Semi-fluorinated Poly(aryl ether sulfone)s via step-growth polymerization of perfluorocyclohexene with bisphenols

Perfluorocyclohexene (PFCH) undergoes step-growth polymerization and copolymerization with variable sulfone and polyaromatic containing bisphenols in the presence of triethyl amine under mild conditions affording a new class of semi-fluorinated poly(aryl ether sulfone)s. The apparent vinyl addition/elimination mechanism provides regio-selective vinyl versus allylic substituted polymers with reactive 1,2-diaryloxyvinylene linkages in the main chain. Moderate to high molecular weight (ca. 50 kDa) polymers gave tough, creaseable films from solution with excellent transparency, and variable refractive indices ranging from 1.61 to 1.65 (at 589.2 nm). The amorphous sulfone copolymers exhibited glass transition temperatures (T g ) ranging from 122 to 225 °C and thermal stabilities with decomposition temperatures (T d at 5% wt. loss) ranging from 336 to 404 °C in N 2 . Enchained PFCH vinylene ether groups provide competing but controllable branch sites during later stages of polymerization and further serve as effective targets for post-polymerization functionalization or simple thermally induced crosslinking. Semi-fluorinated poly(aryl ether sulfone) thermoplastics and tailored networks are pursued for optical, electronic, and gas separation applications. • Poly(aryl ether sulfone)s via base mediated polymerization of decafluorocyclohexene and commercial bisphenols. • Tough flexible films provide high thermal stability, excellent optical transparency, and variable refractive index. • Step-growth addition/elimination affords reactive vinylene ether enchainment available for post reactions or crosslinking.