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研究生:李怡玟
研究生(外文):I-Wen Li
論文名稱:含Schiff base基團液晶環氧樹脂之合成、鑑定及熱性質研究
論文名稱(外文):Synthesis, characterization and thermal properties of a liquid crystalline epoxy resin containing Schiff base mesogen
指導教授:何宗漢何宗漢引用關係鄭錫勳鄭錫勳引用關係
指導教授(外文):HO, TSUNG-HANCHENG, SHI-SHIUN
口試委員:何宗漢鄭錫勳林烈利顏福杉
口試委員(外文):HO, TSUNG-HANCHENG, SHI-SHIUNLIN, LIEH-LIYEN, FU-SAN
口試日期:2017-07-14
學位類別:碩士
校院名稱:國立高雄應用科技大學
系所名稱:化學工程與材料工程系博碩士班
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2017
畢業學年度:105
語文別:中文
論文頁數:97
中文關鍵詞:液晶環氧樹脂希夫鹼介晶基團硬化反應馬賽克紋理熱機械性質
外文關鍵詞:liquid crystalline epoxy resinSchiff base mesogencuring reactionMosaic texturethermal mechanical properties
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  • 被引用被引用:3
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本研究合成出含Schiff base之液晶環氧樹脂4,4’-bis(2,3-epoxypropoxy)benzylidene aniline (LCE),並利用FT-IR、1H-NMR及MS鑑定其結構。使用DSC和POM觀察液晶相變化特性,由DSC熱譜曲線顯示並未有明顯的液晶相變化特性,但由POM可觀察到向列型液晶相的馬爾他十字紋路(Maltese cross)以及層列型液晶相的馬賽克紋理(Mosaic texture),進一步使用WAXD驗證液晶相的存在。分別以二胺基二苯甲烷 (DDM)和二氨基二苯基碸 (DDS)做為硬化劑,製備出LCE/DDM與LCE/DDS兩種液晶環氧樹脂。藉由DSC來探討LCE/DDM與LCE/DDS的熱硬化反應行為,結果顯示LCE/DDM系統在初期的硬化反應比LCE/DDS系統快。依DSC非恆溫條件下探討LCE/DDM與LCE/DDS之硬化動力學,分別使用 Kissinger和 Ozawa法計算活化能,結果顯示LCE/DDS系統的活化能會略高於LCE/DDM系統。再藉由TGA、DMA、TMA及Hot-disk測量硬化液晶環氧樹脂LCE/DDM和LCE/DDS的熱性質、機械性質及熱傳導係數,最後與傳統環氧樹脂(DGEBA)做比較。TMA結果顯示,在玻璃態和橡膠態具有較低的熱膨脹係數;DMA結果顯示,硬化LCE網狀結構比硬化DGEBA網狀結構具有較高的玻璃轉移溫度和儲存模數;TGA結果顯示,硬化LCE系統比DGEBA系統具有較好的熱穩定性和較高的焦炭殘餘率;於Hot-disk結果顯示,硬化LCE網狀結構的熱傳導係數明顯比硬化DGEBA網狀結構增加70%。
A liquid crystalline epoxy resin (LCE) with Schiff base mesogen, 4,4’-bis(2,3-epoxypropoxy)benzylidene aniline, was synthesized and characterized by Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (1H-NMR) and mass spectroscopy (MS). The liquid crystalline phase transition behavior of LCE monomer was observed by differential scanning calorimetry (DSC) and polarizing optical microscope (POM), respectively. Form the DSC result, an endothermal peak and an exothermal peak appeared in the DSC curve which didn’t show any liquid crystalline phase peak. But LCE could observed the liquid crystalline phase of Maltese and Mosatic cross texture during heating and cooling by POM with hot stage. LC texture for LCE was identified further by WAXD. Two curable LCE resins were prepared based on the epoxy monomer with two different curing agent, 4,4'-diaminodiphenyl methane (DDM) and 4,4'-diaminodiphenyl sulfone (DDS), respectively. The curing reaction of mixtures of LCE/DDM and LCE/DDS were monitored by DSC. The results showed that the curing reaction of LCE/DDM proceeded faster than LCE/DDS in the initial stage. The curing kinetics of mixture were investigated by DSC under non-isothermal method. The activation energies (Ea) of curing reaction were calculated by the models of Kissinger’s and Ozawa’s methods, respectively. The results showed that the Ea of LCE/DDS were higher than LCE/DDM.
In this study, the comparison of thermal and mechanical properties between the conventional epoxy diglycidyl ether of bisphenol-A (DGEBA) and rigid rod LCE resin were investigated by thermal gravimetry analysis (TGA), dynamic mechanical analysis (DMA), thermal mechanical analysis (TMA) and thermal conductivity meter (Hot-disk), respectively. The cured LCE showed the higher Tg and storage modules and the lower CTE both in glassy region and rubbery region compared with the cured DGEBA. The TGA results showed that cured LCE had better thermal stability and higher char yield than the cured DGEBA. The thermal conductivity of cured LCE showed higher than cured DGEBA that the value was increased about 70%.
總目錄
摘要 I
Abstract III
誌 謝 V
總目錄 VI
Scheme VIII
表目錄 IX
圖目錄 X
第一章 緒論 1
1-1前言 1
1-2研究目的 2
第二章 文獻回顧 3
2-1液晶簡介 3
2-1-1 液晶的由來 4
2-1-2 液晶的分類 6
2-2液晶高分子簡介 (Liquid crystalline polymer) 13
2-3環氧樹脂簡介 15
2-4液晶環氧樹脂簡介 17
2-4-1 Biphenyl系統 18
2-4-2 Naphthyl系統 22
2-4-3 Ester系統 24
2-4-4α-methylstilbene系統 29
2-4-5 Azine系統 30
2-4-6 Azomethine系統 32
第三章 實驗 39
3-1 實驗流程圖 39
3-2 材料與藥品 40
3-3實驗裝置圖 41
3-4儀器設備 43
3-5實驗步驟 44
3-5-1 4-((4-hydroxybenzylidene)amino)phenol (HBAP)之合成 44
3-5-2 4,4’-bis(2,3-epoxypropoxy)benzylidene aniline (LCE)之合成 45
3-5-3 LCE/硬化劑之硬化反應 47
3-5-4 LCE硬化試片之製備 47
3-6 結構鑑定與物性測試 48
第四章 結果與討論 51
4-1 HBAP及LCE之合成鑑定 51
4-1-1 HBAP與LCE之FT-IR分析 51
4-1-2 HBAP與LCE之1H-NMR分析 52
4-1-3 MS之分析 54
4-2液晶型態之探討 55
4-2-1 DSC分析液晶相變化特性 55
4-2-2 POM觀察液晶相形態 57
4-2-3 WAXD鑑定液晶相種類 58
4-3 熱硬化之探討 60
4-3-1 LCE/DDM和LCE/DDS之DSC分析 60
4-4 硬化動力學參數探討 62
4-4硬化動力學探討 64
4-4-1 Kissinger’s method【46, 47】 64
4-4-2 Ozawa’s method【48-50】 65
4-5 DMA及TMA熱機械性質分析 68
4-5-1 TMA分析 68
4-5-2 DMA分析 70
4-6 硬化環氧樹脂探討 73
4-6-1 TGA熱穩定性分析 73
4-6-2 Hot-disk熱傳導係數分析 75
第五章 結論 77
參考文獻 78

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