American Chemical Society
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2D-NMR Characterization of Sequence Distributions in the Backbone of Poly(vinylidene fluoride-co-tetrafluoroethylene)

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journal contribution
posted on 2012-12-21, 00:00 authored by Linlin Li, Eric B. Twum, Xiaohong Li, Elizabeth F. McCord, Peter A. Fox, Donald F. Lyons, Peter L. Rinaldi
NMR is a powerful tool to study the microstructures of poly­(vinylidene fluoride-co-tetrafluoroethylene), poly­(VDF-co-TFE). This study shows that the microstructures in this copolymer can be established completely on the basis of 2D-NMR, in which improved dispersion is achieved by the second dimension (19F or 13C chemical shifts). 2D-NMR has been proven to be extremely effective for identifying the carbon sequence distributions in the polymer main chain. For lower level sequences (3- or 5-carbon sequences), resonance assignments on the basis of one- and two-bond 19F­{13C} gradient heteronuclear single quantum coherence (gHSQC) experiments are in good agreement with assignments obtained by traditional methods. Higher level sequences (7- or 9-carbon sequences), which can not be assigned unambiguously by traditional methods, were determined by 19F–19F gradient double quantum correlation spectroscopy (gdqCOSY), which provides 19F–19F correlations over 3–5 bonds. A quantitative study was also conducted on the composition of this copolymer. Three different approaches were used to calculate the fraction of TFE and the inversion ratio of VDF units.