臺灣博碩士論文加值系統

本研究以預聚物混合法成功地製備了一系列無溶劑、高固形份、低黏度的水性聚氨酯，先以聚丙二醇 (Polypropylene glycol, PPG)、聚四氫呋喃 (Polytetramethylene ether glycol, PTMG)、親水二醇單體 (Dimethylolpropionic acid (DMPA)及過量的異佛爾酮二異氰酸酯 (Isophorone diisocyanate, IPDI)合成出NCO封端的預聚物，以三乙胺 (Triethylamine, TEA)中和後，分散在含有乙二胺基乙磺酸鈉 (2-[(2-aminoethyl)amino]ethanesulfonic acid sodium salt, AAS)的去離子水中，最後再以乙二胺 (Ethylenediamine, EDA)進行鏈延長，獲得固形份為50%之水性聚氨酯 (WPU)，並探討NCO/OH莫耳比、多元醇側鏈程度以及親水基團含量及比例對WPU黏度的影響，利用傅立葉傳換紅外線光譜儀 (FT-IR)鑑定所合成水性聚氨酯之化學結構，並以凝膠滲透層析儀 (GPC)測定WPU的數目平均分子量 (Mn)及重量平均分子量 (Mw)，證實聚合反應已成功進行，此外，以奈米粒徑分析儀鑑定水性聚氨酯之微胞尺寸，並通過萬能拉伸試驗機測量拉伸強度和斷裂伸長率，研究結果顯示，水性聚氨酯乳液的粒徑隨著PPG/PTMG莫耳比的增加而減少，黏度則隨之增加，因PTMG為長鏈疏水性多元醇，疏水性多元醇會產生較大的粒徑且較長的分子鏈段可能將親水基團包覆住，使親水性較差，進而形成較大粒徑，透過PPG和PTMG共混，莫耳比為1:3，獲得固含量為50 wt%不含有機溶劑之水性聚氨酯，粒徑為703.5 nm，黏度為255.5 cP，最終產品的拉伸強度為20.08 MPa，吸水率為13.48 wt%，水溶解率為12.48 %。

In this work, a series of solvent-free, high solid content and low viscosity waterborne polyurethanes (WPU) were successfully prepared by prepolymer process. The NCO-terminated prepolymer was synthesized by using polypropylene glycol (PPG), polytetramethylene ether glycol (PTMG), hydrophilic di-ol monomer dimethylolpropionic acid (DMPA) and an excess of isophorone diisocyanate (IPDI). After neutralized by TEA, then dispersed in deionized water containing AAS, finally extended chain with ethylenediamine (EDA). WPU dispersion with solid content of 50 wt% was obtained. To explore the effect of the NCO/OH molar ratio, degree of side chain, hydrophilic group content on the viscosity of WPU. The chemical structures of the waterborne polyurethane were characterized by infrared spectroscopy (FT-IR), the number average molecular weight of the WPU were measured by gel permeation chromatography (GPC), which confirmed that the polymerization reaction had been successfully carried out. In addition, the micelle size of the WPU were identified by particle size analyzer. The tensile strength, elongation at break were measured by universal tensile testing machine. The results of experiment indicated that the micelle size of WPU emulsion was decreased as the PPG/PTMG molar ratio increased, and the viscosity increased. Because the PTMG was a long-chain hydrophobic polyol, hydrophobic polyol will produce larger micelle size and longer molecular chain may coat hydrophilic group, resulting poor hydrophilicity, and then form larger micelle size. Finally, 50 wt % solid content solvent free WPU was obtained by incorporating of PPG to blend with PTMG with the molar ratio of 1:3, viscosity of 255.5 cP. The final product displayed water absorption was 13.48 %, water dissolution rate was 12.48 %.

摘要 I
Abstract III
致謝 V
總目錄 VI
流程目錄 (Scheme) X
表目錄 (Table) XI
圖目錄 (Figure) XIII
第一章 緒論 1
1-1 前言 1
1-2 研究動機 3
第二章 文獻回顧 4
2-1 水性聚氨酯(Waterborne Polyurethane, WPU) 4
2-1-1 聚氨基甲酸酯簡介 4
2-1-2 聚氨基甲酸酯乳化技術 6
2-1-3 水性聚氨酯類型 6
2-1-4 水性聚氨酯的製備方法 7
2-2 水性聚氨酯的基本組成 15
2-2-1 異氰酸酯 (Isocyanate) 15
2-2-2 多元醇 (Polyol) 20
2-2-3 親水離子基團 (Hydrophilic ionic group) 22
2-2-4 鏈延長劑 (Chain extander) 24
2-2-5 中和劑 (Neutralizer) 26
2-2-6 觸媒 (Catalysts) 26
2-3 影響水性聚氨酯性質之因素 28
2-3-1 NCO/OH莫耳比之影響 28
2-3-2 異氰酸酯種類及含量之影響 28
2-3-3 多元醇種類及分子量之影響 29
2-3-4 親水離子基團種類及含量之影響 30
2-3-5 鏈延長劑種類及含量之影響 32
2-3-6 催化劑種類之影響 33
2-3-7 中和劑含量之影響 34
2-3-8 分枝劑含量之影響 34
2-4 無溶劑、高固形份水性聚氨酯之合成 36
第三章 實驗 38
3-1 實驗流程圖 38
3-2 材料與藥品 39
3-2-1 合成藥品 39
3-2-2 滴定藥品 40
3-3 實驗裝置圖 41
3-4 儀器設備 42
3-5實驗步驟 45
3-5-1 反應前處理 45
3-5-2 合成步驟 45
3-5-3 異氰酸酯官能基濃度測定 48
3-5-4 實驗樣品命名 49
第四章 結果與討論 50
4-1 水性聚氨酯之結構鑑定 50
4-1-1 水性聚氨酯之化學結構鑑定 50
4-1-2 水性聚氨酯之分子量鑑定 52
4-2 水性聚氨酯側鏈程度不同(PPG/PTMG)之物性探討 53
4-2-1 側鏈程度不同(PPG/PTMG)對平均粒徑大小之影響 53
4-2-2 側鏈程度不同(PPG/PTMG)對黏度之影響 54
4-2-3 側鏈程度不同(PPG/PTMG)對拉伸測試之影響 55
4-2-4 側鏈程度不同(PPG/PTMG)對吸水率、水溶解率之影響 57
4-3 水性聚氨酯之親水基團不同含量之物性探討 58
4-3-1 親水基團不同含量對平均粒徑大小之影響 58
4-3-2 親水基團不同含量對黏度之影響 59
4-3-3 親水基團不同含量對拉伸測試之影響 61
4-3-4 親水基團不同含量對吸水率、水溶解率之影響 62
4-4 水性聚氨酯不同R值 (NCO/OH)之物性探討 63
4-4-1 不同R值 (NCO/OH)對平均粒徑大小之影響 63
4-4-2 不同R值 (NCO/OH)對黏度之影響 64
4-4-3 不同R值 (NCO/OH)對拉伸測試之影響 66
4-4-4 不同R值 (NCO/OH)對吸水率、水溶解率之影響 67
4-5 水性聚氨酯親水基團不同比例(DMPA/AAS)之物性探討 68
4-5-1 親水基團不同比例(DMPA/AAS)對平均粒徑大小之影響 68
4-5-2 親水基團不同比例(DMPA/AAS)對黏度之影響 69
4-5-3 親水基團不同比例(DMPA/AAS)對拉伸測試之影響 71
4-5-4 親水基團不同比例(DMPA/AAS)對吸水率、水溶解率之影響 72
第五章 結論 74
第六章 參考文獻 76

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