臺灣博碩士論文加值系統

本論文係探討ㄧ系列改質gemini型界面活性劑之合成及界面性質，內容包括二種新型界面活性劑，一種為以polyoxyethylenated stearyl ether及fumaric acid合成一系列含陰離子基團及多個非離子基團之多親水基gemini界面活性劑（簡稱modified gemini surfactants (A)），所合成的產物以元素分析（EA）、紅外線光譜分析（IR）、核磁共振光譜（1H-NMR）確認其構造，所測試之界面性質包括表面張力、接觸角、起泡性等。合成物並做鈣離子螯合能力實驗，結果顯示此系列合成產物具有良好的界面性質並具有良好的螯合能力。在精練漂白上，合成產物可使棉布白度增加且吸水性增加，表示其有良好之精練性。
研究modified gemini surfactants (A)用於直接染料染棉之染著情形及與直接染料間之相互作用，結果顯示皆因染料構造不同，有促染（C.I. Direct Orange 39 and C.I. Direct Red 83）或緩染（C.I. Direct Blue 86）之效果及複合體凝集或解凝集之作用。
另ㄧ種改質Gemini型界面活性劑為兩個疏水基及多個親水基組成，先以maleic anhydride將非離子界面活性劑分子加大後，再導入陰離子基團（簡稱modified gemini surfactants (B)）。所合成的產物以元素分析、IR、1H-NMR確認其構造，所測試之界面性質包括表面張力、接觸角、起泡性、螢光等。合成產物並做粒徑分佈及高溫分散性測試，結果顯示此系列合成產物具有良好的界面性質且具有良好的分散能力。
研究modified gemini surfactants (B)用於分散染料染聚酯織物之染著情形，結果顯示助劑的添加對染色有緩染作用。此系列產物與分散染料間之相互作用中，可看出染料在水中之凝集現象因界面活性劑之加入產生分散作用，因而吸光度增加。
Modified gemini surfactants因構造中同時具有疏水基及親水基，呈現界面活性劑之特殊構造及良好的界面性質，較傳統界面活性劑更具附加價值。

In this study, two series of modified gemini surfactants were prepared and the surface activities were investigated. A series containing multi-anionic and nonionic hydrophilic moiety were prepared by reacting fumaric acid with polyoxyethylenated stearyl ether in the presence of a peroxy-type free radical initiator to form a carboxylic acid group-containing addition product (called modified gemini surfactants (A)). The structure of these surfactants has been confirmed by EA, IR, 1H-NMR and the surface activities were evaluated by surface tension, contact angel, foaming properties. The self-sequestering ability was determined by monitoring the sequestering ability of the surfactants toward calcium ions. These surfactants exhibit excellent functional properties of surface activities and self-sequestering. In application on cotton bleaching procedures these surfactants increase the penetration of the fibers of grey fabrics and increase the whiteness of bleached cotton.
The dyeing properties on cotton-direct dye systems were studied by the spectrophotometric method. The degree of aggregation of direct dyes in dye-surfactant systems was found to influence the rate of cotton dyeing. The disaggregations of direct dyes (Orange 39 and Red 83) in the presence of surfactants increase the dye uptake of cotton. On the other hand, the formations of dye-surfactant (Blue 86) complex retard the speed of dye uptake and assist the leveling fabric dyeing.
The other series possesses two identical hydrophobic groups and multiple hydrophilic groups in their structures. The two hydrophobic alkyl chains were appended to maleic anhydride through condensation with polyoxyethylenated stearyl ether; multiply anionic hydrophilic moieties were obtained after modifying the polyoxyethylenated stearyl ether units with fumaric acid groups to form carboxylate group-containing addition products (called modified gemini surfactants (B) ). The structure of these surfactants has been confirmed by EA, IR, 1H-NMR and the surface activities were evaluated by surface tension, contact angel, foaming properties and fluorescence properties. We have also studied the dispersing abilities of these surfactants toward commercial disperse dyes at elevated temperature, and the corresponding effects during polyester dyeing. From measurements of the particle sizes and dispersibilities of the dye solutions, we found that the surfactants exhibited good surface activities and dispersing ability.
During the dyeing of polyester fabrics, the dyeing rate decreased when the surfactants were present because the hydrophilic dye–surfactant complexes enhanced the solubility of the disperse dyes. In this study, we used spectrophotometry to investigate the interactions between the dyes and surfactants in the dye bath. In the case of each of the three disperse dyes, the absorbances of the dye solutions in the presence of the surfactants were higher than those in its absence.
Novel modified gemini surfactants have hydrophilic groups and hydrophobic groups, exhibiting exceptional structure and good surface activities better than traditional surfactants.

