本論文主要合成出雙牙基PIP鋅、鋁錯化合物 (2a; 2b, 3b, 7b-9b; 2c, 3c) 進行己內酯及乳酸交酯的開環聚合反應，並和本實驗室所開發出之三牙基BTPIP鋅、鋁錯化合物 (2d-4d, 7d, 9d; 2e-6e, 7e, 9e; 3f, 7f, 8f) 及文獻上之四牙基Salophen鋅錯化合物 (2g, 7g) 進行環酯類開環聚合的相關比較，藉由改變中心金屬 (鋅 & 鋁)、中心金屬構型 (四面體 & 平行四邊形)、配位基上修飾之官能基 (推、拉電子基 & 立體阻礙官能基)，討論對聚合速率及聚合控制性影響，其中錯化合物的中心金屬為鋅，構型為四面體，配位基上修飾推電子基及立體阻礙官能基，表現出較佳的聚合效果。

The zinc and aluminum complexes (2a; 2b, 3b, 7b-9b; 2c, 3c) with bidentate PIP ligands had been successfully synthesized that could mediate the ring-opening polymerization of-caprolactone and lactide. Furthermore, comparing the results with zinc and aluminum complexes (2d-4d, 7d, 9d; 2e-6e, 7e, 9e; 3f, 7f, 8f) with tridentate BTPIP ligands from our previous work and zinc complexes (2g, 7g) with tetradentate Salophen ligands from literatures. By means of changing the central metal (Zn & Al), conformation (tetrahedral & square planar) and functional groups in ligand (electron donating groups, electron withdrawing groups and steric groups) to discuss how to affect the rate and controllability in ring-opening polymerization. The complexes with zinc as central metal, with tetrahedral as conformation and with electron donating groups and steric groups in ligand showed great polymerization effect.

摘要 I
Abstract II
謝誌 III
表目錄 VII
圖目錄 VIII
式目錄 XIII
第一章 緒論 1
1-1 塑膠的挑戰 2
1-2 活性聚合反應 3
1-3 開環聚合反應 (Ring-Opening Polymerization) 4
1-3-1 自由基開環聚合 (Radical ring-opening polymerization) 9
1-3-2 陽離子開環聚合 (Cationic ring-opening polymerization) 12
1-3-3 陰離子開環聚合 (Anionic ring-opening polymerization) 13
1-3-4 配位插入開環聚合 (Coordination insertion ring-opening polymerization) 15
1-3-5 開環聚合中的副反應 17
1-4 研究動機 19
第二章 鋅與鋁有機金屬錯合物的合成及鑑定 20
2-1 雙牙基PIP之鋅與鋁有機金屬錯合物的合成及鑑定 21
2-2 三牙基BTPIP之鋅與鋁有機金屬錯合物的合成及鑑定 23
2-3 四牙基Salophen之鋅有機金屬錯合物的合成及鑑定 32
第三章 己內酯開環聚合反應 33
3-1 雙牙基PIP之鋅與鋁有機金屬錯合物進行己內酯的開環聚合反應 34
3-2 錯化合物 3c與甲醇的反應 36
3-3 三牙基BTPIP之鋅與鋁有機金屬錯合物進行己內酯的開環聚合反應 41
3-4 比較四、三及雙牙基之鋅有機金屬錯合物對己內酯開環聚合的影響及總結 45
第四章 L-乳酸交酯的開環聚合反應 50
4-1 雙牙基PIP之鋅與鋁有機金屬錯合物進行L-乳酸交酯的開環聚合反應 51
4-2 三牙基BTPIP之鋅有機金屬錯合物進行L-乳酸交酯的開環聚合反應 52
4-3 比較四牙及雙牙基之鋅有機金屬錯合物對L-乳酸交酯開環聚合的影響及總結 54
第五章 rac-乳酸交酯的開環聚合反應 57
5-1 雙牙基PIP之鋅與鋁有機金屬錯合物進行rac-乳酸交酯的開環聚合反應 58
5-2 三牙基BTPIP 之鋅、鋁有機金屬錯合物進行rac-乳酸交酯的開環聚合反應 59
5-3 比較四牙及雙牙基之鋅有機金屬錯合物對rac-乳酸交酯開環聚合的影響及總結 61
5-4 結論 64
第六章 實驗內容 65
6-1 實驗藥品 66
6-2 實驗儀器 67
6-2-1 核磁共振光譜儀 (Nuclear Magnetic Resonance) 67
6-2-2 凝膠滲透層析儀 (Gel Permeation Chromatography) 68
6-3 實驗部分 68
第七章 附錄 83
7-1 1H NMR及 13C NMR 圖譜 84
7-2 X-ray 晶體數據 104
7-3 參考文獻 217

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