Characterization of Backbone Structures in Poly(vinylidene fluoride-co-hexafluoropropylene) Copolymers by Multidimensional 19F NMR Spectroscopy

Advanced modern multidimensional solution NMR experiments have been used to deduce the sequence distribution in poly­(VDF-co-HFP) copolymers. Assignment of 19F resonances from different monomer- and regio-sequences in poly­(VDF-co-HFP) copolymer were identified. In addition to corroborating some assignments reported in earlier literature, this work provides assignments of some new resonances from the spectra of poly­(VDF-co-HFP) copolymer, which resulted from better dispersion of the resonances. These assignments are used for the monomer sequence analyses of two polymers using first-order Markovian statistics, and the relative reactivities of the monomers during polymerization are discussed. The results from this study provide insight into the polymerization chemistry for this fluoropolymer.

本研究采用先进的现代多维溶液核磁共振（Nuclear Magnetic Resonance, NMR）实验技术，推导了聚(偏氟乙烯-六氟丙烯)共聚物[poly(VDF-co-HFP)]的序列分布。本工作完成了该共聚物中不同单体序列与区域序列对应的¹⁹F共振峰的归属鉴定；除佐证早期文献报道的部分归属结果外，得益于共振峰分散性的显著改善，本研究还首次实现了该共聚物谱图中若干新共振峰的归属。上述归属结果被用于基于一阶马尔可夫统计的两种聚合物的单体序列分析，并对聚合过程中单体的相对反应活性展开了讨论。本研究所得结果可为该含氟聚合物的聚合化学研究提供重要参考。