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研究生： 陳冠汝
Chen, Kuan-Ju
論文名稱： 聚胺酸高分子自組裝誘導中孔二氧化矽之合成及其應用為抗反射薄膜
Polypeptide Macromolecular Assemblies-Induced Synthesis of Mesoporous Silica and Their Application as Antireflective Coatings
指導教授： 詹正雄
Jan, Jeng-Shiung
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2018
畢業學年度： 106
語文別： 中文
論文頁數： 101
中文關鍵詞： 嵌段聚胺基酸 、奈米纖維 、多孔性二氧化矽 、層層堆疊法 、生物礦化法 、抗反射薄膜
外文關鍵詞： polypeptides, mesoporous, layer by layer assembly, anti-reflective film
相關次數： 點閱：79  下載：6 
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    • 本研究合成帶有正電荷之雙嵌段聚胺基酸高分子，聚賴胺酸嵌段聚蘇胺酸(PLL-b-PLT)，利用傅立葉轉換紅外線光譜儀以及圓二色光譜儀分析其二級結構，發現此高分子同時具有β-折板及無規則線圈，且利用掃描式電子顯微鏡及穿透式電子顯微鏡等儀器發現在低濃度高分子水溶液中，聚賴胺酸嵌段聚蘇胺酸自組裝形成奈米纖維(nanofibril)結構，在確定此高分子形態後，我們將其作為模板製備出擁有奈米結構的有機/無機複合材料並合成出具有構型之無機氧化物，藉由模板法進行生物仿生的礦化作用，由於雙嵌段聚胺基酸高分子的二級結構是決定孔洞結構和孔隙度的重要因素之一，故可以發現使用不同鏈長之聚賴胺酸嵌段聚蘇胺酸高分子可改變材料形狀、孔隙度和孔洞結構。我們使用一種製程簡單且快速的技術合成出奈米級無機氧化物材料，材料都表現出良好且獨特的特性，能應用於許多相關領域裡。除了應用於合成無機材料外，我們另外將帶正電聚賴胺酸嵌段聚蘇胺酸高分子以及帶負電之聚穀胺酸高分子利用浸泡法結合層層堆疊法的方式，搭配生物礦化法的步驟製備結構為多孔且連續的多孔性抗反射薄膜，並發現藉由控制堆疊層數的不同可調控抗反射薄膜之折射率，除此之外此抗反射薄膜可抵抗膠帶作用力，顯示其有一定機械強度能穩定存在於基材上。此方法製備出來的抗反射薄膜不但能提高基材穿透度，且擁有穩定的貼附性，使其應用性增廣。

    In this study, we synthesis polypeptides poly (L-lysine)-block-poly (L-threonine) (PLL-b-PLT) and poly (L-glutamic acid) (PGA) via ring-opening polymerization. And we proposed a simple method to prepare the polypeptide templated mesoporous silica materials which pore sizes mostly between 2~50 nm after calcination. In addition, we exploited a simple method to prepare polymer/silica composite antireflective (AR) films by combining silica mineralization and layer-by-layer (LBL) assembly. The performance of AR films depends on its thickness and fibrous nanostructure. While the AR composite films coated on glass and poly (methyl methacrylate) (PMMA) substrates exhibited maximum transmission over 96% and 97% at the visible wavelength between 570 and 800 nm.

    目錄 摘要 I Extended Abstract II 致謝 XII 目錄 XIV 表目錄 XVIII 圖目錄 XIX 第一章 緒論 1 1.1 前言 1 1.1.1 奈米材料 1 1.1.2 抗反射薄膜 2 1.2 研究動機與目的 3 第二章 文獻回顧 4 2.1 聚胺基酸 4 2.1.1 胺基酸 4 2.1.2 蛋白質之結構 4 2.1.3 胺基酸之聚合 7 2.2 二氧化矽無機材料之形成與發展 10 2.2.1 二氧化矽水解縮合反應 10 2.2.2 二氧化矽顆粒大小 12 2.2.3 多孔性材料 13 2.3 層層自組裝薄膜技術發展 15 2.3.1 模板法 15 2.3.2 層層自組裝法 17 2.3.3 層層自組裝法結合模板法 18 2.4 抗反射薄膜之設計與發展 19 2.4.1 抗反射薄膜起源與歷程 19 2.4.2 抗反射薄膜之光學理論 20 2.4.3 應用於抗反射薄膜之材料 23 第三章 儀器設備與實驗方法 25 3.1 實驗藥品 25 3.2實驗儀器與原理 27 3.2.1 液態核磁共振儀 27 3.2.2 凝膠滲透層析儀 27 3.2.3 傅立葉轉換紅外線光譜儀(FT-IR) 28 3.2.4 紫外光/可見光譜儀 30 3.2.5 原子力顯微鏡 30 3.2.6 圓二色光譜儀 31 3.2.7 掃描式電子顯微鏡 32 3.2.8 穿透式電子顯微鏡 33 3.2.9 接觸角測定儀 34 3.2.10 熱重分析儀 35 3.2.11 薄膜量測儀 36 3.2.12 氮氣等溫吸附/脫附測量 37 3.3 聚胺基酸高分子之合成 41 3.3.1 溶劑之乾燥去水氧 41 3.3.2製備α-amino acid N-carboxyanhydrids(NCAs) 42 3.3.3 以一級胺作為起始劑對Lys-NCAs 和 Thr-NCAs 進行開環聚合 45 3.3.4以有機鎳作為起始劑對Glu-NCAs進行開環聚合 46 3.3.5 除去聚胺基酸保護基 46 3.4 合成無機氧化物材料 49 3.4.1 高分子自組裝 49 3.4.2 二氧化矽之合成及高分子鍛燒 49 3.5 高分子/二氧化矽抗反射薄膜之製程 50 3.5.1 玻璃基材表面之清洗 50 3.5.2 壓克力基材PMMA表面之改質 51 3.5.3 層層堆疊法製造抗反射薄膜 51 3.5.4 高分子沉析二氧化矽多孔性薄膜 52 第四章 結果與討論 53 4.1嵌段聚胺基酸之合成分析 53 4.1.1 嵌段聚胺基酸之聚合度 54 4.1.2 嵌段聚胺基酸之分子量 60 4.2 嵌段聚胺基酸PLL-b-PLT之二級結構 61 4.3 二氧化矽無機材料之形成 64 4.3.1 PLL-b-PLT嵌段高分子作為模板形成二氧化矽IR、TGA分析 64 4.3.2 PLL-b-PLT嵌段高分子作為模板形成二氧化矽材料結構分析 67 4.3.3 PLL-b-PLT嵌段高分子作為模板形成二氧化矽材料之BET分析 72 4.4 層層堆疊結合浸泡法之抗反射薄膜結果分析 76 4.4.1 PLL20-b-PLT8 抗反射薄膜的結構分析 76 4.4.2 PLL20-b-PLT8 抗反射薄膜的光學性質分析 84 4.4.3 PLL20-b-PLT8 抗反射薄膜的貼附性分析 90 第五章 結論 91 參考文獻 93

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