臺灣博碩士論文加值系統

雙團聯式共聚物(diblock copolymer)可經由自組裝形成一系列具有長程規則排列的微結構(如層狀排列、六面堆積之圓柱、雙連續形態(gyroid)、體心立方堆積之圓球等)。以圓柱微胞而言，因大部分圓柱微胞是屬於”hard cylinder”故傾向於填充空間較有效率的六面堆積(hexagonal packing)。
然而在本研究中，我們發現界面活性劑dodecylbenzene sulfonic acid (DBSA)與對稱型的polystyrene-block-poly(4-vinyl pyridine) (PS-b-P4VP)以離子鍵形成的梳狀超分子團聯式共聚物(supramolecular comb-shaped block copolymer)在特定的組成下呈現四面堆積之圓柱(tetragonally packed cylinder)的微相分離形態。
在這個系統中，我們控制錯合比例x(DBSA與4VP之莫耳比)為0.25 ~ 1.0，發現其皆會形成結構中有結構(structure-within-structure)的階級性自主裝行為(hierarchical assembly)，當x ≥ 0.4時，系統PS鏈段會組裝成直徑十幾nm之圓柱並分散於P4VP(DBSA)梳狀鏈段形成之約3 nm層板連續相中，其中有趣的是當x = 0.5及0.6時，其PS圓柱會呈現四面堆積，但當x ≥ 0.75時，PS圓柱又會變回六面堆積。我們利用大幅度振盪剪切(large amplitude oscillatory shear，LAOS)的技術使樣品具有長程規則排列結構，並藉由不同方向的2-D SAXS圖譜去解析大尺度之PS圓柱與小尺度之層板之相對方向性並推論四面堆積之圓柱形成的原因。

Self-assembly of diblock copolymer can generate a series of microdomains packed in long range ordered lattices (1-D stacked lamellae, hexagonally packed cylinders, gyroid, and body-center-cubic packed sphere). In the case of cylindrical microdomains, hexgonal lattice is the only structure observed thus far, since this packing symmetry has the highest efficiency for space filling for cylindrical micelles with hard coronas.
In the present study we reveal tetragonally packed cylinders in a supramolecular comb-coil block copolymer formed by the complexation of an amphiphilic surfactant, dodecylbenzene sulfonic acid (DBSA), with the poly(4-vinylpyridine) (P4VP) blocks in a symmetric PS-b-P4VP.
Over the binding fractions investigated (x = 0.25 to 1.0), the system exhibited structure-within-structure morphology. When x ≥ 0.4, we found the larger-scale PS cylindrical microdomains embedding in the matrix consisting of the smaller-scale lamellar mesophase organized by the P4VP(DBSA) comb blocks. The PS cylinders were found to organize in the typical hexagonal lattice at x ≥ 0.75. Interestingly, the packing symmetry transformed into a square or tetragonal lattice when x = 0.5 and 0.6. So we use large amplitude oscillatory shear (LAOS) to create macroscopic aligned and probe the relative orientation between the smaller-scale lamellae and the larger-scale PS cylinders by 2-D SAXS pattern along different orientations to infer the reason of tetragonally packed cylinder.

中文摘要 ．．．．．．．．．．．．．．．．．．．．．．．．．．． I
Abstract ．．．．．．．．．．．．．．．．．．．．．．．．．．． II
目錄 ．．．．．．．．．．．．．．．．．．．．．．．．．．． III
圖目錄 ．．．．．．．．．．．．．．．．．．．．．．．．．．． V
表目錄 ．．．．．．．．．．．．．．．．．．．．．．．．．．． VIII


第一章 序論．．．．．．．．．．．．．．．．．．．．．．．．．． 1
1-1 前言．．．．．．．．．．．．．．．．．．．．．．．．．． 1
1-2 超分子化學的發展．．．．．．．．．．．．．．．．．．．． 3
1-3 團聯式共聚物及其摻合體之微相分離形態．．．．．．．．．． 5
1-3.1 無定形-無定形團鏈式共聚物．．．．．．．．．．．．． 6
1-3.2 團聯式共聚物摻合系統之形態變化．．．．．．．．．．． 9
1-4 梳狀超分子共聚物於奈米材料上的應用．．．．．．．．．．． 18
1-5 大幅度振盪剪切(Large amplitude oscillatory shear，LAOS) ．．． 26

第二章 研究動機與實驗方法．．．．．．．．．．．．．．．．．．． 29
2-1 研究動機．．．．．．．．．．．．．．．．．．．．．．．． 29
2-2 材料．．．．．．．．．．．．．．．．．．．．．．．．．． 30
2-3 實驗步驟．．．．．．．．．．．．．．．．．．．．．．．． 31
2-3.1 樣品配製過程．．．．．．．．．．．．．．．．．．．． 31
2-3.2大幅度振盪剪切(Large amplitude oscillatory shear) ．．．．． 31
2-4 儀器原理與實驗項目．．．．．．．．．．．．．．．．．．． 33
2-4.1 偏光顯微鏡(Polarized Optical Microscopy，POM) ．．．． 33
2-4.2 傅立葉轉換紅外線光譜儀(Fourier Transform Infrared Spectrometer，FT-IR) ．．．．．．．．．．．．．．．．．．． 33
2-4.3 小角度X光散射儀(Small Angle X-ray Scattering，SAXS) ．．．．．．．．．．．．．．．．．．．．．．．． 33
2-4.4 穿透式電子顯微鏡(Transmission Election Microscopy，TEM) ．．．．．．．．．．．．．．．．．．．．．．．． 35

第三章 結果與討論．．．．．．．．．．．．．．．．．．．．．．． 37
3-1 PS-b-P4VP(DBSA)x梳狀超分子共聚合物的鍵結鑑定．．．．．． 37
3-2 PS-b-P4VP(DBSA)x梳狀超分子共聚物的介相(mesophase)結構． 41
3-3 PS-b-P4VP(DBSA)x錯合體階層性自組裝結構的微相分離形態．． 43
3-4 以大幅度振盪剪切誘導PS-b-P4VP(DBSA)x錯合體系統形成大範圍長程規則排列結構．．．．．．．．．．．．．．．．．． 64

第四章 結論．．．．．．．．．．．．．．．．．．．．．．．．．． 77

第五章 參考文獻．．．．．．．．．．．．．．．．．．．．．．．． 78

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