鈉、鉀之四牙配體錯合物用於內酯之開環聚合反應

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姓名

吳成修(Chang-Siou Wu) 查詢紙本館藏

畢業系所

化學學系

論文名稱

鈉、鉀之四牙配體錯合物用於內酯之開環聚合反應
(Sodium and potassium tetradentate ligand complexes are used in the ring-opening polymerization of lactones)

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至系統瀏覽論文 (2028-7-26以後開放)

摘要(中)

本研究成功合成出具有四個配位點的氨基配位基，並且與叔丁醇鈉和叔丁醇鉀反應，合成出錯合物Na-1-tBuOH、Na-1、Na-1-nBuOH、K-1-tBuOH、K-2。這些催化劑對ε-Caprolactone、L-Lactide及γ-Valerolactone都具有相當高的活性。K-1-tBuOH對ε-Caprolactone單體的催化中，在分子數比為單體:催化劑:起始劑=100:1:1的催化條件下，4分鐘的反應時間內可達到96%的轉換率，且有優異的分子量分布度(PDI=1.13)。Na-1-tBuOH活性較略低於K-1-tBuOH，於單體:催化劑:起始劑=100:1:1條件下，反應16分鐘可達98%轉換率，但分子量分布度較鉀略有提升 (PDI=1.09)。因此，此類催化劑對於開環聚合反應的應用具有相當高的潛力。

摘要(英)

This study successfully synthesized amino ligands with four coordination sites and reacted them with sodium tert-butoxide and potassium tert-butoxide, resulting in the formation of the corresponding coordination complexes Na-1-tBuOH, Na-1,Na-1-nBuOH,Na-2-tBuOH, K-1-tBuOH, and K-2. These five catalysts exhibited high activity towards ε-Caprolactone, L-Lactide, and γ-Valerolactone. Among them, K-1-tBuOH showed excellent catalytic activity for ε-Caprolactone monomer under the conditions of monomer:catalyst:initiator molar ratio of 100:1:1 and a reaction time of 4 minutes, achieving a conversion rate of 96% with a remarkable molecular weight distribution (PDI=1.13). Na-1-tBuOH exhibited slightly lower activity than K-1-tBuOH, reaching a conversion rate of 98% after 16 minutes of reaction time under the same conditions, but with a slightly improved molecular weight distribution (PDI=1.09) compared to potassium. Therefore, these types of catalysts show great potential for applications in ring-opening polymerization reactions.

關鍵字(中)

★ 開環聚合反應
★ 內酯

關鍵字(英)

★ ring-opening polymerization
★ lactone

論文目次

摘要 i
Abstract ii
謝誌 iii
目錄 v
圖目錄 viii
表目錄 xv
第一章簡介 1
1-1 聚合物的背景以及發展 2
1-2 開環聚合反應之介紹 3
1-3 催化劑的歷史背景 4
1-4 研究動機 35
第二章鈉催化劑進行開環聚合反應 37
2-1 鈉催化劑的合成流程 38
2-1-1合成配位基 38
2-1-2合成鈉催化劑 44
2-1-3 催化反應之實驗步驟 47
2-2 鈉催化劑的開環聚合結果 48
第三章鉀催化劑進行開環聚合反應 57
3-1 鉀催化劑的合成流程 58
3-1-1 合成鉀催化劑 58
3-2鉀催化劑的開環聚合結果 61
第四章理論計算之結果 70
4-1 理論計算方法及設定 71
4-1-1 前言 71
4-1-2 計算方法及設定 71
4-2 理論計算之結果 72
第五章合成之詳細步驟 84
5-1化合物合成之詳細步驟 85
5-1-1 合成3,5-二叔丁基-2-羥基苯甲醛 85
5-1-2 3,5-二叔丁基-2-羥基苯甲醛甲基化的合成步驟 85
5-1-3 ligand-1的合成步驟 86
5-1-4 ligand-2的合成步驟 87
5-1-5 Na-1-tBuOH的合成步驟 88
5-1-6 Na-1-nBuOH的合成步驟 88
5-1-7 Na-2的合成步驟 89
5-1-8 K-1-tBuOH的合成步驟 90
5-1-9 K-1-nBuOH的合成步驟 90
5-1-10 K-2的合成步驟 91
5-2 化合物合成之藥品供應商 93
5-3 鑑定儀器 95
結論 96
參考文獻 98
附錄 101
附錄一結構之NMR圖譜 101
附錄二聚合物之GPC圖譜 111
附錄三開環聚合反應轉換率之NMR圖譜 135
附錄四理論計算之設定 150

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指導教授

吳國暉

審核日期

2023-8-15

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