本論文使用實驗室開發之“非異氰酸酯製程法”，製備水性PU（Polyurethane），並在化合物的選擇及合成比例上做改變，探討其中對材料性質影響的改變因素。

以環氧樹脂（NPEL-128；EEW = 187）為起始物，透過二氧化碳的親核性加成反應製備環狀碳酸酯（Bis(cyclic carbonate)s）；與BDBA（1,4-butanediol bis(3-aminopropyl) ether；MW = 204.31）及Jeffamine® D-2000（MW = 2000）兩不同大小分子量胺類進行聚合反應；再經由馬來酸酐（Maleic Anhydride）的半酯化反應（Half-Esterification Reaction），以及加入適量鹼與羧酸基形成的中和反應，最後形成水性PU分散液（Aqueous-Based Polyurethane Dispersion）。

分別調整起始物與胺類合成上的比例（128-Car : Amine = 1.0 : 0.9；1.0 : 1.0；1.0 : 1.1）進行反應，再以架橋劑TMPTA-AZ，與PU鏈段上的羧酸基反應形成三維交聯網狀結構，探討材料在不同合成比例下，所表現出的各項物理性質、熱性質和機械性質，之間的影響及差異性。

The present paper uses “Isocyanate-Free Process” which developed from the laboratory to prepare aqueous-based polyurethane dispersion. Besides, by changing the choice and synthesis ration of the compound, we discuss the natural influence factors of material.

Using the (NPEL-128; EEW = 187) to be a start material, Bis(cyclic carbonate)s were prepared through the nucleophilic addition reaction of CO2. Then, to polymerize with two different types of molecular weight of amine, BDBA (1,4-butanediol bis(3-aminopropyl) ether; MW = 204.31) and Jeffamine® D-2000 (MW = 2000), then through the Half-Esterification Reaction of maleic anhydride,   and adding the neutralization which is formed by carboxylic group with appropriate amount of base. Finally, the Aqueous-Based Polyurethane Dispersion was formed.

Adjusting the synthesis ration of the start material and amine(128-Car : Amine = 1 : 0.9; 1 : 1.0; 1 : 1.1) partly, then react. After, adding the bridging reagent TMPTA-AZ into the Aqueous-Based Polyurethane Dispersion and react with the carboxylic groups of PU segment to form the three dimensional net working structure. And try to discuss the physics, thermal stability, mechanical properties of the film in a different synthesis ration of materials.

