單雙咪唑苯酚基鋁錯合物之合成、鑑定及對環己內酯開環聚合反應之應用

Aluminium Complexes Containing Imidazolylphenolate or Bis-imidazolylphenolate ligands: Synthesis，Characterization and Application in Ring-Opening Polymerization of ε-Caprolactone

龍之雋

咪唑苯酚 ； 鋁錯合物 ； 開環聚合反應 ； imidazolylphenolate ； aluminium complexes ； polymerization

中興大學化學系所學位論文

2016年

碩士

陳繼添

繁體中文

本論文利用咪唑甲基甲醛苯酚與雙甲醛甲基苯酚，藉由三種不同從醛基合成咪唑的配方，合成出一系列甲基咪唑苯酚R1-R3及2R1-2R3，[R1 = HOPhMeImph；R2 = HOPhMeImH；R3 = HOPhMeImMe與甲基雙咪唑苯酚2R1 = HOPhMebis-Imph ；2R2 = HOPhMebis-ImH；2R3 = HOPhMebis-ImMe]。以1當量的甲基咪唑苯酚配位基前驅物R1-R3與2R2-2R3和1當量的三甲基鋁試劑反應可以成功合成出鋁錯合物14-18。鋁錯合物14及16-18對環己內酯的開環聚合反應在外加9-蒽甲醇的條件下，皆表現出良好的催化活性與狹窄的PDI值分佈，其中鋁錯合物16在100倍與200倍的單體開環聚合反應有良好的控制，但在300倍單體的反應不佳，而鋁錯合物16及17 在不外加醇類的情形下對環己內酯的開環聚合反應有良好的活性，但其做出聚合物呈黏稠狀其分子量與PDI的分佈都偏高。

A series of imidazole-phenolate and bis-imidazole-phenolate ligand precursors R1-R3 and 2R1-2R3，[R1 = HOPhMeImph；R2 = HOPhMeImH；R3 = HOPhMeImMe ；2R1 = HOPhMebis-Imph ；2R2 = HOPhMebis-ImH；2R3 = HOPhMebis-ImMe] have been discovered. These ligand precursors can react with trimethyl aluminum to make complexes 14-18. Complexes 14-18 show good activity and low PDI toward ε-caprolactone ring-opening polymerization with 9-AnOH. The complex 16 shows good activity toward 100 and 200-fold concentrationε-caprolactone，but it shows less control when the concentration of ε-caprolactone reaches 300-fold. The complex 16 and 17 show activity towardε-caprolactone ring-opening polymerization without adding alcohol，while the molecular weight and PDI are much higher than respect.

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