在本研究論文中嘗試使用一種有別於傳統的非異氰酸鹽之合成法來合成聚胺酯化合物(PU)。在常壓的實驗條件下先使用環氧樹脂與二氧化碳進行加成反應合成出環碳酸酯，再使用不同的長鏈雙胺化合物(Jeffamine)與環碳酸酯化合物進行開環反應，使之經由開環加成聚合反應而形成聚胺酯化合物，並對其討論聚合反應後的性質變化。並且藉由麥可加成反應將壓克力官能基導入聚胺酯主鏈段的末端上，即可以得到一新型且紫外光可架橋之非異氰酸鹽合成法的聚胺酯寡聚物(UV-PU)。而在本實驗流程中所使用的溶劑為環保型溶劑，如乳酸乙酯，且同時使用一具有可回收特性的催化劑，如溴化鋰等。故本實驗在合成聚胺酯的過程可以被歸納為符合節能減碳與對環境友善的綠色製程。
　　經由此種製程之PU樹脂紫外光照射成膜後具親水性環保型聚胺酯樹脂薄膜，在物理性質方面，以膠含量、吸水率、對水損失率、吸乙醇率、對乙醇損失率及接觸角進行分析比較；在光學性質方面，利用掃描式電子顯微鏡與薄膜外觀進行分析；在熱性質分析方面，以熱重分析儀與動態機械分析加以探討；最後並藉由AATCC的標準水洗測試來證實本材料具有的長效性親水特性。

In this research,　a new UV-curable hydrophilic PU resin was obtained through a green, nonisocyanate, three-reaction process: (1) cyclic carbonate (BCC or PPG-DCE) compounds are prepared by inserting carbon dioxide into epoxy resins (DGEBA or PPG-DGE) at atmospheric pressure; (2) amino-terminated hydrophilic PUs (NH2-PU) prepolymer are obtained through the ring-opening polymerization of BCC and PPG-DCE utilizing di-functional or tri-functional amino hydrophilic (polyether) compounds such as Jeffamine D-2000 or T-3000; (3) UV-curable acrylate-PU oligomer (UV-PU) are obtained as adducts from the Michael addition of NH2-PU to multi-acrylate-terminated compounds, 3-acryloyloxy-2-hydroxypropyl methacrylate (AHM). We used as ethyl lactate (EL) as a green solvent and a recyclable catalyst as lithium bromide. This is an energy saving and environmental friendly green process toward PU formation.
　　In this research, UV-PU films are compared to the difference of their properties. Finally all the data of each resulted polyurethane resins with different formulations are evaluated and discussed in this report.

誌謝‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧
論文貢獻‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧
中摘‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧
英摘‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧

一、序論‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 1
1-1 前言‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 1
1-2 聚胺酯介紹‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 4
1-2-1 聚胺酯的基本材料：高分子多元醇 (Polyol)‧‧‧‧‧4
1-2-2 聚胺酯的基本材料：二元異氰酸酯 (Diisocyanates) ‧6
1-3 親水性聚胺酯之介紹‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧9
1-3-1 親水性聚胺酯溶液之種類‧‧‧‧‧‧‧‧‧‧‧‧‧9
1-3-2 陰離子型親水性聚胺酯‧‧‧‧‧‧‧‧‧‧‧‧‧‧9
1-3-3 陽離子型親水性聚胺酯‧‧‧‧‧‧‧‧‧‧‧‧‧11
1-3-4 非離子型親水性聚胺酯‧‧‧‧‧‧‧‧‧‧‧‧‧12
1-4 環氧樹脂簡介‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧13
1-4-1 環氧樹脂的開環反應特性‧‧‧‧‧‧‧‧‧‧‧‧13
1-4-2 環氧樹脂與胺類的反應特性‧‧‧‧‧‧‧‧‧‧‧14
1-5 紫外光硬化架橋技術‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧16
1-5-1 紫外光硬化架橋‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧16
1-5-2 不飽和高分子寡聚物‧‧‧‧‧‧‧‧‧‧‧‧‧‧17
1-5-3 活性稀釋劑(光反應型架橋劑) ‧‧‧‧‧‧‧‧‧‧18
1-5-4 光起始劑或光敏化劑‧‧‧‧‧‧‧‧‧‧‧‧‧‧19
1-5-5 光反應機制‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧21
1-6 綠色化學‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧23
1-7 研究動機‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧24

