臺灣博碩士論文加值系統

本文以丙酮製程合成透氣型水溶性聚胺基甲酸酯，對
其物理性質、機械性與透氣特性作較深入的探討。
由IR光譜圖-NCO吸收峰，(C2H5)3NH 吸收峰與-NH吸收峰的出現，和DMDCS特性吸收峰的存在，均顯示透氣型水溶性聚胺基甲酸酯的形成。實驗結果顯示，透氣型水溶性聚胺基甲酸酯溶液的粘度、表面張力以及分子之擴散係數均會隨著DMDCS濃度的增加而變小，但溶液的顆粒大小會隨著DMDCS濃度的增加而變大。當固定DMDCS的濃度而改變 NCO/OH 的當量比例時，則透氣型水溶性聚胺基甲酸酯溶液的粘度、顆粒大小均會隨 NCO/OH 的比值增高而變大。但溶液的表面張力則不受 NCO/OH 的比值改變而受影響。由於聚胺基甲酸酯分子的主鏈上增多了DMDCS之官能基會受其他組成成分及水分子之影響而未能加速分子之硬化。透氣型水溶性聚胺基甲酸酯皮膜的拉應力、伸長率與100%模數會隨著DMDCS的濃度增加而變小，不過當DMDCS的濃度固定而改變 NCO/OH 的當量比例時，透氣型水溶性聚胺基甲酸酯皮膜的拉應力、伸長率與 100% 模數均會隨著NCO/OH的比值增高而變大。含 DMDCS 之水溶性聚胺基甲酸酯薄膜對氧的透氣性比不含DMDCS之水溶性聚胺基甲酸酯薄膜對氧的透氣性較佳。不過當DMDCS的含量增多，其對氧的透氣性也會增高。

The purpose of this study is to synthesize gas-permeable water-based polyurethanes (called GP-PU) by means of acetone process and to explore their physical and gas-permeable properties.
The formation of GP-PU, due to the decrease in the
-NCO absorbance peak, the disappearance of the -OH absorbance peak, the appearance of HN-C=O, (C2H5)3NH and -NH peaks as well as the DMDCS peaks, is demonstrated by IR spectra. The experimental results show that the viscosity, surface tension and diffusion coefficient of the GP-PU molecule decrease with increasing the concentration of the DMDCS present in the system, but the partical size of the GP-PU increases with increasing the concentration of DMDCS in the system. As the concentration of the DMDCS is fixed, the viscosity and partical size of the GP-PU may increase with raising the ratio of NCO to OH. However, the surface tension of the solution is not affected by the variation of the ratio of NCO to OH.
Since the amount of DMDCS on the main chain of polyurthane moleculeincreases and may be affected by
the presence of other major compontents ,therefore ,the rate of the hardness of the water-based polyurethance can not be speeded up. The tensile strength, the elongation and the 100% modulus of GP-PU may decrease with increasing the concentration of DMDCS. As the concentration of DMDCS is fixed, the tensile strength, the elongation and 100% modulus of the GP-PU film may become greater as long as the ratio of NCO to OH is raised.
The thin film of water-based polyurethanes containing DMDCS id better than that of water-based polyurethanes without DMDCS for permeability of this film to oxygen. However, the permeability of this film to the oxygen is increased as the amount of DMDCS present in the water-based polyurethane increases.

