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研究生： 曾鎔塏
Tseng, Jung-kai
論文名稱： 以螢光光譜和二維NOE核磁共振光譜探討聚（N-乙烯甲醯胺）與離子型/非離子型界面活性劑之交互作用
Study of Interactions Between Poly(N-Vinylformamide) and Ionic/Nonionic Surfactants by Fluorescence and Two-dimensional Nuclear Overhauser Effect Spectroscopy
指導教授： 侯聖澍
none
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： 2007
畢業學年度： 95
語文別： 中文
論文頁數： 119
中文關鍵詞： Poly(N-Vinylformamide) 、NOE光譜 、核磁共振 、界面活性劑 、螢光光譜
外文關鍵詞： surfactant, NOESY, Poly(N-Vinylformamide), fluorescence spectroscopy, NMR
相關次數： 點閱：91  下載：3 
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    • 本研究利用螢光光譜和核磁共振光譜，探討PNVF和不同界面活性劑之間交互作用力。在PNVF-SDS溶液系統中，可以從螢光光譜的結果，[SDS]=CAC~CMC時，[I1/I3]py維持定值，推論PNVF-SDS叢集尺寸大小一致；再由螢光衰減子實驗可以得到[SDS]=CAC~CMC時，SDS平均聚集數呈現一致性。從NOE光譜中得到PNVF-SDS叢集中PNVF和SDS相互作用位置PNVF高分子鏈穿過SDS叢集；並和純SDS微胞做比較，PNVF-SDS叢集中SDS碳鏈呈現比較彎曲的構型。
    相對而言，PNVF-CTAB溶液系統中，在Pyrene螢光光譜的[I1/I3]py可知PNVF和CTAB在水溶液中相互作用力極微弱；更從NOE光譜中可知在不論[CTAB]濃度，PNVF和CTAB不具有短距離（0.5 nm）的作用力。
    在PNVF-非離子型界面活性劑系統中，選擇PNVF-TX 100、PNVF-Tergitol 15-S-9、PNVF-C12E7三種系統進行實驗，而Pyrene螢光光譜在上述系統中的結果都顯示出PNVF和非離子型界面活性劑間不存在作用力。

    In this research, interactions between PNVF and surfactants were studied by fluorescence and NMR spectroscopy.
    In the PNVF/SDS systems, when [SDS] is between CAC and CMC, [I1/I3]py shows a plateau and [IE/IM]py sharply decreases, indicating that the size of PNVF–SDS aggregate is uniform. From the result of the pyrene quenching experiment, the mean aggregation number can be obtained as a constant. The NOESY of the PNVF/SDS systems show that the PNVF polymer chain penetrates the SDS aggregates and the curled alkyl chain of SDS is partially associated with the PNVF polymer chain.
    The results of [I1/I3]py and [IE/IM]py indicate the interaction between PNVF and CTAB is very weak.  The NOESY of the PNVF/CTAB systems reveal that no short rang interaction between PNVF and CTAB in the aqueous solution of PNVF and CTAB.
    [I1/I3]py and [IE/IM]py of the PNVF/nonionic surfactant systems also imply that no interaction is between PNVF and nonionic surfactant.

