Title page for etd-0522116-094211


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URN etd-0522116-094211
Author Yu-Qi Liu
Author's Email Address No Public.
Statistics This thesis had been viewed 5560 times. Download 1 times.
Department Chemistry
Year 2015
Semester 2
Degree Master
Type of Document
Language zh-TW.Big5 Chinese
Title I:Strategies for Improving the Catalytic Activity of Aluminum
Complex in the Ring-Opening Polymerization:Bimetallic Effect
II: Strategies for Improving the Catalytic Activity of Aluminum
Complex in the Ring-Opening Polymerization:
Comparative Study of the Ligand Bearing Oxygen and Sulfur
Date of Defense 2016-05-24
Page Count 264
Keyword
  • L-Lactide
  • Caprolactone
  • Aluminum complexes
  • ROP
  • Abstract I:Improving the Catalytic Activity of Aluminum Complex in the Ring-Opening Polymerization:Dinuclear Aluminum Complex Strategy
    A series of mononuclear and dinuclear aluminum complexes was synthesized and their activities for the ring-opening polymerization (ROP) of ε-caprolactone (CL) were investigated. These complexes are (1) ScfAlMe2 (2) m-ScfAl2Me4 (3) p-ScfAl2Me4 (4) KetAlMe2 (5) Ket2Al2Me4 (6) EtOAlMe2 (7) m-EtO2Al2Me4 (8) p-EtO2Al2Me4 (9) ThioAlMe3 (10) m-thioAl2Me6 (11) p-thioAl2Me6 (12) OAlMe2 (13) m-O2Al2Me4 (14) p-O2Al2Me4 (15) SAlMe2 (16) S2Al2Me4 (17) PhAlMe2 (18) PhAl2Me4. According to the catalytic studies, the dinuclear aluminum complexes exhibited higher activities than corresponding mononuclear complexes while using benzyl alcohol as an initiator. The possible reason of the higher activity of dinuclear aluminum complexes may be that one Al atom is regarded as an electron-withdrawing group to influence the other Al atom through the aromatic ligands in the dinuclear aluminum system to enhance the catalytic activity for ROP of CL.
    II:Strategy for Improving the Catalytic Activity of Aluminum Complex in the Ring-Opening Polymerization:Comparative Study of the ligand bearing Oxygen and Sulfur
    A series of Al complexes bearing ligand containing oxygen or sulfur donor atom was synthesized. Their application for the ring-opening polymerization of ε-caprolactone (CL) and L-lactide (LA) was studied. These complexes are (1) LPhOHORAlMe2 (2) LPhSHORAlMe2 (3) LPhOHORAl2Me5 (4) LPhSHORAl2Me5, R = Me、Et、iPr (5) LOHtBu AlMe2 (6) LSHSiMe3 AlMe2 (7) LPhOMe2 AlMe2 (8) LPhSMe2 AlMe2 (9) LfurOH AlMe2 (10) LthioOH AlMe2 (11) LOtBu AlMe2 (12) LStBu AlMe2 (13) LPyS AlMe2. According to the kinetic analysis, it showed that Al complex bearing sulfur-containing ligand showed significant higher polymerization rate than that of Al complexes bearing oxygen-containing ligand (3-5-fold) in CL polymerization. The reason for these higher performances of thio-complexes for the ROP of CL may due to sulfur-containing ligand can decrease the activation energy in the ring-opening polymerization process. In LA polymerization, Al complexes bearing alkyl salicylate ligands have a high catalytic activity than that of Al complexes bearing alkyl thiosalicylate ligands. For other Al complexes bearing ligands without ester group exhibited the opposite phenomenon.
    Advisory Committee
  • Sodio C. N. Hsu - chair
  • Hsing-Yin Chen - co-chair
  • Hsung-Ying Chen - co-chair
  • Michael Yen-Nan Chiang - advisor
  • Files
  • etd-0522116-094211.pdf
  • Indicate in-campus at 3 year and off-campus access at 5 year.
    Date of Submission 2016-06-23

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