臺灣博碩士論文加值系統

本研究將二苯基甲烷二異氰酸酯（MDI）、聚碳酸酯二元醇（PCDL）、甘油（glycerol）反應得聚氨酯前預聚物，再以糠胺（FA）反應得末端基含有呋喃單體的預聚物（PU-furan），最後與雙馬來酰亞胺（BMI）透過Diels-Alder反應得到自我修復型聚氨酯（PU-DA），透過添加不同比例交聯劑（glycerol）對於自我修復型聚氨酯（PU-DA）的影響。透過傅立葉轉換紅外線光譜儀（FT-IR）、核磁共振氫譜儀（1H-NMR）進行結構分析。利用熱差示掃描分析儀（DSC）、熱重分析儀（TGA）進行熱分析。透過光學顯微鏡（OM）、拉伸測試（tensile test）觀察自我修復（self-healing）特性。新型自我修復型聚氨酯具有良好熱穩定及機械性質，其熱裂解點約在250℃，斷裂應力可達46.3 MPa，斷裂延伸率可達526.1%。此外，在130℃持續30分鐘可將材料傷口癒合，其修復效率約70%。在應用方面，新型自我修復型聚氨酯之塗料可將民生衣物透過環套的方式，使織物具有耐洗、耐搓揉特性。可延伸應用於汽車產業塗料、電子產品塗料……等中。

In this study, the diphenylmethane diisocyanate was reacted with polycarbonate diol, glycerol to form a polyurethane prepolymer, and then reacted with furfurylamine (FA) to form a furan-terminal group prepolymer (PU-furan). Finally, the Diels-Alder reaction was performed with bismaleimide (BMI) to obtain a targeted self-healing polyurethane (PU-DA). The self-healing polyurethane was affected by a verity of different proportion of glycerol as a cross-linking agent. The chemical structure was identified by FT-IR and 1H NMR. Thermal analysis was measured via DSC and TGA. The self-healing characteristics were observed through an optical microscope and tensile test. The new self-healing polyurethane has excellent thermal stability and mechanical properties, indicating the degradation temperature, stress and elongation at break could be observed around 250 ℃, 46.3 MPa, and 526.1%, respectively. Furthermore, the self-healing property could be driven at 130℃for 30 minutes with an effective recovery rate of 70%. This the newly synthesized self-healing polyurethane could be applied in a fabric of washing and smashing resistance property via the loop reaction, which could be extended to utilize in the automotive industry, electronic product, coating applications.

摘要 i
ABSTRACT ii
誌謝 iv
目錄 vii
表目錄 ix
圖目錄 x
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 3
2.1.1聚氨酯發展史 3
2.1.2聚氨酯合成機制 5
2.2自我修復材料 10
2.2.1簡介 10
2.2.2自我修復材料分類 10
2.2.3自我修復型聚氨酯 12
第三章　實驗 13
3.1 實驗藥品與器材 13
3.1.1 合成實驗原料 13
3.2 實驗儀器 16
3.2.1 傅立葉紅外線光譜儀 17
3.2.2 核磁共振光譜儀 18
3.2.3 膠體滲透層析儀 19
3.2.4 熱示差掃描分析儀 20
3.2.5 熱重分析儀 21
3.2.6 拉伸試驗機 22
3.2.7 光學顯微鏡 23
3.2.8 動態機械分析儀 24
3.3實驗方法 25
3.3.1實驗流程圖 25
3.3.2自我修復型聚氨酯合成 26
3.4測試方法 28
3.4.1傅立葉紅外線光譜分析 28
3.4.2核磁共振光譜分析 28
3.4.3膠體滲透分析 28
3.4.4熱示差掃描熱分析 29
3.4.5熱重分析 29
3.4.6拉伸試驗 29
3.4.7光學顯微鏡 29
3.4.8動態機械分析 30
3.5 自我修復測定 31
3.5.1 拉伸測試 31
3.5.2光學顯微鏡 31
第四章　結果與討論 32
4.1 基本性質分析 32
4.1.1 FT–IR結構分析（PU-furan） 32
4.1.2 FT–IR結構分析（PU-DA） 34
4.1.3 NMR結構分析（PU-furan） 36
4.1.4 NMR結構分析（PU-DA） 38
4.1.5 GPC分子量測定（PU-furan） 40
4.1.6 GPC分子量測定（PU-DA） 43
4.2熱分析 46
4.2.1 DSC（PU-furan） 46
4.2.2 DSC（PU-DA） 47
4.2.3 TGA（PU-furan） 49
4.2.4 TGA（PU-DA） 50
4.3 機械性質 53
4.3.1 DMA 53
4.3.2 拉伸測試 56
4.4 自我修復測試 58
4.4.1 拉伸測試 58
4.4.2 光學顯微鏡 62
第五章　結論 68
參考文獻 70

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