Open-to-Air RAFT Polymerization on a Surface under Ambient Conditions

Oxygen (O₂)-mediated controlled radical polymerization was performed on surfaces under ambient conditions, enabling on-surface polymer brush growth under open-to-air conditions at room temperature in the absence of metal components. Polymerization of zwitterionic monomers using this O₂-mediated surface-initiated reversible addition fragmentation chain-transfer (O₂-SI-RAFT) method yielded hydrophilic surfaces that exhibited anti-biofouling effects. O₂-SI-RAFT polymerization can be performed on large surfaces under open-to-air conditions. Various monomers including (meth)acrylates and acrylamides were employed for O₂-SI-RAFT polymerization; the method is thus versatile in terms of the polymers used for coating and functionalization. A wide range of hydrophilic and hydrophobic monomers can be employed. In addition, the end-group functionality of the polymer grown by O₂-SI-RAFT polymerization allowed chain extension to form block copolymer brushes on a surface.