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研究生: 賴羽靖
Yu-Ching Lai
論文名稱: 改質聚氧乙烯型界面活性劑之製備、界面性質及其染色性之研究
Preparation, surface-activities and dyeing properties of modified polyoxyethylene surfactants
指導教授: 蘇舜恭
Shuenn-Kung Su
口試委員: 謝國煌
Kuo-Huang Hsieh
邱士軒
Shih-Hsuan Chiu
黃茂全
Mou-Chuan Hwang
林麗惠
Li-Huei 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: 2016
畢業學年度: 104
語文別: 中文
論文頁數: 143
中文關鍵詞: 聚氧乙烯型界面活性劑界面性質螯合染料相互作用分散性聚乳酸纖維染色
外文關鍵詞: Polyoxyethylene surfactant, Interfacial properties, Chelation, Dye interactions, Dispersion, Polylactic acid fiber, dyeing
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  • 本研究主要合成兩系列改質聚氧乙烯型界面活性劑,ST系列型界面活性劑是以Polyoxyethylenated Stearylamine (415ST, 430ST)為原料,利用馬來酸酐和亞硫酸氫鈉進行改質使其結構中之親水基團同時具有非離子基團以及陰離子基團形成多親水基之型態。TR系列型界面活性劑是以Ethylenediamine Propoxylate Ethoxylate (Tetronic701; TR701)為原料,利用馬來酸酐、烷基醇和亞硫酸氫鈉進行改質使其結構形成四端對稱結構且同時含非離子基團、陰離子基團之親水端與不同烷基鏈(C8~C18)之四分子型界面活性劑。所合成之產物以紅外線光譜分析(FT-IR)、核磁共振光譜(1H-NMR)以及元素分析(EA)確認其結構,所測試之界面性質包括表面張力、接觸角、起泡性、導電度、螢光光譜,並與改質前比較其性質差異。實驗中並測試螯合能力、pH緩衝能力、乳化性、分散性以及染料相互作用等性質。
    由界面活性結果顯示改質後產物較改質前之界面活性劑具有較低的表面張力、臨界微胞濃度、分子佔有面積與吉伯士自由能,並具有較佳的濕潤性與起泡性,顯示改質後的產物具有較佳的界面性質。從乳化性質分析結果得知,分子佔有面積較小之合成產物可使分子緊密吸附於油滴表面而具有較佳之乳化安定性。從螯合實驗結果得知,一系列產物皆具有螯合鈣離子之能力。經測試合成產物與分散染料的結合粒徑分佈,結果顯示添加合成產物於染液中可使染料粒徑分佈均一,具有良好的分散能力。探討所合成之產物與分散染料間之相互作用,由結果顯示λmax產生位移即代表合成產物與分散染料分子形成複合體,且隨產物濃度增加染液吸光度隨之上升,即表示染料在水中之凝集現象因界面活性劑的加入產生分散、溶解作用以及形成複合體結構,進而使吸光度增加。研究並針對聚乳酸纖維進行染色,探討其染色製程中添加所合成改質之助劑對於纖維染色之影響。


    In this study, we have prepared two series of modified polyoxyethylene surfactants. The ST-series surfactants were prepared by Polyoxy- ethylenated Stearylamine (415ST, 430ST), Maleic Anhydride (MA) and Sodium Hydrogen Sulfite. The structure of the hydrophilic group also has a non-ionic groups and anionic groups form more hydrophilic groups of patterns. The TR-series surfactants was prepared by Ethylenediamine Propoxylate Ethoxylate (Tetronic701; TR701), Maleic Anhydride (MA), Sodium Hydrogen Sulfite and various Alkyl alcohols (C8-C18). The structure of tetrameric surfactants contain non-ionic groups, anionic hydrophilic end groups and different alkyl chains (C8~C18). The structure of a series of surfactants has been confirmed by FT-IR, 1H-NMR and Elemental analyses. The surface activities were evaluated by surface tension, contact angle, foam properties, conductivity, fluorescence properties, and compared with before modification. The chelating ability, pH buffer capacities, emulsification, dispersibilities and dye-surfactants were also investigated.
    Surface activity results exhibited that surfactants have lower surface tension, CMC, occupied area per molecule and Gibb’s energy, moreover, these compounds possessed better wetting and lower foaming than before modification. From emulsification results, the lower value of occupied area per molecule indicated that molecules packed close on oil surface and resulted in excellent emilsion stability. From measurements of the chelation, we found that these product exhibit chelating ability of calcium ion. From measurements of the particle sizes of dye solutions, we found that the surfactants exhibited uniform partical size distribution and good dispersibilities. We used spectrophotometry to investigate the interactions between the dyes and the surfactants in the dye bath. In the case of each of the three kinds of disperse dyes, the absorbance of the dye solutions in the presence of the surfactants were higher than those in its absence because of the dispersion, dissolution and forming complex formation. We also conducted dyeing polylactic acid fiber of explore the influence of the dyeing process to add the modified surfactants for dyeing.

