臺灣博碩士論文加值系統

隨著環保意識的提升，水性聚氨酯逐漸取代溶劑型聚氨酯，為了提升聚氨酯薄膜的耐溶劑性、熱穩定性等，本實驗研究水性聚氨酯和壓克力形成互穿型網狀(IPN)結構的高分子，IPN結構的特色在於“強迫相互融合”的作用，兩種高分子相互糾結纏繞形成一個整體，不能分離。儘管兩者之間無化學結合，但是又能進一步提升高分子薄膜的機械強度、熱穩定性等。
本實驗的聚氨酯原料選用聚四亞甲基醚二醇(PTMG)與異佛爾酮二異氰酸酯(IPDI)聚合，以二羥甲基丙酸(DMPA)作為親水擴鏈劑，三乙胺(TEA)作為羧酸中和劑，1,4丁二醇(BDO)作為擴鏈劑，雙酚A二縮水甘油醚(BADGE)作為交聯劑，壓克力單體則是1,6-己二醇二丙烯酸酯(HDDA)。
本實驗利用萬能拉力測試儀、掃描式電子顯微鏡(SEM)、傅立葉轉換紅外線光譜儀(FT-IR) 、熱重量分析儀(TGA)、X射線繞射分析(XRD)等儀器觀察聚合物薄膜之各項性質，動態光散射粒徑分析儀 (DLS)則觀察分散液的粒徑尺寸，並利用溶脹法計算高分子薄膜交聯密度。
本實驗成功製備聚氨酯與壓克力互穿結構的高分子分散液並提升其乾燥薄膜的熱穩定性和耐溶劑性，而其分散液在2~3個月內具有流動性且無沉澱，此分散液可應用於織物的塗佈上。

With the improvement of environmental awareness, waterborne polyurethanes have gradually replaced solvent-based polyurethanes. In order to improve the solvent resistance and thermal stability of polyurethane films, the interpenetrating network (IPN) structure of waterborne polyurethane and acrylate was investigated in this study. IN structure is characterized by the role of "forced mutual fusion". The two polymers entangled to form a unity and can’t be separated. Although there is no chemical bond between the two polymers, the mechanical strength and thermal stability of the polymer film can be further improved.

The polyurethane material used in this experiment was polymerized with poly(tetramethylene ether) glycol (PTMG) and isophorone diisocyanate (IPDI), with 2,2-Bis(hydroxymethyl)propionic acid (DMPA) as hydrophilic chain extender and triethylamine (TEA) as a carboxylic acid neutralizing agent. Besides, 1,4 butanediol (BDO) is used as a chain extender, bisphenol A diglycidyl ether (BADGE) is used as a crosslinking agent, and acrylic monomer is 1,6-hexanediol diacrylate (HDDA).

Universal tensile tester, scanning electron microscope (SEM), Fourier transform infrared spectrometer (FT-IR), thermogravimetric analyzer (TGA), X-ray diffraction (XRD) and other instruments are used to measure the properties of the polymer film. The Dynamic Light Scattering (DLS) was used to observe the particle size of the dispersion, and the crosslink density of the polymer film was calculated by the equilibrium swelling theory.

In this experiment, interpenetrating structure polymer dispersion of polyurethane and acryl was successfully synthesized. Moreover, the thermal stability and solvent resistance of the dried film were improved, and the dispersion had fluidity and no precipitation in two to three months. The dispersion can be applied to the coating of fabrics.

目 錄
摘　要 i
ABSTRACT ii
誌 謝 iii
目 錄 iv
表目錄 vii
圖目錄 viii
第一章 緒論 1
1.1 前言 1
1.2研究動機 2
第二章 文獻回顧 3
2.1 聚氨酯(POLYURETHANE)簡介 3
2.1.1聚氨酯-軟硬鏈段組成的影響 4
2.2水性聚氨酯簡介 5
2.2.1 異氰酸酯指數 6
2.2.2水性聚氨酯的交聯改質 6
2.2.3水性聚氨酯自乳化過程 8
2.2.4水性聚氨酯散體粒徑與界達電位 9
2.2.5 水性聚氨酯成膜過程 [18] 10
2.2.6水性聚氨酯乳化 11
2.2.7 NCO官能基濃度測定 13
2.3水性聚氨酯常見加工法 14
2.3.1溶液法[21] [22] 14
2.3.2預聚物混合加工法[23] 15
2.3.3添加乳化劑法 16
2.3.4熔融分散法 16
2.3.5酮亞胺法 16
2.4水性聚氨酯的合成 17
2.4.1聚多元醇(Polyol) 17
2.4.2異氰酸酯(Diisocyanate) 19
2.4.2.1異氰酸酯的二聚反應[28] 20
2.4.2.2異氰酸酯的三聚反應 [29] 21
2.4.3擴鏈劑與交聯劑(Chain extender and Crosslinker) 21
2.4.4催化劑(Catalyst) 22
2.4.5中和劑 23
2.4.6溶劑 23
2.5 互穿型網狀高分子(INTERPENETRATING POLYMER NETWORKS，IPNS) 24
2.6 高分子之交聯密度 26
2.6.1凝膠之溶脹行為 26
2.6.2 作用力參數 (Interaction parameter) 27
2.6.3溶脹比與交聯密度的關係 29
第三章 實驗方法與流程 31
3.1 實驗藥品及材料 31
3.2 實驗儀器 35
3.2.1傅立葉紅外線光譜儀 (FT-IR) 35
3.2.2熱重量分析儀 (TGA) 36
3.2.3動態光散射粒徑分析儀 (DLS) 37
3.2.4場發射掃描式電子顯微鏡 (FE-SEM) 38
3.2.5 X-射線繞射分析儀 (XRD) 39
3.2.6萬能拉力測試儀 40
3.2.7 膠體滲透層析儀 (GPC) 41
3.3實驗流程 42
3.3.1水性聚氨酯分散液之製備 42
3.3.2水性聚氨酯薄膜之製備 45
第四章 結果與討論 46
4.1紅外線光譜分析 (FT-IR) 46
4.2水性聚氨酯預聚物合成之GPC分析 51
4.3熱重量分析(TGA) 56
4.4粒徑分析(DLS) 61
4.5掃描式電子顯微鏡分析(SEM) 66
4.6 X-射線繞射分析儀 (XRD) 70
4.8拉伸試驗分析 72
4.9交聯密度分析 75
4.10吸水性分析 77
4.11耐溶劑分析 80
4.12應用於塗佈衣物分析 86
4.13保存性分析 90
結論 95
參考文獻 96

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