本研究以設計與合成動態醯胺鍵結，並應用於自修復高分子材料與功能性反應型高分子之開發。
第一部份，合成出帶有米氏酸官能基之高分子包括帶有米氏酸的聚氨酯高分子MA_MDI_PEG以及側鏈帶有米氏酸官能基的聚苯乙烯高分子PMAMS。
第二部分，將帶有米氏酸官能基的高分子於高溫下使MA官能基裂解，產生高反應烯酮官能基，迅速與具有龐大側鏈之二級胺反應，合成出具有醯胺鍵結的高分子，再進一步證明因巨大取代基會弱化醯胺鍵結的共振穩定性，使高分子之醯胺鍵結具有動態性質，在相對低溫環境，能進行逆反應。藉此動態鍵結機制，開發功能性反應型高分子材料解決米氏酸衍生物熱裂解溫度偏高的問題。
第三部份，將前一部份證明的醯胺鍵結可逆動態性質，應用在高分子材料，賦予熱固性高分子自我修復能力與二次加工性質，並用儀器測試其自修復效果。

In this study, the dynamic amide bond are applied to develop self-healing thermosetting polymers and functional reactive polymers.
First, two kinds of polymer containing Meldrum’s acid functional group was successfully synthesized. One polymer having urethane structure and Meldrum’s acid functional group was named as MA_MDI_PEG. The other one was named as PMAMS which is the polymer having polystyrene structure with Meldrum’s acid functional group on the side chain .
Meldrum’s acid was decomposed at a high temperature. The highly reactive functional group “ketene" would appear. Use it to react with secondary amine having bulky substituents on the nitrogen atoms. Furthermore, the bulky substituents on the nitrogen atoms of amide bond will weaken the resonance stability of the amide structure, lead to the amide bond having dynamic properties. By this dynamic bond mechanism, the ketene functional group will appear in a relatively low temperature environment. The functional reactive polymer materials were developed to solve the problem that Meldrum’s acid derivatives need high temperature to decompose .
In the last part, reversible dynamic properties of amide bond will be applied to polymer materials and endow thermosetting polymer self-healing property and reprocessing ability.

目錄
摘要...ii
Abstract...iii
目錄...vi
圖目錄...x
表目錄...xvii
第一章 緒論...1
1-1 前言...1
1-2 動態共價化學...3
1-2.1 動態共價化學簡介...3
1-2.2 動態共價鍵結反應條件...6
1-2.3 動態共價鍵結種類...7
1-3 動態共價鍵結在高分子材料中的應用...11
1-3.1 自修復 (self-healing)...11
1-3.2 形狀記憶 (shape-memory)...15
1-3.3 可塑型熱固性樹脂 (Vitrimers)...17
1-4 米氏酸之簡介...18
1-5 研究動機...21
第二章 文獻回顧...22
2-1 動態共價醯胺鍵結...22
2-2 尿素鍵結的可逆動態性質...25
2-3 烯酮官能基...30
2-3.1 烯酮之親核基加成反應...31
2-3.2 烯酮之環加成反應...34
2-4 研究方法...36
第三章 實驗方法...37
3-1 實驗藥品...37
3-2 儀器設備...39
3-3 實驗步驟...42
3-3-1、MA_MDI_PEG 系統...42
3-3-1.1 具米氏酸結構的高分子MA_MDI_PEG製備...42
3-3-1.2 具醯胺官能基的MA_MDI_PEG_amine製備...43
3-3-1.3 具醯胺官能基的MA_MDI_PEG_diamine製備...44
3-3-2、PMAMS系統...45
3-3-2.1 具有米氏酸結構的單體MAMS製備...45
3-3-2.2 具米氏酸結構的高分子PMAMS製備...46
3-3-2.3 具醯胺官能基高分子PMAMS_amine製備...47
3-3-2.4 具醯胺官能基高分子PMAMS_diamine製備...48
3-3-2.5 緻密交聯醯胺鍵結高分子PMAMS_DA_bulk製備...49
3-3-2.6 證明醯胺鍵結動態性之實驗...50
3-3-2.7 具米氏酸高分子之改質...53
3-3-2.8 緻密交聯醯胺鍵結高分子模塊製備...55
第四章 結果與討論...57
4-1 MA_MDI_PEG系統...57
4-1.1 MA_MDI_PEG鑑定...57
4-1.2 MA_MDI_PEG_amine之鑑定...63
4-1.3 MA_MDI_PEG_diamine高分子鑑定...66
4-2 PMAMS 系統...68
4-2.1 單體MAMS鑑定...68
4-2.2 米氏酸結構高分子PMAMS鑑定...72
4-2.3 含醯胺官能基高分子PMAMS_amine鑑定...77
4-2.4 具醯胺官能基高分子PMAMS_Diamine鑑定...81
4-2.5 具醯胺官能基模塊PMAMS_DA_Bulk之鑑定...84
4-2.6 高分子PMAMS_Diamine之醯胺鍵結動態性質證明...87
4-2-7 米氏酸高分子鏈段改質...97
4-2.8 具醯胺鍵結之高分子模塊鑑定...108
4-2.9 醯胺鍵結之高分子模塊自修復檢測...114
第五章 結論...125
第六章 參考文獻...127

 

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