Tetraarylphosphonium perfluorocyclobutyl polyelectrolyte with low critical surface energy, high thermal stability, and high alkaline resistance,Journal of Polymer Science Part A: Polymer Chemistry

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Tetraarylphosphonium perfluorocyclobutyl polyelectrolyte with low critical surface energy, high thermal stability, and high alkaline resistance
Journal of Polymer Science Part A: Polymer Chemistry Pub Date : 2019-11-04 , DOI: 10.1002/pola.29525
Wang Wan ₁ , Monte S. Bedford ₁ , Rhett C. Smith ₁

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Two tetraarylphosphonium polyelectrolytes having perfluorocyclobutyl units in their backbones have been prepared in which the counteranion is either bromide (PFP·Br) or bis(trifluoromethyl)sulfonimide (PFP·NTf₂). These polymers exhibit high thermal stability as assessed by thermogravimetric analysis, with a decomposition temperature of 460 °C for PFP·NTf₂. Even after heating at 300 °C for 72 h, PFP·NTf₂ shows no signs of degradation detectable by nuclear magnetic resonance spectrometry. As is typical for many tetraarylphosphonium species, films of these polymers can be quite resistant to degradation by alkaline solution. Upon alkaline challenge by exposure to 6 M NaOH at 65 °C for 24 h, for example, only 16% of the phosphonium centers in PFP·NTf₂ are degraded, making PFP·NTf₂ one of the most alkaline‐stable phosphonium polymers to date. Despite having ionic backbones, PFP·Br and PFP·NTf₂ exhibit very low critical surface energies of 26.1 and 22.9 mJ m⁻¹, respectively. These values are on par with the values for poly(vinylene fluoride) and dimethylsiloxane. Such low surface energy polycations capable of high alkaline stability may find application as components of alkaline fuel cell membranes. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2267–2272

中文翻译：

具有低临界表面能，高热稳定性和高耐碱性的四芳基，全氟环丁基聚电解质

已经制备了在其主链中具有全氟环丁基单元的两种四芳基phosph聚电解质，其中抗衡阴离子为溴化物（PFP· Br）或双（三氟甲基）磺酰亚胺（PFP· NTf ₂）。通过热重分析评估，这些聚合物表现出高的热稳定性，对于PFP· NTf ₂，其分解温度为460℃ 。即使在300°C加热72小时后，PFP· NTf ₂显示没有核磁共振波谱法检测到的降解迹象。如许多四芳基phosph物种所典型的那样，这些聚合物的膜可以非常耐碱性溶液的降解。例如，在65°C的6 M NaOH中暴露24 h进行碱激发后，PFP ·NTf ₂中只有16％的centers中心被降解，使PFP ·NTf ₂成为最碱性稳定的to聚合物之一。日期。尽管具有离子主链，但PFP· Br和PFP· NTf _2的临界表面能非常低，仅为26.1和22.9 mJ m ^-1，分别。这些值与聚（偏二氟乙烯）和二甲基硅氧烷的值相同。这类能够具有高碱性稳定性的低表面能聚阳离子可以用作碱性燃料电池膜的组分。分级为4 +©2019 Wiley Periodicals，Inc.J.Polym。科学，A部分：Polym。化学 2019，57，2267年至2272年

更新日期：2019-11-04

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