    摘要……………………………………………………………………Ⅰ Abstract………………………………………………………………Ⅲ 誌謝……………………………………………………………………Ⅴ 目錄……………………………………………………………………Ⅶ 圖目錄…………………………………………………………………XI 表目錄…………………………………………………………………XV 第一章 緒論………………………………………………………………1 1-1前言……………………………………………………………………1 1-2 文獻探討……………………………………………………………10 1-2-1 多聚體界面活性劑製備與界面性質……………………………10 1-2-2 本研究室過去之相關研究………………………………………12 1-2-3 聚乳酸纖維染色工程……………………………………………13 1-3研究目的……………………………………………………………15 第二章 實驗……………………………………………………………17 2-1實驗試藥……………………………………………………………17 2-1-1合成原料…………………………………………………………17 2-1-2試藥(劑)…………………………………………………………19 2-1-3 染料………………………………………………………………23 2-1-4 實驗儀器設備……………………………………………………25 2-2實驗方法………………………………………………………………27 2-2-1 合成………………………………………………………………27 2-2-1-1 合成方法(ST系列)……………………………………………27 2-2-1-2 合成步驟(ST系列)……………………………………………28 2-2-1-3 合成方法(TR系列)……………………………………………29 2-2-1-4 合成步驟(TR系列)……………………………………………30 2-2-1-5 酸價測定法……………………………………………………31 2-2-1-6 純化……………………………………………………………34 2-2-1-7 結合硫酸量測定法……………………………………………34 2-2-2 結構分析…………………………………………………………36 2-2-2-1紅外線吸收光譜儀……………………………………………36 2-2-2-2核磁共振光譜儀………………………………………………36 2-2-2-3元素分析儀……………………………………………………36 2-2-3 基本性質測定……………………………………………………37 2-2-3-1 表面張力………………………………………………………37 2-2-3-2 接觸角…………………………………………………………37 2-2-3-3 導電度…………………………………………………………38 2-2-3-4 起泡性…………………………………………………………38 2-2-3-5 螢光光譜………………………………………………………39 2-2-3-6 pH緩衝能力……………………………………………………39 2-2-3-7 乳化性…………………………………………………………40 2-2-3-8 螯合能力………………………………………………………40 2-2-4 應用性質…………………………………………………………42 2-2-4-1 染料分散性……………………………………………………42 2-2-4-2 染料與界面活性劑之相互作用………………………………43 2-2-4-3 聚乳酸纖維染色性……………………………………………44 第三章 結果與討論……………………………………………………46 3-1 合成與結構分析……………………………………………………46 3-1-1 合成………………………………………………………………46 3-1-2 分子結構…………………………………………………………48 3-1-2-1 紅外線光譜分析………………………………………………48 3-1-2-2 核磁共振光譜分析……………………………………………51 3-1-2-3 元素分析………………………………………………………57 3-2 基本性質……………………………………………………………59 3-2-1 表面張力…………………………………………………………59 3-2-2 接觸角……………………………………………………………69 3-2-3 導電度……………………………………………………………73 3-2-4 起泡性……………………………………………………………76 3-2-5 螢光性質…………………………………………………………80 3-2-6 pH緩衝能力………………………………………………………83 3-2-7 乳化性……………………………………………………………85 3-2-7-1 界面電位………………………………………………………88 3-2-7-2 乳化粒徑………………………………………………………91 3-2-8 螯合能力…………………………………………………………95 3-3 應用性質……………………………………………………………97 3-3-1 染料分散性………………………………………………………99 3-3-2 染料與界面活性劑之相互作用…………………………………104 3-3-3 聚乳酸纖維染色性………………………………………………111 第四章 結論………………………………………………………………117 參考文獻…………………………………………………………………119

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