本研究將水性PU樹脂阻燃材料大致上分為兩大主軸，(1)添加型水性PU阻燃材料，(2)反應型水性PU阻燃材料。選用聚磷酸銨為磷系阻燃劑、三聚氰胺為氮系阻燃劑、鈉-蒙脫土為黏土阻燃劑，添加至PU溶液反應後以塗佈棒塗佈至離型紙上烘乾成膜。蒙脫土選用cetyltrimethylammonium bromide (CTMAB)為界面活性劑，經X光繞射鑑定顯示其(001)繞射峰出現左移，代表已拉開層間距離並成功製備有機黏土。TGA熱重分析WPU薄膜具兩階段熱裂解，添加聚磷酸銨及有機黏土能提高WPU的殘留焦炭量。但添加Melamine則會降低熱分解溫度。掃描式電子顯微鏡觀測未添加阻燃劑的WPU薄膜表面平滑，且排列有方向性。觀測聚磷酸銨於PU薄膜中會以不規則形態存在，添加三聚氰胺則看出其為纖維狀，添加黏土則為顆粒狀，分散性佳。UL94垂直燃燒測試中添加三聚氰胺、有機黏土阻燃劑能達V-0等級，而添加聚磷酸胺則可達到V-0等級。顯示添加三聚氰胺能提高PU薄膜的阻燃性質。添加20 wt%三聚氰胺可使PU的LOI值從20提高至27，添加阻燃劑均能使WPU的LOI值提高，顯示成功製備出阻燃型WPU薄膜材料。


關鍵詞：水性聚氨酯、阻燃劑、奈米黏土、燃燒性質、機械性質

In this study, waterborne Polyurethane(WPU) fire retardant polyurethane material is divided into two categories,(1) additive type ans (2) reactive type. Three types of flame retardants based on melamine, ammonium polyphosphate, and Na+-montmorillonite clay were used to blend into the polyurethane resins, and their flammability and mechanical properties were evaluated. The WPU solution was coated on a release paper by rod and subsequently dried to form the polyurethane films. The organic montmorillonite clay modified by the surfactants such as cetyltrimethylammonium bromide (CTMAB) was prepared by ion exchange with the nano-sized Na+-montmorillonite. X-ray diffraction (XRD) indicated that the surfactants were intercalated within the Na+-montmorillonite interlayers. (TGA) that WPU films had two stages of decomposition and the addition of ammonium polyphosphate,clay enhanced the char residue. But the addition of melamine can’t enhance the chat residue and the decomposition temperature had drceease. SEM indicated that flame retardants were well dispersed with WPU. The flammability test indicated that the melamine-containing WPU could reach the satisfactory V-0 rating on the UL94-V vertical flame test. The addition of flame retardant could increase LOI of WPU from 21 to 27.

Keywords：waterborne polyurethane, flame retardants, nanoclay, flammability, mechanical properties.

目錄
誌謝 ii
摘要 iii
圖目錄 viii
表目錄 xi
第一章 前言 1
1.1研究背景 1
1.2研究動機 1
第二章 文獻回顧 3
2.1水性聚氨酯 ( Waterborne Polyurethane, WPU )簡介 3
2.1.1 水性聚氨酯基本結構 4
2.1.2水性聚氨酯合成方法 6
2.1.3 水性聚氨酯之改質 8
2.2阻燃水性聚氨酯 9
2.2.1反應型水性聚氨酯 9
2.2.2添加型阻燃水性聚氨酯(非反應型) 15
2.3 阻燃型水性聚氨酯/黏土奈米複合材料 16
2.4 阻燃機制 20
2.5 阻燃水性聚氨酯材料阻燃性質測試方法 21
2.5.1 極限氧指數(Limiting Oxygen Index,LOI) 21
2.5.2 UL94垂直燃燒測試 21
2.6阻燃材料 22
2.6.1 鹵素阻燃劑 23
2.6.2 磷系阻燃劑 23
2.6.3 氮系阻燃劑 24
2.6.4 黏土阻燃劑 25
2.7有機蒙脫土 (Montmorillonite，MMT)之結構 25
2.7.1蒙脫土在高分子中的分散型態 26
第三章 實驗方法 29
3.1實驗藥品 29
3.1.1添加型水性聚氨酯實驗藥品 29
3.1.2反應型水性聚氨酯實驗藥品 30
3.2 有機黏土的製備 32
3.3有機黏土阻燃劑的儀器分析 33
3.3.1 X光繞射儀( X-ray Diffractometer，XRD ) 33
3.4阻燃性WPU薄膜之製備 33
3.4.1添加型阻燃性水性聚氨酯薄膜之製備 33
3.4.2反應型阻燃性水性聚氨酯薄膜之製備 34
3.5阻燃性WPU&PU材料的儀器分析 38
3.5.1熱重量損失分析儀(Thermo-Gravimetric Analyzer, TGA) 38
3.5.2微差掃描熱卡儀(Differential Scanning Calorimeter, DSC) 38
3.5.3掃描式電子顯微鏡儀(Scanning Electron Microscope, SEM) 38
3.5.4 紅外線光譜儀 38
3.6 阻燃性WPU&PU材料的燃燒性質測試 38
3.6.1極限氧指數(Limiting Oxygen Index, LOI) 38
3.6.2 UL94垂直燃燒測試 39
3.7 WPU薄膜的機械性質測試 39
3.8 樣品代號 39
第四章 結果與討論 42
4.1 阻燃劑的儀器分析 42
4.1.1黏土的X光繞射性質分析 42
4.1.2阻燃劑的TGA分析 44
4.2 反應型WPU薄膜之儀器分析 46
4.3阻燃型WPU&PU薄膜的儀器分析 47
4.3.1添加型水性聚氨酯與溶劑型聚氨酯/有機黏土混合物之X光繞射分析 47
4.3.2 TGA熱重損失分析 49
4.3.3 SEM電子顯微鏡分析 59
4.4 添加型&反應型阻燃型WPU&PU薄膜的燃燒測試 64
4.4.1添加型UL94垂直燃燒測試 64
4.4.2添加型LOI燃燒測試 65
4.4.3 反應型UL94垂直燃燒測試 69
4.4.4 反應型LOI燃燒測試 69
4.4.5 反應型&添加型燃燒測試比較 70
4.5 阻燃WPU薄膜之機械性質 73
4.6 綜合討論 75
第五章 結論 76
第六章 建議未來工作 78
第七章 參考文獻 79

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