劉緒宗臺灣大學：化學研究所柯又升Ko, Yu-ShengYu-ShengKo2007-11-262018-07-102007-11-262018-07-102005http://ntur.lib.ntu.edu.tw//handle/246246/51849在本篇論文中，我們將親水端聚乙二醇甲基醚(polyethylene glycol methyl ether)的末端以醯胺鍵結(amide link)的方式將三級碳溴2-溴-2-甲基丙醯溴(2-bromoisobutyryl bromide)連接上親水端做為巨始劑。利用ATRP(atom transfer radical polymerization)合成出疏水端為丙烯酸甲酯(methyl acrylate)的雙區塊聚合物。利用所合成的雙區塊聚合物在酸性水溶液下來進行孔洞性材料的合成，可以觀察到孔徑(pore size)隨疏水端的增加而增大。而在EO45-N-MA28和EO45-N-MA63、EO114-N-MA113為模板可以合成出立方結構(Im3m)和二維六角排列(p6mm)的特殊結構。 接下來在疏水端(MA)上做3-疊氮丙胺(3-azido-propylamine)官能基的修飾，以反應的時間控制修飾的數量，並且進一步修飾含鈀(Pd)與鎢(W)的金屬錯合物。由於金屬修飾在疏水端上，所以金屬氧化物的粒子會均勻的分散在孔洞裡面，而不是隨機的分佈在孔洞中或是孔壁內，使得金屬的表面是一個完完全全暴露在孔洞內的金屬氧化物。而含鈀和含鎢金屬的矽氧孔洞材料在Suzuki coupling與烯類的氧化反應上皆有不錯的催化效果，另外催化劑回收再利用上也得到不錯的成效。In this thesis, we prepared the amide link of polyethylene glycol methyl ether and 2-bromoisobutyryl bromide as the marcoinitiator. We used ATRP method to prepare amphiphilic diblock copolmers with narrow polydispersity. The hydrophilic end of these amphilic block copolymers is polyethylene glycol methyl ether, and the hydrophobic end of these amphilic block copolymers is methyl acrylate. We used EOm-MAn as templates to synthesize porous silica materials under acid aqueous condition. As the hydrophobic end (MA) increases, we can observe the pore size also increasing. When the templates were EO45-MA28, EO45-MA63,EO114-MA113, the cubic and 2-d hexagonal structures, were successfully made. Moreover, we modified the organic function 3-azido-propylamine on the hydrophobic end, and using the different reaction time to control the modification amount. Using the organic function grafted the Palladium and Tungsten complex on the diblock polymers. Similarly sol-gel process to prepare mesoporous silicas with metal included, which were subjected for catalysis.Suzuki coupling and olefin oxidation by Pd and W respectively, show good activities. For recycle purpose, the catalyst remains activity after 5 run. The metal leach from the porous material was very less in the Tungsten material case.目錄 第一章 緒論……………………………………………………1 1-1孔洞性材料簡介……………………………………………..….1 1-2中孔洞性材料的修飾…………………………………….……..2 1-3中孔洞性材料在催化上的應用………………………………...6 1-4修飾高分子的應用…………………………………………….12 1-5本實驗室之前的研究工作…………………………………….16 1-6本實驗研究目的……………………………………………….17 第二章 兩性共聚物的合成………………………………….18 2-1聚乙二醇甲基醚(polyethylene glycol methyl ether)之末端修飾醯胺化反應………………………………………………………..18 2-2聚丙烯酸甲酯-聚乙二醇甲基醚雙區塊共聚合物(polymethyl acrylate -b-polyethylene glycol methyl ether)……………………..25 2-3聚丙烯酸甲酯-聚乙二醇甲基醚雙區塊共聚合物的修飾(modify on polymethyl acrylate -b-polyethylene glycol methyl ether)……………………………………………………………….30 第三章 以雙區塊共聚物(PEG-N-PMA)為模板進行矽氧孔洞材料的製備…………………………………………………...37 3-1以EO17-N-MAx作為模板…………………………………….37 3-2以EO45-N-MAx作為模板……………………………………..41 3-3以EO114-N-MAx作為模板…………………………………….50 3-4修飾EO45-N-MAx作為模板…………………………………..53 第四章 以雙區塊共聚物(PEG-N-PMA)為模板合成之矽氧孔洞材料在催化上的應用……………………………………...61 4-1矽氧中孔催化劑的鑑定………………………………………61 4-2含鈀金屬的矽氧孔洞材料在催化上的探討…………………63 4-3含鎢金屬的矽氧孔洞材料在催化上的探討…………………67 第五章 結論………………………………………………….74 第六章 實驗部份…………………………………………….75 6-1測試儀器………………………………………………………75 6-2溶劑與試劑的純化……………………………………………79 6-3實驗過程………………………………………………………80 參考文獻……………………………………………………...90 附圖…………………………………………………………...951711139 bytesapplication/pdfen-US兩性雙區塊高分子diblock copolymerthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/51849/1/ntu-94-R92223052-1.pdf