臺灣博碩士論文加值系統

本研究以隨機(random)方式於聚乙二醇(Polyethylene glycol)及聚氧乙烯(Polyethylene oxide，PEO)合成過程中，以不同比例添加環氧丙烷(Propylene oxide，PO)，合成出不同分子量之PO改質PEG及PEO。結果顯示PO分子中的甲基其立體效應影響了PEO的熱性質；而經由凝膠滲透層析、傅立葉紅外光譜、黏度計及微差掃瞄熱卡計的分析證明PO添加會影響高分子結構及高分子熱性質。PO添加改質降低PEO高分子的熔點、玻璃轉化溫度、結晶溫度及結晶度。本研究結果顯示3%莫耳比例的PO添加量，可將PEO的玻璃轉化溫度由-52℃降至-58℃，熔點由66℃降至52℃，結晶度由95%降至64%；此外本研究也探討添加3%~10% PO改質對PEO之熔點、玻璃轉化溫度、結晶溫度及結晶度的影響。

In this study, the polymers of PEG (polyethylene glycol) and PEO (polyethylene oxide) were modified by adding PO (propylene oxide) at random and employed as polymer electrolytes with various molecular weights and PO ratios. It was observed that the thermo behavior of PEO was affected by the steric effect of methyl of propylene oxide. The changes of structure and thermo property of this polymer with various ratios of PO were analyzed and characterized by GPC, DSC, viscosity meter, and FT-IR. The Tg, Tm and crystallinity of PEO were reduced by the PO random modification. The relations between PO ratios and Tg, Tm, crystallization temperature and crystallinity of the modified polymer were investigated. The 3% PO random modification of PEO would cause a decrease of Tg from -52℃ to -58℃, Tm from 66℃ to 52℃, and crystallinity from 95% to 64% of the original PEO polymer.

中文摘要.....................................................I
英文摘要.....................................................Ⅱ
誌謝.........................................................Ⅲ
總目錄.......................................................Ⅳ
圖目錄.......................................................Ⅶ
表目錄.......................................................Ⅸ
第一章 緒論..................................................1
1.1 前言.....................................................1
1.2 PEO之介紹................................................2
1.3 PEO高分子電解質之導電機制................................5
1.3.1 PEO結晶區的離子傳輸....................................5
1.3.2 PEO非結晶區的離子傳輸..................................7
1.4 PEO結晶區與非結晶區陽離子傳輸的比較......................9
1.5 PEO改質..................................................9
1.5.1 添加鹽類或黏土(clay)改質...............................9
1.5.2 有機物混合改質........................................13
1.5.3 PEO末端基改質.........................................15
1.5.4 PEO支鏈形改質.........................................17
1.5.5 PEO網狀改質...........................................19
1.6 研究動機.................................................20
第二章 PEO聚合理論與分析儀器簡介............................22
2.1 PEO聚合原理.........................................22
2.1.1 LMW PEO (PEG)的聚合原理...............................22
2.1.2 MHMW PEO、VHMW PEO的聚合原理..........................23
2.1.3 PEO/PO random polymer的聚合原理.......................24
2.2 GPC層析儀...............................................25
2.3 FT-IR光譜儀.............................................29
2.4 黏度分析儀..............................................32
2.5 DSC分析儀...............................................33
2.5.1 功率補償DSC...........................................33
2.5.2 熱流式DSC.............................................34
第三章 實驗設備、藥品與步驟..................................35
3.1 藥品與材料..............................................35
3.2 儀器與設備..............................................35
3.2.1 反應設備..............................................35
3.2.2 反應後處理設備........................................36
3.2.3 分析儀器..............................................36
3.3 實驗方法................................................36
3.3.1 起始劑及觸媒合成......................................37
3.3.2 PEG聚合...............................................37
3.3.3 終止反應及觸媒中和....................................37
3.3.4 PEO聚合...............................................37
3.3.5 PEO之PO 隨機改質聚合..................................38
3.4 樣品分析................................................38
3.4.1 GPC分析...............................................38
3.4.2 黏度分析..............................................39
3.4.3 FT-IR分析.............................................39
3.4.4 DSC分析...............................................39
第四章 結果與討..............................................40
4.1 PEO及PEPO聚合...........................................40
4.2 GPC分析.................................................41
4.2.1 建立標準校正曲線......................................41
4.2.2 樣品分析..............................................42
4.3 黏度分析................................................44
4.4 FT-IR分析...............................................47
4.4.1 FT-IR分析結果.........................................51
4.5 DSC分析.................................................54
4.5.1 PEO之DSC分析探討......................................57
4.5.2 PO改質之PEPO DSC分析探討..............................57
4.5.3 PO改質之PEPO與PEO之DSC圖譜比較........................59
4.5.4 PO改質之PEPO結晶區分析................................61
4.5.5 PO改質之PEO作為高分子電解質之探討.....................63
第五章 結論..................................................67
5.1 未來研究方向............................................68
第六章 參考文獻..............................................69

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