19F DOSY diffusion‐NMR spectroscopy of fluoropolymers

• Published in: Magnetic resonance in chemistry 2017-05, Vol.55 (5), p.472-484
• Main Authors: Xu, Chenglong, Wan, Yingbo, Chen, Dongxue, Gao, Chun, Yin, Hongnan, Fetherston, Daniel, Kupce, Eriks, Lopez, Gerald, Ameduri, Bruno, Twum, Eric B., Wyzgoski, Faith J., Li, Xiaohong, McCord, Elizabeth F., Rinaldi, Peter L.
• Format: Article
• Language: English
• Subjects: Adaptation; Chemical Sciences; Chlorotrifluoroethylene; Coupling (molecular); Couplings; Data acquisition; Diffusion; DOSY; Experiments; Fluorination; Fluorine; Fluoropolymers; Molecular weight; NMR; NMR spectroscopy; Optimization; Polymers; Sequences; Solubility; Spectra; Spectroscopic analysis; Spectrum analysis; Vinylidene; Vinylidene fluoride
• ISSN: 0749-1581; 1097-458X
• DOI: 10.1002/mrc.4454

A new pulse sequence for obtaining 19F detected DOSY (diffusion ordered spectroscopy) spectra of fluorinated molecules is presented and used to study fluoropolymers based on vinylidene fluoride and chlorotrifluoroethylene. The performance of 19F DOSY NMR experiments (and in general any type of NMR experiment) on fluoropolymers creates some unique complications that very often prevent detection of important signals. Factors that create these complications include: (1) the presence of many scalar couplings among 1H, 19F and 13C; (2) the large magnitudes of many 19F homonuclear couplings (especially 2JFF); (3) the large 19F chemical shift range; and (4) the low solubility of these materials (which requires that experiments be performed at high temperatures). A systematic study of the various methods for collecting DOSY NMR data, and the adaptation of these methods to obtain 19F detected DOSY data, has been performed using a mixture of low molecular weight, fluorinated model compounds. The best pulse sequences and optimal experimental conditions have been determined for obtaining 19F DOSY spectra. The optimum pulse sequences for acquiring 19F DOSY NMR data have been determined for various circumstances taking into account the spectral dispersion, number and magnitude of couplings present, and experimental temperature. Pulse sequences and experimental parameters for optimizing these experiments for the study of fluoropolymers have been studied. Copyright © 2016 John Wiley & Sons, Ltd. A new pulse sequence for obtaining 19F diffusion‐ordered spectroscopy (DOSY) spectra of fluorinated molecules is used to study fluoropolymers. A systematic study of the various methods for collecting DOSY NMR data, and the adaptation of these methods to obtain 19F DOSY data, has been performed using a mixture of low‐molecular‐weight, fluorinated model compounds. The optimum pulse sequences for acquiring 19F DOSY NMR data from fluoropolymers have been determined for various circumstances, taking into account the spectral dispersion and couplings present.