臺灣博碩士論文加值系統

本研究分別合成含酯基團之液晶環氧樹脂 （LCE）及含DOPO阻燃硬化劑 (TDCA-DOPO)，利用紅外線光譜儀 (FTIR)、核磁共振儀 (1H-NMR、31P-NMR)及質譜儀 (MS)鑑定其結構。透過微分掃描熱卡計 （DSC）及偏振光學顯微鏡 （POM）觀察LCE的液晶相變行為，於DSC結果顯示，出現一個吸熱峰和兩個放熱峰，在降溫過程中，使用POM可觀察到層列型液晶相的扇形焦錐紋理 (fan-shaped focal-conic texture)。
將LCE分別使用不同比例的TDCA-DOPO和DDM當共硬化劑來製備熱固性環氧樹脂 （LCE / TDCA-DOPO / DDM）。利用DSC研究熱固性環氧樹脂玻璃化轉移溫度 （Tg），結果顯示，隨著TDCA- DOPO含量的增加，Tg以些微溫度差異逐漸下降。透過熱重分析儀（TGA）及Hot-Disk研究LCE / TDCA-DOPO / DDM的熱性質，TGA結果顯示，透過增加TDCA-DOPO含量可以提高熱穩定性和焦炭殘餘率;而Hot-Disk結果顯示，導熱係數隨TDCA-DOPO含量增加而下降，但均高於市售環氧樹脂的導熱係數。
利用LOI、UL-94及錐形量熱儀探討熱固性環氧樹脂之難燃性，結果顯示，當磷含量達0.54 wt%時LOI值達到33%且通過UL-94 V-0等級，而熱釋放速率及總煙產生量均降低。
透過SEM、EDS及Raman光譜來探討焦炭殘餘物，結果顯示，添加TDCA-DOPO之焦炭殘餘物較為緻密且膨脹，並含有磷及氮元素，具氮磷共乘效應；Raman光譜結果顯示含有TDCA-DOPO之熱固性環氧樹脂較能產生保護型焦炭。

The liquid crystalline epoxy resin (LCE) containing ester group and curing agent based on DOPO (TDCA-DOPO) were synthesized respectively. The chemical structure of LCE and TDCA-DOPO were characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (1H-NMR, 31P-NMR) and mass spectroscopy (MS). The liquid crystalline phase transition behavior of LCE was investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). From the DSC result, one endothermal peak and two exothermal peaks were appeared in the DSC curve. The sematic liquid crystalline texture of fan-shaped focal-conic texture was observed during cooling by POM.
The TDCA-DOPO and diaminodiphenylmethane (DDM) were used as co-curing agent and further cured with LCE, and the thermosetting epoxy resin (LCE/TDCA-DOPO/DDM) were prepared by different ratios of TDCA-DOPO/DDM. The glass transition temperature (Tg) was investigated by DSC. The results showed that the Tg was slight differences decreasing gradually by increasing TDCA-DOPO content. The thermal properties of LCE/TDCA-DOPO/DDM were investigated by thermal gravimetric analyzer (TGA) and Hot-Disk. The results of TGA showed that the thermal stability, char yield were increased by increasing TDCA-DOPO content; and Hot-disk results showed that the thermal conductivity was decreasing by increasing TDCA-DOPO content, but all were higher than the commercially available epoxy resins.
The flame retardancy of thermosetting epoxy resin were investigated by LOI, UL-94 and cone calorimeter. The results show that when the phosphorus content was 0.54 wt%, the LOI value of 33% and passes the UL-94 V-0 rating, and the heat release rate and the total smoke production were reducing.
The char residues after cone calorimeter were investigated by SEM, EDS and Raman spectroscopy. The results show that the char residue of added TDCA-DOPO was dense and expanded, and contains phosphorus and nitrogen elements, with nitrogen and phosphorus synergistic effect. Raman results showed that the thermosetting epoxy resin contains TDCA-DOPO was more capable of producing protective char.

摘要 I
Abstract III
致謝 V
總目錄 VI
表目錄 X
圖目錄 XII
SCHEME XVI
第一章 緒論 1
1-1前言 1
1-2歐盟電機電子設備有害物質限用指令 (RoHS) 2
1-3未來材料發展趨勢及要求 5
1-4研究目的 8
第二章 文獻回顧 9
2-1環氧樹脂（Epoxy Resin）9
2-1-1環氧樹脂簡介 9
2-1-2環氧樹脂特性 10
2-2液晶簡介 11
2-2-1液晶起源[15–17] 12
2-2-2液晶分子結構 13
2-2-3液晶分類 14
2-3液晶環氧樹脂簡介 20
2-3-1 Ester液晶環氧樹脂 22
2-4硬化劑簡介 27
2-4-1硬化劑的分類 28
2-4-2共硬化劑 31
2-5高分子燃燒機構 35
2-6難燃原理 37
2-6-1鹵素系難燃原理 39
2-6-2磷系難燃原理 42
2-7含DOPO硬化劑 44
第三章 實驗 49
3-1實驗流程圖 49
3-2材料與藥品 51
3-3實驗裝置圖 53
3-4儀器設備 56
3-5實驗步驟 58
3-5-1 4,4'-dihydroxybiphenyl ester (DHDP)之合成[64] 58
3-5-2 4,4'-di(2,3-epoxypropenyloxy)phenyl benzoate (LCE)之合成 59
3-5-3 1,4-phenylene-bis((6-oxido-6H-dibenz[c,e][1,2]-oxaphosphorinyl)carbinol) (TDCA-DOPO)之合成[65] 61
3-5-4 LCE/TDCA-DOPO/DDM之配製 63
3-5-5硬化試片之製備 65
3-6結構鑑定與物性測試 66
第四張 結果與討論 73
4-1 DHDP與LCE合成及鑑定 73
4-1-1 DHDP與LCE之FT-IR分析 73
4-1-2 DHDP與LCE之1H-NMR分析 75
4-1-3 DHDP與LCE之MS分析 77
4-2 TDCA-DOPO合成及鑑定 79
4-2-1 TDCA-DOPO之FTIR分析 79
4-2-2 TDCA-DOPO之1H-NMR與31P-NMR分析 81
4-2-3 TDCA-DOPO之MS分析 83
4-3 LCE液晶型態之探討 84
4-3-1 DSC分析液晶相範圍 84
4-3-2 POM液晶相觀察 86
4-4熱硬化之探討 88
4-4-1 LCE/TDCA-DOPO/DDM之DSC分析 88
4-5 LCE/TDCA-DOPO/DDM硬化環氧樹脂熱性質探討 89
4-5-1以DSC探討玻璃轉移溫度 89
4-5-2以TGA探討熱穩定性 91
4-5-3以Hot-Disk探討熱傳導係數 93
4-6 LCE/TDCA-DOPO/DDM 硬化環氧樹脂阻燃性探討 95
4-6-1 LOI及UL-94測試 95
4-6-2 Cone calorimeter測試 97
4-7 LCE/TDCA-DOPO/DDM硬化環氧樹脂焦炭分析 99
4-7-1以SEM觀察焦炭形貌 99
4-7-2以EDS檢測焦炭元素 100
4-7-3以Raman光譜測定焦炭石墨化程度 101
第五章 結論 103
第六章 參考文獻 105

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