二、文獻回顧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧27
2-1 傳統型聚胺酯(Polyurethane)‧‧‧‧‧‧‧‧‧‧‧‧‧27
2-2 非異氰酸合成法製備聚胺酯 (Non-isocyanate Routes Polyurethane)‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧29
2-2-1 環碳酸酯法製備聚胺酯‧‧‧‧‧‧‧‧‧‧‧‧‧29
2-2-2 環氮丙烷法製備聚胺酯‧‧‧‧‧‧‧‧‧‧‧‧‧34

三、實驗‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧35
3-1 儀器(Instruments)‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧35
3-2 藥品 (Materials)‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧37
3-3 實驗步驟‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧40
3-3-1 Bis (cyclic carbonate)s 合成步驟‧‧‧‧‧‧‧‧‧‧40
3-3-2 Bis (cyclic carbonate)s 純化步驟‧‧‧‧‧‧‧‧‧‧41
3-3-3 Model reaction（Ring-opening）的反應步驟‧‧‧‧‧‧42
3-3-4 Model reaction（Michael-addition）的反應步驟‧‧‧‧‧43
3-3-5 末端胺基型聚胺酯(H2N-PU)合成步驟‧‧‧‧‧‧‧‧45
3-3-6 末端胺基型聚胺酯(H2N-PU)合成步驟－pH值的影響‧‧46
3-3-7 末端胺基型聚胺酯(H2N-PU)合成步驟－溫度的影響‧47
3-3-8 末端胺基型聚胺酯(H2N-PU) ‧‧‧‧‧‧‧‧‧‧‧48
3-3-9 末端胺基型聚胺酯(H2N-PU)之分子量‧‧‧‧‧‧‧49
3-3-10 紫外光架橋型聚胺酯(UV-PU) ‧‧‧‧‧‧‧‧‧‧50
3-3-11 紫外光架橋型聚胺酯(UV-PU) 薄膜之製備‧‧‧‧‧51
3-3-12 固含量測試 (Solid Content)‧‧‧‧‧‧‧‧‧‧‧51
3-3-13 光譜鑑定測試－紅外線光譜(FT-IR) ‧‧‧‧‧‧‧‧52
3-3-14 光譜鑑定測試－核磁共振光譜(FT-NMR) ‧‧‧‧‧52
3-3-15 薄膜物理性質測試－膠含量(Gel Content) ‧‧‧‧‧53
3-3-16 薄膜物理性質測試－去離子水浸泡吸水率 (Water- uptake %)與對水損失率(Weight % loss in water)‧‧‧53
3-3-17 薄膜物理性質測試－95%乙醇溶液浸泡吸收率(Ethanol- uptake %)與對乙醇損失率(Weight % loss in ethanol) ‧54
3-3-18 薄膜物理性質測試－薄膜接觸角(Contact Angle) ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧55
3-3-19 薄膜熱性質測試－熱重分析(Thermalgravimetric analysis, TGA)‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧56
3-3-20 動態機械分析(Dynamic Mechanical Analysis, DMA)
‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧57
3-3-21 薄膜光電學性質測試－掃描式電子顯微鏡測試(SEM)
‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧58
3-3-22 Poly(propene glycol) Carbonates合成‧‧‧‧‧‧‧‧59
3-3-23 聚丙烯醚型聚胺酯(PPG-PU)合成‧‧‧‧‧‧‧‧‧60
3-3-24 紫外光架橋型聚胺酯(UV-PU)合成‧‧‧‧‧‧‧‧61
3-3-25 紫外光架橋型聚胺酯(UV-PU)薄膜之製備‧‧‧‧‧62
3-3-26 三官能基聚醚型聚胺酯(Tri-PU)‧‧‧‧‧‧‧‧‧63
3-3-27 紫外光架橋型聚胺酯(UV-PU) ‧‧‧‧‧‧‧‧‧‧65
3-3-28 紫外光架橋型聚胺酯(UV-PU)薄膜之製備‧‧‧‧‧67
3-3-29 傳統異爾佛酮二異氰酸酯型聚胺酯(IPD-PU) ‧‧‧‧68
3-3-30 聚胺酯預聚物異氰酸酯含量（NCO %）測定‧‧‧‧‧ 70
3-3-31 紫外光架橋型聚胺酯（IPDI UV-PU (2-HEMA)）‧‧‧72
3-3-32 紫外光架橋型聚胺酯（IPDI UV-PU (AHM)）‧‧‧‧‧74
3-3-33 傳統己烷二異氰酸酯型聚胺酯（HDI-PU）‧‧‧‧‧‧76
3-3-34 紫外光架橋型聚胺酯（HDI UV-PU (2-HEMA)）‧‧‧78
3-3-35 紫外光架橋型聚胺酯（HDI UV-PU (AHM)）‧‧‧‧‧80

