本研究利用Hydrosilylation合成帶有米氏酸結構之反應性聚矽氧烷高分子，具可進行熱致自交聯與進行改質反應之特性。首先，以具雙苯乙烯官能基之米氏酸衍生物MA-VB為單體與雙端帶有矽氫官能基的矽氧烷化合物進行矽氫加成聚合反應，獲得帶有米氏酸團基的聚矽氧烷高分子，利用紅外光譜儀(FT-IR)與核磁共振光譜儀(NMR)鑑定證實結構，所合成的高分子具有良好的有機溶劑溶解性，有利於後續之反應以及加工使用，且可於240oC下交聯反應形成具彈性可透光薄膜。接著，以PTSA作為催化劑，使帶有米氏酸結構之聚矽氧烷高分子在130oC即可開環，並導入具有防燃效果之單體DOPO與米式酸官能基進行親核加成反應，利用紅外光譜儀(FT-IR)、核磁共振光譜儀(NMR)鑑定結構，證明米氏酸親核反應之可行性。最後，以具苯乙烯官能基及呋喃之米氏酸衍生物MA-FV為單體對雙端帶有矽氫官能基的矽氧烷化合物進行封端，利用紅外光譜儀(FT-IR)與核磁共振光譜儀(NMR)進行結構鑑定，所合成的分子具良好的有機溶劑溶解性，利於後續之反應以及加工使用，且可於240oC下交聯形成網狀結構具彈性塊膜。

The study focuses on a Meldrum's acid (MA)-containing polysiloxanes synthesized by means of hydrosilylation reactions and its property of thermal self-crosslinking. In the first section, MA derivatives (MA-VB) that contains two styrene groups has been used to react with hydride-terminated PDMS. The resulting polymers (MA-PDMS) structure was confirmed by FT-IR, 1H-NMR and 29Si-NMR. It has good solubility in organic solvent and can undergo thermal-induced dimerization at 240oC to form a flexible light-permeable film. Next, taken p-Toluenesulfonic acid (PTSA) as a catalyst, MA groups in MA-PDMS polymer chain was reacted with the nucleophilic DOPO molecule. The feasibility of MA groups proceed with nucleophilic addition was verified by FT-IR, 1H-NMR, 29Si-NMR and 31P-NMR. In the second section, a furan-terminated MA-containing siloxanes (MA-DMS-MA) was synthesized via hydrosilylation. The resulting molecule also performs good solubility in organic solvent and can be cured at 240oC to form a flexible film. The product has the potential to further develop its application in self-healing material by Diels-Alder reaction.

摘要 I
Abstract II
誌謝 III
目錄 IV
圖目錄 VII
表目錄 XII
第一章 緒論 1
1-1 前言 1
1-2 聚二甲基矽氧烷(Polydimethylsiloxane,PDMS)簡介 2
1-2-1 PDMS結構與特性 2
1-2-2 PDMS做為增韌劑 3
1-2-3 形成網狀交聯之PDMS 4
1-3 研究方向 7
第二章 文獻回顧 8
2-1 帶可交聯與具反應性官能基之聚二甲基矽氧烷 8
2-2 帶米氏酸衍生物及Ketene官能基之高分子 17
2-3 研究動機 24
第三章 實驗 25
3-1 實驗藥品 25
3-2 實驗儀器 28
3-3 實驗步驟 30
3-3-1 以Hydrosilylation反應合成帶有米氏酸之聚矽氧烷高分子MA-PDMS： 30
3-3-2 熱交聯反應帶米氏酸之高分子MA-PDMS 33
3-3-3 帶米氏酸官能基高分子反應性 35
3-3-4 以Hydrosilylation反應合成含有米氏酸及呋喃官能基封端之MA-DMS-MA： 37
3-3-5 熱交聯反應含米氏酸及呋喃官能基峰端之MA-DMS-MA 40
第四章 結果與討論 41
4-1 以Hydrosilylation反應合成帶有米氏酸之聚矽氧烷高分子MA-PDMS 41
4-1-1 聚矽氧烷高分子MA-PDMS-8鑑定 41
4-1-2 以短鏈矽氧烷合成之MA-PDMS結構鑑定 48
4-1-3 帶米氏酸之聚矽氧烷MA-PDMS性質比較 52
4-2 熱交聯反應含米氏酸之聚矽氧烷高分子MA-PDMS 56
4-2-1 C-MA-PDMS-8(C1)塊膜 56
4-2-2 C-MA-PDMS-8膜 (改變步驟與升溫條件) (C2) 59
4-2-3 短鏈矽氧烷合成之MA-PDMS熱交聯 63
4-3 帶米氏酸官能基高分子反應性 68
4-3-1 高分子米氏酸開環測試 68
4-3-2 MA-PDMS-8之親核加成反應 71
4-3-3 親核加成後產物之後續加工 78
4-4 以Hydrosilylation反應合成含有米氏酸及呋喃官能基封端之MA-DMS-MA鑑定 81
4-5 熱交聯反應含米氏酸及呋喃官能基封端之MA-DMS-MA 88
第五章 結論 92
第六章 參考文獻 93

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