Synthesis of perfluoroalkylene-vinylene-arylene copolymers via the Mizoroki-Heck co-polymerization of 1,4-divinylperfluorobutane and 1,6-divinylperfluorohexane with dihalogenated arylene monomers

Abstract

Semi-fluorinated aromatic polymers containing perfluoroalkylene [-(CF2)n-, n = 4, 6], vinylene, and arylene units in their main chains were synthesized via the Mizoroki-Heck co-polymerization of 1,4-divinylperfluorobutane and 1,6-divinylperfluorohexane with arylene monomers. The co-polymerization of 1,4-divinylperfluorobutane and 1,4-diiodobenzene was catalyzed by a ligand-less Pd(OAc)2/Bu4NBr system (“Jeffrey conditions”), while a Herrmann-type palladacycle complex (“Herrmann's catalyst”) effectively catalyzed the co-polymerization of dibrominated arylene monomers (such as 1,4-dibromobenzene). The number-average molecular weights (Mn) and weight-average molecular weights (Mw) values of the synthesized semi-fluorinated aromatic polymers were in the ranges of 2.3 × 103 to 5.4 × 103 and 3.7 × 103 to 1.1 × 104, respectively. These polymers exhibited high thermal stability, as indicated by their 5% weight loss temperatures (Td5% up to 415 °C).