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標題: 兩性型規則樹枝狀高分子應用於製備多孔性蜂窩狀聚乳酸高分子膜之研究
Honeycomb-like Poly(D,L-lactide) Films Based on Amphiphilic Poly(urea/malonamide) Dendrons
作者: 吳建欣
Wu, Chien-Hsin
關鍵字: 規則蜂窩狀高分子膜;Honeycomb;樹枝狀高分子;界面活性劑;Dendrimer;Surfactant
出版社: 化學工程學系所
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實驗使用的poly (urea/malonamide) dendrons,內部是相對親水性,具有強氫鍵的urea/malonamide結構;外圍是相對疏水性,具有較強凡得瓦力的長烷鏈段,高代數下長烷鏈段較多,氫鍵較豐富,形成的兩性高分子親疏水平衡較佳,也使得蜂窩狀多孔膜的規則性與代數呈高度相關。
進一步將dendrons焦點開環,藉由接上不同醇基數目的官能基,來改變dendron焦點的親水性,搭配代數的變化造成末端長烷鍊段數目的改變,合成出一系列氫鍵數目與凡德瓦力不同的兩性型dendron。dendron的焦點分別接上帶有兩個醇與三級胺的雙醇系列(A series),只接上一個醇的單醇系列(E series),以及純粹烷基沒有醇的無醇烷基系列(B series),實驗結果也發現,焦點官能基的變化同樣也會對孔洞型態產生重大影響。
使用具有兩個醇基與一個三級胺官能基的APDEA開環,反應成具有長碳鏈的2.5代兩性型A-[G-2.5]-C18 dendron,具有相當豐富強氫鍵與較強凡德瓦力;混摻入聚乳酸高分子,進行Breath Figure之後,生成高規則度的單層與多層蜂窩狀高分子膜。除了代數、焦點與末端官能基,混摻濃度與溶劑量皆影響最後孔洞的形成。
除了嘗試討論親疏水平衡HLB值,利用理論計算來評估Dendron的界面活性能力之外,還使用拉環法,得到與表面形態結果相吻合的實驗值。透過量測不同溶質濃度的界面張力,可動態觀察到Breath Figure過程中界面張力的變化。

A building block, 4-isocyanato-4’(3,3-dimethyl-2,4-dioxo-azetidino) diphenylmethane (IDD), featuring dual functional groups, has a highly reactive isocyanate functional group, and a selectively reactive azetidine-2,4–dione functional group. Utilizing high reactivity of isocyanate and selective reactivity of azetidine-2,4-dione, higher generation poly(urea/malonamide) dendrons were obtained by addition reaction with another building block diethyltriamine (DETA). The sequential addition reactions were developed under mild condition without resorting to painstaking protection-deprotection or activation methodology. Besides, a convergent synthesis approach made it much easier to remove impurities.
Higher generation dendrons exihibited better hydrophilic/ hydrophobic balance owing to their abundance of urea/malonamide linkages and peripheral long alkyl chains. Furthermore, A-[G-2.5]-C18 ,2.5 generation dendron with 18 carbons long alkyl chain react with APDEA , patterned the best morphology. Bearing two alcohols and a tertiary amine exihibited the best hydrophilic/hydrophobic balance among dendrons studied in this article ,A-[G-2.5]-C18 dendron has stronger hydrogen bonding interaction at the focal segment and intense van der Waals force at perepheral part, repcetively.
These amphiphilic dendrons were then blended with PLA. Consequently, mono- or multi-layered hexagonal porous structure with good quality could be easily obtained by a breath-figure process. Morphologies of the porous structures would depend on generations of dendrons, hydrophilic/hydrophobic balance and concentrations of amphiphilic dendrons.
During the process of film fabrication, the concentrations of the polymer and surfactant in the solution were gradually increased as the solvent evaporated. Interfacial tension measurements by Du Noüy ring method demonstrated that amphiphilic dendrons would lower the surface free energy between water droplets and poly(D,L-lactide). The theoretical surfactant ability, hydorphilic-lipophilic balance (HLB) was also investigated in the research.
These investigations revealed that the formation of honeycomb films based on the dendrons was subtly controlled by the hydrophilic/lipophilic balance. It is well known that poly (lactic acid) (PLA) is a biodegradable and bioabsorbable material, which can be apply to tissue engineering for cell adhesion and growth. The applications of PLA honeycomb films in biomedical field were also studied.
其他識別: U0005-2108201212115400
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