臺灣博碩士論文加值系統

本研究以米氏酸進行聚合反應，推測其聚合反應機制，並探討其熱硬化後之聚合物之性質。第一部分，將米氏酸衍生物摻混等當量之氧代氮代苯并環己烷(benzoxazine)單體，因其帶有三級胺的結構為Lewis bases可將米氏酸活化，使米氏酸開環反應溫度降低，藉由微差掃描卡計儀(DSC), 熱重分析儀(TGA), 紅外光譜儀(FT-IR)與核磁共振光譜儀(NMR)儀器證實其催化效果，並推測其催化反應機制。更進一步，藉由此反應機制，以不同當量米氏酸衍生物(MA-F)改質聚氧代氮代苯并環己烷單體(BPA-FBZ)，然而其產生酯基的鍵結較弱，因此隨著添加的MA-F比例越高其熱穩定性則有較差的表現。
第二部分，將米氏酸衍生物(MA-FBCB)與雙馬來醯亞胺化合物進行Diels-Alder加成反應而聚合得到高分子(MA-FBCB-BMI)，藉由微差掃描卡計儀(DSC), 熱重分析儀(TGA)與紅外光譜儀(FT-IR)鑑定其結構與純度，而此高分子相對於反應物米氏酸單體有更好的溶解度，增加了其後續加工的能力，而經由熱處理後所得到的交聯高分子，具有好的熱穩定性與低介電常數。

This study focuses on Meldrum’s acid (MA) polymerization mechanism as well as the properties of the correspond crosslinked polymers. In the first part, MA derivatives are blended with benzoxazine compound (F-BZ) with tertiary amine structure, which is a Lewis base, to undergo thermolysis at a much lower temperature. By means of DSC, TGA, FT-IR and NMR characterization, we confirmed its catalytic effect and mechanism. Furthermore, by this reaction mechanism, different equivalent MA derivative (MA-F) are applied to modify polybenzoxazine. Results indicate polymers modified with MA-F have poor thermal stability due to the week bonding of ester group.

In the second part, MA monomer with two furan group (MA-FBCB) was synthesized and used to polymerize with a bismaleimide compound through Diels-Alder reaction (DA reaction). The molecular structure was further verified by DSC, TGA, FT-IR. This polymer has better solubility and hence better potential than MA monomer (MA-FBCB). After crosslinking, a material with better thermal behavior and low dielectric constants was obtained.

中文摘要 I
Abstract II
誌謝 III
目錄 V
圖目錄 IX
表目錄 XV
第一章 緒論 1
1-1 前言 1
1-2 米氏酸(Meldrum’s acid)簡介 2
1-3 烯酮(ketene)之簡介 5
1-4 研究方向 8
第二章 文獻回顧 9
2-1米氏酸之縮合反應 9
2-2含烯酮官能基之高分子合成與應用 12
2-3低烯酮生成溫度之催化作用 16
2-4氧代氮代苯并環己烷(benzoxazine) 21
2-4-1氧代氮代苯并環己烷(benzoxazine)簡介 21
2-4-2氧代氮代苯并環己烷(benzoxazine)之催化反應 24
2-4-3氧代氮代苯并環己烷(benzoxazine)之聚合 26
第三章 實驗 31
3-1　實驗藥品 31
3-2　儀器設備 34
3-3　實驗步驟 36
3-3-1含有呋喃官能基的米氏酸單體MA-F之合成 36
3-3-2兩端帶有呋喃官能基的米氏酸單體(MA-FBCB)之合成 37
3-3-3氧代氮代苯并環己烷單體(FBz)之合成 38
3-3-4氧代氮代苯并環己烷單體(BPA-FBz)之合成 39
3-3-5米氏酸高分子(MA-FBCB-BMI)之合成 40
第四章 米氏酸衍生物與氧代氮代苯并環己烷之催化機制研究 41
4-1前言 41
4-2單體結構鑑定 42
4-2-1米氏酸單體MA-F之鑑定 42
4-2-2氧代氮代苯并環己烷單體F-bz之鑑定 45
4-2-3氧代氮代苯并環己烷單體BPA-FBZ之鑑定 48
4-3米氏酸衍生物與氧代氮代苯并環己烷單體(F-bz)摻混 50
4-4米氏酸衍生物(MA-F)與氧代氮代苯并環己烷單體(BPA-FBZ)共聚合反應及其共聚物性質 60
4-4-1 MA-F與BPA-FBZ共聚合反應 60
4-4-2 MA-F與BPA-FBZ共聚合物合成鑑定與其性質研究 65
第五章 具有米氏酸主鏈分子基團之迪爾新-阿爾德(Diels-Alder)高分子 (MA-FBCB-BMI)之性質研究 72
5-1前言 72
5-2米氏酸單體(MA-FBCB)與高分子(MA-FBCB-BMI)之鑑定與其性質 73
5-2-1米氏酸單體(MA-FBCB)合成鑑定 73
5-2-2米氏酸高分子(MA-FBCB-BMI)合成鑑定與其性質 75
5-3米氏酸高分子(MA-FBCB-BMI)之熱固型高分子製備與其性質 81
5-3-1米氏酸高分子(MA-FBCB-BMI)之熱固型高分子製備 81
5-3-2米氏酸高分子(MA-FBCB-BMI)之熱固型高分子鑑定與其性質 84
第六章 結論 90
第七章 參考文獻 91
附錄 95

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