    中文摘要……………………………..……………………...…………………I 英文摘要………………………………...…………..…………………II 誌謝……………………………………………………………………III 總目錄……………………………………………….………………….V 表目錄………………………...………………………………………..XI 圖目錄……………………………………………...…………………XIII 第一章、緒論...........................................................................................1 1-1 前言....................................................................................................1 1-2 研究動機與目的.................................................................................2 第二章 文獻回顧.....................................................................................5 2-1 界面活性劑系統................................................................................5 2-2 高分子和界面活性劑混合系統........................................................8 2-2-1 水溶性高分子/界面活性劑系統臨界濃度之分析........................8 2-2-2 以螢光探針探討高分子界面活性劑系統...................................10 2-2-3 高分子/界面活性劑叢集型態之探討...........................................14 第三章 實驗部份.....................................................................................16 3-1 實驗藥品與儀器設備......................................................................16 3-1-1 實驗藥品.......................................................................................16 3-1-2 分析儀器.......................................................................................18 3-1-3 實驗用分析器材...........................................................................20 3-2 實驗製備方法和步驟......................................................................20 3-2-1 NVF 單體純化和減壓蒸餾..........................................................20 3-2-2 Poly(N-vinylformamide)聚合反應步驟........................................21 3-3 螢光光譜分析用樣品製備..............................................................22 3-3-1 含螢光探針Pyrene溶液樣品製備….........................................22 3-3-2 穩態螢光猝熄法待測樣品製備...................................................24 3-3-3 Dipyme/PNVF/界面活性劑水溶液製備.......................................25 3-3-4 Dipyme在溶液樣品中分散性.......................................................26 3-3-5螢光光譜儀設定.............................................................................31 3-4 核磁共振光譜樣品製備..................................................................32 3-4-1 PNVF0.5 wt%/SDS/D2O待測樣品製備........................................32 3-4-2 PNVF 0.5 wt%/CTAB/D2O NMR待測樣品製備.........................33 第四章 實驗原理....................................................................................35 4-1 螢光光譜原理..................................................................................35 4-1-1 螢光原理.......................................................................................35 4-1-2 螢光探子Pyrene原理與應用…..................................................35 4-1-3 螢光探針di(1-pyrenyl methyl)ether（Dipyme）原理及應用....40 4-1-4 穩態螢光猝熄法（平均聚集數測定原理）...............................41 4-2 核磁共振理......................................................................................44 4-2-1 核磁共振的基本介紹..................................................................44 4-2-2二維核磁共振光譜簡介……….….................................…..........47 4-2-3 NOE光譜原理..............................................................................49 4-3 高分子本質黏度實驗原理..............................................................53 4-3-1 測定高分子本質黏度..................................................................53 4-3-2高分子本質黏度之物理意義........................................................55 第五章 結果與討論...............................................................................56 5-1 PNVF高分子溶液型態之討論.......................................................56 5-1-1 PNVF高分子溶液中本質黏度.....................................................56 5-1-2 PNVF 分子量之鑑定…………………………………………...57 5-2 PNVF/SDS混合溶液中PNVF/SDS相互作用探討......................58 5-2-1 Pyrene螢光光譜在PNVF/SDS系統中結果分析……...............58 5-2-2 PNVF/SDS叢集尺寸和數目之定量分析………........................62 5-2-3 PNVF/SDS系統中1H-NMR光譜化學位移對[SDS]趨勢分析.66 5-2-4 PNVF/SDS間短距離相互作用對SDS濃度趨勢變化...............71 5-2-5 二維NOE核磁共振光譜在PNVF-SDS溶液系統，關聯共振交 叉峰的產生和混合時間之關係..............................................................76 5-2-6 PNVF和SDS叢集中PNVF-SDS相對位置分析........................77 5-2-7 PNVF和SDS叢集和SDS微胞示意圖.......................................84 5-2-8 PNVF/SDS溶液系統中，在不同[SDS]區間相對應PNVF/SDS叢 集形態………………………..................................................................85 5-2-9 Dipyme螢光光譜在PNVF-SDS溶液系統中結果分析..............88 5-2-10 高分子/界面活性劑系統作用力反應性(reactivity)和高分子化 學結構之關係..................................................................................90 5-3 PNVF/CTAB 系統交互作用之探討...............................................93 5-3-1 PNVF/CTAB溶液系統中，Pyrene螢光光譜分析.......................93 5-3-2 PNVF/CTA溶液系統中1H-NMR光譜化學位移對[CTAB]變化趨勢分析.....................................................................................................98 5-3-3 PNVF-CTAB系統中PNVF-CTAB相互作用位置....................101 5-3-4 不同CTAB濃度區間下，PNVF-CTAB相互作用形態.............102 5-4 非離子型界面活性劑/PNVF溶液系統中相互作用探討...........107 5-4-1 Pyrene螢光光譜在PNVF/C12E7與PVNF/Tergitol 15-S-9系統中結果分析................................................................................................107 5-4-2 Pyrene螢光光譜在PNVF/TX 100系統中結果分析..................112 第六章 結論..........................................................................................114 第七章 參考文獻..................................................................................116

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