Abstract
Polymerizations of trityl (TMA), diphenylmethyl (DMA) and benzyl (BMA) methacrylates were carried out mainly by n-butyllithium (n-BuLi) and the tacticities of the polymers were studied by NMR spectroscopy. Polymerization of TMA by n-BuLi gave a highly isotactic polymer in toluene as well as in tetrahydrofuran (THF). The polymer obtained in radical polymerization by AIBN catalyst had about 60% isotacticity in triads. From these results the growing-chain-controlled mechanism was proposed to this polymerization. In the polymerization of DMA by n-BuLi a highly isotactic polymer was obtained in toluene at lower temperatures and a highly syndiotactic one in THF. The radical polymerization gave a predominantly syndiotactic polymer. Temperature dependence of the NMR signal-width of the isotactic polymer indicates that the conformational arrangement of the polymer chain in solution is much rigid up to a fairly higher temperature. These results suggest that the growing-chain-controlled mechanism may contribute to some extent to the stereoregulation of DMA in toluene. BMA behaved very similarly to methyl methacrylate in the polymerization by n-BuLi. Probably the same polymerization mechanisms can be applied for both monomers. Polymerization of TMA, DMA and BMA by phenylmagnesium bromide or diethylaluminum diphenylamide was also investigated.
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Yuki, H., Hatada, K., Niinomi, T. et al. Stereospecific Polymerization of Trityl, Diphenylmethyl and Benzyl Methacrylates. Polym J 1, 36–45 (1970). https://doi.org/10.1295/polymj.1.36
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DOI: https://doi.org/10.1295/polymj.1.36
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