Synthesis and characterization of new polymethacrylates bearing perfluorocyclobutyl and sulfonyl units

A new methacrylate monomer containing perfluorocyclobutyl and sulfonyl units, p-(2-(p-(benzenesulfonyl)phenoxy)perfluorocyclobutoxy)phenyl methacrylate, was synthesized from commercially available reagents in good yield and this kind of methacrylate can be homopolymerized by free radical polymerization using 2,2′-azobis(isobutyronitrile) as initiator or atom transfer radical polymerization using methyl 2-bromopropionate as initiator and CuBr/PMDETA as catalytic system. The reactivity ratios for BSPPFCBPMA and MMA were found to be r1 = 1.2436 and r2 = 0.8171 determined by Fineman–Ross method, and r1 = 1.2279 and r2 = 0.8023 by Kelen–Tudos method respectively. The resultant polymethacrylates bearing perfluorocyclobutyl and sulfonyl functionalities exhibit excellent thermal stability as evidenced from thermogravimetric analysis and the decomposition temperature rose dramatically with the increasing of molecular weights. Random copolymers of BSPPFCBPMA and methyl methacrylate were obtained by free radical copolymerization and their thermo-stabilities increase while raising the contents of BSPPFCBPMA.