• 作者： Li, Kuo-Tseng; Tsai, I-Tien
• 中文摘要： 本論文研究三種碘添加物對於兩種以溴化銅為基礎之2,6-二甲基酚聚合觸媒催化性能的影響。此三種碘添加物為碘化鈉，碘化鉀以及甲基碘，此兩種2,6-二甲基酚聚合觸媒為溴化銅/正丁胺及氧化銅/氫溴酸/正丁胺。碘的添加導致聚合物分子量之增加，分子量增加之順序為碘化鈉>碘化鉀>甲基碘。碘化鈉的添加顯著的增長聚合反應的誘導時間，但碘化鉀和甲基碘的濃度對反應誘導時間之影響不大。將四級氨鹽加入已添加碘化鈉之觸媒中大大的減短反應誘導時間及減少所需之銅觸媒量。UV-VIS吸收光譜顯示當碘化鈉添加於溴化銅為基礎之觸媒中時發生了溴→碘交換反應。此外，當甲基三(辛基)氨氮加入已添加碘化鈉之觸媒中，我們觀察到碘→氯交換反應之發生。此碘→氮交換反應之發生是由於碘陰離子和四級氨陽離子結合，也因此產生氮化銅/正丁胺之錯合物。
• 英文摘要： The effects of three iodide additives on the performances of two 2, 6 dimethylphenol polymerization catalysts based on copper bromide were studied. The iodide additives were sodium iodide, potassium iodide and methyl iodide. The polymerization catalysts were CuBr/sub 2//n-butylamine and Cu/sub 2/O/HBr/n-butylamine. Iodide addition resulted in the higher polymer molecular weight which decreased in the following order: NaI > KI > CH/sub 3/I. Polymerization induction period increased significantly with NaI addition, but was insensitive to the concentrations of KI and CH/sub 3/I. Addition of quaternary ammonium salt to the NaI-added catalyst dramatically shortened the induction period and greatly decreased the amount of copper catalyst needed. UV-VIS absorption spectroscopy showed that the Br.arrr.I exchange occurred with the addition of NaI into the copper bromide-based catalyst. Besides, I.arrr.Cl exchange was observed with the addition of methyltrioctylammonium chloride to the NaI-added catalyst. The I.arrr.Cl exchange was caused by the binding of the iodide anion to the quaternary ammonium cation. Copper chloride/n-butylamine complex was generated after the I.arrr.Cl exchange.
• 中文關鍵字： 二甲基酚; 溴化銅; 碘加成; 丁基胺; 催化劑
• 英文關鍵字： Dimethylphenol; Copper Bromide; Iodide Addition; Butylamine; Catalyst