1,6-己二異氰酸酯(HDI)為聚氨酯(PU)的重要原料之一，目前被廣泛運用於黏著劑、塗料、絕緣體及人工橡膠、皮革的製造。傳統上，採用光氣法合成HDI，但光氣劇毒，不僅危害人體也汙染環境，過程中產生的HCl更嚴重腐蝕設備，近年來，許多替代方法被探討，熱裂解六亞甲基-1,6-二氨基甲酸甲酯(HDC)生成HDI的途徑符合綠色化學的概念，因此成為熱門的替代方案。
本次重點放在HDC熱裂解生成HDI反應，此步驟需要足夠溫度才能使反應發生，生成的產物HDI在高溫下卻容易產生副反應，適當的操作條件極為重要，為了達到最佳的HDC轉化率及HDI產率，許多實驗條件列入考量，包含溶劑、溫度、觸媒、反應時間、HDC濃度、氮氣。實驗結果顯示，最佳的操作條件為HDC初始濃度9.0wt%、觸媒為0.06質量比的ZnO(ZnO：HDC)、溫度為180℃、反應時間為4小時，此條件下，HDC轉化率趨近100%、HDI產率為88%。
分析實驗數據結果得知，為了有效促使裂解反應進行，必須通入氮氣將產生的甲醇適時移除，否則產生的甲醇會抑制裂解，不利於反應進行，若溶劑含有提供電子的特性，並且搭配ZnO上具有良好吸引電子能力的Zn2+，能促使E1cb的反應機制，並大幅地提高HDC裂解成HDI的反應性。

1,6-hexamethylene diisocyanate (HDI) is one of the most important materials of polyurethane and has been widely used in the manufacture of adhesive, paint, insulator, and synthetic rubber and leather. Traditionally, the HDI synthesis route not only involves extremely toxic phosgene which causes severe hazards to both human body and environment, but also produces seriously corrosive byproduct HCl. Recently, the alternative process of thermal decomposition of dimethylhexane-1,6-dicarbamate (HDC) has become a popular non-phosgene route for the HDI synthesis due to green-chemistry concept.
In the study, the effects of including solvent, temperature, catalyst, reaction time, concentration of HDC, and nitrogen flow are subsequently investigated in order to achieve the highest HDC conversion and HDI yield. The best reaction conditions found are solvent used: PGDE, starting concentration of HDC: 9.0wt%, catalyst: ZnO amount 0.06 (mass ratio of ZnO to HDC), temperature: 180℃, reaction time: 4hr. The conversion of HDC is near 100%, and yield of HDI is 88%.
Analysis of data found that it is important to remove methanol during the process by nitrogen flow. Besides, electron donor ability of the solvent with catalyst ZnO which contains the great electron withdrawing ability of Zn2+ is most critical to inducing the E1cb mechanism and enhancing reactivity of HDC to HDI.

摘要 I
Abstract II
致謝 III
目錄 IV
圖目錄 VI
表目錄 VIII
第一章 緒論 1
1-1研究背景 1
1-1-1前言 1
1-1-2 路徑中主要物質簡介 2
1-1-3 1,6-己二異氰酸酯製備方法比較 7
1-2文獻回顧 15
1-3研究動機、目的 19
1-4章節安排 20
第二章 HDC合成HDI研究方法 21
2-1 實驗設備與儀器 21
2-2 實驗藥品 22
2-3 實驗流程 23
2-3-1 HDC標準品配製 23
2-3-2 HDC裂解實驗 26
第三章 HDC合成HDI結果與討論 31
3-1 溶劑因素 31
3-2 溫度因素 38
3-3 觸媒因素 40
3-4 反應時間因素 44
3-5 HDC濃度因素 46
3-6 氮氣因素 48
第四章 總結 50
參考文獻 52

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