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研究生: 謝宏政
Sheng, Horng-Jeng
論文名稱: 大環胺醚壓電晶體膜及冠狀醚應用於不飽和烴氣體偵測及有機取代催化反應研究
Applications of Cryptand/ Piezoelectric Crystal Membranes and Crown Ethers in Detection of Olefin Vapours and Catalyzed Organic Substitution
指導教授: 施正雄
Shih, Jeng-Shong
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
畢業學年度: 82
語文別: 中文
論文頁數: 106
中文關鍵詞: 大環胺醚壓冠狀醚
論文種類: 學術論文
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  • 在本研究中研製大環胺醚/壓電晶體膜,並用來偵測不飽和烴(Olefin);及利用各種冠狀醚來催化1-已炔(1-hexyne)在鹼(NaNH2)下與鹵化物(溴化甲基苯Benzyl bromide)取代反應。
    石英壓電塗佈膜感測器被發展出用來偵測氣態微量不飽和烴如烯類或炔類,塗佈物質為Ag+/Cryptand[2, 2]/乙二胺/NH2/PVC時吸附烯類分子如順-2-庚烯(cis-2-heptene)最佳。
    此Ag+/Cryptand [2, 2]/乙二胺/NH3/PVC壓電感測器反應時間(Response time)約小於等於四分鐘,對順-2-庚烯之感應靈敏度約80Hz/(mg/L)可維持到一星期以上。
    本研究亦探討烯類立體結構影響發現順式(cis)-2-庚烯比反式(trans) -2-庚烯感應好。同時發現碳數大的氣態烯類感應較佳,而烯類比醇類感應較佳,同時水氣會有影響,但可用乾燥去除其干擾。
    在本研究中各種冠狀醚如單苯15冠5 (B15C5)相轉移催化劑亦被應用於催化有機鹵化物(溴化甲基苯)和1-已炔陰離子取代反應,而1-已炔陰離子亦由1-已炔和NaNH2在冠狀醚催化下形成。發現利用單苯15冠5可活化1-已炔陰離子而和溴化甲基苯反應。在冠狀醚催化下在4小時75℃下可得約60% 產率,反之沒有冠狀醚下反應,產率小於0.3%。本研究又發現反應的溫度效應升高溫度可造成產率增加之效果。在各種冠狀醚催化效果為B15C5>15C5>DB18C6>12C4。在各種溶劑中反應產率依次為苯>甲苯>氰甲烷,亦即在非極性溶劑催化反應較易進行。在本研究中也探討冠狀醚濃度,鹼種類、濃度及鹵化物種類對催化反應的影響並加予討論。

    Macrocyclic polyethers, e. g. cryptands and crown ethers were synthesized and applied as coating materials on quartz piezoelectric crystal membranes for detection of olefin vapours and as phase transfer catalysts for substitution of aromatic halides ( ArX) with hexyne in base (NaNH2) organic solutions.
    Piezoelectric crystal membranes sensors based on cryptand -22/Ag+/PVC/en/NH2 for olefin vapours e. g. alkene and alkyne were developed in this study. The cryptand gas sensor exhibited a high sensitivity with a frequency shift about 80Hz/(mg/L) for 1-heptene short response time with <4.0 min and good reproducibility for reusage. The cryptand 22/Ag+showed as a sensitive coating for olefin vapours but not for saturated organic vapours such as alcohols and amines. Steric effect and isomer effect on frequency shifts of the cryptand /Ag+ sensor were abso investigated. Alkenes with higher carbon number showed better sensetive than smaller alkenes and cis-type alkenes gave better response than trans-type alkenes.
    Various crown ethers, e. g monobenzo-15-crown-5 (B15C5), dibenzo 18 crown 6 (DB18C6), 15-crown-5 (15C5) and 12-crown-4 (12C4) were synthesized and applied as phase transfer catalysts for substition of aromatic halides with hexyne. Among crown ethers B15C5 exhibited the best catalyst and can catalyze the substitution with the yields from 0.3% ( blank without crown ether ) to 60% (with crown ether ) in 4 hr at 75℃. . The catalytic abilities of these crown ethers exhibited in the order B15C5>15C5>DB18C6>12C4. The catalyzed subistitution showed higher yieds in lower polar solvents such as benzene and toluene and higher reaction temperature. In addition effects of concentiations of crown ethers and reactants, type and concentration of base were investigated and discussed.

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