Paper
Redox polymerization, 4. Kinetics of the polymerization of acrylic acid derivatives initiated by the system cyanoacetic acid/Mn(OCOCH3)3 in dimethylformamide†
Published Jun 1, 1980 · M. Haragopal, V. Mahadevan
Macromolecular Chemistry and Physics
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Abstract
The kinetics of the polymerization of acrylonitrile, methyl methacrylate, and acrylamide initiated by the redox system cyanoacetic acid/manganese triacetate in dimethylformamide solution were investigated in the temperature range of 25 – 40°C. It was found that an initial complexation between the reactants followed by an electron transfer yields radicals. In contrast to acrylamide, acrylonitrile and methyl methacrylate effectively suppress further oxidation of the primary radicals. Exclusively the mutual termination accounts for the kinetics of these polymerizations. Data on the average degrees of the polymerizations support the suggested mechanisms. Rate and equilibrium constants were evaluated and their significance is discussed.
The kinetics of polymerization of acrylic acid derivatives initiated by cyanoacetic acid/manganese triacetate in dimethylformamide solution is primarily driven by mutual termination, with acrylonitrile and methyl methacrylate effectively suppressing further oxidation of primary radicals.
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