The Studies in the application of the Calix[4]arene grafted silica gel

• Main Authors: Shie Dung Shiue, 謝東學
• Other Authors: 林立錦
• Format: Others
• Language: zh-TW
• Published: 2009
• Online Access: http://ndltd.ncl.edu.tw/handle/92673897704251990122

碩士 === 中國文化大學 === 應用化學研究所 === 97 === Calixarenes, which are cyclic oligomers of p-substituted phenols and formaldehyde, are able to include small organic molecules or metal ions within molecular cavities to from the “host-guest complexes”. This phenomenon has been proposed in the research area of micro-analysis detection devices, ion separation, and enzyme-mimic studies. The main purpose of this thesis is to develop a standard procedure for grafting the calix[4]arene onto silica gel. The grafted product was then subjected to serve as a stationary phase for the ion separation. In the presence of a base, p-tert-butylphenol and formaldehyde was polymerized to form an yellowish precursor. Refluxing of this precursor in diphenyl ether for two hours yielded the p-tert-butylcalix[4]arene. The p-tert-butyl groups were then removed by AlCl3-catalyzed reverse Friedel-Crafts reaction to give parent calix[4]arene. The calix[4]arene grafted silica gel was prepared in a four-step procedure. An 3-aminopropyl groups was introduced by reacting triethoxy silane with silica gel, and the resulting aminopropyl silica gel (APSG) was further treated with p-nitrobenzoyl chloride to supply a p-nitrobenzoate moiety. The nitro group was then reduced by sodium dithionite, and the diazotization of the resulting aniline followed with diazo-coupling reaction with calix[4]arene gave the red calix[4]arene grafted silica gel. The thermal gravimetric analysis (TGA) was applied to the products to determine the composition of the organic portion on grafted silica gel. The amount of the organic portion was in the range of 17.91% for the calix[4]arene grafted silica gel, which is equivalent to 0.2925 mmole of calix[4]arene per gram of calix[4]arene grafted silica gel . The preliminary ionic extraction resulted for Cu+2 indicated that calix[4]arene grafted silica gel composed a better extraction that each gram of calix[4]arene gragted silica gel was able to extract 1.53×10-4 gram of Copper(II) ion from 4 ppm of Cu+2 solution in basic conditions.