四、結果與討論‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧82
A-1 Bis (cyclic carbonates)s系列光譜分析‧‧‧‧‧‧‧‧‧‧‧82
4-1 光譜分析‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧82
4-2 Model reaction（Ring-opening）的光譜分析‧‧‧‧‧‧‧‧88
4-3 Model reaction（Michael-addition）的光譜分析‧‧‧‧‧‧‧94
B-1 Bis (cyclic carbonates)s系列物理性質分析‧‧‧‧‧‧‧‧100
4-4 分子量 （Molecular Weight）‧‧‧‧‧‧‧‧‧‧‧‧‧100
4-4-1 使用LiCl與EA(80℃)為反應條件的GPC分析‧‧‧100
4-4-2 使用不同pH值為反應條件的GPC分析‧‧‧‧‧‧102
4-4-3 使用不同溫度為反應條件的GPC分析‧‧‧‧‧‧105
4-5 膠含量（Gel Content）‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧108
4-6 吸水率（Water-Uptake, WA%）及對水損失率（Weight loss in water, WL%）‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧109
4-7 吸乙醇率（Ethanol-Uptake, EA%）及對乙醇損失率（Weight loss in ethanol, EL%）‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧110
4-8 表面對水接觸角（Contact Angle）‧‧‧‧‧‧‧‧‧‧‧111
C-1 Bis (cyclic carbonates)s系列熱性質分析‧‧‧‧‧‧‧‧‧113
4-9 熱重分析（Thermalgravity Analysis, TGA）‧‧‧‧‧‧‧113
4-10 動態機械分析（Dynamic Mechanical Analysis, DMA）‧‧127
D-1 Bis (cyclic carbonates)s系列外觀與電子顯微鏡性質‧‧‧‧135
4-11 耐水洗測試分析（Washing Durability）‧‧‧‧‧‧‧‧‧135
4-12電子顯微鏡分析（Scanning Electron Microscope, SEM）‧‧137
A-2 Poly(propene glycol) Carbonates系列光譜分析‧‧‧‧‧‧‧141
4-13 聚丙烯型環碳酸酯合成光譜分析‧‧‧‧‧‧‧‧‧‧141
4-14 Ring-opening的光譜分析‧‧‧‧‧‧‧‧‧‧‧‧‧‧143
B-2 聚丙烯醚型聚胺酯系列物理性質‧‧‧‧‧‧‧‧‧‧145
4-15 膠含量（Gel Content）‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧145
4-16 吸水率（Water-Uptake, WA%）及對水損失率（Weight loss in　water, WL%）‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧147
4-17 吸乙醇率（Ethanol-Uptake, EA%）及對乙醇損失率（Weight loss　in ethanol, EL%）‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧148
C-2 聚丙烯醚型聚胺酯系列熱性質分析‧‧‧‧‧‧‧‧‧‧‧150
4-18 熱重分析（Thermalgravity Analysis, TGA）‧‧‧‧‧‧‧150
4-19 動態機械分析（Dynamic Mechanical Analysis, DMA）‧‧156
D-2 聚丙烯醚型聚胺酯系列外觀性質‧‧‧‧‧‧‧‧‧‧‧‧163
4-20 聚丙烯醚型聚胺酯外觀照片‧‧‧‧‧‧‧‧‧‧‧‧163
A-3 三官能基聚醚型聚胺酯系列光譜分析‧‧‧‧‧‧‧‧‧‧165
4-21 Ring-opening的光譜分析‧‧‧‧‧‧‧‧‧‧‧‧‧‧165
B-3 三官能基聚醚型聚胺酯系列物理性質分析‧‧‧‧‧‧‧‧168
4-22 膠含量（Gel Content）‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧168
4-23 吸水率（Water-Uptake, WA%）及對水損失率（Weight loss in　water, WL%）‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧170
4-24 吸乙醇率（Ethanol-Uptake, EA%）及對乙醇損失率（Weight loss　in ethanol, EL%）‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧171
C-3 三官能基聚醚型聚胺酯系列熱性質分析‧‧‧‧‧‧‧‧‧173
4-25 熱重分析（Thermalgravity Analysis, TGA）‧‧‧‧‧‧‧173
4-26 動態機械分析（Dynamic Mechanical Analysis, DMA）‧‧179
D-3 三官能基聚醚型聚胺酯系列外觀性質‧‧‧‧‧‧‧‧‧‧187
4-27 三官能基聚醚型聚胺酯外觀照片‧‧‧‧‧‧‧‧‧‧187
A-4 傳統異氰酸鹽型聚胺酯系列光譜分析‧‧‧‧‧‧‧‧‧‧189
4-28 IPDI型聚胺酯的光譜分析‧‧‧‧‧‧‧‧‧‧‧‧‧‧189
4-29 HDI型聚胺酯的光譜分析‧‧‧‧‧‧‧‧‧‧‧‧‧‧193
B-4 以非異氰酸鹽法合成的新型聚胺酯系列物理性質分析‧‧‧197
4-30 膠含量（Gel Content）‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧197
4-31 吸水率（Water-Uptake, WA%）及對水損失率（Weight loss in water, WL%）‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧199
4-32 吸乙醇率（Ethanol-Uptake, EA%）及對乙醇損失率（Weight loss in ethanol, EL%）‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧120
C-4 傳統異氰酸鹽型聚胺酯系列熱性質分析‧‧‧‧‧‧‧‧‧202
4-33 熱重分析（Thermalgravity Analysis, TGA）‧‧‧‧‧‧ 202
4-33-1 異氰酸鹽型與非異氰酸鹽型UV-PU的熱重分析（TGA）
‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧203
4-33-2 不同壓克力單體應用於UV-PU的熱重分析 （TGA）
‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧208
4-34 動態機械分析（Dynamic Mechanical Analysis, DMA）‧‧213
4-34-1 異氰酸鹽型聚胺酯的動態機械分析（DMA）‧‧‧‧213
4-34-2 異氰酸鹽型與非異氰酸鹽型聚胺酯的動態機械分析（DMA）‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧221

