Abstract
Anionic polymerization of MMA in THF was studied by a capillary flow method with the dianion of α-methylstyrene tetramer and sodium naphthalene as initiators. From the analysis of the methanol formed, it was found that both the initiation and propagation reactions proceed without side reaction at −78°C. However, at ca. −65°C, a certain amount of initiator is consumed by carbonyl attack in the initiation step though no side reaction is observed in the propagation step. At room temperature, the carbonyl attack is found in both steps and the polymerization stops at a certain degree of polymerization. The apparent propagation rate constants were determined at −78°C and ca. −65°C. They increase with rising temperature and become too high to be determined at room temperature. The dependence of the rate constants on the propagating anion concentration revealed that the contribution of free ion to the propagation is relatively small and that the propagation rate constant of ion pair is about 1×102 l mol−1 sec−1 at these low temperatures. These data are compared with the rates of homopolymerization of styrene and the reactivities of the propagating species of the two monomers are discussed.
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Mita, I., Watabe, Y., Akatsu, T. et al. Anionic Polymerization of Methyl Methacrylate in Tetrahydrofuran. Polym J 4, 271–278 (1973). https://doi.org/10.1295/polymj.4.271
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DOI: https://doi.org/10.1295/polymj.4.271