本研究以逐步聚合反應合成主鏈含有米氏酸結構的高分子，並探討其熱硬化後之聚合物之性質。第一部分直接利用米氏酸為單體與二-氯甲基-苯化合物進行縮合反應，合成帶有米氏酸結構的長鏈高分子，利用紅外光譜儀(FTIR)探討其基本鑑定及結構。所合成高分子可以於270 oC下進行交聯反應，形成網狀交聯的分子，但所合成之高分子其於有機溶劑中之溶解度不佳，導致不易加工，雖改用帶有甲基取代基的二-氯甲基-苯化合物作為單體，所得到的高分子之溶解度也沒因此而有所改善，應該是分子結構過於剛硬以及分子間作用力太強致使此類高分子之溶解度不佳。
第二部分則先合成帶有雙呋喃基的米氏酸化合物作為單體，利用紅外光譜儀(FTIR)、核磁共振光譜儀(NMR)、質譜儀(mass spectrometry)、元素分析儀(EA)鑑定其化學結構，接著將其與雙馬來醯亞胺化合物經由Diels-Alder加成反應進行聚合，形成帶有米氏酸官能基的高分子，此高分子亦可進行熱交聯反應，透過米氏酸結構開環聚合形成網狀高分子，交聯樹脂具有良好的熱性質。

Abstract
This study focuses on the synthesis of polymers possessing Meldrum’s acid (MA) groups at the main chains and the studies on their crosslinking reactions and the properties of the corresponding crosslinked polymers. In the first part, MA is used as a monomer to directly polymerize with 1,4-bis(chloromethyl)benzene or 2,5-bis(chloromethyl)-p-xylene through the dehydrochlorination condensation reaction. The resulting polymers contain MA groups which could perform thermally-induced dimerization, so as to make the polymers thermally crosslinkable. The thermally crosslinking reactions were monitored with a Fourier transform infrared spectroscopy to demonstrate the MA decomposition, formation of active ketene groups, and dimerization of ketene groups take place in the crosslinking process. As a result, crosslinked polymers could be obtained at 270 oC for 1 h. Nevertheless, the solubility of the obtained polymers was poor so as to limit their molecular weights and processing properties. Although 2,5-bis(chloromethyl)-p-xylene was used as a monomer instead, the solubility of the polymer was not therefore improved. It could be referred that intermolecular structure was too rigid and intermolecular forces was so strong to cause such a polymer of poor solubility.
In the second section, a MA monomer possessing two furan groups (MA-FBCB) was synthesized and used as a monomer to polymerize with a bismaleimide compound through Diels-Alder (DA) reaction. The polymer also possessed MA groups at the main chains and was thermally crosslinkable. After being cured at 230 oC for 15 minutes, the corresponding crosslinked polymer was obtained to show good thermal properties.

目錄
第一章 緒論 1
1.1 前言 1
1.2 研究方向 3
第二章 文獻回顧 4
2.1 米氏酸(Meldrum's acid)簡介 4
2.2 烯酮(ketene)的形成 8
2.3 米氏酸與醛基化合物之Knoevenagel condensation 10
2.3.1. Knoevenagel condensation之反應條件 10
2.3.2. Knoevenagel condensation之還原劑 13
2.4 米氏酸與鹵化物之condensation reaction 15
2.5 Diene與dienophile進行Diels-Alder reaction 18
2.6 側鏈帶有米氏酸結構的高分子之合成及應用 20
2.7 米氏酸衍生物及ketene官能基之合成及應用 27
第三章 實驗 32
3.1 實驗藥品 32
3.2 實驗儀器 35
3.3 實驗步驟 37
3.3.1. 單體及高分子合成 37
第四章 結果與討論 42
4.1 利用米氏酸-氯甲基苯聚縮合反應合成主鏈帶有米氏酸結構的可交聯高分子 43
4.1.1. 文獻與本研究差異及比較 43
4.1.2. 使用1,4-bis(chloromethyl)benzene為單體之高分子PMA-BCB之鑑定 45
4.1.3. 使用2,5-bis(chloromethyl)-p-xylene為單體之高分子PMA-BCPX之鑑定 54
4.1.4. PMA-BCB與PMA-BCPX比較 59
4.2 含有可反應性呋喃官能基之米氏酸單體 62
4.2.1. 帶有一個呋喃官能基的米氏酸單體MA-F之鑑定 62
4.2.2. 帶有兩個米氏酸以及兩個呋喃基的單體MA-FBCB之鑑定 66
4.3 透過Diels-Alder加成反應含有米氏酸的高分子PMA-FB之鑑定 73
4.4 含有米氏酸結構的單體及高分子性質討論 82
第五章 結論 85
第六章 參考文獻 86

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