採用二階段反應方式合成軟硬段不飽和聚酯寡聚體，硬段由間苯二甲酸與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，軟段則使用二乙基二醇取代1,2-丙二醇反應。在先前的研究中二醇類採過量20 wt%反應，而在此研究計劃將分別降為過量10與5 wt%。二醇類由過量20 wt%降為5 wt%，軟硬段寡聚體之數目平均分子量約可從1000 g/mole左右增加30~40%，同時使軟段寡聚體馬來酸的異構化程度由40.5%提升至57.3%。將合成之純軟段或硬段寡聚體由0∼100%以固定改變20%的比例作混摻，其與苯乙烯熟化後進行機械性質測。

二醇類過量5與20 wt%系統比較，熟化後軟段與硬段聚酯微尺寸試片之抗張強度分別增加了8倍與1.3倍，故藉由改變合成時二醇類過量比例可使機械性質達到阻燃層需求。分別選擇二醇類過量10與5 wt%合成可符合機械性質需求之混摻聚酯為基材（硬段60 wt%，軟段40 wt%），並且採用氫氧化鎂取代立德粉進行硝化甘油滲移與燒蝕率的評估。二醇類過量10 wt%系統，硝化甘油在無限長時間下的滲移吸收量（M∞）隨著氫氧化鎂由5增加至30 wt%而由12.78降至8.47 wt%。二醇類過量5 wt%系統，阻燃層在固定相同的氫氧化鎂含量下較過量10 wt%系統具有較高的抗張強度與較低的硝化甘油吸收量。隨著氫氧化鎂含量由10 wt%增加至30 wt%，兩系統燒蝕率由0.036 mm/s降至0.021 mm/s。兩系統阻燃層配方的硝化甘油滲移吸收量、燒蝕率較目前使用的商業化阻燃層明顯減少許多，而且當氫氧化鎂的添加量達20 wt%以上會有自熄現象發生。

Oligomers of hard and soft segments of unsaturated polyesters were synthesized in two steps. For the hard segment, isophthalic acid was reacted with 1,2-propanediol first, then maleic anhydride was added for further esterification. For the soft segment, diethylene glycol was used to replace 1,2-propanediol. In the previous study, the excess amount of glycol was 20% in weight. In this study, glycol was 10 and 5 wt% in excess, respectively. Decreasing the excess amount of glycol from 20 to 5 wt%, the number average molecular weight of both hard and soft segments increased about 30-40% from 1000 g/mol, and the degree of isomerization of maleic acid changed from 40.5 to 57.3% for the oligomers of the soft segment. The hard and soft segments synthesized in this study were blended in weight ratios from 0 to 100 % in an interval of 20 %, and then cured with styrene for further mechanical testing.

The micro-tensile strength of cured soft and hard segments increased 1.3 and 8 times, respectively, in this study compared with that of specimens prepared under the condition of 20 wt% in excess of glycol. Therefore, the criteria of inhibitors can also be achieved by varying the excess amount of glycols. To evaluate the nitroglycerine migration and the erosion rate, only two (60% hard segment and 40% soft segment) of the formulas which passed the criteria of mechanical properties were investigated by replacing lithophone with magnesium hydroxide. In the case of 10 wt% in excess of glycol, the migration of nitroglycerine at infinite time (M

目 錄
Abstract I
摘要 II
目錄 III
Scheme contents V
表目錄 VI
圖目錄 VII
一、前言 1
二、文獻回顧 3
2.1 材料之阻燃機制 3
2.2 阻燃劑 4
2.3 阻燃層 6
2.4 不飽和聚酯阻燃層 7
2.4.1 不飽和聚酯之寡聚體生成 9
2.4.2 不飽和聚酯之熟化成型 10
2.4.3 含鹵素不飽和聚酯之單體與性質 11
2.4.4 不含鹵素不飽和聚酯之單體與性質 12
2.5 矽氧基橡膠阻燃層 12
2.6 阻燃層之硝化甘油滲移 13
2.7 研究目的與方法 15
三、實驗 17
3.1 藥品與材料 17
3.2 儀器設備 18
3.3 聚酯基材合成 18
3.3.1 硬段聚酯合成 18
3.3.2 軟段聚酯合成 20
3.3.3 酸值測定 21
3.4 寡聚體結構與分子量測定 21
3.4.1 核磁共振光譜分析 21
3.4.2 凝膠滲透層析分析 22
3.5 聚酯基材之熟化 22
3.6 熱穩定性分析 23
3.7 機械性質拉力試驗 23
3.8 硝化甘油滲移測定 24
3.9 氫/氧燒蝕試驗 25
四、實驗結果與討論 27
4.1 寡聚體分子量測定與結構分析 27
4.2 機械性質 29
4.2.1 軟段與硬段聚酯基材不同比例混摻 29
4.2.2 聚酯基材（ex10-CP6）與不同比例聚二甲基矽氧烷之混摻 34
4.2.3 聚酯基材（ex10-CP6）與含不同比例氫氧化鎂之阻燃層固體填料混摻 38
4.3 熱穩定性分析 40
4.3.1 二醇類過量5,10,20 wt%之軟硬段聚酯熟化後之熱穩定性 40
4.3.2 聚酯基材（ex10-CP6）與聚二甲基矽氧烷混摻熟化後之熱穩定性 41
4.4 硝化甘油滲移吸收與燒蝕率 42
4.4.1 硝化甘油滲移吸收 42
4.4.2 燒蝕率 51
五、結 論 56
參考文獻 58
附 錄 61
附錄 1 硬段聚酯寡聚體（oligomer-1）之GPC圖譜 61
附錄 2 軟段聚酯寡聚體（oligomer-2）之GPC圖譜 64
附錄 3 硬段聚酯寡聚體（oligomer-1）之1H-NMR圖譜 67
附錄 4 軟段聚酯寡聚體（oligomer-2）之1H-NMR圖譜 70

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