五、結論‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧229
5-1 雙酚A型聚胺酯‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧229
5-2 聚丙烯醚型聚胺酯‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧231
5-3 三官能基聚醚型聚胺酯‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧232
5-4 異氰酸鹽型聚胺酯與非異氰酸鹽型聚胺酯的綜合比較‧‧233

六、參考文獻‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧235

Resume‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧239

Award‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧239

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圖    表    目    錄

Scheme 1-1  陰離子型水性聚胺酯分散液‧‧‧‧‧‧‧‧‧‧10
Scheme 1-2  陽離子型水性聚胺酯分散液‧‧‧‧‧‧‧‧‧‧11
Scheme 1-3  非離子型水性聚胺酯分散液‧‧‧‧‧‧‧‧‧‧12
Scheme 2-1  常見的聚胺酯(PU)簡易合成圖‧‧‧‧‧‧‧‧‧27
Scheme 2-2  開環加成反應合成環碳酸酯‧‧‧‧‧‧‧‧‧‧ 30
Scheme 2-3  不同催化劑進行開環加成反應合成環碳酸酯‧‧‧31
Scheme 2-4  不同酸、鹼度條件下環碳酸酯的開環聚合反應‧‧‧32
Scheme 2-5  環碳酸酯經胺類化合物進行開環聚合反應通式‧‧33
Scheme 2-6  環氮乙烷經超臨界流體二氧化碳進行開環聚合反應
‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧34
Scheme 3-1  Bis(cyclic carbonate)化合物之合成‧‧‧‧‧‧‧‧41
Scheme 3-2  Model reaction (Ring-opening)的反應步驟‧‧‧‧‧43
Scheme 3-3  Model reaction (Mechal-addition)的反應步驟‧‧‧‧44
Scheme 3-4  末端胺基型聚胺酯(H2N-PU)合成步驟‧‧‧‧‧‧45
Scheme 3-5  末端胺基型聚胺酯(H2N-PU)合成步驟‧‧‧‧‧‧46
Scheme 3-6  末端胺基型聚胺酯(H2N-PU)合成步驟‧‧‧‧‧‧47
Scheme 3-7  末端胺基型聚胺酯(H2N-PU)合成步驟‧‧‧‧‧‧48
Scheme 3-8  紫外光架橋型聚胺酯(UV-PU)合成步驟‧‧‧‧‧‧50
Scheme 3-9  PPG-DCE化合物之合成‧‧‧‧‧‧‧‧‧‧‧‧59
Scheme 3-10 聚丙烯醚型聚胺酯(PPG-PU)合成步驟‧‧‧‧‧‧60
Scheme 3-11 紫外光架橋型聚胺酯(UV-PU)合成步驟‧‧‧‧‧‧61
Scheme 3-12 三官能基聚醚型聚胺酯(Tri-PU)合成步驟‧‧‧‧‧64
Scheme 3-13 紫外光架橋型聚胺酯(UV-PU)合成步驟‧‧‧‧‧‧66
Scheme 3-14 傳統異爾佛酮二異氰酸酯型聚胺酯(IPDI-PU)合成步驟
‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧69
Scheme 3-15 紫外光架橋型聚胺酯(IPDI UV-PU (2-HEMA))合成步驟
‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧73
Scheme 3-16 紫外光架橋型聚胺酯(IPDI UV-PU (AHM))合成步驟
‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧75
Scheme 3-17 傳統己烷二異氰酸酯型聚胺酯(HDI-PU)合成步驟‧77
Scheme 3-18 紫外光架橋型聚胺酯(HDI UV-PU (2-HEMA)) 合成步驟
‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧79
Scheme 3-19 紫外光架橋型聚胺酯(IPDI UV-PU (AHM))合成步驟
‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧81



