本論文針對咪唑類離子液體探討其物理化學性質與實務應用分兩部份進行研究。第一部分為自製固相微萃取裝置並將離子液體塗佈於裝置尖端的毛細管外壁製成微萃取吸附相。利用Nafion薄膜修飾毛細管表面增加離子液體吸附層之厚度與均勻性，以達高萃取效率。此離子液體固相微萃取裝置被應用在頂空法萃取水樣中多環芳香烴化合物（PAHs）並以氣相層析連結離子阱質譜儀進行定量分析，由於經Nafion薄膜修飾後再塗佈離子液體作萃取相可提高萃取相之均勻性與塗佈量加上質譜儀選擇離子操作模式，本方法具備高靈敏度與經濟效益，對於水樣中多環芳香烴化合物的偵測極限可達4-5 pg mL-1。論文的第二部份為將溴化乙烯咪唑環的另一個氮原子衍生接上長鏈烷基或芳香基團，聚合成側鏈型之離子液體聚合物。聚合後之材質為橡膠或粉末狀之固體，再利用陰離子交換法將溴離子置換為PF6- (hexafluorophosphate)， TFSI- (bis-trifluoromethylsulfonylimide)，或BETI- (bis-perfluoroethylsulfonylimide)。將不同陰陽離子組合之離子液體聚合物個別進行溶解度，熱穩定性測試，發現含溴陰離子的聚合物其極性最高，熱穩定性最低；含TFSI-的聚合物具備較低極性與最高熱穩定性。再分別將這類聚合物以靜態塗佈法製備成毛細管氣相層析管柱，以氣相層析火焰游離偵測儀進行靜相定性分析，利用Abraham solubility model選擇特定化合物當指標分析物，以氣相層析法取得分析物的滯留因子，代入Abraham solubility model所提供的分析物代表作用力參數，以線性迴歸法求出五組代表性作用力的係數定性靜相作用力，並建立成表討論離子液體聚合物陽離子取代基團與其對應的陰離子團對整體作用力的影響，並可利用在未來設計新離子液體聚合物之參考。此外，以正烷類，醇類，及多環芳香烴等混合物對此離子聚合物管柱進行分析測試，所有靜相皆具備高分離效率，理論板數可達每米兩，三千板。以二甲苯混合物測試發現間位和對位二甲苯可在PVOIm+TFSI-，和PVOIm+BETI-兩組靜相幾乎完全分離。

In this study, characterizations and practical applications were carried out for imidazolium based ionic liquids. The study is emphasized in two directions; first is the applications of the Nafion membrane supported room temperature ionic liquids used as the extraction fibers for solid phase microextraction. Ultra trace PAHs in water samples were analyzed by the head space-Nafion/ ionic liquid solid phase microextraction combined with gas chromatograph-mass spectrometer. The pre-coated Nafion membrane on the fiber made the latter-coated ionic liquid layer more even and thick, and results in higher extraction efficiency for the analytes (4-5 pg mL-1). The second is to synthesize vinylimidazolium bromide based ionic liquids and then polymerized them to form rubber/ solid type ionic liquid polymers. Simple anion exchange reactions were conducted to replace the bromide ion to PF6- (hexafluorophosphate), TFSI- (bis-trifluoromethylsulfonylimide), or BETI- (bis-perfluoroethylsulfonylimide). Thermal analyses and solubility tests were carried out; it seemed the anions have significant effects on both thermal stability and polarity. The ionic liquid polymers were coated into fused silica tubing to be the stationary phases for gas chromatography. Abraham solubility model was applied and a gas chromatograph-flame ionization detector was used to carry out the experiment, linear solubility parameters for each stationary phase were constructed. The characterizations for different substituted functional groups on the imidazolium cation or the different combination of anions were studied and discussed. These ionic liquid polymer columns were also tested by mixtures of n-alkanes, alcohols, and PAHs. Good separation efficiencies were achieved for all tested columns (ca. 2000-3000 plates/m). Some of the ionic liquid polymer columns possess structural selectivity; m- and p-xylenes could be distinguished in PVOIm+TFSI-, and PVOIm+BETI-.

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