Abstract
Dendritic polyarylether 2-bromoisobutyrates with different generations (Gn-Br, n = 1–3) were prepared by reaction of the Fréchet-type hydroxyl-terminated polyarylether with 2-bromoisobutyryl bromide and triethylamine. Gn-Br as a macroinitiator for the controlled free-radical polymerization of N-phenylmaleimide (PhMI, M1) and styrene (St, M2) was investigated. The copolymerization carried out in anisole with CuBr/bpy catalyst afforded polymers with well-defined molecular weights and low polydispersities (1.12 < Mw/Mn < 1.35). When the molar fraction of PhMI was 0.50, the apparent activation enthalpy of copolymerization was 38.2 kJ/mol. The effects of monomer feed on the apparent activation enthalpy and copolymer composition were also studied. The monomer reactivity ratios were determined to be r1 = 0.0325 and r2 = 0.0524 according to the Kelen–Tüdős method. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3960–3966, 2001
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