Table 3-1  Preparing ratios of UV-curable polyurethane‧‧‧‧‧‧62
Table 3-2  Preparing ratios of UV-curable polyurethane‧‧‧‧‧‧67
Table 4-1  Average Molecular Weight of NH2-PU by GPC (LiCl / EA, 80℃) ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧101
Table 4-2  Average Molecular Weight of NH2-PU by GPC (TEA / EA, 80℃) ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧103
Table 4-3  Average Molecular Weight of NH2-PU by GPC (pH = 11~12)
          ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧106
Table 4-4  Physical Properties of UV-PU Films‧‧‧‧‧‧‧‧112
Table 4-5 Different thermal stabilities between DGEBA and Bis- (cycliccarbonate)s‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧117
Table 4-6  Thermal stability of non-isocyanate UV-cured PU and its raw materials‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧121
Table 4-7  Thermal Stabilities of UV-PU Films‧‧‧‧‧‧‧‧126
Table 4-8  Dynamic Mechanical Properties of UV-PU Blending with TPGDA‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧134
Table 4-9  Physical Properties of UV-PU Films‧‧‧‧‧‧‧‧149
Table 4-10 Thermal Stabilities of UV-PU Films‧‧‧‧‧‧‧‧155
Table 4-11 Dynamic Mechanical Properties of PPG-PU Hybrids with AHM‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧162
Table 4-12 Physical Properties of UV-PU Films‧‧‧‧‧‧‧172
Table 4-13 Thermal Stabilities of UV-PU Films‧‧‧‧‧‧‧178 
Table 4-14 Dynamic Mechanical Properties of Tri-PU Hybrids with AHM‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧186
Table 4-15 Physical Properties of UV-PU Films‧‧‧‧‧‧‧‧‧201
Table 4-16 Thermal Stabilities of Isocyanate Process and Non-isocyanate Route UV-PU Films‧‧‧‧‧‧‧‧‧‧‧‧‧‧207
Table 4-17 Thermal Stabilities of UV-PU Films‧‧‧‧‧‧‧‧‧212
Table 4-18 Dynamic Mechanical Properties of Isocyanate Process UV-PU‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧220
Table 4-19 Dynamic Mechanical Properties of Isocyanate Process and
Non-isocyanate Route UV-PU‧‧‧‧‧‧‧‧‧‧228