目 錄

1-1 前言......................................................................................... 1
1-2 研究動機..................................................................................... 3
二、文獻回顧..................................................................................... 7
2-1 聚氨酯介紹................................................................................... 7
2-2 水性聚氨酯之介紹............................................................................ 13
2-3 次乙亞胺之介紹.............................................................................. 24
2-4 環氧化物之反應性介紹<21>.................................................................... 28
2-5 分子量與分子量分佈.......................................................................... 29
2-6 羥基懸掛型PU（Hydroxyl Polurethane）的介紹<12>.............................................. 31
三、實驗........................................................................................ 35
3-1 藥品........................................................................................ 35
3-2 儀器........................................................................................ 36
3-3 實驗步驟.................................................................................... 37
3-A 【Part A】 Amine = 1,4-butanediol bis(3-aminopropyl) ether（BDBA）.......................... 37
3-3A-1 環狀碳酸酯（Bis(cyclic carbonate)s）化合物合成........................................... 38
3-3A-2 羥基側鏈懸掛型PU（Hydroxyl-PU）化合物合成................................................ 39
3-3A-3 羧酸基側鏈懸掛型PU（Carboxylic PU）化合物合成............................................ 40
3-3A-4 羧酸基側鏈懸掛型水性PU（Aqueous-Based Carboxylic PU）.................................... 41
3-B 【Part B】 Amine = JeffamineR D-2000........................................................ 43
3-3B-1 環狀碳酸酯（Bis(cyclic carbonate)s）化合物合成........................................... 44
3-3B-2 羥基側鏈懸掛型PU（Hydroxyl-PU）化合物合成................................................ 45
3-3B-3 羧酸基側鏈懸掛型PU（Carboxylic PU）化合物合成............................................ 46
3-3B-4 羧酸基側鏈懸掛型水性PU（Aqueous-Based Carboxylic PU）.................................... 47
3-4 化學性質測試................................................................................ 48
3-4-1 環氧樹脂當量（Equivalent Epoxy Weight, EEW）測定.......................................... 48
3-4-2 膠體層析法（Gel Permeation Chromatography, GPC）.......................................... 50
3-5 物理性質測試<36,37,38,39,40,41,42> ......................................................... 51
3-5-1 固含量（Solid Content）................................................................... 51
3-5-2 膠含量（Gel Content）..................................................................... 51
3-5-3 吸水率（Water-Uptake, WA %）及對水損失率（Weight loss in water, WL %）.................... 52
3-5-4 吸乙醇率（Ethanol-Uptake, EA %）及對乙醇損失率（Weight loss in ethanol, EL %）............ 53
3-5-5 接觸角（Contact Angle）................................................................... 54
3-6 熱性質測試.................................................................................. 55
3-6-1 熱重分析（Thermalgravity Analysis, TGA）.................................................. 55
3-7 機械性質測試................................................................................ 56
3-7-1 動態機械分析（Dynamic Mechanical Analysis, DMA）.......................................... 56
3-7-2 抗張應力（Tensile Strength）及伸長率（Elongation）........................................ 57
3-8 光譜鑑定.................................................................................... 59
3-8-1 核磁共振（Nuclear Magnetic Resonance, NMR）光譜........................................... 59
3-8-2 傅立葉轉換紅外線（Fourier Transform - Infrared Rays, FT-IR）光譜.......................... 59
四、結果與討論.................................................................................. 61
4-A 【Part A】 Amine = 1,4-butanediol bis(3-aminopropyl) ether（BDBA）.......................... 63
4-1A 光譜鑑定................................................................................... 64
4-1A-1 核磁共振（Nuclear Magnetic Resonance, NMR）光譜鑑定...................................... 64
4-1A-2 傅立葉轉換紅外線（Fourier Transform - Infrared Rays, FT-IR）光譜鑑定..................... 65
4-1A-3 各比例傅立葉轉換紅外線（Fourier Transform – Infrared Rays, FT-IR）光譜鑑定.............. 68
4-2A 物理性質................................................................................... 71
4-2A-1 膠含量（Gel Content）.................................................................... 72
4-2A-2 吸水率（Water-Uptake, WA %）及對水損失率（Weight loss in water, WL %）................... 73
4-2A-3 吸乙醇率（Ethanol-Uptake, EA %）及對乙醇損失率（Weight loss in ethanol, EL %）........... 75
4-2A-4 接觸角（Contact Angle）.................................................................. 76
4-3A 熱性質..................................................................................... 79
4-3A-1 熱重分析（Thermalgravity Analysis, TGA）................................................. 79
4-4A 機械性質................................................................................... 85
4-4A-1 動態機械分析（Dynamic Mechanical Analysis, DMA）......................................... 85
4-B 【Part B】 Amine = JeffamineR D-2000 ....................................................... 91
4-1B 光譜鑑定................................................................................... 92
4-1B-1 核磁共振（Nuclear Magnetic Resonance, NMR）光譜鑑定...................................... 92
4-1B-2 傅立葉轉換紅外線（Fourier Transform - Infrared Rays, FT-IR）光譜鑑定..................... 93
4-1B-3 各比例傅立葉轉換紅外線（Fourier Transform - Infrared Rays, FT-IR）光譜鑑定............... 97
4-2B 物理性質................................................................................... 99
4-2B-1 膠含量（Gel Content）................................................................... 100
4-2B-2 吸水率（Water-Uptake, WA %）及對水損失率（Weight loss in water, WL %）.................. 101
4-2B-3 吸乙醇率（Ethanol-Uptake, EA %）及對乙醇損失率（Weight loss in ethanol, EL %）.......... 103
4-2B-4 接觸角（Contact Angle）................................................................. 104
4-3B 熱性質.................................................................................... 107
4-3B-1 熱重分析（Thermalgravity Analysis, TGA）................................................ 107
4-3B-2 羧酸基側鏈懸掛型PU（Carboxylic PU）化合物熱性質探討..................................... 114
4-4B 機械性質.................................................................................. 117
4-4B-1 動態機械分析（Dynamic Mechanical Analysis, DMA）........................................ 117
4-4B-2 抗張應力（Tensile Strength）及伸長率（Elongation）...................................... 123
五、結論....................................................................................... 127
參考文獻....................................................................................... 129


