嵌段共聚物/多巴胺混摻體自組裝製備三維多尺度孔隙模板

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姓名

古孟凡(Meng-Fan Ku) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

嵌段共聚物/多巴胺混摻體自組裝製備三維多尺度孔隙模板
(Three-Dimensional Networks Fabricated by Self-assembly of Block Copolymer/Dopamine Mixtures)

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摘要(中)

本研究報告了一種簡單的方法，製備出由聚(苯乙烯-b-環氧乙烷)（PS-b-PEO）和多巴胺（DA）混合物組成之三維(3-D)多尺度孔隙。將混合物(BCP/DA)分別溶於不同的共溶劑中，THF/水和DMF/水。隨後HCl的添加不僅增強了PEO和DA之間的電荷−偶極相互作用、抑制了DA在溶液中的氧化反應，還可以提高混合物之間的有效Flory−Huggins參數，並在DMF/水之共溶劑系統中誘導3-D多尺度孔隙凝膠的形成。此溶液−凝膠的相轉變需要遵循兩步驟反應。首先，PS-b-PEO在共溶劑中形成微胞。接著，通過添加HCl獲得斑點狀微胞。作為物理性的交聯點，斑點狀微胞會自發的形成凝膠。此凝膠具有疏水性通道組成的3-D孔洞結構。將溶液或凝膠乾燥時，THF/水之共溶劑中的低分子量兩親性微胞會經歷快速的微胞融合過程，形成洋蔥狀囊胞。相比之下，DMF/水之共溶劑系統中的3-D多尺度孔隙凝膠能支撐自身的孔洞結構。接著在氨氣環境下引發DA的氧化聚合反應。發現由混合物(BCP/PDA)所構成之3-D多尺度孔隙結構仍保持不變。儘管在當前的製程中，高溫碳化後之3-D多尺度孔隙結構會塌陷，但此種具有高比表面積之3-D多尺度孔隙模板仍是非常具有應用價值。

摘要(英)

Abstract
Three-dimensional (3D) network templates show great potential and interest in the fabrication of electronic devices, electrocatalysis, and supercapacitors. The 3D-network templates provide favorable characteristics, such as high specific surface area, high mass, and diffusion transfer. In this work, we report a simple method to fabricate 3-D micelle networks through self-assembly of mixtures of polystyrene-block-poly(ethylene) (PS-b-PEO) and dopamine (DA) in solution. Mixtures are dissolved in two different co-solvents, THF/water, and DMF/water, respectively, followed by HCl addition HCl addition not only enhances charge−dipole interactions between PEO and DA but also prohibits the oxidation reaction of DA in solution. In addition, HCl can increase the effective Flory-Huggins parameter of PS-b-PEO for the mixtures and triggers formation of a gel-like structure in the DMF/water system. Two-steps are necessary to induce the sol−gel transition. First, low-molecular-weight (low-Mw) PS-b-PEO formed core-shell micelles in co-solvent. Second, deformed micelles were obtained by adding HCl. Patchy micelles were formed and acted as cross-linking points for gelling. The gel structure is a 3-D micellar network with hydrophobic channels. The network framework evolved from patchy micelles. Upon drying from THF/water co-solvent, micelles of low-Mw PS-b-PEO formed onion-like vesicles . In contrast, the 3-D gel structure could support the porous framework that had formed in DMF/water co-solvent. DA oxidative polymerization was induced by NH4OH vapor. It was found that 3-D porous structure of BCP/PDA mixtures remained unchanged after DA polymerization for the micelles in DMF/water. Nevertheless, 3-D porous networks could collapse after carbonization at a high temperature.

關鍵字(中)

★ 嵌段共聚物
★ 微胞
★ 共溶劑
★ 溶液
★ 凝膠
★ 相轉變
★ 多孔結構

關鍵字(英)

★ DIBLOCK−COPOLYMERS
★ MICELLES
★ CO-SOLVENT
★ PHASE−TRANSITION
★ SO
★ GEL
★ POROUS STRUCTURE

論文目次

中文摘要 II
Abstract III
目錄 IV
圖目錄 VI
第一章緒論 1
1.1前言 1
1.2溶液中之兩親性嵌段共聚物 5
1.2.1微胞的生成機制 5
1.2.2微胞的形貌 6
1.2.3共聚物/前驅物的共組裝混摻物微胞 8
1.3研究動機 9
第二章實驗方法 10
2.1實驗藥品 10
2.2實驗樣品製備流程 12
2.2.1純嵌段共聚物之共溶劑系統 12
2.2.2嵌段共聚物/多巴胺混合物之共溶劑系統 13
2.2.3固體樣品之製備 13
2.3實驗儀器 15
2.3.1冷場發射掃描式電子顯微鏡（Cold Feld Electron Emission Scanning Electron Microscope, CFE-SEM） 15
2.3.2小角度X光散射（Small Angle X-ray Scattering, SAXS） 16
2.3.3穿透式X光顯微鏡（Transmission X-ray Microscopy, TXM） 17
2.4擬合軟體（SasView） 19
2.4.1 Guinier_Porod模型 19
2.4.2 Core_Shell_Sphere模型 20
2.4.3 Core_Shell_Cylinder模型 21
2.4.4 Schulz分佈 22
2.4.5 Sticky-Hard-Sphere, SSHS(q) 23
2.4.6 Hayter_MSA, SSC(q) 24
第三章實驗結果與討論 25
3.1嵌段共聚物微胞在兩種共溶劑系統之自組裝行為 25
3.1.1中性溶液的共聚物隨機線圈 25
3.1.2兩親性的共聚物微胞 27
3.1.3純兩親性微胞的鹽酸效應 29
3.2嵌段共聚物微胞在DMF/水之共溶劑系統之分子量效應 33
3.2.1分子量效應下之微胞形態轉變 33
3.2.2分子量效應下之凝膠化過程 33
3.3嵌段共聚物/多巴胺混合物微胞在共溶劑系統之自組裝行為 36
3.3.1兩親性的共聚物/多巴胺混合物微胞 36
3.3.2在混合物微胞中導入鹽酸的關鍵作用 38
3.4乾燥之嵌段共聚物/多巴胺混合物(Solid state) 41
3.4.1乾燥過程中的微胞融合行為 41
3.4.2嵌段共聚物/聚多巴胺混合物及高溫碳化後之型態探討 44
總結 49
參考文獻 50

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指導教授

孫亞賢(Ya-Sen Sun)

審核日期

2021-8-5

推文