Regioselective nucleophilic substitution of perfluoropyridine with functionalized phenols provided a facile route toward the preparation of 2,6-bis(4-ethynylphenoxy)-3,5-difluoro-4-phenoxypyridine, a monomer that can be polymerized neat via thermal [2 + 2+2] cyclopolymerizations affording intractable polyarylene networks or via copper-assisted step-growth 1,3-dipolar alkyne-azide “click” cycloaddition reactions with bis(azidomethyl)benzene. Both reactive pathways afforded polymers with high thermal stability and good char yields, which is comparable to acetylene-based resins. Notably, the opportunity for programmable thermal properties is realized through the operationally simple monomer synthesis was shown to be adaptive to various regioselective and nucleophile addition scenarios that can lead to the production of a library of perfluoropyridine monomers. Herein, we highlight the synthesis and characterization of these new perfluoropyridine-based polymer architectures for potentially tunable high performance applications.

用功能化的酚对全氟吡啶进行区域选择性亲核取代，为制备2,6-双（4-乙炔基苯氧基）-3,5-二氟-4-苯氧基吡啶提供了一条简便的途径，该单体可以通过热[2 + 2]进行纯净聚合。 +2]环聚合提供难处理的聚亚芳基网络，或通过铜辅助逐步增长的1,3-偶极炔-叠氮化物与双（叠氮基甲基）苯的“点击”环加成反应。两种反应途径均提供了具有高热稳定性和良好焦炭收率的聚合物，可与乙炔基树脂媲美。尤其，通过操作简单的单体合成实现了可编程热性能的机会，表明该方法可适应各种区域选择性和亲核试剂加成方案，这些情况可导致产生全氟吡啶单体库。在本文中，我们重点介绍了这些新的基于全氟吡啶的聚合物结构的合成和表征，这些结构可用于潜在的可调高性能应用。