合成及研究含有二(環戊二烯)亞鐵的樹枝狀高分子

Abstract

本論文探討以收斂法合成外圍含二(環戊二烯)亞鐵之聚醚類樹枝狀高分子 。首先以2莫耳的3-溴丙基 二(環戊二烯)亞鐵與一莫耳的3,5-二羥苯醇進 行醚類合成反應，再將產物的苯甲醇官能基轉換成溴化合物。此溴基再與 另一個3,5-二羥苯醇苯環上的羥基官能基進行醚類的偶合反 應，如此重 覆醚類的偶合反應及溴化反應，可合成溴基及楔形結構之分子。將具有楔 形結構溴化合物與多官能基核進行偶合反應形成樹枝狀高分子。所形成的 樹枝狀結構可以用光譜鑑定其性質，每增加一個成長層分子量約增加一倍 ，其分子結構變的更緻密，此樹枝狀高分子具有非常 低的分子量分佈。 以電化學測試其性質，顯示這些樹枝狀高分子有單一的氧化還原過程，其 外圍每一個二(環戊二烯)亞鐵皆有一個獨立不互相作用的電子轉移。 The novel convergent growth approach to topology macromole -culars based on dendritic fragments is described.The polyether dendritic fragments are prepared by starting from what will bec -come the periphery on the macromolecular and progressing inward .In here,we used convergent growth approach to synthesis containferrocene functional group at the periphery of the drndritic mac -romolecular.In the first stage,2 mole of 3-bromopropanyl ferro-cene is condensed with 1 mole 3,5-dihydroxylbenzyl alcohol,under phase-transfer condition. After transformation of the benzylic al -cohol functionality of the growing moleculars into the correspo -nding bromide.The procedure is repeated with stepwise addition of the monomer followed again by activation of benzylic site.In the other way, the resulting dendritic wedge,in their benzyl brom -ide can be coupled to polyfuctional core 1,1,1-tris(4-hydroxyph -yl)ethane to form the hyperbranched macromolecular.The dendri- mer structure can be characterized by use of spectroscopic tech- nology.At each growth step.their macromolecular weight about two fold,the molecular structure become progressively denser and more compact,and have a very low despersity.Electrochemical mea- sures show that all of the dendritic macromolcular show a singlereversible ovidation process.Every ferrocene at the periphera po