Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3687
標題: 反應型規則樹枝狀高分子的合成與應用
Synthesis and Characterization of Reactive Poly(urethane/malonamide) Dendritic Structures with Blocked/ Deblocked Isocyanate
作者: 吳文毅
Wu, Wen-Yi
關鍵字: reactivity
反應型
dendrimer
methyl ethyl ketoxime (MEKO)
規則樹枝狀高分子
methyl ethyl ketoxime (MEKO)
出版社: 化學工程學系所
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摘要: 規則樹枝狀聚合物(dendrimer)是一具有高度分枝型態之三維立體結構,藉由小分子的不斷相互交替反應而形成各種不同應用性之新穎分子構型。因此,近年來針對規則樹枝狀高分子的合成與應用已有許多文獻或專利發表。由於樹枝狀材料本身之合成較為複雜,確立高代數之樹枝狀高分子之可行性仍具困難。在本論文中,我們將利用具有反應性與選擇性之雙官能基單體MIA (4-isocyanato-4’(3,3-dimethyl-2,4-dioxo-azetidino)diphenylmethane)為重複單元以免除保護去保護方式之收斂型步驟進行高代數dendron材料的製備,本樹枝狀高分子末端具有經加熱可離去之methyl ethyl ketoxime (MEKO)單體進行可變末端分子為一大特色。論文內容主要可分為兩部份,首先為dendron系統之選擇,因MIA中之異氰酸鹽官能基(isocyanate)可先行與含可離去特徵之MEKO單體中之氫氧基(hydroxyl)形成urethane鍵結,再配合azetidine-2,4-dione官能基之選擇性與一級胺所形成的malonamide鍵結,進行dendron材料之合成至高代數。論文第二部份,即進行dendron的應用,我們希望可以製備出視其應用環境不同,而變化的dendron。在實驗中不同代數的dendron末端皆有MEKO與異氰酸鹽官能基所形成的urathane鍵結,由多篇文獻中我們得知此urethane鍵結在高溫時將會斷裂,使得異氰酸鹽官能基重新出現,由於異氰酸鹽官能基的高反應性,我們在反應中所添加含有活性氫(active hydrogen)的親核劑(nucleophile)將會與異氰酸鹽官能基反應,形成完全不同末端官能基之dendron。 實驗中先以MIA與MEKO和diethylenetriamine (DETA)反應合成出[G-0.5]-MEKO到[G-2.5]-MEKO 的dendrons,將上述[G-0.5]-MEKO到[G-2.5]-MEKO dendrons分子進行結構鑑定,實驗證明我們可以成功合成末端具有MEKO (blocking agent)之樹枝狀高分子。於偶數代中因結構上具有可與異氰酸鹽官能基反應之二級胺結構,故本實驗選取[G-0.5]-MEKO、[G-1.5]-MEKO、[G-2.5]-MEKO dendrons等單數代進行斷鍵反應,隨後於130 oC下並藉由真空裝置的輔助下讓重新出現的isocyanate與stearyl alcohol (C18-OH)反應。在[G-0.5]-MEKO、[G-1.5]-MEKO dendrons我們可以成功的將原本用來保護isocyanate的MEKO置換為stearyl alcohol (C18-OH) 成功製備出相對應高產率之[G-0.5]-C18、[G-1.5]-C18 dendrons。至於[G-2.5]-MEKO dendron則無法完全轉換為[G-2.5]-C18 dendrons。推測可能由於高代數dendron在接枝時存在立體障礙或甚至isocyanate在高溫下可能自行聚合的關係,使得接枝率最多僅能到達75%。此高代數接枝率僅達75%的問題則需要近一步了解isocyanate的化學性質,以尋求接枝率可能達到100%。
Dendrimers are a new class of three-dimensional macromolecules produced by multiplicative growth from small molecules that incorporates repetitive branching sequences to create a novel molecular architecture. Over the last few decades, the synthesis of a large number of dendritic polymers have been reported. In this work, a bi-functional compound, 4-isocyanato-4'(3,3-dimethyl-2,4-dioxo-azetidino) diphenylmethane (MIA) has been utilized as a building block to synthesis a novel poly(urethane/malonamide) dendrons bearing methyl ethyl ketoxime (MEKO) as the end-group for blocking the isocyanate groups. Subsequently, the dendrons with blocked isocyanates ([G-0.5]-MEKO, [G-1.5]-MEKO, [G-2.5]-MEKO) were heated to regenerate the isocyanate groups. The regenerated isocyanate groups were then reacted with a compound with active hydrogens, such as stearyl alcohol, to form novel dendrons with various terminal functional moieties. [G-0.5]-MEKO and [G-1.5]-MEKO bearing MEKO as the blocking agent of isocyanate were successfully reacted with stearyl alcohol to form [G-0.5]-C18, [G-1.5]-C18 with high yields. For [G-2.5]-MEKO, the grafting ratio of only 75% was obtained. This is possibly due to the presence of steric effect in the higher generation of dendron, or the occurrence of crosslinking reactions between the isocyanate groups at high deblocked temperature.
URI: http://hdl.handle.net/11455/3687
其他識別: U0005-1608200817300300
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-1608200817300300
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