Surface-Initiated PET-RAFT via the Z-Group Approach

Surface-initiated reversible addition–fragmentation chain transfer (SI-RAFT) is a user-friendly and versatile approach for polymer brush engineering. For SI-RAFT, synthetic strategies follow either surface-anchoring of radical initiators (e.g., azo compounds) or anchoring RAFT chain transfer agents (CTAs) onto a substrate. The latter can be performed via the R-group or Z-group of the CTA, with the previous scientific focus in literature skewed heavily toward work on the R-group approach. This contribution investigates the alternative: a Z-group approach toward light-mediated SI photoinduced electron transfer RAFT (SI-PET-RAFT) polymerization. An appropriate RAFT CTA is synthesized, immobilized onto SiO₂, and its ability to control the growth (and chain extension) of polymer brushes in both organic and aqueous environments is investigated with different acrylamide and methacrylate monomers. O₂ tolerance allows Z-group SI-PET-RAFT to be performed under ambient conditions, and patterning surfaces through photolithography is illustrated. Polymer brushes are characterized via X-ray photoelectron spectroscopy (XPS), ellipsometry, and water contact angle measurements. An examination of polymer brush grafting density showed variation from 0.01 to 0.16 chains nm^–2. Notably, in contrast to the R-group SI-RAFT approach, this chemical approach allows the growth of intermittent layers of polymer brushes underneath the top layer without changing the properties of the outermost surface.