Polyfluorinated mercaptoalcohol as a H-bond modifier of poly(2,3,4,5,6-pentafluorostyrene) (PPFS) enhancing miscibility of hydroxylated-PPFS with various acceptor polymers

Novel strong hydrogen-bond donor hydroxylated-poly(2,3,4,5,6-pentafluorostyrene) (PPFSOH) copolymers were synthesized via a versatile and chemoselective thiol-para-fluoro coupling using an unprotected bis(trifluoromethyl)mercaptoalcohol as modifier. Their ability to form miscible blends or interpolymer complexes through H-bond with three different partners (poly(4-vinyl pyridine) (P4VP), poly(ethylene oxide) (PEO) and poly(butyl acrylate) (PBA)) is presented, and compared with the cases of PPFS-based copolymers modified with hydrogenated mercaptoalcohols bearing either one or two hydroxyl groups. For all three tested complementary partners, the extent of H-bond interactions and thus miscibility are enhanced with PPFSOH, as revealed by FTIR, X-ray photoelectron spectroscopy, Differential scanning calorimetry and Atomic force microscopy. This work highlights the tremendous impact of the H-bond donation of the OH interacting groups imparted by the peculiar chemical structure of the grafted mercaptoalcohol, as predicted by comparing the relevant H-bond parameters of model molecules.