Fig. 2-1  Distribution of polyurethane soft and hard segments‧‧‧28
Fig. 2-2  The relationship between carbonate dioxide import conversion ratios and reaction time‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧30
Fig. 4-1  FT-IR Spectra of (a) 2,2-Bis-4-glycidyloxypheyl Propane (DGEBA); (b) Bis-cyclic Carbonate (BCC)‧‧‧‧‧83
Fig. 4-2  1H-NMR Spectra of (a) 2,2-Bis-4-glycidyloxypheyl Propane (DGEBA); (b) Bis-cyclic Carbonate (BCC)‧‧‧‧‧‧86
Fig. 4-3  13C-NMR Spectra of (a) 2,2-Bis-4-glycidyloxypheyl Propane (DGEBA); (b) Bis-cyclic Carbonate (BCC)‧‧‧‧‧‧ 87
Fig. 4-4  FT-IR Spectra of (a) Propylene Carbonate (PPC); (b) PPC-BA
‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧89
Fig. 4-5  1H-NMR Spectra of (a) Propylene Carbonate (PPC); (b) n-Butyl Amine (BA); (c) PPC-BA‧‧‧‧‧‧‧‧‧‧92
Fig. 4-6  13C-NMR Spectra of (a) Propylene Carbonate (PPC); (b) n-Butyl Amine (BA); (c) PPC-BA‧‧‧‧‧‧‧‧‧‧93
Fig. 4-7  13C-NMR Spectra of (a) Methyl acrylate (MA); (b) Methyl methacrylate (MMA); (c) n-Propyl amine (PA); (d) MA-PA‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧98
Fig. 4-8  13C-NMR Spectra of (a) Methyl acrylate (MA); (b) Methyl methacrylate(MMA); (c) n-Propyl amine(PA); (d) MA-PA‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧99
Fig.4-9  Curve of Different pH Values and Reactive Time‧‧‧‧104
Fig. 4-10 Curve of Different Temperature and Average Molecular Weight‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧107
Fig. 4-11 TGA Thermogram under Nitrogen, DGEBA (●); Bis- (cycliccarbonate)s (◇)‧‧‧‧‧‧‧‧‧‧‧‧‧115
Fig. 4-12 DTA Thermogram under Nitrogen, DGEBA (●); Bis- (cycliccarbonate)s (◇)‧‧‧‧‧‧‧‧‧‧‧‧‧116
Fig. 4-13 TGA Thermogram under Nitrogen, Jeffamine (●); pre-PU (◇)
; UV-PU (＊)‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧119
Fig. 4-14 DTA Thermogram under Nitrogen, Jeffamine (●); pre-PU (◇)
; UV-PU (＊)‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧120
Fig. 4-15 TGA Thermogram of TPGDA 0 phr; TPGDA 1 phr (●)
; TPGDA 3 phr (◇); TPGDA 5 phr (＊)‧‧‧‧‧‧‧124
Fig. 4-16 DTA Thermogram of TPGDA 0 phr; TPGDA 1 phr (●)
; TPGDA 3 phr (◇); TPGDA 5 phr (＊)‧‧‧‧‧‧‧125
Fig. 4-17 Storage Modulus Curve of TPGDA 0 phr; TPGDA 1 phr (●); TPGDA 3 phr (◇); TPGDA 5 phr (＊)‧‧‧‧‧‧‧‧131
