臺灣博碩士論文加值系統

近年來，國內外發生數件因為苯乙烯單體所引發的火災爆炸事故，由國內外文獻可知苯乙烯單體在低溫下的動力學仍不明瞭，本研究首先使用微差掃描熱卡計 (DSC) 進行初步的熱掃描，可獲得聚合反應的起始放熱溫度與聚合熱，再使用多頻道微量熱卡計 (TAM) 進行接近室溫下的恆溫放熱行為量測，再配合傅利葉轉換紅外線光譜儀 (FT-IR) 進行中間產物的探討，以提供完整的苯乙烯單體動力學、熱力學資料庫以及提供後續反應機制推估之參考。
本研究延續本實驗室先前一系列研究有機過氧化物之方法，針對苯乙烯單體進行低溫放熱行為分析及模擬失控反應研究，研究結果發現，苯乙烯單體其恆溫動力學於高溫部分 (120℃以上) 屬n階反應，而於50℃至80℃低溫部分則屬自催化反應，且其自催化放熱溫度可低於50℃。較以一般熱卡計量測的文獻值低約40℃。本研究論文主要之研究方式為以微差掃描熱卡計 (DSC) 及多頻道微量熱卡計 (TAM) 探討恆溫狀態下之放熱行為及恆溫熱力、動力學探討，可得苯乙烯單體在低溫部分之反應階數為0.5級，活化能為62.8 kJ/mole，頻率因子為5.039×104 (1/sec)，反應速率常數即為5.039×104 exp (-62,083/8.314×T)。此外，利用上述參數求取苯乙烯單體儲運過程之自加速分解溫度，以提供給製程工廠應用於如溫度單元控制、緊急排放系統等安全，實際應用於工廠化學災害之預防。

Styrene Monomer (SM) has been widely used for polystyrene (PS), acrylonitrile-butadiene-styrene (ABS), styrene-acryonitrile (SAN) in the petrochemical industry. In recent years, from 1994 to 2001, several serious accidents occurred in Taiwan due to human errors, its inherent instability, accidents or external fire.
Compared with other calorimrtries on thermal hazard analysis, such as differential scanning calorimetry (DSC), vent sizing package, (VSP) which can not detect such weak exothermic phenomena, in this research, the exothermic polymerization is characterized by an isothermal microcalorimeter, thermal activity monitor (TAM). Thermograms show that in the temperature range from 50℃ to 80℃, follows the autocatalytic reaction. In addition, the reaction order, activation energy and rate constant are verified be 0.5, 62.8 kJ/mol and 5.039×104 exp (-62,083/8.314×T), respectively. Finally, the practical suggestions can be provided to prevent the specific plant from accidents, especially at low temperature conditions during storage and transportation.

目錄
目次 頁次
中文摘要 i
英文摘要 ii
致謝 … iii
目錄 iv
表目錄 vi
圖目錄 vii
符號說明 ix
第一章﹑緒論 1
1.1 研究緣起 1
1.2 研究目的 5
1.3 研究內容 5
1.4 預期成果 6
第二章﹑文獻回顧 8
2.1 國外文獻資料 8
2.2 國內文獻資料 10
第三章﹑苯乙烯單體與抑制劑特性 12
3.1 苯乙烯單體 12
3.1.1 苯乙烯單體特性 12
3.1.2 聚合反應機制 13
3.1.3 苯乙烯單體製造流程 13
3.1.4 苯乙烯單體製程危害分析 17
3.2 抑制劑/第三丁基鄰苯二酚特性 17
3.2.1 TBC特性 17
3.2.2 TBC防止化學反應之詳細化學機制 19
3.3 苯乙烯單體安全管理、運輸相關規定 20
第四章﹑理論及應用 24
4.1 恆溫分解動力學 24
4.1.1 n階反應機制 25
4.1.2 自催化反應機制 26
4.2 熱動力參數應用技術 28
第五章﹑結果與討論 31
5.1 昇溫與恆溫熱危害分析 31
5.1.1 DSC昇溫熱聚合掃描 31
5.1.2 DSC與TAM恆溫熱聚合掃描 33
5.2 反應動力學探討 34
5.2.1 反應階數求法 34
5.2.2 反應速率常數 34
5.2.3 半生期確認 34
5.2.4 活化能計算 37
5.2.5 頻率因子計算 39
5.2.6 動力學總體探討 39
5.3 自加速反應分解溫度計算 41
5.4 傅利葉轉換紅外線光譜儀實驗 44
第六章﹑結論與建議 56
6.1 結論 56
6.2 建議 57
參考文獻 58
附錄一﹑苯乙烯單體於恆溫烘箱70℃後DSC餘熱掃描熱譜圖 62
附錄二﹑苯乙烯單體於DSC恆溫120℃至180℃實驗熱譜圖 65
附錄三﹑實驗方法 68
附錄四﹑期刊投稿 87
自傳 104

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