摘 要
本文以三種不同的異氰酸鹽Toluene Diisocyanate, 4,4-Diphenylmethane Diisocyanate, Isophorone Diisocyanate其不同含量導入聚胺基甲酸酯分子中即可形成陰離子型聚胺基甲酸酯的陰離子體，並對其物性做深入的探討。
Toluene Diisocyanate, 4,4-Diphenylmethane Diisocyanate, Isophorone Diisocyanate分別與其他添加劑反應成水性陰離子型聚胺基甲酸酯之分子結構，由IR光譜圖證實其存在。
實驗結果顯示，陰離子型聚胺基甲酸酯的粘度會分別隨Toluene Diisocyanate 4,4-Diphenylmethane Diisocyanate Isophorone Diisocyanate濃度之增高而增大，原因是因為水性PU分散劑分子與分子間之作用，而使得PU分散劑分子之自由體積變大，結果導致陰離子型聚胺基甲酸酯之溶液粘度增大。實驗結果也顯示改變異氰酸酯之濃度而固定其他組成成分所合成的水性PU樹脂薄膜伸長率似乎會隨異氰酸酯之濃度增大而變大，是因為水性PU樹脂分子與分子間的作用力增強,使得水性PU樹脂的架橋力增大,結果造成水性PU樹脂薄膜伸長率增大。

Abstract
The reaction of respective toluene diisocyanate (TDI), 4,4-diphenylmethane (MDI) and isophorone diisocyanate (IPDI) with polyester and other additives to form the conformation of polyurethane (PU) ionomer coatings has been demonstrated by IR spectra. The experimental results show that both viscosities and average particle sizes of anionic-type polyurethane ionomer-type polyrethane ionomer coatings in aqueous solution appear to increase with increasing concentraction of TDI, MDI and IPDI, respectively. This is the result of increased free volume of polyurethane ionomer molecules resulting from increasing intermolecular interaction between PU ionomer molecules themselves and between PU ionomer molecule and water molecule. In aqueous solution, the surface tension of anionic-type PU ionomer is seen to increase with an increase of diisocyanate concentration, as a result of hydrophobics adsorbed at the surface becoming even more ordered.
Experimental results also indicate that the tensile strength of film made by anionic-type PU ionomer coatings appear to increase with increasing concentration of TDI, MDI and IPDI, respectively. This is because increased intermolecular interaction between PU ionomer molecles themselves may make the crosslinking capability of PU ionomer coatings molecule become stronger. Therefore, the tensile strength of the film made by anionic-type PU ionomer coatings increases.

