採用二階段反應方式合成軟、硬段不飽和聚酯寡聚體，硬段不飽和聚酯由間苯二甲酸與1,2-丙二醇先行反應後再加入馬來酸酐進行後續的酯化反應，軟段不飽和聚酯則使用二乙基二醇取代1,2-丙二醇反應。將合成之純軟段或硬段寡聚體作不同比例混摻，改變苯乙烯含量並量測熟化後之機械性質、熱性質及利用SEM觀察其形態。並利用溶凝膠反應，將四乙基矽氧烷及聚二甲基矽氧烷成功地均勻分散於不飽和聚酯基材中形成有機無機混成材料，此種材料不僅具有奈米尺寸孔隙且為塊材，才能有效達到阻燃效果。進一步利用29Si-NMR、拉力試驗機、動態機械熱分析儀、掃瞄式電子顯微鏡、和熱重分析儀檢測，結果顯示形成之有機無機混成材料仍可使機械性質達到阻燃層之需求。燒蝕試驗結果顯示，添加阻燃填料之不飽和基材及有機無機混成材料有助抵抗高溫火焰沖刷，表面形成緻密碳化層。

Oligomers of hard and soft segments of unsaturated polyesters (UP) were synthesized. They were blended in different ratios and cured with various amounts of styrene. Based on the criteria of tensile strength and strain, hard segment/soft segment (60/40 wt %) UPs containing 35 wt % and 45 wt % of extra amount of styrene were chosen for further studies. Inorganic-organic hybrid materials were prepared by incorporating tetraethoxysilane and poly(dimethylsiloxane) into the UP resins via the sol-gel process by changing the ratios of HCl/TEOS, H2O/TEOS, TEOS/PDMS and the reaction time. The specimens of these hybrid materials after curing were characterized using the tensile tester, rheometer, scanning electron microscope (SEM), 29Si-NMR and thermogravimeter. In the condition of HCl/TEOS molar ratio 0.07, H2O/TEOS molar ratio 4, TEOS/PDMS weight ratio 90/10 and the reaction time 3 hours, the results of 29Si-NMR, SEM and silicone mapping indicate that these silica gels with 3D network were well dispersed in the UP resins. These specimens had tensile strength of 512±16 kgf/cm2 and elongation of 11±4 % which are above the criteria of inhibitors. From the erosion testing, flame retardants was added unsaturated polyester and inorganic-organic hybrid materials that can help to resist heat flame, remain of a fire on the surface had the char forming.

摘要 I
Abstract II
目錄 III
Scheme contents VI
表目錄 VII
圖目錄 VIII
第一章 前言 1
第二章 文獻回顧 3
2.1 不飽和聚酯樹脂之化學 3
2.1.1 不飽和聚酯原料 3
2.1.2 不飽和聚酯酯化方法和熟化反應 6
2.2 溶凝膠反應(Sol-gel process) 7
2.2.1 溶凝膠反應之發展及優異點 8
2.2.2 溶凝膠反應控制因素 9
2.2.2.1 觸媒的選用及含量影響 11
2.2.2.2 pH值影響 11
2.2.2.3 水量影響 13
2.2.2.4 聚二甲基矽氧烷分子量及含量影響 13
2.2.2.5 無機矽氧烷和有機聚矽氧烷結構上對阻燃機制影響 14
2.3 有機無機混成材料 14
2.4 阻燃層之介紹 16
2.4.1 阻燃機理 16
2.4.2 阻燃層之填料成分 17
2.5 研究目的與方法 18
第三章 實驗部分 19
3.1 實驗藥品 19
3.1.1 聚酯藥品 19
3.1.2 矽氧基化合物 19
3.1.3 固體和液態填料 19
3.1.4 其他試藥 20
3.2 儀器設備 20
3.3 實驗步驟 22
3.3.1 不飽和聚酯合成 22
3.3.1.1 硬段聚酯合成 22
3.3.1.2 軟段聚酯合成 23
3.3.1.3 酸值測定 24
3.3.2 聚酯基材之熟化 24
3.3.3 溶凝膠反應 25
3.3.4 加入固體及液態填料 25
3.4 氫氧燒蝕試驗 26
第四章 結果與討論 28
第一部份 不飽和聚酯之研究 28
4.1 不飽和聚酯寡聚體合成酸價及結構分析 28
4.1.1 聚酯寡聚體之1H-NMR圖譜與模擬分析 28
4.1.2 不飽和聚酯熟化後之FTIR圖譜 29
4.2 不飽和聚酯混摻熟化之機械性質 33
4.3 不飽和聚酯混摻熟化之熱性質 41
4.3.1 添加苯乙烯外含比對聚酯基材的玻璃轉換溫度之影響 41
4.3.2 外含比65 %苯乙烯時不同比例聚酯基材的玻璃轉換溫度之影響 41
4.3.3 不同比例聚酯混摻熟化後的玻璃轉換溫度之影響 42
4.3.4 軟硬段不飽和聚酯熟化後之熱穩定性 46
4.4 不飽和聚酯混摻熟化後之形態 48
第二部份 有機無機混成材料於溶凝膠反應之研究 51
4.5 有機無機混成材料之矽譜分析 51
4.5.1 酸量變化 51
4.5.2 水量變化 52
4.5.3 聚二甲基矽氧烷含量變化 53
4.5.4 時間變化 53
4.6 有機無機混成材料之機械性質與動態機械性質 61
4.7 有機無機混成材料之熱性質 67
4.8 試片之透明度 72
4.9 有機無機混成材料之形態 73
4.10 阻燃層之燒蝕測試 74
第五章 結論 81
第一部份 不飽和聚酯之研究 81
第二部份 有機無機混成材料於溶凝膠反應之研究 81
第六章 未來展望 82
第七章 參考文獻 83
附錄 86
附錄一 硬段聚酯寡聚體(oligomer-1)之1H-NMR 圖譜 86
附錄二 軟段聚酯寡聚體(oligomer-2)之1H-NMR 圖譜 87
附錄三 硬段聚酯寡聚體之模擬1H-NMR 圖譜 88
附錄四 軟段聚酯寡聚體之模擬1H-NMR 圖譜 89

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