臺灣博碩士論文加值系統

本研究主要目的是合成出以酮基為介晶基團之液晶型環氧樹脂(LCE)，並利用FTIR、1H-NMR、MS、DSC與POM鑑定其結構、熔點以及液晶相變化特性。在DSC曲線中，出現兩個吸熱峰和一個放熱峰；在升溫及降溫過程中，使用POM可觀察到雙折射液晶相。LCE從室溫加熱至111°C，其相態會從結晶相轉變為層列型液晶相，再加熱至121°C，則從液晶相轉變為等向性液體。以二胺基二苯甲烷 (DDM)和二胺基二苯碸 (DDS)當硬化劑，藉由DSC來探討出LCE的熱硬化反應，其結果顯示在初步硬化反應階段，LCE/DDM進行之硬化反應比LCE/DDS來得快，而在硬化過程中，使用POM觀察LCE/DDM及LCE/DDS，皆有雙折射液晶相的存在。LCE與DDM在硬化溫度範圍95至230°C會顯示出層列型液晶相；與DDS在硬化溫度範圍160至300°C也可觀察出層列型液晶相。藉由DSC在非恆溫條件下來探討LCE/DDM及LCE/DDS之硬化動力學，然後使用Kissinger、Ozawa和Vachuska-Voboril的方法來計算出活化能，LCE/DDS的活化能高於LCE/DDM，其值LCE/DDM約在72.6–83.2 kJ mol-1之間，而LCE/DDS約在112.4–99.9 kJ mol-1之間。使用TGA及DMA來研究硬化LCE網狀結構的熱性質，其結果顯示，LCE交聯網狀結構的熱穩定性可達到360以上；而且Tg高於220°C。

The goal of this research is focused on the synthesis of a liquid crystalline epoxy resin (LCE) based on ketone mesogen, 1,5-bis(p-glycid-
yloxy-phenyl)-1,4-pentadiene-3-one. The chemical structure, melting range and liquid crystalline phase transition behavior of LCE were characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (1H-NMR), mass spectroscopy (MS), differential scanning calorimetry (DSC) and polarized optical microscopy (POM). Two endothermal peaks and one exothermal peak appeared in the DSC curves. Birefringent liquid crystalline texture was observed during heating and cooling by POM. LCE was crystal phase at room temperature and turned to smectic at 111°C upon heating, then turned isotropic at 121°C.The curing reaction of LCE was monitored by DSC using diaminodipheylmethane (DDM) and diaminodiphenylsulfone (DDS) as curing agents. The results showed that the curing reaction of LCE/DDM proceeded faster than that of LCE/DDS in the initial stage of the curing reaction. Birefringent was also observed during curing processes by POM. LCE network cured with DDM displayed smectic phase in the curing temperature range between 95 and 230°C, while that cured with DDS formed one between 160 and 300°C.The cure kinetics of mixtures of LCE/DDM and LCE/DDS were studied by DSC under non-isothermal conditions and the activation energies (Ea) of curing reaction were calculated according to the models of Kissinger, Ozawa and Vachuska-Voboril, respectively. The results showed that the Ea of LCE/DDS about 99.9–112.4 kJ mol-1 were higher than that of LCE/DDM about 72.6–83.2 kJ mol-1. The thermal properties of cured LCE network were investigated by thermal gravimetric analyzer (TGA) and dynamic mechanical analysis (DMA). The results showed that LCE crosslinked networks were thermally stable up to 360°C, and the glass transition temperature of cured LCEs were higher than 220°C.

摘要 i
ABSTRACT ii
誌謝 iv
目錄 v
Scheme vi
表目錄 viii
圖目錄 ix
第一章 緒 論 1
1-1 前 言 1
1-2 液晶簡介 2
1-2-1 液晶起源 3
1-2-2 液晶分類 5
1-3 環氧樹脂簡介 12
1-4 液晶環氧樹脂簡介 13
1-5 硬化劑簡介 14
第二章 文獻回顧 17
2-1 液晶高分子 17
2-2 液晶環氧樹脂之系統 21
2-2-1 biphenyl 系統 22
2-2-2 ester 系統 28
2-2-3 α-methylstilbene 系統 40
2-2-4 naphthalene 系統 46
2-2-5 azine 系統 48
2-2-6 azomethine 系統 49
2-3 研究之目的 51
第三章 實驗部分 52
3-1 實驗流程圖 52
3-2 材料與藥品 53
3-3 實驗裝置圖 54
3-4 儀器設備 56
3-5 實驗步驟 57
3-5-1 1,5-Bis(4-hydroxyphenyl)-1,4-pentadiene-3-one (BHPPDO)之合成 57
3-5-2 1,5-bis(p-glycidyloxy-phenyl)-1,4-pentadiene-3-one (LCE)之合成 58
3-5-3 LCE/硬化劑之硬化反應 60
3-5-4 硬化反應動力學之探討 60
3-5-5 硬化試片之製備 61
3-6 結構鑑定與物性測試 62
第四章 液晶環氧樹脂之合成與鑑定及其物性研究 64
4-1 LCE之合成鑑定 64
4-2液晶相之觀察 69
4-3 熱硬化之探討 76
4-4 硬化動力學參數探討 80
4-5 硬化技術之探討 92
4-6 熱穩定性分析 94
4-7 動態機械分析 97
第五章 結論 99
參考文獻 100
自傳簡歷 106

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