摘 要 Ⅰ
ABSTRACT Ⅲ
目 錄 Ⅴ
圖 表 Ⅹ
第1章 緒論 1
1.1 前言 1
1.2 文獻探討 2
1.2.1 Gemini型界面活性劑定義及發展 2
1.2.2 ㄧ般界面活性劑及gemini型界面活性劑之構造 3
1.2.3 Gemini型界面活性劑之界面性質 4
1.2.4 Gemini型界面活性劑之重要性及應用 5
1.2.5 過去改質之方法 5
1.2.6 本研究室過去之相關研究 6
1.3 研究目的 7
第2章 實驗 8
2.1 實驗用試藥 8
2.1.1 合成原料 8
2.1.2 試藥 8
2.1.3 螢光試劑 10
2.1.4 染料 11
2.2 主要實驗設備 13
2.3 實驗方法 15
2.3.1 合成 15
2.3.1.1 Modified gemini surfactants (A)之製備 15
2.3.1.2 Modified gemini surfactants (B)之製備 18
2.3.2 分析 18
2.3.2.1 純化 18
2.3.2.2 酸價（Acid Value）測試 17
2.3.2.3 構造分析 21
2.3.3 基本性質測定 21
2.3.3.1 表面張力 21
2.3.3.2 接觸角 22
2.3.3.3 起泡性 22
2.3.3.4 耐酸鹼性 23
2.3.3.5 螢光光譜（pyrene試劑） 23
2.3.3.6 分散性 24
2.3.3.6.1 粒徑大小分佈 24
2.3.3.6.2 高溫分散性 24
2.3.3.7 鈣離子螯合能力 25
2.3.3.8 陰離子基數 26
2.3.3.9 精練性 27
2.3.4 應用性質測定 27
2.3.4.1 染料與界面活性劑之相互作用 28
2.3.4.2 染色性 28
第3章 結果與討論 31
3.1 Modified gemini surfactants (A)系列 31
3.1.1 合成與構造分析 31
3.1.1.1 合成 31
3.1.1.2 分子構造之確認 33
3.1.2 基本性質 36
3.1.2.1 表面張力 36
3.1.2.2 接觸角 39
3.1.2.3 起泡性 41
3.1.2.4 耐酸鹼性 43
3.1.2.5 螯合能力 45
3.1.2.6 精練性 47
3.1.3 應用性質 49
3.1.3.1 相互作用 49
3.1.3.2 染色性 58
3.1.4 結論 61
3.2 Modified gemini surfactants (B)系列 63
3.2.1 合成與構造分析 63
3.2.1.1 合成 63
3.2.1.2 分子構造之確認 63
3.2.2 基本性質 66
3.2.2.1 表面張力 66
3.2.2.2 接觸角 69
3.2.2.3 起泡性 71
3.2.2.4 螯合能力 72
3.2.2.5 螢光光譜探討疏水度 74
3.2.2.6 分散性 76
3.2.2.6.1 粒徑大小分佈 76
3.2.2.6.2 高溫分散性 78
3.2.3 應用性質 80
3.2.3.1 相互作用 80
3.2.3.2 染色性 88
3.2.4 結論 91
第4章 總結論與建議 93
4.1 總結論 93
4.2 建議 94
第5章 參考文獻 95

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