Organometallic-Mediated Radical Polymerization of Vinylidene Fluoride

An unprecedented level of control for the radical polymerization of vinylidene fluoride (VDF), yielding well-defined PVDF (at least up to 14500 g mol(-1)) with low dispersity (<= 1.32), was achieved using organometallic-mediated radical polymerization (OMRP) with an organocobalt compound as initiator. The high chain-end fidelity was demonstrated by the synthesis of PVDF-and PVAc-containing di-and triblock copolymers. DFT calculations rationalize the efficient reactivation of both head and tail chain end dormant species.