Fig. 4-18 Loss Modulus Curve of TPGDA 0 phr; TPGDA 1 phr (●); TPGDA 3 phr (◇); TPGDA 5 phr (＊)‧‧‧‧‧‧‧‧132
Fig. 4-19 Tan δ Curve of TPGDA 0 phr; TPGDA 1 phr (●); TPGDA 3 phr (◇); TPGDA 5 phr (＊) ‧‧‧‧‧‧‧‧‧‧‧‧‧‧133
Fig. 4-20 Photos of (a) Original PET Textile; (b) After Coating UV-PU; (c) After 30 Washing Cycles‧‧‧‧‧‧‧‧‧‧‧‧‧136
Fig. 4-21 SEM Microgram of Original PET Textile (a) 1,000X (b) 3,000X‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧138
Fig. 4-22 SEM Microgram of Hydrophilic-treated PET Textiles with UV-PU before Washing (a) 1,000X (b) 3,000X‧‧‧‧139
Fig. 4-23 SEM Microgram of Hydrophilic-treated PET Textiles with UV-PU after 30 Washing Cycles (a) 1,000X (b) 3,000X‧140
Fig. 4-24 FT-IR Spectra of (a) Poly(propylene glycol) diglycidyl ether; (b) Poly(propene glycol) Dicarbonate Ether‧‧‧‧‧‧‧‧142
Fig. 4-25 FT-IR Spectra of (a) PPG-DCE; (b) PPG-type Polyurethane (PPG-PU)‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧144
Fig. 4-26 TGA Thermogram of PPG-DCE D-2000 (2N) (●); PPG-DCE D-2000 (3N) (◇); PPG-DCE D-2000 (4N) (＊)‧‧‧‧153
Fig. 4-27 DTA Thermogram of PPG-DCE D-2000 (2N) (●); PPG-DCE D-2000 (3N) (◇); PPG-DCE D-2000 (4N) (＊)‧‧‧‧154
Fig. 4-28 Storage Modulus Curve of PPG-DCE D-2000 (2N) (●); PPG-DCE D-2000 (3N) (◇); PPG-DCE D-2000 (4N) (＊)
‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧159
Fig. 4-29 Loss Modulus Curve of PPG-DCE D-2000 (2N) (●); PPG-DCE D-2000 (3N) (◇); PPG-DCE D-2000 (4N) (＊)‧‧‧‧160
Fig. 4-30 Tan δ Curve of PPG-DCE D-2000 (2N) (●); PPG-DCE D-2000 (3N) (◇); PPG-DCE D-2000 (4N) (＊) ‧‧‧‧‧‧‧‧161
Fig. 4-31 Photo of the PPG-type UV-PU Film‧‧‧‧‧‧‧‧‧164
Fig. 4-32 FT-IR Spectra of (a) PPG-DCE; (b) Tri-functional Polyurethane (Tri-PU)‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧167
Fig. 4-33 TGA Thermogram of PPG-DCE T-3000 (5.0N) (●); PPG-DCE T-3000 (7.5N) (◇); PPG-DCE T-3000 (10.0N) (＊)‧‧‧176
Fig. 4-34 DTA Thermogram of PPG-DCE T-3000 (5.0N) (●); PPG-DCE T-3000 (7.5N) (◇); PPG-DCE T-3000 (10.0N) (＊)‧‧‧177
Fig. 4-35 Storage Modulus Curve of PPG-DCE T-3000 (5.0N) (●); PPG-DCE T-3000 (7.5N) (◇); PPG-DCE T-3000 (10.0N) (＊)‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧183
Fig. 4-36 Loss Modulus Curve of PPG-DCE T-3000 (5.0N) (●); PPG-DCE T-3000 (7.5N) (◇); PPG-DCE T-3000 (10.0N) (＊)‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧184
