摘要

聚苯乙烯、聚甲基丙烯酸甲酯及樹枝狀高分子聚醚亞醯胺之傳統分析方法是以NMR及SEC (Size exclusion chromatography)來鑑定其合成的結果，而這些分析方法最主要的缺點是無法判定合成分子的大小。基質輔助雷射脫附游離/飛行時間質譜法(MALDI/TOF)因具有分析時間短，樣品製備簡單，又可偵測大分子的特性，因此目前已被廣泛應用在工業高分子的分析上。然而選擇適當的基質及正確的樣品製備方法，是決定MALDI/TOF是否能成功的關鍵。
本研究中第一部份是以all-trans-Retinoic acid、2-Indole Acrylic acid及2,5-DHB等有機酸為MALDI基質，來分析一系列具不同分子量之聚苯乙烯及聚甲基丙烯酸甲酯高分子化合物。對聚苯乙烯而言，截至目前為止已知的報導中，MALDI分析的最高分子量是由加拿大的Li於1996年所報導的具150萬Da的高分子量聚苯乙烯(標準品)。本實驗以直線型的MALDI-TOF來分析聚苯乙烯高分子，成功的得到分子量範圍由數千到7,110,000Da的分析物訊號。對聚甲基丙烯酸甲酯而言，已知的報導中其測得之最高分子量為25萬是由Danis於1993年報導，本實驗以一系列具不同分子量之PMMA標準品當作分析物; 成功的得到分子量範圍由數千到1,520,000Da之PMMA訊號。由實驗結果證實對小分子而言，質譜中所得之訊號，主要來自+1價之分子離子。至於較大分子而言，則質譜訊號主要來自帶+2及+3價或多價電荷之分子離子。本研究便是在探討，究竟以MALDI來分析大分子化合物，其最高之偵測質量極限是多少？
另外第二部份是以MALDI-TOF來鑑定樹枝狀高分子聚醚亞醯胺(dendritic polyether imide)，以及探討影響MALDI中分子離子形成的原因。研究結果發現以雷射脫附游離法(Laser desorption ionization, LD)方式分析，與以DHB、9-Nitroanthracene 當作基質進行分析，可得到不同的碎片離子訊號，顯示不同基質對樹枝狀高分子在MALDI游離過程中有很大的影響。除此之外，在添加不同金屬離子（如Cu、Ag、Ni等）於基質内時，發現除了可以形成金屬加成離子外，不同金屬的添加也會影響上述物種分子離子的形式以及碎片離子的形成。

NONE.

目 錄
論文摘要………………………………………………………….I
目 錄………………………………………………………...III
圖 目 錄…………………………………………………………V
壹、緒論…………………………………………………………1
一、 前言…………………………………………………….1
二、 基質輔助雷射脫附游離質譜法……………………….4
(一) MALDI操作原理………………………………….5
(二) 飛行時間質量分析器……………………………..6
(三) MALDI中基質的功能…………………………….9
(四) MALDI離子形成的機構探討……………………10
三、 論文目標………………………………………………13

第一部份：以基質輔助雷射脫附游離/飛行時間質譜法分析具大分子量的物……………….13
包括有聚苯乙烯(polystyrene; PS)及聚甲基丙烯酸甲酯(PMMA)
第二部份：以基質輔助雷射脫附游離/飛行時間質譜法分析樹枝狀高分子聚醚亞醯胺
貳、 實驗………………………………………………………15
一、 儀器裝置……………………………………………15
二、 試劑配製及實驗操作………………………………16
參、 結果與討論………………………………………………27
一、 以基質輔助雷射脫附游離/飛行時間質譜法快速分析高分子量聚合物
(一) 聚苯乙烯PS分析……………………………..29
(二) 聚甲基丙烯酸甲酯PMMA分析……………..46
二、以基質輔助雷射脫附游離/飛行時間質譜法分析
樹枝狀高分子聚醚亞醯胺………………………….54
肆、結論………………………………………………………66
伍、參考資料…………………………………………………67

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