摘要
一、前言……………………………………………… 1
二、理論部分………………………………………… 4
2.1 水性聚胺基甲酸乙酯……………………….. 4
2.1-1 水性聚胺基甲酸乙酯之簡介及其優點…. 4
2.1-2 水性聚胺基甲酸乙酯的特徵……………. 5
2.2 原料………………………………………….. 6
2.2-1 異氰酸酯…………………………………. 6
2.2-2 多元醇……………………………………. 11
2.2-3 鏈延長劑…………………………………. 12
2.2-4 離子基單體………………………………. 12
2.2-5 催化劑……………………………………. 14
2.2-6 架橋劑……………………………………. 15
2.2-7 溶劑的選擇………………………………. 17
2.3 水性聚胺基甲酸乙酯之合成……………….. 17
2.4 透氣型水性聚胺基甲酸乙酯……………….. 20
2.4-1 聚合物的擴散作用………………………. 20
2.4-2 氣體擴散作用與聚合物型態學的關係…. 21
2.4-3 聚合物的擴散係數與擴散性質…………. 22
2.4-4 薄膜的透氣理論…………………………. 24
2.4-5 透氣型水性PU樹脂之合成…………….. 26
三、實驗部分……………………………………….. 27
3.1 實驗分析儀器……………………………….. 27
3.2 實驗藥品…………………………………….. 29
3.3 透氣型水性PU樹脂之製備…………………. 30
3.3-1 實驗步驟…………………………………. 30
3.3-2 透氣型水性PU樹脂之皮膜及薄膜的製備 31
3.4 物性之測試………………………………….. 31
3.4-1 紅外線光譜儀測試………………………. 31
3.4-2 粒徑及擴散係數之測定…………………. 32
3.4-3 機械性質之測定…………………………. 33
3.3-4 氣體滲透性質的測試……………………. 34
四、結果與討論…………………………………….. 37
4.1 IR 光譜圖之探討……………………………. 37
4.2 改變二甲醇基丙酸(Dimethylol Propionic
Acid)及苯氨酸(Aminobenzenic Acid)對PU
樹脂剛性影響情形………………………….. 46
4.3 改變二甲醇基丙酸(Dimethylol Propionic
Acid)及苯氨酸(Aminobenzenic Acid)對PU
樹脂伸長率影響之情形…………………….. 49
4.4 改變二甲醇基丙酸(Dimethylol Propionic
Acid)及苯氨酸(Aminobenzenic Acid)之濃
度對PU樹脂透濕性影響之情形……………. 52
4.5 改變二甲醇基丙酸(Dimethylol Propionic
Acid)及苯氨酸(Aminobenzenic Acid)的濃
度對PU樹脂拉應力影響之情形……………. 55
五、結論..…………………………………………… 58
六、參考文獻……………………………………….. 60
圖 目 錄
圖1 合成水性PU之反應機構…..…………………… 3
圖2 芳香族及脂肪族異氰酸鹽………………………. 7
圖3 丙酮製程…………………………………………. 18
圖4 預聚合物混合攪拌製程…………………………. 19
圖5 滲透或透析………………………………………. 20
圖6 逆滲透……………………………………………. 21
圖7 高分子薄膜透氣圖………………………………. 24
圖8 實驗裝置圖………………………………………. 27
圖9 透氣測定裝置圖…………………………………. 34
圖10 甲苯二異氰酸酯之IR光譜圖………………... 38
圖11 二甲醇基丙酸(DMPA)之IR光譜圖…………... 39
圖12 苯胺酸(ABA)之IR光譜圖…..…………….…. 40
圖13 反應前之IR光譜圖……...………………….. 41
圖14 加入二甲醇基丙酸(DMPA)反應中之IR光譜圖. 42
圖15 加入二甲醇基丙酸(DMPA)反應後之IR光譜圖. 43
圖16 加入苯胺酸(ABA)反應時之IR光譜圖……….. 44
圖17 加入苯胺酸(ABA)反應後之IR光譜圖……….. 45
圖18 Plot 100% Modulus versus the concentration
of dimethyl acetamide for the film of
polyurethane resin, at 25±0.05 ℃ …..….. 47
圖19 Plot 100% Modulus versus the concentration
of aminobenzoic acid for the film of
polyurethane resin, at 25±0.05 ℃ ……… 48
圖20 Plot Elongation(%) versus the concentration
of dimethyl acetamide for the film of
polyurethane resin, at 25±0.05 ℃ ……… 50
圖21 Plot Elongation(%) versus the concentration
of dimethyl acetamide of aminobenzoic acid
for the film of polyurethane resin, at
25±0.05 ℃…………………………………….. 51
圖22 Plot water vapor permeability versus the
concentration of dimethyl acetamide for
the film of polyurethane resin, at
25±0.05 ℃…………………………………….. 53
圖23 Plot water vapor permeability versus the
concentration of aminobenzoic acid of
dimethyl acetamide for the film of
polyurethane resin, at 25±0.05 ℃……… 54
圖24 Plot Tensile strength versus the
concentration of dimethyl acetamide
for the film of polyurethane resin,
at 25±0.05 ℃…………………………………. 56
圖25 Plot Tensile strength versus the
concentration of aminobenzoic acid
of dimethyl acetamide for the film of
polyurethane resin, at 25±0.05 ℃………. 57
表 目 錄
表1 二異氰酸鹽與CH3OCH2CH2OH的反應性………… 6
表2 TDI 的物理性質………………………………… 8
表3 催化劑對於 Diisocyanate反應的催化效果…. 14
表4 聚合物的滲透係數…………………………….. 23
表5 紅外線光譜特性吸收峰頻率………………….. 32

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