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概要 |
Treatment of H[(CH_2)_4O]_nSiR_3, which were prepared by the silane induced polymerization of THF with acyl halides catalyzed by (μ_3:η^2:η^3:η^5-acenaphthylene)Ru_3(CO)_7, provides a novel synthetic ...method for polybutylene oxides bearing terminal ester groups. Various acyl halides such as acetyl chloride, benzoyl bromide, adipoyl chloride, acryloyl chloride, and 2-bromoisobutyryl bromide could be used as the acyl halide component; the reactivity of acyl halides increased in the order RCOBr>RCOCl>RCOF, whereas little difference in reactivity was observed among poly-butylene oxides bearing PhMe_2Si-, Et_3Si-, and EtMe_2Si- moieties. All of the products were completely characterized by IR, ^1H, ^<13>C, H-H, and H-C COSY NMR techniques, revealing that they have one terminal butyl and one terminal acyloxy groups. In the case of the reaction with adipoyl chloride, a polymer having two H[(CH_2)_4O]_n units at both ends of the adipoyl moiety was available. The methodology involving the silane-induced ring-opening polymerization followed by treatment with acyl halides was also applied to the synthesis of polycyclohexene oxide bearing 2-bromoisobutyryl bromide. The polymers bearing isobutyryloxy or acryloyloxy groups could be used as a macroinitiator or macromonomers to produce other functional polymers.続きを見る
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