Free Radical Copolymerization of ω-(p-Vinylbenzyl Ether) Macromonomer of Poly(2,6-Dimethyl-1,4- Phenylene Oxide) with Methyl Methacrylate in the Presence of Different Initiators

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The free radical copolymerization of ω-(p-vinylbenzyl ether) macromonomer of poly(2, 6-dimethyl-l&-phenylene oxide) (PPO-VBE, M2, [Mbar]n = 18300 g/mol, [Mbar]w/[Mbar]n = 1.19) with methyl methacrylate (MMA, M1) initiated with dicumyl peroxide, di-tert-butyl peroxide, and 2, 2′-azobisisobutyronitrile (AIBN) was investigated. The determined reactivity ratio of MMA, r1, was 0.71 and 0.72 for the copolymerizations using di-tert-butyl peroxide and respectively dicumyl peroxide. For the copolymerization initiated by AIBN, the r1 was 0.86. No definitive explanation for the difference between the determined reactivity ratios is reached. Speculations are discussed based on the copolymerization kinetic parameters and the possible correlations with the side reactions in which primary radicals derived from initiators may participate, and with the difference between the onset of the micelle formation.