遷移金属触媒重合の新展開　ＩＩ　　遷移金属／キラル配位子を触媒とするＮ‐置換マレイミドの不斉アニオン重合

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タイトル別名
  • Recent Developments in Toransition Metal-Catalyzed Polymerization. II. Asymmetric Anionic Polymerizations of N-Substituted Maleimides with Transition Metal/Chiral Ligand Complexes.
  • センイ キンゾク キラル ハイイシ オ ショクバイ ト スル N チカン マレイミド ノ フセイ アニオン ジュウゴウ

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Asymmetric anionic homopolymerizations of N-substituted maleimides (RMI) (R=cyclohexyl (CHMI), phenyl (PhMI), 1-naphthyl (1-NMI), α-methylbenzylmaleimide (MBZMI)) were carried out using complexes of organometal compounds (alkyllithium, diethylzinc (Et2Zn)) with chiral ligands to obtain optically active polymers. The polymers prepared with Et2Zn-bisoxazoline derivatives showed higher specific rotations ([α] 435-155.3° to+762.3°) and had higher stereoregularity than those synthesized with alkyllithium/chiral ligand complexes. When asymmetric anionic polymerizations of chiral N-α-methylbenzylmaleimide ((R) -MBZMI, (S) -MBZMI) were carried out with chiral ligand/organometal complexes, chiroptical properties of polymers were strongly affected by the chirality of N-substituent and chiral ligand. The polymerization of (S) -MBZMI by Et2Zn/Sp at-35°C for 144 h produced poly [ (S) -MBZMI] with a relatively high specific rotation ([α] 435=+466.2°). THF-insoluble parts of the poly [ (S) -MBZMI] showed the highest specific rotation ([α] 435=+551.7°). According to the exciton chirality method, relationships between specific rotation and configuration of poly (1-NMI) were found to be as follows: (+) -poly (1-NMI) contains more (S, S) -than (R, R) -configuration and (-) -poly (1-NMI) contains more (R, R) -than (S, S) -configuration. The chiroptical properties of poly (RMI) could be attributed to threo-diisotactic structures, which arises from the excess of chiral stereogenic centers (S, S) or (R, R) and a partial helical conformation.

収録刊行物

  • 高分子論文集

    高分子論文集 59 (6), 287-297, 2002

    公益社団法人 高分子学会

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