臺灣博碩士論文加值系統

本論文描述具希夫鹼之配位基鈷、鎳及鋅金屬錯合物 1 – 9 之合成，並探討藉由改變配位基上推拉電子及立體效應之取代基對共聚合反應性之影響。所有錯合物均經由元素分析、熔點測定、霍氏紅外線光譜鑑定組成及物理性質，其中錯合物 1-3、6及9經X-光單晶繞射儀鑑定，分別為三核及五核之結構。鎳錯合物1-3 對二氧化碳與環氧環己烷的共聚合反應皆具有良好之催化活性。此外，錯合物 1 亦可成功催化二氧化碳與不同環氧化物單體之共聚合反應，其在二氧化碳與1,2-環氧-4-乙烯基環己烷之共聚合反應中，有優異的聚合物選擇性且對於分子量及其分佈度展現良好的控制性。

A series of novel cobalt, nickel and zinc complexes 1 – 9 supported by NNO-tridentate Schiff base ancillary ligands with various electronic and steric effect of substituents have been synthesized. All of these complexes have been characterized by elemental analysis and FT-IR spectroscopic studies, X-ray diffraction study of complexes 1-3、6 and 9 indicate these complexes are either trinuclear or pentanuclear species. Experimental results demonstrate that nickel complexes 1-3 all show efficient activity for the copolymerization of carbon dioxide and cyclohexene oxide. Additionally, complex 1 is also active catalyst for the copolymerization of carbon dioxide with a variety of epoxides. Among them, complex 1 illustrates a living character with the molecular weight of polymers increased linearly with respect to the gradually enlarged conversion of monomer for the copolymerization of carbon dioxide with 1,2-epoxy-4-vinylcyclohexane.

目錄 iii
表目錄 v
圖目錄 vi
第一章 緒論 1
一、 前言 1
二、 生物可分解材料 3
三、 二氧化碳/環氧化物之共聚合 6
四、 金屬催化劑之設計 27
第二章 實驗部分 29
一、 儀器鑑定 29
二、 藥品與溶劑之處理 33
三、 操作技巧 37
四、 希夫鹼配位基之合成 37
五、 錯合物之合成 41
六、 聚合物之反應 50
第三章 結果與討論 52
一、 含氮側臂希夫鹼配位基及其錯合物之合成方法與光譜研究 52
二、 錯合物之晶體結構解析 54
三、 錯合物之光譜研究 64
四、 CO2/Epoxide 共聚合反應 (Copolymerization) 70
第四章 結論 86
第五章 參考文獻 88
第六章 附錄 92

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