Facile Estimation of Catalytic Activity and Selectivities in Copolymerization of Propylene Oxide with Carbon Dioxide Mediated by Metal Complexes with Planar Tetradentate Ligand

DOI Web Site 研究データあり 被引用文献21件 参考文献59件
  • Takahiro Ohkawara
    Department of Chemistry and Biotechnology, Graduate School of Engineering, the University of Tokyo 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
  • Kohei Suzuki
    Department of Chemistry and Biotechnology, Graduate School of Engineering, the University of Tokyo 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
  • Koji Nakano
    Department of Organic and Polymer Materials Chemistry, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588, Japan
  • Seiji Mori
    Faculty of Science, Ibaraki University, 2-1-1 Bunkyo, Mito, Ibaraki 310-8512, Japan
  • Kyoko Nozaki
    Department of Chemistry and Biotechnology, Graduate School of Engineering, the University of Tokyo 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

この論文をさがす

説明

Mechanistic studies were conducted to estimate (1) catalytic activity for PPC, (2) PPC/CPC selectivity, and (3) PPC/PPO selectivity for the metal-catalyzed copolymerization of propylene oxide with carbon dioxide [PPC: poly(propylene carbonate); CPC = cyclic propylene carbonate; PPO: poly(propylene oxide)]. Density functional theory (DFT) studies demonstrated that the ΔGcrb – ΔGepx value should be an effective indicator for the catalytic activities [ΔGepx: dissociation energy of ethylene oxide from the epoxide-coordinating metal complex; ΔGcrb: dissociation energy of methyl carbonate from the metal–carbonate complex]. In addition, metal complexes with a subthreshold ΔGepx value were found to show low PPC/CPC selectivity. The PPC/PPO selectivity was related to the ΔGalk – ΔGepx value and steric environment around the metal center (ΔGalk: dissociation energy of alkoxide ligand from the metal center). Based on the mechanistic studies, two metal complexes were designed and applied to the copolymerization to su...

収録刊行物

被引用文献 (21)*注記

もっと見る

参考文献 (59)*注記

もっと見る

関連研究データ

もっと見る

関連プロジェクト

もっと見る

詳細情報 詳細情報について

問題の指摘

ページトップへ