圖 表 索 引

Scheme 2-1 陰離子型水性聚氨酯分散液............................................................. 15
Scheme 2-2 陽離子型水性聚氨酯分散液............................................................. 16
Scheme 2-3 非離子型水性聚氨酯分散液............................................................. 17
Scheme 2-4 丙酮加工法PU製備流程圖............................................................... 19
Scheme 2-5 預聚物混合加工法PU製備流程圖......................................................... 20
Scheme 2-6 熱熔加工法PU製備流程圖............................................................... 21
Scheme 2-7 酮亞胺/酮連氮法流程圖................................................................ 23
Scheme 2-8 一級胺與碳酸酯反應................................................................... 31
Scheme 2-9 酯類與胺類之Model Reaction........................................................... 32
Scheme 2-10 環氧乙烷和二氧化碳的反應............................................................ 33
Scheme 2-11 環氧乙烷和二氧化碳常壓下的反應...................................................... 33
Scheme 2-12 環狀碳酸酯和二胺的聚合反應.......................................................... 33

Fig 4-1A-1.1 NPEL-128之NMR光譜.................................................................. 64
Fig 4-1A-1.2 環狀碳酸酯（Bis(cyclic carbonate)s）之NMR光譜...................................... 65
Fig 4-1A-2.1 NPEL-128之FT-IR光譜................................................................ 66
Fig 4-1A-2.2 環狀碳酸酯（Bis(cyclic carbonate)s）之FT-IR光譜.................................... 67
Fig 4-1A-2.3 BDBA系列羥基側鏈懸掛型PU（Hydroxyl-PU）之FT-IR光譜................................. 67
Fig 4-1A-2.4 BDBA系列羧酸基側鏈懸掛型水性PU（Aqueous-Based Carboxylic PU）之FT-IR光譜........... 68
Fig 4-1A-3.1 BDBA系列各比例羥基側鏈懸掛型PU（Hydroxyl-PU）之FT-................................. 69
Fig 4-1A-3.2 BDBA系列各比例羧酸基側鏈懸掛型水性PU（Aqueous-Based Carboxylic PU）之FT-IR光譜..... 70
Fig 4-3A-1.1 BDBA系列【128-Car : BDBA = 1.0 : 1.1】水性PU薄膜於氮氣系統之TGA圖；（●）PU含TMPTA-AZ 20 phr；（□）PU含TMPTA-AZ 30 phr；（◆）PU含TMPTA-AZ 40 phr............... 80
Fig 4-3A-1.2 BDBA系列【128-Car : BDBA = 1.0 : 1.1】水性PU薄膜於氮氣系統之TGA一次微分圖；（●）PU含TMPTA-AZ 20 phr；（□）PU含TMPTA-AZ 30 phr；（◆）PU含TMPTA-AZ 40 phr....... 80
Fig 4-3A-1.3 BDBA系列【128-Car : BDBA = 1.0 : 1.0】水性PU薄膜於氮氣系統之TGA圖；（●）PU含TMPTA-AZ 20 phr；（□）PU含TMPTA-AZ 30 phr；（◆）PU 含TMPTA-AZ 40 phr.............. 81
Fig 4-3A-1.4 BDBA系列【128-Car : BDBA = 1.0 : 1.0】水性PU薄膜於氮氣系統之TGA一次微分圖；（●）PU含TMPTA-AZ 20 phr；（□）PU含TMPTA-AZ 30 phr；（◆）PU含TMPTA-AZ 40 phr....... 81
Fig 4-3A-1.5 BDBA系列【128-Car : BDBA = 1.0 : 0.9】水性PU薄膜於氮氣系統之TGA圖；（●）PU含TMPTA-AZ 20 phr；（□）PU含TMPTA-AZ 30 phr；（◆）PU含TMPTA-AZ 40 phr............... 82
Fig 4-3A-1.6 BDBA系列【128-Car : BDBA = 1.0 : 0.9】水性PU薄膜於氮氣系統之TGA一次微分圖；（●）PU含TMPTA-AZ 20 phr；（□）PU含TMPTA-AZ 30 phr；（◆）PU含TMPTA-AZ 40 phr....... 82
Fig 4-4A-1.1 BDBA系列【128-Car : BDBA = 1.0 : 1.1】水性PU薄膜之DMA圖；（●）PU含TMPTA-AZ 20 phr；（□）PU含TMPTA-AZ 30 phr；（◆）PU 含TMPTA-AZ 40 phr........................ 85