目錄
第一章 前言……………………………………………………………1
第二章 理論部份………………………………………………………3
2-1 PU離子體……………………………………………………………4
2-1-1水性PU分類………………………………………………………6
2-1-2 PU離子體的合成反應…………………………………………….7
2-2 原料………………………………………………………………...10
2-2-1 異氰酸酯（Isocyanate）…………………………………………10
2-2-2 多元醇（Polyol）………………………………………………..16
2-2-3 鏈延長劑(linkage extender)……………………………………..21
2-2-4 催化劑(catalyst)………………………………………………….22
2-2-5 內部乳化劑(Internal emulsifiers)………………………………..23
2-2-6 溶劑的選擇……………………………………………………...25
2-2-7 水：蒸餾水、去離子水………………………………………....25
2-3 PU離子體的製造……………………………………………….….26
2-3-1 溶液法(solutlonprocess)…………………………………………26
2-3-2 預聚物混合法(prepolymer mixing process)…………………….28
2-3-3 熱熔法(melt dispersion process)………………………………...29
2-3-4 Ketimine/Ketazine法……………………………………………..31
第三章 實驗部份………………………………………………………32
3-1實驗之分析儀器設備………………………………………………32
3-1-1實驗裝置………………………………………………………….32
3-1-2分析儀器………………………………………………………….33
3-2-2實驗藥品…………………………………………………………34實驗步驟………………………………………………………………..35
3-3 物性之測試………………………………………………………...36
3-3-1 紅外光譜儀之測試……………………………………………...36
3-3-2 表面張力之測試（Wilhelmy法）……………………………….37
3-3-3 黏度之測試……………………………………………………...38
3-3-4 粒徑及擴散係數之測定………………………………………...40
3-3-5 機械性質之測定………………………………………………...41
3-3-6原子力學顯微鏡之測定…………………………………………43
第四章 實驗結果圖表…………………………………………………45
第五章 參考文獻………………………………………………………69
圖目錄
圖 2-1 The urethane link ………………………………………………..3
圖 2-2 分子結構與PU之關係圖……………………………………….3
圖 2-3 離子體結構圖…………………………………………………..4
圖 2-4 PU樹脂海島狀結晶相…………………………………………..5
圖 2-5 PU結構以X-ray 繞射和熱分析結果顯示……………………...5
圖 2-6 陽離子型PU離子體之製程反應……………………………….8
圖 2-7 羧酸型PU陰離子體之製程反應………………………………..9
圖 2-8 磺酸型PU離子體之製程反應………………………………....9
圖 2-9 芳香族及脂肪族異氰酸鹽…………………………………….11
圖 2-10 溶液法之製程………………………………………………...27
圖 2-11 預聚物混合法之製程………………………………………...29
圖 3-1 實驗裝置圖…………………………………………………….32
圖 3-2 原理力學顯微鏡裝置圖………………………………………44
Figure 1.Spectrum of toluene diisocyanate at 25±0.05℃………………47
Figure 2.Spectrum of polyurethane ionomer prepolymer
formed after 10mins reaction at 25±0.05℃………………….48
Figure 3.Spectrum of polyurethane ionomer prepolymer
formed after 2 hours reaction at 25±0.05℃………………….49
Figure 4. Plot of the viscosity versus the concentration
of toluene diisocyanate used to prepare the
anionic PU resins,at 25±0.05℃………………………………50
Figure 5. Plot of the viscosity versus the concentration
of diphenylmethane diisocyanate used to prepare
the anionic PU resins,at 25±0.05℃…………………………..51
Figure 6. Plot of the viscosity versus the concentration
of isophorone diisocyanate used to prepare the anionic PU resins,at 25±0.05℃…………………………………………...52
Figure 7. Plot of the surface tension versus the
concentration of toluene diisocyanate used to prepare the anionic PU resins,at 25±0.05℃………………………………53
Figure 8. Plot of the surface tension versus the
concentration of diphenylmethane diisocyanate used to prepare the anionic PU resins,at 25±0.05℃…………………………..54
Figure 9. Plot of the surface tension versus the
concentration of isophorone diisocyanate used to prepare the anionic PU resins,at 25±0.05℃………………………………55
Figure 10. Plot of the number average particle size versus the
concentration of toluene diisocyanate used to prepare the
anionic PU resins, at 25±0.05℃………………………….....56
Figure 11. Plot of the number average particle size versus the
concentration of diphenylmethane diisocyanate used to
prepare the anionic PU resins, at25±0.05℃………………...57
Figure 12. Plot of the number average particle size versus the
concentration of isophorone diisocyanate used to prepare the
anionic PU resins, at 25±0.05℃…………………………….58
Figure 13. Plot of the tensile strength versus the concentration of toluene
diisocyanate used to prepare the anionic PU resins, at
25±0.05℃…………………………………………………...59
Figure 14. Plot of the tensile strength versus the concentration of
diphenylmethane diisocyanate used to prepare the anionic PU
resins,at 25±0.05℃…………………………………………60
Figure 15. Plot of the tensile strength versus the concentration of
isophorone diisocyanate used to prepare the anionic PU
resins,at 25±0.05℃…………………………………………61
Figure 16. Plot of the elongation versus the concentration of toluene
diisocyanate used to prepare the anionic PU resins, at
25±0.05℃…………………………………………………..62
Figure 17. Plot of the elongation versus the concentration of
diphenylmethane diisocyanate used to prepare the anionic PU
resins, at 25±0.05℃…………….…………………………..63
Figure 18. Plot of the elongation versus the concentration of isophorone
diisocyanate used to prepare the anionic PU resins, at
25±0.05℃…………………………………………………..64
Figure 19. TDI型水性PU樹脂之5 micrometer 表面及phase圖…..65
Figure 20. TDI型水性PU樹脂之1 micrometer 表面及phase圖…..66
Figure 21. TDI型水性PU樹脂之1 micrometer 立體圖…………….67
Figure 22. TDI型水性PU樹脂之1 micrometer 表面分析圖……….68
表目錄
表2-1 異氰酸鹽的黃變情形…………………………………………..13
表2-2 二異氰酸鹽對CH3OCH2CH2OH之相對反應率……………..15
表2-3 polyol分子量和熔點關係圖………………………………….18
表2-4 PU樹脂聚二醇原料種類及特性……………………………..19
表2-5 催化劑對於Diisocyanate反應催化效果………………………23
表2-6 內部乳化劑種類………………………………………………..24
表3-1 TDI型水性PU塗料分散劑配方實例………………………..36
表3-2 紅外線光譜特性吸收峰頻率…………………………………..37

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