臺灣博碩士論文加值系統

[Part I]
本實驗以 2,6-di-tert-butyl-4-methoxyphenol 及3-tert-butyl-4-hydroxy-anisole為原料，經由四步驟合成四系列二胺單體。
接著將二胺單體與市售二酸酐以熱閉環法製備聚醚醯亞胺。
S-series擁有柔軟的核心，因此擁有較佳的有機溶解度，而F-series的核心較為剛硬，因此擁有較優異的玻璃轉移溫度，且導入雙官能第三丁基會使其醚鍵轉動不易，主鏈剛硬性提升，玻璃轉移溫度因而增加。而導入雙官能第三丁基之聚醯亞胺，因增加其立體障礙，自由體積因而增加，因此其溶解度較佳，同時，自由體積增加，使介電常數較低，其最低可達2.56。
 
[Part II]
本實驗以1,4-丁二醇二缩水甘油醚在二氧化碳(CO2)環境下形成環碳酸酯(Cyclic Carbonates)，再與胺基反應形成末端具有胺基之前驅物，接著再與環氧樹脂反應即可得到具有親水核心鏈段與疏水末端環氧鏈端之界面活性劑(C-4 Oxyalkylene Epoxy)。
將合成之C-4 Oxyalkylene Epoxy添加至環氧樹脂與水中可使環氧樹脂水性化，且添加 3 Wt % 即可達到最小粒徑，目前此概念已由長春人造樹脂集團開發當中。

[Part I]Synthesis, characterization and application of low dielectric Polyetherimide
Four novel aromatic diamines (S-T-NH2, F-T-NH2, S-DT-NH2, and F-DT-NH2) were successfully synthesized through four steps from 3-tert-butyl-4-hydroxyl-anisole.
Two series of polyimides (S and F-series polyimide) were prepared based the four dimaines and three commercial dianhydride (PMDA, ODPA, and 6FDA).
S-polyimides are soluble in common organic solvents because of the non-coplanar conformation of diphenylsulfone (ph-SO2-ph) linkage that retards the stacking of polyimide chains. On the other hand, F-polyimides has a better glass transition temperature due to the more coplanar conformation of perfluorobiphenyl linkage. The introduction of di-tert-butyl groups to increase the free volume, and thus improved the dielectric properties. Polyimides with dielectric constant as low as 2.56 U and dissipation factor as low as 4 mU can be obtained. 

[Part II] Surfactants for epoxy/water emulsion
A gemini surfactant (C-4-Oxyalkylene-Epoxy) with a core of hydroxyl urethane was successfully prepared through three steps from 1,4-butanediol diglycidyl ether.
An emulsion of bisphenol A-type epoxy in water can be obtained using 3 wt% C-4-Oxyalkylene-Epoxy as a surfactant. The particle size of the emulsion is 760 nm, and does not precipitate during storage. After curing with a water-soluble hardener, epoxy thermosets with adhesion 5B can be achieved.

