臺灣博碩士論文加值系統

本篇論文主要分為兩個部分，第一部分為利用親核性取代法合成一具新穎性，包含1,3,5-triazine 結構之氧代氮代苯并環己烷(Benzoxazine)，並利用傅立葉轉換紅外光譜儀(FT-IR) 在不同溫度下針對其單體的開環機制，進行追蹤偵測，其結果顯示該單體開環機制與Benzoxazine/Cyanate ester 混摻系統相似，皆會形成 alkyl isocynarute與diphenyl ether linkage結構，並且高溫固化後的Polybenzoxazine經過性質測試，顯示有高的熱穩定性(空氣下Td5% = 427 oC)，高的玻璃轉移溫度(279 oC)，低的介電常數(Dk = 2.4)等優異的性質，適合發展作為航空、航太、微電子設備等之高溫耐燃性材料。
第二部分為利用可再生資源為雙酚單體(Acetovanillone)為合成之基材，合成出含有巨大基團之磷系聚芳醚碸，並將懸掛在主鏈段上之甲氧官能基去甲基化，成功得到一具有反應性之熱塑型高分子，另與市售三種環氧樹脂(DGEBA、HP7200、CNE)進行硬化增韌改質，得到的環氧樹脂固化物，不僅擁有高的耐熱性質，並保有聚芳醚碸之高穿透度和透明性，對於電子產品封裝製程的改進上提供一優秀的材料與方法以供選擇。

This research is divided into two parts. In the first part, cyanurate-containing benzoxazine (Triazine-BZ) was synthesized by nucleophilic substitution of cyanuric chloride with 4-aminophenol/phenol-based benzoxazine (OH-BZ). The reaction mechanism between benzoxazine and cyanurate moieties was monitored by FTIR. Also, the alkyl isocyanurate and diphenyl ether structures were formed at a high temperature. It suggests that the rearrangement of cyanurate with benzoxazine moiety was carried out. Moreover, the thermosets exhibit excellent thermal properties, thermal stabilities and dielectric properties.
The bio-based phosphinated bisphenol (1) was synthesized by using acetovanillione as the starting material. A novel phosphinated poly(ether sulfone), DPES-OCH3, with methoxy group was prepared for the work. The poly(ether sulfone), DPES-OH, with a phenol pendent group in the repeating unit was synthesized from demethylation of DPES-OCH3 provides phenol linkages as reacting sites for epoxy resins. Subsequently, the curing procedure of DPES-OH with three epoxy resins was performed. Flexible and transparent films of thermosets can be obtained and exhibits great thermal properties.

摘要 i
Abstract ii
總目錄 iii
Scheme 目錄 vi
Figure 目錄 ix
Table 目錄 xiii
PART I 1
第一章 緒論 2
第二章 原理與文獻回顧 3
2.1. 氧代氮代苯并環己烷(Benzoxazine)文獻回顧 3
2.1.1. Benzoxazine發展 3
2.1.2. 氰酸酯與Benzoxazine樹脂共聚機構文獻回顧 8
2.2. 研究動機 21
第三章 實驗 22
3.1. 實驗藥品 22
3.1.1. 化合物 22
3.1.2. 溶劑 23
3.2. 儀器設備 24
3.3. Benzoxazine單體合成規劃 29
3.4. 實驗步驟 30
3.4.1. 單體(1)合成 30
3.4.2. 單體(2)合成 31
3.4.3. 含Benzoxazine單體三步法合成 32
3.4.3.1. 單體(3)合成 32
3.4.3.2. 單體(4)合成 33
3.4.3.3. 單體(5)合成 34
第四章 結構鑑定與分析 35
4.1. 單體(1)光譜鑑定與分析 35
4.1.1. 1H NMR 鑑定 35
4.2. 單體(2)光譜鑑定與分析 36
4.2.1. 1H NMR 鑑定 36
4.3. 單體(3)光譜鑑定與分析 37
4.3.1. 1H NMR 鑑定 37
4.3.2. 微差掃描熱卡計(DSC)分析 38
4.4. 單體(4)光譜鑑定與分析 39
4.4.1. 1H NMR 鑑定 39
4.4.2. 13C NMR 鑑定 41
4.5. 單體(5)光譜鑑定與分析 44
4.5.1. 1H NMR 鑑定 44
4.5.2. 13C NMR 鑑定 46
4.5.3. 微差掃描熱卡計(DSC)分析 49
4.5.4. LC/MASS 光譜鑑定 50
第五章 結果與討論 51
5.1. 三酚單體合成探討 51
5.2. Benzoxazine 合成探討 57
5.3. 固化微結構分析 60
5.4. Polybenzoxazine熱性質探討 64
5.5. 介電性質 69
5.6. 儲存安定性分析 71
第六章 結論 72
PART II 73
第一章 緒論 74
第二章 原理與文獻回顧 75
2.1. 可再生資源簡介 75
2.2. 聚碸高分子簡介 78
2.3. 親核取代反應簡介 79
2.4. 應用於環氧樹脂的增韌改質劑 83
2.5. 新型聚醚碸的合成與功能 86
2.6. 研究動機 91
第三章 實驗 93
3.1. 實驗藥品 93
3.1.1. 化合物 93
3.1.2. 溶劑 94
3.2. 儀器設備 95
3.3. 實驗步驟 101
3.3.1. 單體合成 101
3.3.1.1. 單體(1)合成 101
3.3.1.2. 單體(2)合成 102
3.3.2. 聚合物之合成 103
3.3.2.1. 聚合物DPES-OCH3-1之合成 103
3.3.2.2. 聚合物DPES-OH之合成 104
4.1. 單體(1)、(2)的合成特性 105
4.2. 單體(1)光譜鑑定與分析 107
4.3. 單體(2)結構鑑定與分析 112
第五章 聚合物合成討論與性質分析 117
5.1. 聚合物的合成與特性 117
5.1.1. 聚合物DPES-OCH3-1合成與特性 117
5.1.2. 聚合物DPES-OCH3-2合成與特性 123
5.1.3. 聚合物DPES-OH合成與特性 125
5.2. 聚合物熱性質測試 127
5.3. DPES-OH /環氧樹脂固化物之合成 131
5.3.1. DPES-OH /環氧樹脂薄膜製備條件 131
5.4. 環氧樹脂固化物熱性質測試 134
5.5. 聚合物DPES-epoxy光學穿透度 140
5.6. 接觸角測試 143
第六章 結論 145
第七章 參考文獻 146

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