Abstract
The polymerization initiated by 1-phenylethyl radical (PER) and diphenylmethyl radical (DPMR) at 50°C was studied to clarify the causes of deviation in the polymerization rate Rp from Rp∝[C]1/2[M] ([C], initiator concentration and [M], monomer concentration). In the polymerization of styrene initiated by PER, the term defined as primary radical termination (PRT) can not be used to explain the deviation, because of ki≃kp (ki, rate constant of addition of primary radical to monomer and kp, propagation rate constant). Thus, the deviation should be explained by the dependence of polymer-polymer termination (PPT) on chain length. In the polymerization initiated by DPMR, both the PRT term and the dependence of PPT on chain length are necessary to explain the deviation, because of ki≪kp, where ki=37 dm3 mol−1 s−1 (styrene) and 2.5 (methyl methacrylate).
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Ito, K., Omi, M. & Ito, T. Kinetics of Radical Polymerization with Primary Radical Termination. Polym J 14, 115–120 (1982). https://doi.org/10.1295/polymj.14.115
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DOI: https://doi.org/10.1295/polymj.14.115