Part I 低介電聚醚醯亞胺
第一章 緒論 1
第二章 文獻回顧 2
2.1聚醯亞胺(Polyimide,PI)簡介 2
2.2低介電聚醯亞胺 5
2.3 主鏈結構 8
2.3.1 聚醚結構 8
2.3.2 十氟結構 10
2.3.3 砜結構 11
2.4 側鏈基團 12
2.5 研究動機 14
第三章 實驗 15
3.1 實驗藥品 15
3.1.1 化合物 15
3.1.2 溶劑 16
3.2 儀器設備 17
3.3. 實驗規劃 19
3.4單體合成步驟 22
3.4.1 單體 T-OCH3 的合成 22
3.4.2單體 T-OH 的合成 22
3.4.3 單體 S-T -NO2 的合成 23
3.4.4 單體 S-T-NH2 的合成 23
3.4.5 單體 F-T-NO2 的合成 24
3.4.6 單體 F-T-NH2 的合成 24
3.4.7 單體 DT-OCH3 的合成 25
3.4.8 單體 DT-OH 的合成 25
3.4.9 單體 S-DT -NO2 的合成 26
3.4.10 單體 S-DT-NH2 的合成 26
3.4.11 單體 F-DT-NO2 的合成 27
3.4.12 單體 F-DT-NH2的合成 27
3.5 高分子合成步驟 28
第四章 結構鑑定與分析 30
4.1 單體T-OCH3光譜鑑定與分析 30
4.1.1 1H-NMR 鑑定 30
4.1.2 13C-NMR 鑑定 32
4.1.3 高解析質譜儀鑑定 34
4.1.4 示差掃瞄熱分析儀(DSC)分析 35
4.2 單體T-OH光譜鑑定與分析 36
4.2.1 1H-NMR 鑑定 36
4.2.2 13C-NMR 鑑定 38
4.2.3 高解析質譜儀鑑定 40
4.2.4 示差掃瞄熱分析儀(DSC)分析 41
4.3 單體S-T-NO2光譜鑑定與分析 42
4.3.1 1H-NMR 鑑定 42
4.3.2 13C-NMR 鑑定 44
4.3.3 高解析質譜儀鑑定 46
4.3.4 示差掃瞄熱分析儀(DSC)分析 47
4.4 單體S-T-NH2光譜鑑定與分析 48
4.4.1 1H-NMR 鑑定 48
4.4.2 13C-NMR 鑑定 50
4.4.3 高解析質譜儀鑑定 52
4.4.4 示差掃瞄熱分析儀(DSC)分析 53
4.5 單體F-T-NO2光譜鑑定與分析 54
4.5.1 1H-NMR 鑑定 54
4.5.2 13C-NMR 鑑定 56
4.5.3 高解析質譜儀鑑定 58
4.5.4 示差掃瞄熱分析儀(DSC)分析 59
4.6 單體F-T-NH2光譜鑑定與分析 60
4.6.1 1H-NMR 鑑定 60
4.6.2 13C-NMR 鑑定 62
4.6.3 高解析質譜儀鑑定 64
4.6.4 示差掃瞄熱分析儀(DSC)分析 65
4.7 單體DT-OCH3光譜鑑定與分析 66
4.7.1 1H-NMR 鑑定 66
4.7.2 13C-NMR 鑑定 68
4.7.3 高解析質譜儀鑑定 70
4.7.4 示差掃瞄熱分析儀(DSC)分析 71
4.8 單體DT-OH光譜鑑定與分析 72
4.8.1 1H-NMR 鑑定 72
4.8.2 13C-NMR 鑑定 74
4.8.3 高解析質譜儀鑑定 76
4.8.4 示差掃瞄熱分析儀(DSC)分析 77
4.9 單體S-DT-NO2光譜鑑定與分析 78
4.9.1 1H-NMR 鑑定 78
4.9.2 13C-NMR 鑑定 80
4.9.3 高解析質譜儀鑑定 82
4.9.4 示差掃瞄熱分析儀(DSC)分析 83
4.10 單體S-DT-NH2光譜鑑定與分析 84
4.10.1 1H-NMR 鑑定 84
4.10.2 13C-NMR 鑑定 86
4.10.3 高解析質譜儀鑑定 88
4.10.4 示差掃瞄熱分析儀(DSC)分析 89
4.11 單體F-DT-NO2光譜鑑定與分析 90
4.11.1 1H-NMR 鑑定 90
4.11.2 13C-NMR 鑑定 92
4.11.3 高解析質譜儀鑑定 94
4.11.4 示差掃瞄熱分析儀(DSC)分析 95
4.12 單體F-DT-NH2光譜鑑定與分析 96
4.12.1 1H-NMR 鑑定 96
4.12.2 13C-NMR 鑑定 98
4.12.3 高解析質譜儀鑑定 100
4.12.4 示差掃瞄熱分析儀(DSC)分析 101
4.13聚醯亞胺結構鑑定 102
4.13.1 S-series PI結構鑑定 102
4.13.2 F-series PI結構鑑定 103
第五章 結果與討論 104
5.1 聚醯亞胺製備條件探討 104
5.2薄膜性質 107
5.3 廣角XRD結晶性測試 108
5.4聚醯亞胺溶解度測試 110
5.5薄膜熱性質分析 112
5.5.1 DSC分析 112
5.5.2 DMA分析 114
5.5.3 TMA分析 116
5.5.4 TGA分析 118
5.6 材料親疏水性測試 122
5.7 吸水性測試 124
5.8薄膜介電常數分析 127
第六章 結論 129
 
PartII 環氧樹脂水性化之界面活性劑製備及應用
第一章 緒論 132
第二章 文獻回顧 134
2.1 Gemini Surfactants文獻回顧 134
2.2 環氧官能樹脂水性化 136
2.3 主鏈結構 139
2.2 研究動機 141
第三章 實驗 142
3.1 實驗藥品 142
3.2 儀器設備 142
3.3 實驗規劃 143
3.4單體合成步驟 144
3.4.1 C-4 Biscarbonate合成 144
3.4.2 C-4 Oxyalkylene Bisamine合成 144
3.4.3 C-4 Oxyalkylene Epoxy合成 145
第四章 結構鑑定與分析 146
4.1 C-4 Biscarbonate 結構鑑定 146
4.2 C-4 Oxyalkylene Bisamine 結構鑑定 148
4.3 C-4 Oxyalkylene Epoxy結構鑑定 150
第五章 結果與討論 152
5.1 材料親疏水性測試 152
5.2 表面張力測試 153
5.3 環氧樹脂水性化分散性測試 154
5.3.1 有無添加C-4 Oxyalkylene Epoxy 154
5.3.2 添加共溶劑PM 155
5.3.3 添加共溶劑ETOH 157
5.4 環氧樹脂水性化硬化 159
5.4.1 環氧樹脂水性化樣品與硬化劑固化 159
5.4.2 環氧樹脂水性化開發品 160
第六章 結論 164
第七章 參考文獻 165

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