Fig 4-4A-1.2 BDBA系列【128-Car : BDBA = 1.0 : 1.1】水性PU薄膜之Tanδ對溫度DMA圖；（●）PU含TMPTA-AZ 20 phr；（□）PU含TMPTA-AZ 30 phr；（◆）PU含TMPTA-AZ 40 phr.............. 85
Fig 4-4A-1.3 BDBA系列【128-Car : BDBA = 1.0 : 1.0】水性PU薄膜之DMA圖；（●）PU含TMPTA-AZ 20 phr；（□）PU含TMPTA-AZ 30 phr；（◆）PU含TMPTA-AZ 40 phr......................... 86
Fig 4-4A-1.4 BDBA系列【128-Car : BDBA = 1.0 : 1.0】水性PU薄膜之Tanδ對溫度DMA圖；（●）PU含TMPTA-AZ 20 phr；（□）PU含TMPTA-AZ 30 phr；（◆）PU含TMPTA-AZ 40 phr.............. 86
Fig 4-4A-1.5 BDBA系列【128-Car : BDBA = 1.0 : 0.9】水性PU薄膜之DMA圖；（●）PU含TMPTA-AZ 20 phr；（□）PU含TMPTA-AZ 30 phr；（◆）PU含TMPTA-AZ 40 phr......................... 87
Fig 4-4A-1.6 BDBA系列【128-Car : BDBA = 1.0 : 0.9】水性PU薄膜之Tanδ對溫度DMA圖；（●）PU含TMPTA-AZ 20 phr；（□）PU含TMPTA-AZ 30 phr；（◆）PU含TMPTA-AZ 40 phr.............. 87
Fig 4-1B-1.1 NPEL-128之NMR光譜........................................................................................................ 92
Fig 4-1B-1.2 環狀碳酸酯（Bis(cyclic carbonate)s）之NMR光譜............................................................................ 93
Fig 4-1B-2.1 NPEL-128之FT-IR光譜...................................................................................................... 94
Fig 4-1B-2.2 環狀碳酸酯（Bis(cyclic carbonate)s）之FT-IR光譜.......................................................................... 95
Fig 4-1B-2.3 JeffamineR D-2000之FT-IR光譜............................................................................................. 95
Fig 4-1B-2.4 JeffamineR D-2000系列羥基側鏈懸掛型PU（Hydroxyl-PU）之FT-IR光譜.......................................................... 96
Fig 4-1B-2.5 JeffamineR D-2000系列羧酸基側鏈懸掛型水性PU（Aqueous-based Carboxylic PU）之FT-IR光譜.................................... 96
Fig 4-1B-3.1 JeffamineR D-2000系列各比例羥基側鏈懸掛型PU（Hydroxyl-PU）之FT-IR光譜.................................................... 98
Fig 4-1B-3.2 JeffamineR D-2000系列各比例羧酸基側鏈懸掛型水性PU（Aqueous-Based Carboxylic PU）之FT-IR光譜.............................. 98
Fig 4-3B-1.2 JeffamineR D-2000系列【128-Car : JA = 1.0 : 1.1】水性PU薄膜於氮氣系統之TGA一次微分圖；（●）PU含TMPTA-AZ 15 phr；（□）PU含TMPTA-AZ 20 phr；（◆）PU含TMPTA-AZ 25 phr；（○）PU含TMPTA-AZ 0 phr..................................................... 108
Fig 4-3B-1.3 JeffamineR D-2000系列【128-Car : JA = 1.0 : 1.0】水性PU薄膜於氮氣系統之TGA圖；（●）PU含TMPTA-AZ 15 phr；（□）PU含TMPTA-AZ 20 phr；（◆）PU含TMPTA-AZ 25 phr；（○）PU含TMPTA-AZ 0 phr............................................................. 109
Fig 4-3B-1.4 JeffamineR D-2000系列【128-Car : JA = 1.0 : 1.0】水性PU薄膜於氮氣系統之TGA一次微分圖；（●）PU含TMPTA-AZ 15 phr；（□）PU含TMPTA-AZ 20 phr；（◆）PU含TMPTA-AZ 25 phr；（○）PU含TMPTA-AZ 0 phr..................................................... 109
Fig 4-3B-1.5 JeffamineR D-2000系列【128-Car : JA = 1.0 : 0.9】水性PU薄膜於氮氣系統之TGA圖；（●）PU含TMPTA-AZ 15 phr；（□）PU含TMPTA-AZ 20 phr；（◆）PU含TMPTA-AZ 25 phr；（○）PU含TMPTA-AZ 0 phr............................................................. 110
Fig 4-3B-1.6 JeffamineR D-2000系列【128-Car : JA = 1.0 : 0.9】水性PU薄膜於氮氣系統之TGA一次微分圖；（●）PU含TMPTA-AZ 15 phr；（□）PU含TMPTA-AZ 20 phr；（◆）PU含TMPTA-AZ 25 phr；（○）PU含TMPTA-AZ 0 phr..................................................... 110
