Evaluation of Ring Expansion-Controlled Radical Polymerization System by AFM Observation

We here present a direct link between the reaction mechanisms for the ring-expansion "vinyl" polymerization system and atomic force microscopy (AFM) observations. The brush-modification clearly discriminates the desired cyclic species with the contour lengths (L_c) of 28-132 nm and molar masses (M_AFM) of 60.2-283 kg mol^-1 from the other linear ones. The 293 polymer blushes observed in a 1.0 μm × 1.0 μm AFM image are individually characterized, eventually providing clear answers about the mechanisms of this rare polymerization system, which include ring-expansion vinyl polymerizations to generate cyclic polymers, fusions of the generated cycles to form multimers, and their scission to form linear or ring-opened species. The relationship between the molecular chain lengths and the cyclic versus linear morphologies is highlighted.