A series of three fluorine containing and three non‐fluorinated Diels–Alder step‐growth polyarylene polymers and copolymers was synthesized via conventional oil bath heating (days/weeks). A drastic time reduction was realized with a microwave‐assisted polymerization (hours). The polymers were characterized by multinuclear (¹H, ¹³C, and ¹⁹F) NMR and attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy, thermal analysis (thermogravimetric analysis [TGA], differential scanning calorimetry [DSC], and dynamic mechanical analysis [DMA]), gel permeation chromatography, X‐ray diffraction (XRD), water contact analysis, and refractive index (RI) measurements. The NMR spectra indicated a mixture of para and meta conformations through the polymer backbone increasing to more para with greater fluorine content. TGA revealed the fluorine‐containing polyarylenes possessed the highest char yields at almost 80% at 1000°C under nitrogen, and all the polyarylenes possessed onset of degradation temperatures above 550°C under nitrogen and air atmospheres. XRD analysis indicated more ordering for the fluorine‐containing polyarylenes which afforded the high char yields. DMA gave storage moduli values in the range of 1–10 GPa for the polyarylenes. Molecular weights for all samples were above 100 kg/mol. Water contact angles did not change with fluorine content due to the shielding effect of the pendant phenyl groups. However, the RI decreased to 1.6497 at 632.8 nm for the polyarylene with the highest fluorine content.

中文翻译：

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半氟化聚亚芳基：微波辅助合成与结构-性质关系

通过常规油浴加热（天/周）合成了一系列三种含氟和三种非氟化Diels-Alder分步生长的聚亚芳基聚合物和共聚物。微波辅助聚合（小时）可大大减少时间。聚合物通过多核（¹ H，¹³ C和¹⁹ F）NMR和衰减的全反射傅立叶变换红外（ATR-FTIR）光谱，热分析（热重分析[TGA]，差示扫描量热法[DSC]和动态）进行表征。机械分析[DMA]），凝胶渗透色谱，X射线衍射（XRD），水接触分析和折射率（RI）测量。NMR谱表明对位和对位的混合物通过聚合物主链的元构象增加至更多对位氟含量更高 TGA显示，在氮气氛下（1000℃），含氟的聚亚芳基在90％时具有最高的焦炭收率，并且所有的聚亚芳基在氮和空气气氛下都具有高于550°C的降解温度。XRD分析表明，含氟聚亚芳基的订购更多，可提供较高的炭收率。DMA对于聚亚芳基的储能模量值在1-10 GPa范围内。所有样品的分子量均高于100 kg / mol。由于苯基侧基的屏蔽作用，水接触角不随氟含量而变化。但是，对于氟含量最高的聚亚芳基，RI在632.8 nm处降至1.6497。