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Stereospecific polymerization of benzyl vinyl ether by BF3·OEt2
Authors:Heimei Yuki  Koichi Hatada  Koji Ota  Ikuya Kinoshita  Shunsuke Murahashi  Katsuhiro Ono  Yoshiyuki Ito
Abstract:Polymerization of benzyl vinyl ether was carried out by BF3·OEt2, and the effects of polymerization conditions on the stereoregularity of the polymer were studied by NMR analysis. The polymerization at ?78°C in toluene gave a highly isotactic polymer. The isotacticity of the polymer was independent of the catalyst concentration but increased with a decrease in the initial monomer concentration and decreased slightly on raising the reaction temperature. When the polymerizations were carried out in toluene—nitroethane mixtures, a gradual decrease in the isotacticity and a rapid decrease in the molecular weight of the polymer were observed with increasing nitroethane in the solvent. The molecular weight of the polymer was almost constant, regardless of the catalyst concentration, and increased with increasing initial monomer concentration and decreasing polymerization temperature. When the polymerization was performed in toluene at ?78°C with a small amount of water or benzyl alcohol, a linear relationship was found between the reciprocal DP of the polymer and water or benzylalcohol concentration. The mechanisms of the initiation reaction and the stereoregulation in the polymerization were also discussed.
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