Synthesis and characterization of original alternated fluorinated copolymers bearing glycidyl carbonate side groups

A vinyl ether bearing a carbonate side group (2-oxo-1,3-dioxolan-4-yl-methyl vinyl ether, GCVE) was synthesized and copolymerized with various commercially available fluoroolefins [chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), and perfluoromethyl vinyl ether (PMVE)] by radical copolymerization initiated by tert-butyl peroxypivalate. Although HFP, PMVE, and vinyl ether do not homopolymerize under radical conditions, they copolymerized easily yielding alternating poly(GCVE-alt-F-alkene) copolymers. These alternating structures were confirmed by elemental analysis as well as 1H, 19F, and 13C NMR spectroscopy. All copolymers were obtained in good yield (7385%), with molecular weights ranging from 3900 to 4600 g mol-1 and polydispersities below 2.0. Their thermogravimetric analyses under air showed decomposition temperatures at 10% weight loss (Td,10%) in the 284330 degrees C range. The HFP-based copolymer exhibited a better thermal stability than those based on CTFE and PMVE. The glass transition temperatures were in the 1565 degrees C range. These original copolymers may find potential interest as polymer electrolytes in lithium ions batteries. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012