Toward a toolbox of functional block copolymers via free-radical addition of mercaptans

This work demonstrates the applicability of the free-radical addition of ω-functional mercaptans onto 1,2-polybutadienes as a modular synthetic pathway toward a toolbox of diverse functional block copolymers. Functional groups included, for instance electrolytes (carboxylic acid and amine), l-amino acid, and fluorocarbon. The number of functional groups attached to the polymer was lower than that of double bonds reacted (degree of functionalization=50–85%, typically 70–80%) due to cyclization of two neighboring units, but the narrow molecular-weight distribution of the parent (co)polymer was always maintained.