利用高分子嵌段共聚物(block copolymer) 的微觀相分離(microphase separation)與具特殊性質之混摻材料如樹枝狀分子等所形成之大範圍有序排列的高分子混成塊材，具有廣泛之應用範圍與高的應用價值，一直是熱門研究之領域。但如何製備大範圍有序排列之高分子嵌段共聚物摻混快材，同時適度地控制摻混材料比例與分散將是應用上之最終考量因素。因此本計畫將研究探討影響高分子嵌段共聚物摻混薄膜之微結構取向排整。實驗上將利用混摻(blending)方式使摻混材料藉由選擇性官能基誘導，有效地進入高分子嵌段共聚物(block copolymer)的微相分離系統中，並搭配溶劑退火(solvent annealing)方式與熱退火(thermal annealing)方式誘導高分子混成塊材之進行微結構排整，研究探討摻混材料之極性強弱、官能基數目、化學結構差異以及摻混比例與溶劑退火對高分子混成塊材之取向排整及相轉換影響，以期製備出具不同相分離結構之大範圍有序排列之高分子嵌段共聚物摻混塊材。

Single-handed helical phase driven by external twisting stack of non-planar dendrons is first discovered in achiral self-assembly of dendron jacketed block copolymers (DJBCP). Various self-assembled microstructures including lamella, hexagonally-packed cylinder, hexagonally perforated layer and even biomimetic helix were obtained in the achiral hybrids of polystyrene-block-poly(4-vinyl pyridine)(PS-P4VP) BCPs with dendron molecules by hydrogen-bonding interaction. To ravel the origins of the helical phase in the achiral hybrids, different controlling factors such as composition (i.e., PS-rich or P4VP-rich PS-P4VP), molecular weight (i.e., low- or high-molecular-weight PS-P4VP at a constant composition) and molecular architecture (i.e., dendrons with 3, 4-positional or 3, 5-positional alkyl chains) were further investigated. Unlike the typical microphase-separated microstructures in the PS-P4VP/S5 hybrids, in which S5 dendron has two alkyl chains in both meta positions (i.e, 3, 5-positional), the selective association of S1 dendron possessing two alkyl chains in meta and para positions (i.e, 3, 4-positional) with the P4VP block chain is able to induce the formation of hexagonally-packed PS helices at a specific ratio of pyridine to S1. The molecular simulation indicates that the S1 and S5 dendrons prefer to form non-planar and planner structures, respectively. In contrast to untwisting H-aggregates consisting of the planner S5 dendrons in the PS-P4VP/S5 hybrids, this non-planar structure of the S1 dendron can lead to form twisting J-aggregates, by which the helical conformation of the P4VP chain is thus fixed as evidenced by circular dichroism (CD) spectroscopy, giving rise to the helical phase with a preferred single handedness in the PS-P4VP/S1 hybrids. As a result, the helices only form in the PS-P4VP/S1 hybrid at a specific composition and molecular weight due to strong twisting power by J-aggregation. Surprisingly, the well-aligned hexagonally-packed nanohelices can be carried out after applying oscillatory shear, verified by the X-shaped texture in the two-dimensional ultra-small-angle X-ray scattering pattern. Consequently, this discovery may provide a new concept for the formation of helical phase from achiral self-assembly of DJBCPs.

Contents
論文審定書 i
摘要 ii
Abstract iii
List of Figures vii
List of Table xi
Chapter 1. Introduction 1
1.1 Block Copolymer (BCP) Self-assembly 1
1.2 PVP-Based BCPs 3
1.3 Microphase Separation of Small molecule/PVP 5
1.4 Dendron Jacketed Block Copolymer (DJBCP) 8
1.5 Helical Structures from Self-assembly 10
1.6 Hydrogen bond 12
1.7 Chirality Effect on Helical Formation 14
1.8 Chirality 17
1.9 Helical Phase from Self-Assembly of Chiral Block Copolymers 20
1.10 Induced Circular Dichroism 23
1.11 Induced Circular Dichroism in Stereoregular Polymers 24
1.12 Helical Phase from Achiral Block Copolymers 26
1.13. Helices from Self-Assembly of Achiral Polymers 29
Chapter 2. Materials and Experimental Methods 31
2.1 Materials 31
2.1.1 Block Copolymer 31
2.1.2 Small molecules 31
2.2 Sample Preparation 32
2.3Microstructural Characterization 32
2.3.1 Transmission Electron Microscopy (TEM) 32
2.3.2 Field-Emission Scanning Electron Microscopy (SEM) 33
2.3.3 Small Angle X-ray Scattering (SAXS) 33
2.3.4 Differential Scanning Calorimetry (DSC) 33
2.3.5 Fourier Transform Infrared (FTIR) Spectroscopy 34
2.3.6 Circular Dichroism (CD) Spectroscopy 34
2.3.7 Ultraviolet–Visible Absorption Spectroscopy 35
2.3.8 Photoluminescence Spectroscopy 35
Chapter 3. Results and Discussion 36
3.1. Self-Assembled Morphologies of PS-P4VP BCPs in Bulk 36
3.2. Microphase Separations of As-Cast PS151-P4VP163/S1 Hybrids 38
3.3. Molecular Interactions between S1 and Pyridine 43
3.4. Morphological Observations by FESEM 45
3.5. Effect of Dendron Architecture: As-Cast PS151-P4VP163/S5 Hybrids 46
3.6. Chain Conformations of Hybridization 48
3.7. Molecular Architecture of Dendrons 51
3.8. Molecular Stacking of Dendrons in Helical Microdomains 53
3.9. Effect of Molecular Weight: Low-Mw PS21-P4VP22/S1 Hybrids 56
3.10. Effect of Compositions: PS240-P4VP20/S1 Hybrids 59
3.11. Alignment of Helical Phase 62
Chapter 4. Conclusion 66
Chapter 5. References 67

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