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標題: Study on the Interfacial Properties and Adsorption Separation Applications of the Membranes Immobilized with Dendron-Type Surfactants
作者: 孫幸宜
關鍵字: Dendron
Ionic surfactant
Ion-exchange membrane
Interfacial phenomena
摘要: An efficient alternative for packed column is adsorptive membrane which can overcome themass-transfer limitations such as intraparticle diffusion and high pressure drop in operation. Withresearch experiences on this area for a couple of years, the PI aims to develop the hydrophobicmembranes based on dendritic materials for phenolic compound adsorption process. The dendriticmaterial adopted in this project will be the derivatives of a waxy type (urea/malonamide) dendron,which is synthesized by the following procedures. First, an important reactive molecule,4-isocyanato-4'(3,3-dimethyl-2,4-dioxo-azetidino) diphenyl methane (IDD), will be obtained byreacting methylene-di-p-phenyl diisocyanate and isobutyryl chloride under the catalysis oftriethylamine. IDD has an isocyanate group for easily coupling the OH group and anazetidine-2,4-dione for quickly reacting with primary aliphatic amine at high efficiency. To form aseries of C18 dendrons, for example, IDD will be designed to react with 1-octadecanol forproducing [G-0.5]-C18, which could then couple with diethylenetriamine to obtain [G-1]-C18. Byrepeating the same ring-opening or addition reaction, higher-generation dendrons will besynthesized.Proposed in the first year of this project is the intensive investigation on the interfacialproperties of immobilized dendron-type surfactants on ion-exchange membranes. In our previousstudies with the collaboration of Prof. Conte at Western Kentucky University, ion-exchangemembranes could be successfully employed as the substrate to immobilize straight-carbon-chainionic surfactants and hence form the hydrophobic adsorbents. In this project, the cationicdendron-type surfactant (e.g. amino-[G-1]-C18)) will be attained by reacting the dendron (e.g.[G-1]-C18 or [G-2]-C18) with HCl. The parameters to be evaluated include carbon chain length (e.g.C8, C10, C12, C18), feed surfactant amount, and immobilization time, which could lead to differentarrangements of immobilized surfactants on membrane surface (e.g. hemimicelle or admicelle). Theconditions for different surfactant immobilization percentages (e.g. 50, 100, and 150%) and thehydrophobic degrees of the prepared membranes will be thoroughly investigated.In the second year this project will focus on the preparation of hydrophobic membranes basedon dendritic-side-chain polyurethane. The hydrophobic dendron synthesized in the first year will bereacted with polyurethane as the side chains. The obtained dendritic-side-chain polymer could bedirectly adopted to prepare the honeycomb-pore membrane by spin-coating, or be coated on acommercial porous membrane substrate to form the hydrophobic membrane.The prepared hydrophobic membranes prepared in these two years will be applied to theadsorption/desorption process of phenolic compounds. In the batch process, the adsorptionisotherms and rate curves will be measured and studied. In the flow process, both the disc andtubular (spiral-wound) module designs will be tested. The process efficiency such as adsorptionpercentage, recovery, concentration factor, process time, and pressure drop will be evaluated. Theresults will also be compared with our previous data for the membranes immobilized withstraight-carbon-chain surfactants.
本計畫擬使用具疏水基的樹枝狀分子為基本架構,製備相關的疏水性薄膜,以應用於酚類物質的吸附/脫附程序。第一年度重點為製備樹枝狀分子型界面活性劑,頭基設計為陽離子,尾基為疏水基,可有多種分岔數目或不同碳鏈長度,並探討其於陽離子交換薄膜上的吸附固定量與界面行為。首先是由methylene-di-p-phenyl diisocyanate (MDI)與isobutyryl chloride 在TEA 催化下生成4-isocyanato-4’(3,3-dimethyl-2,4-dioxo-azetidino)diphenyl methane (IDD)。當設計疏水鏈長為C18 時,IDD 先與1-octadecanol 反應,基於醇類在室溫下只與isocyanate 反應生成urethane 鏈段,合成[G-0.5]-C18 分子;搭配azetidine-2,4-dione 只與脂肪族一級胺開環反應生成malonamide 鏈段,將[G-0.5]-C18 與diethylenetriamine (DETA)進行加成反應,合成[G-1]-C18 樹枝狀分子。反覆利用高產率的開環反應及加成反應,可進一步合成其他代數的樹枝狀分子。再經由氯化氫的酸化反應,即可形成具二級銨之陽離子界面活性劑amino-[G-1]-C18 或amino-[G-2]-C18。此類樹枝狀分子型陽離子界面活性劑因具分叉的長碳鏈,在相同固定率下,應比固定單一長碳鏈陽離子界面活性劑之薄膜的疏水性更強,更適合應用於疏水物質之吸附分離程序。本計畫亦將調整樹枝狀分子界面活性劑的進料濃度,以獲得不同的界面結構,如單層之hemimicelle 與雙層之admicielle 結構。本計畫第二年度則建議導入第一年度所製備的不同代數或不同鏈長樹枝狀分子於聚胺酯高分子側鏈上,製備蜂窩狀孔洞之高分子膜,亦或直接塗佈於含孔洞之薄膜基材上,形成疏水性薄膜。本計畫將比較以上不同方法所製備薄膜的相關性質,探討不同代數與長度的樹枝狀分子對疏水性的影響,進而挑選最適當的疏水性薄膜。兩個年度所得的疏水性薄膜均將應用於酚類物質的吸附分離程序,此部分將於美國Conte 教授實驗室合作。因本計畫所得固定樹枝狀分子陽離子界面活性劑之薄膜或接枝樹枝狀分子之高分子所製備的薄膜,均具強疏水性,需要Conte 教授的協助,尋找適當脫附條件。酚類物質吸附/脫附的流動操作,本計畫將考慮以圓片模組或捲筒式模組進行,量測酚類物質的貫穿曲線,以設計適當的流動程序操作條件。希望藉由此國際合作計畫,雙方可吸收到更多知識,獲致更多研究經驗,提升研究品質,進而擴展研究範圍與增加研究深度。
其他識別: NSC99-2221-E005-077
Appears in Collections:化學工程學系所



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