臺灣博碩士論文加值系統

本論文合成一系列之錯合物1-5及6-7 ([(L1-H)Li]2 (1)、[(L1-H)Li(THF)]2 (2)、[(L1-H)Li(BnOH)]2 (3) 、[L1Zn]2 (4)、 [L1AlOBn]2 (5) 、L2MgBu (6)及L2ZnEt (7))，其中L1-H2為O,O,O-三牙之雙酚配位基而L2-H為N,N,N- Schiff base形式之三牙配位基。對於錯合物1-3、5、6及7之晶體結構作詳細解析。上述錯合物1-7對於左旋乳酸交酯或環己內酯，於不外加或外加BnOH下，進行開環聚合反應皆具有良好活性，所合成之聚合物分子量可控制且分子量分佈度也可以維持在很狹窄的範圍。根據錯合物2與3之晶體結構可以間接證明左旋乳酸交酯之開環聚合反應機構。以錯合物7於外加BnOH下進行動力學研究得知其速率反應式為-d[LA]/dt = k [LA]1 [7]2，針對單體為一級反應而對於催化劑濃度為二級反應。

A family of metal complexes of the type ([(L1-H)Li]2 (1), [(L1-H)Li(THF)]2 (2), [(L1-H)Li(BnOH)]2 (3), [L1Zn]2 (4), [L1AlOBn]2 (5), L2MgBu (6) and L2ZnEt (7)), where L1-H2 = O,O,O-tridentate bis(phenolate) ligand and L2-H = N,N,N-anilido-aldimine ligand, has been synthesized and characterized, including a structural determination of complexes 1, 2, 3, 5, 6 and 7. Their suitability for initiating the ring-opening polymerization (ROP) of L-lactide (LA) and ε-caprolactone (CL) has been investigated in the presence or absence of benzyl alcohol (BnOH). All the metal complexes have shown efficient and controlled activity toward the ring-opening polymerization of cyclicesters as shown by the linear relationship between the percentage conversion and the number-average molecular weight in short period of time. In the anilido–aldimine system, the activity of magnesium complex is higher than that of zinc complex, which is probably due to the better Lewis acidity and more oxophilic nature of magnesium metal. And for bis(phenolate) system, the activity of lithium complex is investigated for ROP of lactide where as aluminium and zinc complexes used for ROP of caprolactone. The polymerization kinetics using complex 7 in the presence of BnOH as an initiator was also studied, and the experimental results reveal that the rate of reaction is first-order dependence on monomer and second-order dependency on catalyst 7 concentration. On the basis of literature report, polymerization results and crystal structure of 2 and 3, a mechanism for ROP of lactide has been proposed.

目 錄

第一章 緒論 1
一、前言 1
二、含O配位基及其錯合物於環酯類開環聚合反應之應用 9
三、含N配位基及其錯合物於環酯類開環聚合反應之應用 18
四、研究目的 25
第二章 實驗部份 27
一、鑑定儀器 27
二、溶劑、分子篩及藥品處理 29
三、操作技巧 31
四、配位基之合成 34
五、錯合物之合成 36
六、聚合物之合成 43
第三章 結果與討論 46
一、錯合物1-7之合成與光譜研究 46
二、錯合物1-3及5 -7之晶體結構解析 52
三、開環聚合反應 (Ring-Opening Polymerization) 58
四、錯合物3凝固點下降與變溫NMR實驗之探討 79
五、錯合物3對於左旋乳酸交酯開環聚合反應之機構探討 83
六、錯合物7對左旋乳酸交酯開環聚合反應之動力學探討 85
七、錯合物7與BnOH反應之NMR研究 88
第四章 結論 93
第五章 參考文獻 94
第六章 附錄 99
一、錯合物1晶體資料 99
二、錯合物2晶體資料 113
三、錯合物3晶體資料 124
四、錯合物5晶體資料 136
五、錯合物6晶體資料 147
六、錯合物7晶體資料 156

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