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Novel Source of Trifluoromethyl Radical As Efficient Initiator for the Polymerization of Vinylidene Fluoride
Author(s) -
Boschet Frédéric,
Ono Taizo,
Ameduri Bruno
Publication year - 2012
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.201100737
Subject(s) - radical , polymer chemistry , polymerization , fluoride , radical polymerization , chemistry , crystallinity , radical initiator , trifluoromethyl , molar mass , polymer , organic chemistry , crystallography , inorganic chemistry , alkyl
A persistent perfluoroalkyl radical (PPFR), perfluoro‐3‐ethyl‐2,4‐dimethyl‐3‐pentyl, is shown to be a good source of •CF 3 radicals and a useful radical capable of initiating the polymerization of vinylidene fluoride (VDF). NMR characterizations of the resulting PVDF homopolymers showed that polymerization of VDF was exclusively initiated by •CF 3 radicals. The addition of •CF 3 radical onto VDF was regioselective leading to CF 3 ‐CH 2 ‐CF 2 ‐PVDF and the CF 3 end‐group acted as an efficient label to assess the molecular weights by 19 F NMR spectroscopy. Various [PPFR] 0 /[VDF] 0 initial molar ratios lead to CF 3 –PVDF–CF 3 of different molecular weights. When that ratio decreased, both the molecular weights and the thermostability of these PVDFs increased, showing less defects of chaining and higher crystallinity.