臺灣博碩士論文加值系統

本研究主要利用離子液體當作觸媒，乙二醇作為溶劑，進行聚對苯二甲酸乙二酯(PET)的降解反應。PET降解反應使用微波反應器，於酸性、中性及鹼性等不同性質的離子液體中，篩選對PET降解反應最具活性的離子液體，且在不同的反應時間、反應溫度、微波瓦數、PET/ 乙二醇/ 離子液體重量比等因素下，探討對PET的重量損失百分率與二聚體和BHET單體 (Bis-2-hydroxyethyl terephthalate) 回收率的影響。PET降解後之殘留固體及產物，以TGA、DSC、GPC、FTIR、HPLC及1H-NMR和13C-NMR進行性質分析，鑑定即為寡聚體、二聚體和BHET 單體。基於離子液體高昂的價格，且實驗需要使用到大量的離子液體來進行反應，因此本實驗也自行合成實驗中使用到的離子液體。經實驗結果發現中性離子液體1-丁基-3-甲基咪唑氯鹽[Bmim]Cl 對PET降解具有降解活性，但1-丁基-3-甲基咪唑氫氧基[Bmim]OH 鹼性離子液體又比該中性離子液體為佳。因此本實驗先合成中性離子液體再加以改質為鹼性離子液體，並以1H-NMR與FTIR分析其結構。
結果發現：自行合成的離子液體與市售和文獻相同離子液體之1H-NMR與FTIR圖譜和對應數據亦相符合，顯示可自行合成所需離子液體。PET降解反應以 [Bmim]OH 做為觸媒，200 W的微波輸出功率、PET/乙二醇/離子液體 = 5/ 25/ 4 與反應時間50分鐘時，可得到100%的重量損失百分率與57.89%的BHET單體回收率。離子液體[Bmim]OH在反應後，回收並純化，可重複使用9次，且不影響PET的重量損失百分率與BHET單體的回收率。

Glycolysis of polyethylene terephthalate (PET) in the presence of ionic liquids was carried out using microwave-assisted method. The effects of degradation conditions, including reaction temperature, microwave out-put power, reaction time, and dosage of ionic liquids, on PET percentage weight loss and BHET recovery were examined. Different kinds of ionic liquid were tested , and [Bmim] OH was found to be the most effective in PET degradation with excess ethylene glycol. Ionic liquids were characterized by 1H-NMR and FTIR. Products of PET degradation were classified as oligomer, dimer and monomer BHET (Bis-2-hydroxyethyl terephthalate), and was separated, purified and analyzed by TGA, DSC, GPC, FTIR, HPLC and NMR. Under the optimum degradation condition, the weight ratio of [Bmim]OH : Ethylene glycol : PET = 4 : 25 : 5, microwave out-put power 200 W and reaction time of 50 min, the PET percentage weight loss and BHET recovery is 100% and 57.89% respectively. After products separation and purification, the ionic liquid can be reused 9 times with no obvious catalytic decline on PET degradation.

明志科技大學碩士學位論文指導教授推薦書 i
明志科技大學碩士學位論文口試委員審定書 ii
明志科技大學學位論文授權書 iii
誌謝 iv
摘要 v
Abstract vi
目錄 vii
圖目錄 x
表目錄 xii
第一章 緒論 1
1.1 對苯二甲酸二乙酯概述 1
1.1.1 對苯二甲酸二乙酯簡介 1
1.1.2 聚對苯二甲酸乙二酯製程技術 2
1.1.3 聚對苯二甲酸乙二酯市場概況 4
1.2 離子液體概述 6
1.2.1 離子液體的化學結構與物理性質 6
1.2.2 離子液體發展背景 10
1.2.3 離子液體特色與應用 11
第二章 文獻回顧 14
2.1 聚對苯二甲酸乙二酯回收處理技術 14
2.1.1 物理回收法 14
2.1.2 化學回收法 14
2.2 離子液體於塑膠降解的應用 17
2.3 研究目的與動機 21
2.3.1 研究目的 21
2.3.2 研究內容 22
第三章 實驗設備與方法 23
3.1 藥品 23
3.2 實驗儀器設備 26
3.3 離子液體合成方法 27
3.4 實驗步驟 31
3.5 分析鑑定之儀器 33
3.5.1 熱重分析儀(TGA) 33
3.5.2 熱示差掃描卡量計(DSC) 34
3.5.3 核磁共振儀(NMR) 35
3.5.4 高效液相層析儀(HPLC) 37
3.5.5 聚焦式微波反應儀 38
3.5.6 掃描式電子顯微鏡(SEM) 39
3.5.7 傅立葉轉換紅外線光譜儀(FTIR) 40
3.5.8 凝膠滲透層析儀(GPC) 41
3.6 重量損失率與產物回收率之計算方法 42
3.6.1 PET重量損失率 42
3.6.2 產物回收率 42
第四章 結果與討論 43
4.1 離子液體合成鑑定 43
4.1.1 1H-NMR分析鑑定 43
4.1.2 FTIR分析鑑定 45
4.2 離子液體對PET降解反應活性之篩選 48
4.3 產物分析 50
4.3.1 TGA固體產物分析鑑定 50
4.3.2 DSC固體產物分析鑑定 52
4.3.3 GPC固體產物分析鑑定 53
4.3.4 SEM對PET的表面分析 55
4.3.5 HPLC主產物分析鑑定 57
4.3.6 NMR主產物分析鑑定 58
4.3.7 FTIR 主產物分析鑑定 59
4.4 PET降解反應途徑之探討 60
4.5 PET降解反應影響因素之探討 62
4.5.1 離子液體之用量影響 62
4.5.2 反應變因對PET降解之影響 63
4.5.3 離子液體之重複使用性 72
第五章 結論 73
第六章 參考文獻 74

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