Abstract
Free radical polymerization of captodative substituted methyl 2-methoxyacrylate (MMOA) was carried out in bulk with or without azo initiators at 90–130 °C. At higher temperatures, bimodal molecular weight distribution polymer was obtained by the polymerization of MMOA irrespective of the presence of initiator in contrast to the polymerization at 90 °C where unimodal polymer was produced. In addition, block copolymers were conveniently obtained by heating the comonomers including vinyl acetate and acrylonitrile at 130 °C in the presence of poly(MMOA) without any initiator. These unique reactions were reasonably explained by the cleavage of captodative substituted carbon–carbon single bond at head-to-head structure in polymer chain, which was produced by recombination termination.
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