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研究生： 林冠宏
Kuan-Hung Lin
論文名稱： 含有聚醚交聯奈米區域之環氧-胺網狀物之形成及其性質之研究
Formation and Properties of Epoxy-Amine Networks Containing Nanostructured Ether-Crosslinked Domains
指導教授： 許應舉
Ying-Gev Hsu
口試委員: 陳志堅
Jyh-Chien Chen
陳燿騰
Yaw-Terng Chern
戴子安
Chi-An Dai
林江珍
Jiang-Jen Lin
學位類別： 博士
Doctor
系所名稱： 工程學院 - 材料科學與工程系
Department of Materials Science and Engineering
論文出版年： 2012
畢業學年度： 100
語文別： 中文
論文頁數： 61
中文關鍵詞： 聚醚交聯奈米區域 、咪唑衍生物 、奈米區域增韌劑 、環氧-胺網狀物
外文關鍵詞： nanostructured ether-crosslinked domains, imidazole derivatives, nanodomain toughener, epoxy-amine networks
相關次數： 點閱：279  下載：4 
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    • 本研究旨在探討一含有奈米區域增韌劑(nanodomain toughener)—軟性聚醚交聯奈米區域(nanostructured ether-crosslinked domains, NECDs)之環氧-胺網狀物之形成，進而研究其提升靭性(toughness)的反應機制。環氧樹脂—雙酚A二縮水甘油醚(diglycidyl ether bisphenol A epoxy resin, DGEBA)和硬化劑—二胺基二苯甲烷(4,4′-methylene dianiline, MDA)之混合液，於不同含量之咪唑衍生物(簡稱“咪唑”)—1-甲基咪唑(1-methylimidazole, 1-MI)或2-甲基咪唑(2-methylimidazole, 2-MI)—的存在下加熱硬化，則DGEBA的環氧基團不僅和MDA苯環上的胺基進行聚加成反應(polyaddition)以形成環氧-胺之剛性網狀結構基材(matrix)，更可以藉由自身的陰離子開環聚合(anionic ring-opening polymerization)以形成與環氧-胺網狀硬性結構相連接之軟性NECDs。本論文藉由微差掃描卡計(DSC)和傅立葉轉換紅外光譜儀(FTIR)研究DGEBA/MDA混合液在咪唑存在(或不存在)下之硬化反應行為，亦藉由原子力顯微鏡(AFM)研究產物—含5~30奈米NECDs之環氧-胺網狀物—之形態(morphology)。研究發現，DGEBA/MDA溶液在最適含量(~0.15至0.30 wt%)的咪唑存在下所產生的NECDs，可以在不大幅影響玻璃轉移溫度(Tg)下，能有效的提升環氧-胺網狀物之拉伸、破壞韌性和熱安定性質，其獨特的韌性機構和熱行為亦在論文中做詳細的討論。

    Epoxy-amine networks with a nanodomain toughener-soft nanostructured ether-crosslinked domains (NECDs), which could increase the fracture and tensile toughness of the networks, were simply obtained when a mixture of diglycidyl ether bisphenol A (DGEBA) epoxy resin and 4,4′-methylene dianiline (MDA) hardener was heat-cured in the presence of varying amounts of the imidazole derivatives (called imidazoles)—1-methylimidazole (1-MI) or 2-methylimidazole (2-MI). Under these conditions, the epoxide groups in DGEBA underwent not only polyaddition with the aromatic amine of the MDA to form a hard epoxy-amine networked matrix but also anionic ring-opening polymerization by itself to build soft NECDs connected to the epoxy-amine matrix. The curing chemistry of the DGEBA/MDA mixture, both with and without the imidazoles, was studied using differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The morphology of the networks dispersed with 5~30 nm-sized NECDs was investigated by atomic force microscopy (AFM). When the optimum amount (~0.15–0.30 wt%) of imidazoles was added, the NECDs produced were effective in significantly increasing the tensile and fracture toughness and the thermal stability of the epoxy-amine networks without markedly sacrificing the glass transition temperature (Tg). The novel toughening mechanism and thermal behavior of the epoxy-amine networks were discussed.

    目錄 中文摘要................................................Ⅰ 英文摘要................................................Ⅲ 目錄....................................................Ⅵ 附圖索引................................................Ⅷ 附表索引................................................Ⅹ 一、 前言................................................1 二、 文獻回顧............................................5 三、 基本原理............................................9 3.1 空洞增韌機制........................................11 3.2 去鍵結(debonding)增韌機制...........................13 3.3 原子力顯微鏡原理....................................15 四、 實驗...............................................18 4.1 實驗藥品............................................18 4.2 環氧-胺網狀物之製備.................................20 4.3 儀器測試與分析......................................22 4.3.1 微差掃描卡計分析..................................22 4.3.2 傅立葉轉換紅外線光譜分析..........................22 4.3.3 原子力顯微鏡分析..................................22 4.3.4 動態機械性質分析..................................23 4.3.5 拉伸韌性測試......................................23 4.3.6 破壞韌性測試......................................23 4.3.7 掃描式電子顯微鏡分析..............................24 4.3.8 熱重量損失分析....................................24 五、 結果與討論.........................................26 5.1 DGEBA/MDA混合液在咪唑存在下之反應...................26 5.1.1 微差掃描卡計分析..................................28 5.1.2 傅立葉紅外線光譜分析..............................33 5.2 聚醚交聯結構之環氧-胺網狀物之成型...................36 5.3 環氧-胺網狀物之形態.................................38 5.4 環氧-胺網狀物之性質.................................42 5.4.1 動態機械性質分析..................................42 5.4.2 拉伸韌性..........................................45 5.4.3 破壞韌性和破壞機構................................47 5.4.4 熱安定性質........................................51 六、 結論...............................................56 七、 參考文獻...........................................57

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