請用此 Handle URI 來引用此文件: http://hdl.handle.net/11455/90550
標題: Lithium Complexes Containing Pyrazolyl-bisphenolate Ligands: Synthesis, Characterization and Application in Ring-Opening Polymerization of Lactides
&#x5421唑雙苯酚基鋰金屬錯合物之合成、鑑定及其對乳酸交酯在開環聚合反應之應用
作者: 鐘婉菁
Wan-Ching Chung
關鍵字: pyrazolyl-bisphenolate
lithium complexes
L-Lactide
ring-opening polymerization
&#x5421唑雙苯酚
鋰金屬錯合物
左旋乳酸交酯
開環聚合反應
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摘要: The pyrazolyl-bisphenolate ligand precursors 38-41 (38=L1CH3;39=L1tBu;40= L2CH3;41=L2tBu) were synthesized via C-N coupling reaction. Treatment of ligand precursors 38-41 with 2.2 equivalent of nBuLi in tetrahydrofuran affords lithium complexes 42-45. All these compounds were characterized by NMR spectroscopy and elemental analysis. The molecular structures of complex 43 and 45 were determined by single-crystal X-ray diffraction techniques. The catalytic activities of complexes 42-45 towards the ring-opening polymerization of L-Lactide in the presence of BnOH were studied. The catalytic activities for ring-opening polymerization of L-Lactide follow the order: 43>45>44>42. The order might result from the different steric hindrance of ligands. Complex 43 exhibited both 'living' and 'immortal' characters. Kinetic study of 43 for ring-opening polymerization were experimented. End group analysis of the polymer was characterized by 1H NMR and ESI mass spectra. The catalytic stereo-selectivities towards the ring-opening polymerization of rac-lactide using complexes 42-45 were described.
本論文經由碳-氮耦合反應,成功製備&#x5421唑雙苯酚配位基前驅物38-41(38=L1CH3;39=L1tBu;40= L2CH3;41=L2tBu),並將配位基前驅物38-41與2.2當量的正丁基鋰金屬試劑在四氫呋喃溶劑中反應,可以成功合成四核雙取代的鋰金屬錯合物42-45。合成之鋰金屬錯合物,利用核磁共振光譜以及元素分析儀數據進行鑑定,經由X光單晶繞射儀確定了鋰金屬錯合物43及45的分子結構。將鋰金屬錯合物42-45在外加苯甲醇的條件下,對左旋乳酸交酯進行開環聚合反應,活性大小為:43>45>44>42,其活性受到配位基立障大小的影響。鋰金屬錯合物43在開環聚合反應上有良好的活性,並有良好的living及Immortal性質。而論文中將錯合物43進行動力學實驗,計算數據得知單體、催化劑濃度以及外加醇類之反應級數。將催化後的高分子聚合物進行電噴霧電離質譜儀以及核磁共振氫光譜分析末端官能基鑑定。論文中亦會探討錯合物43-45對外消旋乳酸交酯進行開環聚合反應之選擇性。
URI: http://hdl.handle.net/11455/90550
文章公開時間: 2018-07-16
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