET-RAFT in flow: improved control over polymer brush growth

Surface-initiated photoinduced electron transfer-reversible addition–fragmentation chain transfer (SI-PET-RAFT) provides a light-dependent tool to synthesize polymer brushes on different surfaces that tolerates oxygen and water, and does not require a metal catalyst. Here we introduce improved control over SI-PET-RAFT polymerizations via continuous flow conditions. We confirm the composition and topological structure of the brushes by X-ray photoelectron spectroscopy, ellipsometry, and AFM. The improved control compared to no-flow conditions provides prolonged linear growth of the polymer brush (up to 250 nm, where no-flow polymerization maxed out <50 nm), and improved polymerization control of the polymer brush that allows the construction of diblock polymer brushes. We further show the linear correlation between the molecular weight of the polymer brush and its dry thickness by combining ellipsometry and single-molecule force spectroscopy.