兩性雙區塊高分子的合成與應用

Synthesis diblock copolymer and it’s application

柯又升(Yu-Sheng Ko)

指導教授 ： 劉緒宗

國立臺灣大學/理學院/化學研究所/碩士(2005年)

https://doi.org/10.6342/NTU.2005.00269

摘要

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。

關鍵字

兩性雙區塊高分子

並列摘要

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.

並列關鍵字

diblock copolymer

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