A unique stepped multifunctionality of perfluorinated aryl compound and its versatile use in synthesizing grafted polymers with controlled structures and topologies

A unique stepped multifunctionality of perfluorinated aryl compound for the first time was studied by using model reactions between 2,5‐dipentafluorophenyl‐1,3,4‐oxadiazole (FPOx) and mono functional p‐cresol at different reaction conditions. Four distinctively different levels of reactivity were discovered for the para and ortho C? F of FPOx, which could be easily triggered by the reaction temperature in the range of r.t. to 160 °C. C? F of all levels of reactivity could react quantitatively with nucleophiles (such as phenoxide); and by controlling the reaction conditions, the low‐level‐reactivity C? F would not interfere with the reaction of C? F of higher reactivity. Application of this multistepped reactivity of FPOx in quantitative postpolymerization functionalization of polymer was successfully demonstrated. Stoichiometric amount of p‐cresol, with the molar feed ratio of p‐cresol in relative to the repeat unit of the polymer of FPOx and 6F‐BPA in the range of 1–4, could be readily grafted onto the polymer by simply controlling the reaction temperature. FPOx‐based, versatile one‐pot synthesis of high molecular‐weight grafted polymers with well‐controlled structures and topologies were also demonstrated. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011