臺灣博碩士論文加值系統

偶氮化合物常被廣泛地使用在染料和顏料中的各種應用，而聚合物反應的製程中當作發泡劑和引發劑等用途，然而其活潑的特性乃因本身含有不穩定的偶氮基 (–N=N–)，因高溫環境下容易斷鍵產生大量的熱能及氣體，造成反應溫度及壓力急速上昇，這種自加速放熱反應現象，若無良好的冷卻系統，可能造成反應器失控，最終釀成火災或熱爆炸等災害。
為能更瞭解偶氮化合物的熱分解途徑及本質危害特性，本研究將針對偶氮化合物偶氮二異丁腈、偶氮二異丁脒鹽酸鹽、偶氮二異戊腈、偶氮二異庚腈及偶氮二異丁酸二甲酯主要之熱分解特性及潛在製程危害進行熱動力學研究，從本質安全的角度著手，以提供妥善的製程安全設計及參考資訊。
本研究以微差掃描熱卡計、多頻道微量熱卡計及緊急排放處理儀，以昇溫、恆溫及絕熱的模式下，獲取物質反應之熱圖譜及相關熱動力學參數，後續以氣相層析質譜儀及熱顯像儀進行分解機制及吸放熱探討，使用多種經驗方程式來估算活化能及頻率因子，最後將研究成果彙整成偶氮化合物熱危害資料庫 (Azo compounds thermal hazard database, ACTHD)，提供工業界及相關研究領域查詢或參考之價值。

Azo compounds are widely used in dyes, pigments, blowing agent, and initiator in industrial processes. Unfortunately, azo compounds contain the bivalent –N=N- composition which might be broken readily even during the high ambient temperature. The self-accelerating decomposition might cause the runaway reaction and lead to a fire or explosion when the cooling system failed or other upsets.
To investigate the thermal stability parameters of 2,2’-azobis (isobutyronitrile), 2,2'-Azobis(2-methylpropionamidine) dihydrochloride, 2,2'-Azobisisovaleronitrile, 2,2’-azobis-(2-4-dimethylvaleronitrile), and dimethyl 2,2’-azobis (2-methylpropionate) with thermal hazard and mechanism, differential scanning calorimetry, thermal activity monitor III and vent sizing package 2 were applied with non-isothermal conditions, isothermal conditions, and adiabatic conditions to obtain thermal curve and thermodynamic parameters of substances. Then gas chromatography/mass spectrometer and thermal image camera were applied to realize the decomposition mechansem and the behavior of thermal curve. Moreover, we utilized the robust computational model to receive apparent activation energy and pre-exponential factor. The results would be selected to construct the azo compounds thermal hazard database for searching or reference example in terms of provide industry and related research areas.

摘要………………………………………………………………………………………i
ABSTRACT……………………………………………………………………………..ii
誌　謝…………………………………………………………………………………..iii
圖目錄…………………………………………………………………………………viii
1. Introduction…………………………………………………………………………1
1.1 Backgroud of research……………………………………………………………...1
1.2 Purpose of research ………………………………………………………………...6
1.3 Procedure of research………………………………………………………………8
1.4 Predicting results…………………………………………………………………...9
2. Review of redferences……………………………………………………………..10
2.1 Azo compounds…………………………………………………………………..10
2.2 Properties of AIBN……………………………………………………………….11
2.3 Properties of AIBA……………………………………………………………….15
2.4 Properties of AMBN……………………………………………………………...17
2.5 Properties of ABVN………………………………………………………………19
2.6 Properties of AIBME……………………………………………………………..22
3. Experimental method and instrument……………………………………………...25
3.1 Samples…………………………………………………………………………...25
3.2 Differential scanning calorimetry (DSC)…………………………………………26
3.3 Thermal activity monitor III (TAM III) ………………………………………….28
3.4 Vent sizing package 2 (VSP2)……………………………………………………31
3.5 Gas chromatography/mass spectrometer (GC/MS)………………………………32
3.6 Thermal imaging camera (TIC)…………………………………………………..33
4. Results and discussion……………………………………………………………..34
4.1 Inherent hazard study……………………………………………………………..35
4.1.1 DSC tests…………………………………………………………………….....35
4.1.2 TAM III tests……………………………………………………………………46
4.1.2.1 Isothermal analysis of TAM III………………………………………………46
4.1.2.2 Thermal behaviors of the autocatalytic reaction and n-order rraction……….54
4.2 Runaway reaction………………………………………………………………...59
4.3 Model fitting……………………………………………………………………..69
4.3.1 Computation of thermokinetic parameters using the Flynn-Wall-Ozawa equation …………………………………………………………………………………….69
4.3.2 Frank-Kameneskii approximate solution of DSC………………………………..73
4.3.3 Arrhenius of TAM III…………………………………………………………….79
4.3.4 Estimatation of TMRiso ………………………………………………………….84
4.4 Decomposition product analysis by GC/MS……………………………………..89
4.5 TIC and phase transformation…………………………………………………..101
4.6 Data base MSDS………………………………………………………………...105
Conclusion…………………………………………………………………………….115
References……………………………………………………………………………..117

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