Fig. 4-37 Tan δ Curve PPG-DCE T-3000 (5.0N) (●); PPG-DCE T-3000 (7.5N) (◇); PPG-DCE T-3000 (10.0N) (＊) ‧‧‧‧‧‧185
Fig. 4-38 Photo of the Tri-functional Type UV-PU Film‧‧‧‧‧188
Fig. 4-39 FT-IR Spectra of (a) IPDI-PU; (b) IPDI UVPU (2-HEMA)
‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧191
Fig. 4-40 FT-IR Spectra of (a) IPDI-PU; (b) IPDI UVPU (AHM)
‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ ‧‧‧‧‧‧192
Fig. 4-41 FT-IR Spectra of (a) HDI-PU; (b) HDI UVPU (2-HEMA)
‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧195
Fig. 4-42 FT-IR Spectra of (a) HDI-PU; (b) HDI UVPU (AHM)
‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ ‧‧‧‧‧‧196
Fig. 4-43 TGA Thermogram of BCC D-2000 (4N); PPG-DCE D-2000 (4N) (●); PPG-DCE T-3000 (10N) (◇); HDI PPG-2000 (2-HEMA) (＊)‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧205
Fig. 4-44 DTA Thermogram of BCC D-2000 (4N); PPG-DCE D-2000 (4N) (●); PPG-DCE T-3000 (10N) (◇); HDI PPG-2000 (2-HEMA) (＊)‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧206
Fig. 4-45 TGA Thermogram of HDI PPG-2000 (2-HEMA) (●); HDI PPG-2000 (AHM) (◇)‧‧‧‧‧‧‧‧‧‧‧‧‧‧210
Fig. 4-46 DTA Thermogram of HDI PPG-2000 (2-HEMA) (●); HDI PPG-2000 (AHM) (◇)‧‧‧‧‧‧‧‧‧‧‧‧‧‧211
Fig. 4-47 Storage Modulus Curve of IPDI PPG-2000 (2-HEMA); IPDI PPG-2000 (AHM) (●); HDI PPG-2000 (2-HEMA) (◇); HDI PPG-2000 (AHM) (＊) ‧‧‧‧‧‧‧‧‧‧‧‧‧‧217
Fig. 4-48 Loss Modulus Curve of IPDI PPG-2000 (2-HEMA); IPDI PPG-2000 (AHM) (●); HDI PPG-2000 (2-HEMA) (◇); HDI PPG-2000 (AHM) (＊) ‧‧‧‧‧‧‧‧‧‧‧‧‧‧218
Fig. 4-49 Tan δ Curve of IPDI PPG-2000 (2-HEMA); IPDI PPG-2000 (AHM) (●); HDI PPG-2000 (2-HEMA) (◇); HDI PPG-2000 (AHM) (＊)‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧219
Fig. 4-50 Storage Modulus Curve of BCC D-2000 (4N); PPG-DCE D-2000 (4N) (●); PPG-DCE T-3000 (10N) (◇); IPDI PPG-2000 (2-HEMA) (＊)‧‧‧‧‧‧‧‧‧‧‧‧225
Fig. 4-51 Loss Modulus Curve of BCC D-2000 (4N); PPG-DCE D-2000 (4N) (●); PPG-DCE T-3000 (10N) (◇); IPDI PPG-2000 (2-HEMA) (＊)‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧226
Fig. 4-52 Tan δ Curve of BCC D-2000 (4N); PPG-DCE D-2000 (4N) (●); PPG-DCE T-3000 (10N) (◇); IPDI PPG-2000 (2-HEMA) (＊)
‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧227

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