By utilizing the unique regioselective nucleophilic aromatic substitution (SNAr) of pentafluoropyridine with bisphenols, a series of 4-substituted tetrafluoropyridine (TFP) aryl ether monomers were prepared in nearly quantitative yields from a facile, base-promoted methodology. Sequential regioselective SNAr of TFP monomers with bisphenols afforded linear amorphous, solution-processable fluorinated pyridine aryl ether polymers as well as networks. Room-temperature kinetic experiments using ¹⁹F NMR revealed high-molecular-weight polymers with nearly quantitative conversions. By the nature of the bisphenol substitution and its electronic effects, the polymer microstructure was tuned for a broad range of glass transition temperatures for optically transparent materials. This work will provide insights into synthetic routes toward TFP monomers, step-growth polymerization kinetics, molecular weight determination, and thermal properties.

中文翻译：

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具有明确微观结构、多样化结构和可调热性能的氟化吡啶芳基醚聚合物


利用五氟吡啶与双酚的独特区域选择性亲核芳香取代（SNAr），通过简单的碱促进方法以接近定量的产率制备了一系列4-取代四氟吡啶（TFP）芳基醚单体。 TFP 单体与双酚的顺序区域选择性 SNAr 提供了线性无定形、可溶液加工的氟化吡啶芳基醚聚合物以及网络。使用 ¹⁹ F NMR 进行的室温动力学实验揭示了高分子量聚合物具有接近定量的转化率。通过双酚取代的性质及其电子效应，聚合物微观结构被调整以适应光学透明材料的广泛玻璃化转变温度。这项工作将为 TFP 单体的合成路线、逐步增长聚合动力学、分子量测定和热性能提供见解。