Organometallic‐Mediated Radical Polymerization of Vinylidene Fluoride

• Published in: Angewandte Chemie International Edition Vol. 57; no. 11; pp. 2934 - 2937
• Main Authors: Banerjee, Sanjib, Ladmiral, Vincent, Debuigne, Antoine, Detrembleur, Christophe, Poli, Rinaldo, Améduri, Bruno
• Format: Journal Article Web Resource
• Language: English
• Published: Germany Wiley Subscription Services, Inc 05-03-2018; Wiley-VCH Verlag; Wiley
• Edition: International ed. in English
• Subjects: Activation; Block copolymers; Chemical Sciences; Chemical synthesis; Chemistry; Chimie; cobalt; cobalt-mediated radical polymerization (CMRP); Engineering, computing & technology; Fluorides; fluorinated polymer; Ingénierie, informatique & technologie; Materials science & engineering; one pot synthesis; organometallic-mediated radical polymerization; Physical, chemical, mathematical & earth Sciences; Physique, chimie, mathématiques & sciences de la terre; Polymerization; Polymers; Polyvinyl acetates; Science des matériaux & ingénierie; Vinylidene; Vinylidene fluoride; block copolymers; cobalt; one pot synthesis; organometallic-mediated radical polymerization; vinylidene fluoride; Vinylidene fluoride; Organometallic-mediated radical polymerization; Cobalt; Block copolymers; One pot synthesis
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201712347

An unprecedented level of control for the radical polymerization of vinylidene fluoride (VDF), yielding well‐defined PVDF (at least up to 14 500 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.
Head and tails above the rest: An organocobalt compound allows organometallic‐mediated radical polymerization (OMRP) of vinylidene fluoride (VDF) yielding well‐defined PVDF (at least up to 14 500 g mol−1) with low dispersity (≤1.32). The PVDF could be reactivated at both the head and tail chain ends, as evidenced by DFT calculations.