Double nucleophilic addition of established Grignard reagent, p-MgBr-C6H4-OCF=CF2, to acenapthenequinone afforded the corresponding diol, which upon treatment with TiCl4 / NEt3 was converted in a single-pot reaction to the bis-trifluorovinyl ether (TFVE) containing ring-cleaved dione and ring-retained acenaphthylene monomers in moderate to good yield. The new high melting (Tm >120 °C) monomers were characterized by common analytical methods in addition to X-ray crystallography. Monomers underwent bulk or solution thermal cyclopolymerization to soluble film-forming perfluorocyclobutyl (PFCB) aromatic ether polymers exhibiting high Tg (~208 °C) and excellent thermal stability. The new semi-fluorinated polymers represent the first example of fused aromatic acenaphthylene enchainment in PFCB aryl ether polymers. The development of polycyclic aromatic hydrocarbon (PAH) cores with enhanced solubility (due to the stereo-random 1,2-disubstituted PFCB aryl ether linkage) should provide much needed insight into established PFCB platforms targeted for tailored passive and active optoelectronic, dielectric, and gas separation membrane materials.
Behzad Farajidizaji, Ketki E. Shelar, Ganesh Narayanan, Karl M. Mukeba, Bruno Donnadieu, Charles U. Pittman, Jr., Andrzej Sygula, Dennis W. Smith, Jr.* J. Polym. Sci. Part A: Polym. Chem., 2019 DOI: 10.1002/pola.29388
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