含吡唑配位基之多核鋁錯合物的合成與在環己內酯開環聚合反應的應用

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姓名

胡宇婷(Yu-Ting Hu) 查詢紙本館藏

畢業系所

化學學系

論文名稱

含吡唑配位基之多核鋁錯合物的合成與在環己內酯開環聚合反應的應用

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摘要(中)

酯類聚合物因其酯基具有可降解性，因此相對於石化塑膠而言更容易被環境分解，但應用於開環聚合反應的金屬催化劑，可能因為金屬外部缺乏配位基保護修飾，而無法有效控制每條聚合物鏈長，因此設計催化劑結構時，可以透過修飾配位基的立體障礙和電子效應，改善催化劑活性並減少副反應，以獲得狹窄分子量分散性，甚至使用複數金屬時，可利用金屬間協同效應並調節金屬中心特性提升催化效能。基於上述原因，本篇研究參考了過去相關文獻，合成一系列含吡唑配位基之多核鋁錯合物，且產物結晶性高，並在取代基上做了不同的修飾，應用於環己內酯開環聚合反應結果顯示，其皆具有高催化活性及狹窄分子量分布

摘要(英)

Polyester is more biodegradable than fossil fuel based plastic because of ester linkages. However, metal catalysts for the cyclic ester ring-opening polymerization infficiently control the length of polymer chains in absence of protecting group on metal center. Ligands can be modified by steric hindrance and electronic effect to improve the catalytic efficiency , prevent side reaction, and obtain narrow polymer dispersity. Moreover, cooperation between multiple metals and adjusting properties of central metal lead growth activity of catalyst. On the basis of above, in spired by related reports, we synthesized a series of multinuclear aluminum complexes bearing pyrazoles and modified their substitute group. The results showed that they are highly active for ring-opening polymerization of ε-caprolactone and yield narrow molecular weight distributions.

關鍵字(中)

★ 開環聚合
★ 吡唑
★ 鋁
★ 催化劑

關鍵字(英)

★ ring-opening polymerization
★ pyrazole
★ aluminium
★ catalyst

論文目次

國立中央大學圖書館學位論文授權書 i
國家圖書館學位論文延後公開申請書 ii
指導教授推薦書 iii
口試委員審定書 iv
中文摘要 v
Abstract vi
謝誌 vii
目錄 viii
圖目錄 x
表目錄 xiii
第一章緒論 1
1-1 前言 1
1-2 單體及聚合物介紹 2
1-3 開環聚合反應 4
1-3-1 開環聚合催化機制 4
1-3-2 聚合物分子量分布度 6
1-3-3 開環聚合副反應：分子內及分子間交酯化 7
1-4 文獻回顧 8
1-4-1 單核鋁金屬催化劑 10
1-4-2 多核鋁金屬催化劑 19
1-5 研究動機 29
第二章實驗內容 30
2-1 使用儀器 30
2-2 器材、試劑與溶劑處理方法 31
2-3 產物合成 33
2-3-1 配位基合成 33
2-3-2 三苯基鋁AlPh3(THF)合成 35
2-3-3 單核&雙核&三核鋁錯合物合成 36
2-4 鋁錯合物再結晶及晶體結構 40
2-5 開環聚合反應 42
第三章結果與討論 43
3-1 單核鋁錯合物之CL開環聚合反應 43
3-2 雙核鋁錯合物之CL開環聚合反應 55
3-3 三核鋁錯合物之CL開環聚合反應 62
3-4 多核鋁錯合物之CL開環聚合活性比較 64
第四章結論 66
參考文獻 67
附錄 71
NMR圖譜 71
GPC圖譜 103
Turnitin電子回條 111

參考文獻

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指導教授

吳國暉(Kuo-Hui Wu)

審核日期

2024-8-20

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