Fig 4-3B-2.1 JeffamineR D-2000系列【128-Car : JA = 1.0 : 0.9】水性PU薄膜於氮氣系統之TGA圖；（●）PU含TMPTA-AZ 15 phr；（□）PU含TMPTA-AZ 20 phr；（◆）PU含TMPTA-AZ 25 phr；（○）PU含TMPTA-AZ 0 phr；（■）羧酸基側鏈懸掛型PU（Carboxylic PU）化合物............ 114
Fig 4-3B-2.2 JeffamineR D-2000系列【128-Car : JA = 1.0 : 0.9】水性PU薄膜於氮氣系統之TGA一次微分圖；（●）PU含TMPTA-AZ 15 phr；（□）PU含TMPTA-AZ 20 phr；（◆）PU含TMPTA-AZ 25 phr；（○）PU含TMPTA-AZ 0 phr；（■）羧酸基側鏈懸掛型PU（Carboxylic PU）化合物.... 114
Fig 4-4B.1 JeffamineR D-2000系列【128-Car : JA = 1.0 : 1.1】水性PU薄膜之DMA圖；（●）PU含TMPTA-AZ 15 phr；（□）PU含TMPTA-AZ 20 phr；（◆）PU含TMPTA-AZ 25 phr................................................................................................... 117
Fig 4-4B.2 JeffamineR D-2000系列【128-Car : JA = 1.0 : 1.1】水性PU薄膜之Tanδ對溫度DMA圖；（●）PU含TMPTA-AZ 15 phr；（□）PU含TMPTA-AZ 20 phr；（◆）PU含TMPTA-AZ 25 phr ....................................................................................... 117
Fig 4-4B.3 JeffamineR D-2000系列【128-Car : JA = 1.0 : 1.0】水性PU薄膜之DMA圖；（●）PU含TMPTA-AZ 15 phr；（□）PU含TMPTA-AZ 20 phr；（◆）PU含TMPTA-AZ 25 phr................................................................................................... 118
Fig 4-4B.4 JeffamineR D-2000系列【128-Car : JA = 1.0 : 1.0】水性PU薄膜之Tanδ對溫度DMA圖；（●）PU含TMPTA-AZ 15 phr；（□）PU含TMPTA-AZ 20 phr；（◆）PU含TMPTA-AZ 25 phr ....................................................................................... 118
Fig 4-4B.5 JeffamineR D-2000系列【128-Car : JA = 1.0 : 0.9】水性PU薄膜之DMA圖；（●）PU含TMPTA-AZ 15 phr；（□）PU含TMPTA-AZ 20 phr；（◆）PU含TMPTA-AZ 25 phr................................................................................................... 119
Fig 4-4B.6 JeffamineR D-2000系列【128-Car : JA = 1.0 : 0.9】水性PU薄膜之Tanδ對溫度DMA圖；（●）PU含TMPTA-AZ 15 phr；（□）PU含TMPTA-AZ 20 phr；（◆）PU含TMPTA-AZ 25 phr ....................................................................................... 119
Fig 4-4B-2.1 JeffamineR D-2000系列【128-Car : JA = 1.0 : 1.1】水性PU薄膜之應力-應變關係圖；（Black, 1）PU含TMPTA-AZ 15 phr；（Red, 2）PU含TMPTA-AZ 20 phr；（Blue, 3）PU含TMPTA-AZ 25 phr ....................................................................... 123
Fig 4-4B-2.2 JeffamineR D-2000系列【128-Car : JA = 1.0 : 1.0】水性PU薄膜之應力-應變關係圖；（Black, 1）PU含TMPTA-AZ 15 phr；（Red, 2）PU含TMPTA-AZ 20 phr；（Blue, 3）PU 含TMPTA-AZ 25 phr ...................................................................... 123
Fig 4-4B-2.3 JeffamineR D-2000系列【128-Car : JA = 1.0 : 0.9】水性PU薄膜之應力-應變關係圖；（Black, 1）PU含TMPTA-AZ 15 phr；（Red, 2）PU含TMPTA-AZ 20 phr；（Blue, 3）PU 含TMPTA-AZ 25 phr ...................................................................... 124

Table 4-2A BDBA 系列水性PU 薄膜之物理性質........................ 71
Table 4-3A-1 BDBA 系列水性PU 薄膜之熱裂解溫度與Tg ............... 79
Table 4-2B JeffamineR D-2000 系列水性PU 薄膜之物理性質........... 99
Table 4-3B-1 JeffamineR D-2000 系列水性PU 薄膜之熱性質.......... 107

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