Abstract
It is confirmed from NMR data on the polymers and the initiator that there are two distinct propagation mechanisms of stereospecific polymerization in the methyl methacrylate–9-fluorenyllithium initiator system.Various kinds of tactic poly(methyl methacrylate) were prepared by the use of 9-fluorenyllithium under various compositions of the mixed solvents of toluene–THF and at different polymerization temperatures. Their microtacticities estimated from high resolution nuclear magnetic resonance (NMR) spectroscopy were analysed with the aid of the testing formulae for ultimate and penultimate unit effects in propagation step. From these analyses it was found that the microtacticities were remarkably dependent on the composition of solvents and on temperatures. The dependence on the composition of the solvents appearing in the plots of the testing formulae have been interpreted reasonably well by the introduction of two kinds of propagation mechanisms.NMR spectra of 9-fluorenyllithium and -sodium were also measured. Chemical shifts of protons in these salts varied with the composition of solvents and temperatures. This behavior has been interpreted in terms of two kinds of ion pairs, i.e., solvent-separated ion pairs and contact ion pairs. This difference in the states of the catalyst must influence on the microtacticities of the polymer obtained. It is concluded that the two distinct propagation mechanisms in the stereospecific polymerization must have originated from the two different kinds of catalyst.
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Inoue, Y., Chûjô, R. & Nishioka, A. Polymerization Mechanism in Methyl Methacrylate–9-Fluorenyllithium Initiator System. Polym J 2, 13–21 (1971). https://doi.org/10.1295/polymj.2.13
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DOI: https://doi.org/10.1295/polymj.2.13