聚氨基甲酸乙酯（PU）的使用與日俱增，經使用後的處理與處置問題，愈來愈受重視。廢PU的主要處理方法有掩埋處理法、資源回收法、物質回收法及化學處理回收法等。而就化學處理回收法來說，廢PU泡綿經由添加化學物質，在適當的觸媒催化及反應條件下產生化學反應，反應後可得到PU的原料或初級石化原料。醇解反應（glycolysis）為化學處理回收法之一種，影響醇解反應的因素有溶劑的種類及濃度、觸媒配方及反應條件的控制。有鑑於此，本研究探討上述因素對PU醇解過程及產物性質的影響，以做為實廠設計之參考資料。
本研究採用的樣品為軟質PU泡綿，以添加不同配比的化學反應劑及觸媒，在常壓及恆溫下進行醇解反應。實驗使用的反應劑為二甘醇(DEG)
，觸媒為醋酸鉀（CH3COOK），反應溫度為220℃。醇解產物性質分析項目包括氫氧基值、重量平均分子量、黏度及PU泡綿中-NCOO-官能基的轉化率。研究結果顯示，以DEG / PU＝ 150%，KAc / PU = 1%，反應時間90 min為適當反應配比、觸媒濃度及反應時間。在純化研究中發現，第二階段蒸餾（氣相溫度245~260℃）之餾出物比例最高，其氫氧基值與DEG者接近。從DEG添加量、-NCOO-轉化率、觸媒濃度及反應時間的分析結果，
得到適當反應配比及觸媒濃度（DEG / PU = 150%，KAc / PU = 1%）下之反應動力式可表示為：dX/dt=0.014×(1-X)3.71×(KAc)0.6×(DEG)1.12，其決斷係數為0.8202，表示反應動力式是可接受的。

The treatment of waste polyurethanes (PU) is more and more important, as the application of PU is steadily on the increase. The major methods for treating waste PU include landfill, energy recovery, material recycling, and chemicals recycling etc. The chemicals recycling is the chemical conversion of waste PU into the raw materials of PU or primary petrochemicals by the adequate choice of reagents and catalysts in the chemical glycolysis conditions. Glycolysis is one of the principal methods in chemicals recycling. The factors that affect the glycolysis of PU include the types of solvent and catalyst, the concentrations of solvent and catalyst and the reaction time. In this study, the glycolysis of PU is investigated to provide the useful data for the design of a pilot scale plant.
The study for the glycolysis of flexible PU foam are carried out at various formulas consisted of reagent and catalyst. The experiments are performed under the atmospheric pressure and isothermal condition (220℃). Diethylene glycol (DEG), potassium acetate (CH3COOK) are used as the solvent and catalyst, respectively. The properties of glycolysis products such as hydroxyl value, mass mean molecular weight, viscosity and the conversion of the -NCOO- functional group in PU are analyzed with different experimental conditions. The results indicate that the concentrations with DEG/PU = 150%, KAc/PU = 1%, and the reaction time = 90 min are the best ratio of solvent and polyurethane, the concentration of catalyst, and the reaction time, respectively. The amounts of the distillate in the second stage distillation (gas-phase temperature 245 ~ 260 ℃) are about 13.4 ~ 43.78% under the experimental conditions. Since the hydroxyl value of the distillate obtained from the second stage distillation is closed to that of the DEG. The recycling of PU by the glycolysis will be attractive. The conversion of -NCOO- functional group in PU at the optimum formula (DEG/PU = 150% and KAc/PU = 1%) can be expressed by the total rate equation, dX/dt = 0.014 × (1-X) 3.71 × (KAc) 0.6×(DEG) 1.12. The proposed kinetic model can be accepted with the coefficients of determination 0.8202.

第一章 緒 論..................................................1
1.1前言..................................................1
1.2研究目的與內容........................................4
第二章 文獻回顧...............................................6
2.1 PU泡綿之介紹.........................................6
2.2 PU之組成及製造.......................................7
2.2.1 異氰酸酯.........................................8
2.2.2 多元醇...........................................9
2.2.3 添加物..........................................10
2.3 PU泡綿之回收技術....................................11
2.4 PU泡綿醇解之反應機制................................13
2.5 PU泡綿之醇解及相關研究..............................14
2.5.1 軟質PU泡綿醇解反應..............................16
2.5.2 硬質PU泡綿醇解反應..............................20
2.5.3 其他PU泡綿相關研究..............................21
2.6 產物的純化..........................................31
2.7 研究方向............................................32
第三章 實驗設備與方法........................................34
3.1 實驗設備............................................34
3.1.1 醇解實驗........................................34
3.1.2 純化實驗........................................34
3.2 實驗樣品及藥品......................................36
3.3 實驗步驟............................................36
3.3.1 軟質PU泡綿醇解步驟..............................36
3.3.2 醇解產物之純化步驟..............................38
3.4 分析方法與分析設備..................................39
3.4.1 樣品水分含量之分析..............................39
3.4.2 樣品粒徑分佈之分析..............................40
3.4.3 元素分析........................................41
3.4.4 重金屬分析......................................42
3.4.5 氫氧基值之分析..................................42
3.4.6 膠體滲透色層分析................................45
3.4.7 Fourier轉換紅外線光譜分析.......................48
3.4.8 黏度分析........................................49
第四章 結果與討論............................................51
4.1 實驗結果............................................51
4.2 操作條件對產物性質的影響............................65
4.2.1 反應時間對醇解之影響............................65
4.2.2 反應劑DEG對醇解之影響...........................73
4.2.3 觸媒KAc對醇解之影響.............................78
4.3 醇解產物之純化......................................85
4.4 醇解反應動力模式之建立..............................93
4.4.1 動力方程式推導..................................93
4.4.2 反應模式與實驗值之比較..........................96
第五章 結論與建議...........................................111
5.1 結論...............................................111
5.2 建議...............................................111
參考文獻....................................................113
附錄A：KAc濃度不為0時之反應動力方程式.......................117
附錄B：包含KAc濃度為0時之反應動力方程式.....................121

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