臺灣博碩士論文加值系統

苯乙烯單體 (styrene monomer, SM) 廣泛地被使用在石化工業中並成為現今生活中不可或缺之物質。本研究針對苯乙烯單體在一般儲存中，受空氣中氧氣之氧化形成苯甲醛 (benzaldehyde)，其與苯乙烯衍生物 [α-甲基苯乙烯 (α-methylstyrene, AMS) 與反-β-甲基苯乙烯 (trans-β-methylstyrene, TBMS)] 混合反應於昇溫與恆溫條件下之放熱失控行為進行探討。針對苯乙烯衍生物分別加入苯甲醛進行相關效應探討，研究其放熱行為分析及不相容性，以微差掃描熱卡計 (differential scanning calorimetry, DSC) 進行昇溫實驗並以多頻道微量熱卡計 (thermal activity monitor Ⅲ, TAM Ⅲ) 進行恆溫實驗。根據本實驗結果可得知二聚合反應之放熱起始溫度皆隨苯甲醛之加入皆提前，熱聚合反應雖有提高溫度的現象，但其昇高之熱量並不足影響其儲存過程的安全，反而更需擔心其氧化物苯甲醛是否影響苯乙烯聚合後之品質，研究結果可使製程人員瞭解化學物質於儲存過程中應控制其溶氧量，避免在儲運過程裡所可能造成的危害。本研究並做氧化物苯甲醛的加入後之熱力學與動力學之探討。

Styrene monomer (SM) is widely used in petrochemical industries and it becomes a necessary material in daily life. SM may mixing with oxygen to oxidize as benzaldehyde in storage circumstance. Benzaldehyde was contacted with SM and its derivatives that involves α-methylstyrene (AMS) and trans-β-methylstyrene (TBMS) to confer reaction in exothermic runaway behaviors. Differential scanning calorimetry (DSC) and thermal activity monitor Ⅲ (TAM Ⅲ) were employed to determine the thermokinetics and safety index of AMS and TBMS mixed with benzaldhyde, respectively. The exothermic onset temperature (T0) occurred at high temperature and the total heat of reaction (Qtotal) was increasing in styrene comparing with benzaldehyde solutions. The above reaction did not result in potential thermal hazards in the polymerization process, except for degrading its product quality.

中文摘要……………………………………………………………………i
英文摘要……………………………………………………………………ii
誌謝…………………………………………………………………………iii
目錄…………………………………………………………………………iv
表目錄………………………………………………………………………vi
圖目錄……………………………………………………………………vii
第一章 緒論…………………………………………………………………1
1.1 研究緣起……………………………………………………………………1
1.2 研究目的…………………………………………………………………12
1.3 研究內容…………………………………………………………………12
1.4 預期成果…………………………………………………………………12
1.5 研究流程…………………………………………………………………13
第二章 文獻回顧…………………………………………………………15
2.1國外文獻資料………………………………………………………………15
2.1.1 苯乙烯單體……………………………………………………………15
2.1.2 α-甲基苯乙烯…………………………………………………………18
2.1.3 反-β-甲基苯乙烯……………………………………………………19
2.1.4苯乙烯其它衍生物……………………………………………………19
2.2國內文獻資料………………………………………………………………21
第三章 實驗設備與方法…………………………………………………34
3.1 實驗物質…………………………………………………………………34
3.1.1 苯乙烯…………………………………………………………………35
3.1.2 α-甲基苯乙烯…………………………………………………………36
3.1.3 反-β-甲基苯乙烯……………………………………………………39
3.1.4 苯甲醛與甲醛…………………………………………………………39
3.2 實驗儀器…………………………………………………………………40
3.2.1 微差掃瞄熱卡計………………………………………………………40
3.2.2 多頻道微量熱卡計 III………………………………………………43
3.3 實驗設計與方法…………………………………………………………46
3.3.1 微差掃瞄熱卡計………………………………………………………46
3.3.2 多頻道微量熱卡計 III………………………………………………46
3.3.3 恆溫分解動力學估算…………………………………………………46
第四章 結果與討論………………………………………………………48
4.1 微差掃瞄熱卡計實驗結果………………………………………………48
4.1.1 α-甲基苯乙烯與 α-甲基苯乙烯混合苯甲醛之熱譜圖……………48
4.1.2 反-β-甲基苯乙烯與苯乙烯混合苯甲醛之熱譜圖…………………50
4.1.3 苯乙烯與苯乙烯混合甲醛之熱譜圖…………………………………52
4.1.4 α-甲基苯乙烯與α-甲基苯乙烯混合甲醛之熱譜圖………………54
4.1.5 反-β-甲基苯乙烯與反-β-甲基苯乙烯混合甲醛之熱譜圖………56
4.2 多頻道微量熱卡計 III實驗結果…………………………………………58
4.2.1 α-甲基苯乙烯與 α-甲基苯乙烯加入苯甲醛後之實驗結果………58
4.2.2 反-β-甲基苯乙烯與 反-β-甲基苯乙烯加入苯甲醛後之實驗結果61
4.2.3 恆溫活化能推估計算…………………………………………………64
第五章 結論與建議………………………………………………………67
5.1 結論………………………………………………………………………67
5.2 建議………………………………………………………………………69
參考文獻…………………………………………………………………70

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