Facile one-pot synthesis and thermal cyclopolymerization of aryl bistrifluorovinyl ether monomers bearing reactive pendant groups

Abstract

A diverse pool of aryl bistrifluorovinyl ether (BTFVE) compounds with reactive pendant groups were prepared in a facile, high yielding three step “one-pot” synthesis from commercial 4-bromo(trifluorovinyloxy)benzene. Monomers were confirmed from ATR–FTIR, 1H, 13C, and 19F NMR, and HRMS analysis. Aryl BTFVE compounds were thermally polymerized to afford perfluorocyclobutyl (PFCB) aryl ether polymers with high number–average molecular weight (Mn) for homopolymers (17,050–27,090) and copolymers with 4,4′-bis(trifluorovinyloxy)biphenyl monomers (27,860–56,500). The PFCB aryl ether homo- and copolymers collectively possess high thermal stability (>299 °C in N2) and are readily solution processable producing optically transparent films. The thermal polymerization was achieved and reactive moieties remained intact, aside from those functionalized with acrylates. In the case with acrylate functionalized polymers, orthogonal polymerization was achieved by first photopolymerizing the acrylates followed by thermal curing of the aryl trifluorovinyl ether endgroups. Preliminary results in this study produced the successful preparation of photodefinable PFCB aryl ether material. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1887–1893, 2010