Single molecule force spectroscopy (SMFS) is employed to gain insight into reversible addition–fragmentation chain transfer (RAFT) polymerization processes with living characteristics on glass surfaces. Surface-initiated (SI)-RAFT was selected to grow poly(hydroxyethyl methacrylate) (PHEMA). After aminolysis of the RAFT chain termini, thiol moieties serve as anchoring points for the gold tip of an atomic force microscope.
The results allow to directly monitor the macromolecular growth of the surface-initiated polymerization. The obtained SMFS-based molecular weight distribution data of the polymers present on the surface indicate that the RAFT chain extension proceeds linearly with time up to high conversions. The current study thus adds SMFS as a valuable tool for the investigation of SI-RAFT polymerizations.