Comparison of Long-Term Stability of Initiating Monolayers in Surface-Initiated Controlled Radical Polymerizations.

The reproducibility of polymer brush synthesis via surface-initiated controlled radical polymerization is interrogated. Experiments compare the stability of initiating monolayers for surface-initiated (SI) reversible addition-fragmentation chain transfer polymerization (SI-RAFT) and SI atom transfer radical polymerization (SI-ATRP). Initiator-functionalized substrates are stored under various conditions and grafting densities of the resulting polymer brush films are determined via in situ ellipsometry.

SI-PET-RAFT: Surface-Initiated Photoinduced Electron Transfer-Reversible Addition-Fragmentation Chain Transfer Polymerization.

In this communication, surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer polymerization (SI-PET-RAFT) is introduced. SI-PET-RAFT affords functionalization of surfaces with spatiotemporal control and provides oxygen tolerance under ambient conditions. All hallmarks of controlled radical polymerization (CRP) are met, affording well-defined polymerization kinetics, and chain end retention to allow subsequent extension of active chain ends to form block copolymers.