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Teaching Old Polymers New Tricks: Improved Synthesis and Anomalous Crystallinity for a Lost Semi-Fluorinated Polyaryl Ether via Interfacial Polymerization of Hexafluoroacetone Hydrate and Diphenyl Ether
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2022-10-22 , DOI: 10.1002/marc.202200737 Gustavo Muñoz 1 , Kari M Chamberlain 1 , Sumudu Athukorale 1 , Guorong Ma 2 , Xiaodan Gu 2 , Charles U Pittman 1 , Dennis W Smith 1
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2022-10-22 , DOI: 10.1002/marc.202200737 Gustavo Muñoz 1 , Kari M Chamberlain 1 , Sumudu Athukorale 1 , Guorong Ma 2 , Xiaodan Gu 2 , Charles U Pittman 1 , Dennis W Smith 1
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A practical and direct electrophilic polymerization of hexafluoroacetone hydrate with diphenyl ether toward the preparation of semi-fluorinated polyaryl ethers (PAE) is reported. Electrophilic aromatic substitution (EAS) polymerization under interfacial conditions with phase transfer catalyst (Aliquat 336) proceeds in trifluoromethanesulfonic anhydride by generation of trifluoromethanesulfonic acid and the protonated hexafluoroacetone (HFA) in situ affording 1,1,1,3,3,3-hexafluoroisopropylidene (6F) PAE with high regioselectivity (4,4’-DPE) and high molecular weight (≈60 kDa). Although first reported in a 1966 US Patent by DuPont using harsh conditions, improved synthetic methods or modern characterization has not been disclosed until now. Despite the presence of the 6F group, known to impart disordered morphology, this simple semi-fluorinated PAE exhibits anomalous crystallinity with polymorphic melting points (Tm) ranging from 230–309 °C, high solubility in common organic solvents, a glass transition (Tg) of 163 °C, and thermo-oxidative stability above 500 °C. Tough optically clear films prepared from solution give transmittance higher than 90% throughout the visible region. Synthesis, mechanistic aspects, and characterization including surface and dielectric properties are discussed.
中文翻译：
教授老聚合物新技巧：通过六氟丙酮水合物和二苯醚的界面聚合改进合成和反常结晶度丢失的半氟化聚芳基醚
报道了六氟丙酮水合物与二苯醚的实用和直接亲电聚合，用于制备半氟化聚芳基醚 (PAE)。在界面条件下使用相转移催化剂 (Aliquat 336) 进行亲电芳族取代 (EAS) 聚合，在三氟甲磺酸酐中通过生成三氟甲磺酸和原位质子化六氟丙酮 (HFA) 进行，得到 1,1,1,3,3,3-六氟异亚丙基(6F) 具有高区域选择性 (4,4'-DPE) 和高分子量 (≈60 kDa) 的 PAE。尽管杜邦公司在 1966 年的美国专利中首次报道了使用苛刻的条件，但直到现在才公开改进的合成方法或现代表征。尽管存在已知赋予无序形态的 6F 基团，T m ) 范围为 230–309 °C，在普通有机溶剂中具有高溶解度，玻璃化转变 ( T g ) 为 163 °C，热氧化稳定性高于 500 °C。由溶液制备的坚韧光学透明薄膜在整个可见光区域的透射率高于 90%。讨论了合成、机械方面和表征，包括表面和介电特性。
更新日期：2022-10-22
中文翻译：
教授老聚合物新技巧：通过六氟丙酮水合物和二苯醚的界面聚合改进合成和反常结晶度丢失的半氟化聚芳基醚
报道了六氟丙酮水合物与二苯醚的实用和直接亲电聚合，用于制备半氟化聚芳基醚 (PAE)。在界面条件下使用相转移催化剂 (Aliquat 336) 进行亲电芳族取代 (EAS) 聚合，在三氟甲磺酸酐中通过生成三氟甲磺酸和原位质子化六氟丙酮 (HFA) 进行，得到 1,1,1,3,3,3-六氟异亚丙基(6F) 具有高区域选择性 (4,4'-DPE) 和高分子量 (≈60 kDa) 的 PAE。尽管杜邦公司在 1966 年的美国专利中首次报道了使用苛刻的条件，但直到现在才公开改进的合成方法或现代表征。尽管存在已知赋予无序形态的 6F 基团，T m ) 范围为 230–309 °C，在普通有机溶剂中具有高溶解度，玻璃化转变 ( T g ) 为 163 °C，热氧化稳定性高于 500 °C。由溶液制备的坚韧光学透明薄膜在整个可见光区域的透射率高于 90%。讨论了合成、机械方面和表征，包括表面和介电特性。
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