聚氧代氮代苯并環己烷(polybenzoxazine 簡稱PBz)為一新型熱固性材料，可選用不同單體進行分子設計以改變材料之特性，本研究導入呋喃官能基，使其具有狄耳士–阿爾德反應(Diels–Alder reaction簡稱DA reaction)之反應性。
本研究首先合成帶有呋喃(furan)官能基之二胺單體，接著利用此單體二呋喃二胺與雙酚A (Bisphenol A)和三聚甲醛(Paraformaldehyde 簡稱PF) 透過曼尼希(Mannich)縮合反應合成出主鏈型聚氧代氮代苯并環己烷(polybenzoxazine 簡稱PBz)。並以紅外光譜儀(FTIR)以及核磁共振光譜儀(NMR)鑑定其化學結構，以及使用微差掃描卡計(DSC)和熱重損失分析儀(TGA)測定其熱性質，可於 240 ℃ 下進行熱交聯反應，交聯薄膜具有高熱裂解溫度(350 ℃)以及殘碳率(50 %)，顯示出良好之熱穩定性。
接著將呋喃官能化之PBz與雙馬來醯胺(Bismaleimide簡稱BMI)透過狄耳士–阿爾德反應在60 ℃ 下進行高分子交聯，使材料可以在氮氧雜環開環前交聯，加工製備出薄膜。並以紅外光譜儀(FTIR)鑑定其交聯反應結構，以及使用微差掃描卡計(DSC)和熱重損失分析儀(TGA)測定其熱性質。

Polybenzoxazine(PBz), as a novel type of thermosets, exhibits extraordinarily rich molecular design flexibility which could be obtained from cheap raw materials. In this study, Furan groups have been incorporated to polybenzoxazines making the resulting furan-functionalized polybenzoxazines being capable of carring out the Diels–Alder (DA) reaction.
We first synthesized difuranic diamine and then introduced into the synthesis of furanic polybenzoxazine(PBz). The furan-containing main-chain type polybenzoxazine(PBz) precursors were successfully prepared through the Mannich-type polycondensation of bisphenol A, paraformaldehyde, and difuranic diamine. After that, we use FTIR and NMR to characterize the chemical structure of PBz which proves PBz has been successfully prepared. Then thermal analysis was carried out by differential scanning calorimetric (DSC) and thermogravimetric analysis (TGA). The PBz polymer could be crosslinked under 240℃ and show good thermal stability.
Furan functionalized polybenzoxazine could react with bismaleimide (BMI) under 60℃ through Diels–Alder reaction before oxazine ring-opening polymerization and fabricate a freestanding membrane. The DA crosslinking structure was proved by FTIR. By the means of DSC and TGA, the thermal properties are also tested.

摘要 I
Abstract II
致謝 III
目錄 IV
圖目錄 VII
表目錄 XI
第一章 緒論 1
1-1 聚氧代氮代苯并環己烷(polybenzoxazine) 1
1-2 呋喃(furan)與狄耳士–阿爾德反應(Diels–Alder) 3
1-3 研究方向 6
第二章 文獻回顧 7
2-1 聚氧代氮代苯并環己烷(polybenzoxazine) 7
2-1-1 PBz之合成及應用 7
2-1-2 PBz之分子設計 9
2-1-3 主鏈型PBz 15
2-2 呋喃官能基單體 21
2-2-1 呋喃有機單體 21
2-2-2 二呋喃二胺之合成 22
2-3反應性呋喃高分子之應用 25
2-3-1可回收熱固性高分子(Recycling Thermoset Polymers) 25
2-3-2自修復材料(Self-healing & mendable polymer) 28
2-3-3混成材料(Hybrids Materials) 32
第三章 實驗方法 36
3-1實驗藥品 36
3-2 實驗儀器 38
3-3實驗步驟 41
3-3-1二呋喃二胺(DFDA)之合成 41
3-3-2含有呋喃官能基的PBz-DFDA之合成 41
3-3-3含有呋喃官能基的PBz-DFDA/oda共聚合物之合成 42
3-3-4 PBz-DFDA開環聚合交聯膜的製備 42
3-3-5 PBz-DFDA進行Diels-Alder 反應測試 43
3-3-6 PBz-DFDA 狄耳士–阿爾德反應交聯膜的製備 43
第四章 結果與討論 44
4-1二呋喃二胺(DFDA)單體之鑑定 44
4-2含有呋喃官能基的PBz之性質討論 48
4-2-1 PBz-DFDA的性質分析 48
4-2-2 PBz-DFDA開環交聯膜的性質分析 53
4-2-3 含有呋喃官能基的PBz-DFDA/oda共聚合物之鑑定 55
4-2-4 PBz-DFDA/oda共聚合物開環交聯膜的性質分析 59
4-3 PBz-DFDA之DA反應與薄膜性質 63
4-3-1 PBz-DFDA之DA反應測試 63
4-3-2 DA交聯膜之性質討論 63
第五章 結論 69
第六章 參考文獻 70
附錄 77

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