Abstract
The polymerization of methyl α-phenylacrylate was carried out in toluene by n-BuLi at −78∼30°C. The yield of the polymer was highest at −45°C and then decreased with increasing the temperature. No polymer was obtained above 0°C. The polymer obtained at −78°C was rich in isotacticity. By increasing the polymerization temperature the fraction of isotactic triads decreased in association with the increases in the fracrions of heterotactic and syndiotactic triads. Above −45°C, the proportion, I:H:S of the polymer obtained was close to 1:2:1, suggesting the random stereoregulation in the propagating step. The random polymer was also obtained by n-BuLi in polar solvent such as THF at low temperature as well as by AIBN. The addition of a small amount of methanol to the polymerization system by n-BuLi in toluene increased the yield, isotacticity, and molecular weight of the polymer, and the maximum values were obtained at CH3OH/n-BuLi=0.83. The polymerization by (iso-Bu)2AlNPh2 in toluene at −78°C gave a syndiotactic polymer in low yield. The reactivity of methyl α-phenylacrylate in anionic polymerization is briefly discussed in comparison with those of some other methyl α-alkylacrylates.
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Yuki, H., Hatada, K., Niinomi, T. et al. Stereospecific Polymerization of Methyl α-Phenylacrylate. Polym J 2, 629–639 (1971). https://doi.org/10.1295/polymj.2.629
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DOI: https://doi.org/10.1295/polymj.2.629