本研究將PU樹脂依比例調配成溶液，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Cetylpyridinium chloride及Cetyl trimethyl ammonium chloride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PU薄膜具兩階段熱裂解，添加聚磷酸銨及有機黏土能提高PU的殘留焦炭量。DSC微差掃描熱卡儀分析，添加阻燃劑能提高PU的玻璃轉移溫度。掃描式電子顯微鏡觀測未添加阻燃劑的PU薄膜表面平滑，且排列有方向性。觀測聚磷酸銨於PU薄膜中有數個長條狀顆粒，添加三聚氰胺則看出其為方形顆粒狀，分散性佳。UL94垂直燃燒測試中添加三聚氰胺阻燃劑能達V-2等級，FMVSS-302水平燃燒測試中添加三聚氰胺能從B分類提升至SE分類，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23，添加阻燃劑均能使PU的LOI值提高，顯示成功製備出阻燃型PU薄膜材料。機械性質的量測中顯示黏土的添加有助於提高PU的拉伸強度及伸長率，但是會降低PU的軟度。

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 PU 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 cetylpyridinium chloride (CPC) and cetyl trimethyl ammonium chloride (CTAC) 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. It was shown from thermo-gravimetric analyzer (TGA) that PU films had two stages of decomposition and the addition of flame retardant enhanced the char residue. Results from differential scanning calorimeter (DSC) indicated that the glass transition temperature of PU increased slightly by addition of flame retardants. SEM indicated that flame retardants were well dispersed with PU. The flammability test indicated that the melamine-containing PU could reach the satisfactory V-2 rating on the UL94-V vertical flame test and the satisfactory SE rating on the FMVSS-302 testing. The addition of flame retardant could increase LOI of PU from 20 to 23. The addition of clay could increase the tensile strength and elongation of PU, but also decrease the softness of PU.

誌謝 i
摘要 iii
目錄 v
圖目錄 ix
表目錄 xi
第一章 緒論 1
1.1 前言 1
1.2 研究動機 1
第二章 文獻回顧 1
2.1 聚氨酯（Polyurethane, PU）簡介 3
2.1.1 PU基本結構 3
2.1.2 PU聚合反應 5
2.1.3 PU合成方法 7
2.2 阻燃機制 8
2.2.1 氣相阻燃 9
2.2.2 凝聚相阻燃 9
2.2.3 中斷熱交換阻燃 9
2.2.4 焦炭產量與阻燃性的關聯性 10
2.3 阻燃性質測試方法 10
2.3.1 極限氧指數(limiting oxygen index, LOI) 10
2.3.2 UL94垂直燃燒測試 11
2.3.3 FMVSS-302燃燒測試 12
2.4 阻燃材料 13
2.4.1 鹵素阻燃劑 14
2.4.2 磷系阻燃劑 15
2.4.3 氮系阻燃劑 15
2.4.4 黏土阻燃劑 16
2.5 高分子奈米黏土複合材料 17
第三章 實驗方法 19
3.1 實驗藥品 19
3.2 有機黏土阻燃劑的製備 21
3.3 有機黏土阻燃劑的儀器分析 22
3.3.1 X光繞射儀( X-ray Diffractometer，XRD ) 22
3.4 阻燃型PU薄膜的樣品製備 22
3.5 阻燃型PU薄膜的儀器分析 24
3.5.1 熱重量損失分析儀(Thermo-Gravimetric Analyzer, TGA) 24
3.5.2 微差掃描熱卡儀(Differential Scanning Calorimeter, DSC) 24
3.5.3 掃描式電子顯微鏡儀(Scanning Electron Microscope, SEM) 24
3.6 阻燃型PU薄膜的燃燒測試 24
3.6.1 極限氧指數(Limiting Oxygen Index, LOI) 24
3.6.2 UL94垂直燃燒測試 24
3.6.3 FMVSS-302燃燒測試 25
3.7 阻燃型PU薄膜的機械性質測試 25
3.8 樣品代號 25
第四章 結果與討論 27
4.1 阻燃劑的儀器分析 27
4.1.1 黏土的X光繞射性質分析 27
4.1.2 阻燃劑的TGA性質分析 29
4.1.3 阻燃劑的SEM電子顯微鏡分析 32
4.2 阻燃型PU薄膜的儀器分析 34
4.2.1 PU與有機黏土混合物之X光繞射分析 34
4.2.2 TGA熱重損失分析 35
4.2.3 DSC微差掃描熱卡儀分析 38
4.2.4 SEM電子顯微鏡分析 40
4.3 阻燃型PU薄膜的燃燒測試 42
4.3.1 單一阻燃劑對於PU阻燃性之影響 42
4.3.2 混合阻燃劑對於PU阻燃性之影響 45
4.3.3 添加量對於PU阻燃性之影響 47
4.4 阻燃型PU薄膜的機械性質 50
4.4.1 單一阻燃劑對於PU機械性質之影響 50
4.4.2 混合阻燃劑對於PU機械性質之影響 51
4.4.3 添加量對於PU機械性質之影響 53
4.5 综合討論 55
第五章 結論 56
第六章 建議未來工作 58
參考文獻 59

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