Brand-New Method toward Widely Regulating Polymer Dispersity by Two-Dimensional Confining Radical Polymerization

Polymer dispersity (D?) is a key parameter in polymer materials' design and directly affects the properties and performances of the polymer. Numerous charming research studies based on the controlled/living polymerization have been carried out in this field, but the complicated initiation systems and specific experimental conditions are still inevitable. Here, we report a two-dimensional confining radical polymerization (TDCRP) through fluorinated graphene (FG) toward widely regulating the D? of vinyl polymers. Vinyl monomers attack the C-F bonds for initiating polymerization by the single-electron transfer reaction, showing the unique "region reaction " behavior. On account of the steric effect of the two-dimensional structure and the tunable interactions between the formed polymer segment and two-dimensional plane during the region reaction, the D? of vinyl polymers presents a time-dependent characteristic and is widely adjustable. Meanwhile, TDCRP also has the ability of tailoring D? from a wide range of vinyl monomers, which can be driven under different external fields including heat, light, and force. The changed surface morphology of the FG plane and polymerization temperature can further regulate the D? of the formed polymer. The versatile and robust nature of our strategy combined with the cutting-edge two-dimensional materials effectively regulates the radical polymerization, which may create an extensive interest among the polymer community and beyond.