金剛烷具有高熱穩定性、疏水性以及低表面能等等的性質，而本身的剛硬性除了可以有效增強鍵結聚合物的熱性質，也能以側鏈的方式鍵結在嵌段共聚物中來提升嵌段間的構型不對稱性，並產生不同於coil-coil類型和rod-coil類型嵌段共聚物的特殊自組裝行為。在這篇論文中系統性地探討了兩種不同系列的金剛烷基嵌段共聚物αAdDVB-b-tBMA和βAdDVB-b-2VP的熱性質、相行為以及所產生的階層性結構。
金剛烷基聚合物在熱分析實驗中展現出了優異的熱穩定性和熱性質，並且也在變溫的小角度X光散射實驗中有著非常穩定的相行為。αAdDVB-b-tBMA嵌段共聚物經過長時間的退火後，在小角度X光散射圖譜中出現了一系列無法確認其結構的特殊比例散射峰，並在穿透式電子顯微鏡的觀察下推測其奈米結構可能為由柱狀微域所形成的無序雙連續相網狀結構。另外兩種不同重量分率的βAdDVB-b-2VP嵌段共聚物則皆在短暫的退火後產生了層狀結構。其中，βAdDVB11.6k-b-2VP7k在260℃下退火6小時後產生了從層狀到六角柱狀的結構轉變，並在穿透式電子顯微鏡下可以觀察到相轉換的過程中所產生的各種過渡結構，如：波浪狀層板結構和網狀結構。此外，我們也提出了βAdDVB-b-2VP的非對稱相圖，顯示βAdDVB-b-2VP的有序層狀相邊界會向較低金剛烷基嵌段的體積分率偏移。
同時我們也通過小角度X光散射和偏光顯微鏡的實驗來證實金剛烷基均聚物和嵌段共聚物皆會產生液晶相，並在經過更長時間的退火處理後發現αAdDVB8.8k-b-tBMA4.6k和βAdDVB7k-b-2VP14.2k嵌段共聚物會產生中間尺度的層狀結構，確認金剛烷基嵌段共聚物會產生由金剛烷基嵌段有序排列而產生的小尺度結構以及嵌段共聚物本身的微分相分離所產生的大尺度結構所組合而成的階層性奈米結構。

Adamantyl group is a bulky and rigid moiety which can provide significant improvement in the thermal properties when it is introduced into the polymer. Moreover, the attachment of the adamantyl group on the polymer backbone may effectively stiffen the chain, rending semiflexible conformational characteristic to the polymer. Therefore, the block copolymers composed of an adamantane-containing block and a coil block may be considered as an interesting class of soft material showing the self-assembly behavior intermediate between that of the conventional coil-coil and rod-coil block copolymers.
This thesis systematically studies the phase behavior and the hierarchical structures of the diblock copolymers composed of adamantyl groups. Two systems were investigated, namely, poly(α-adamantyl-divinylbenzene)-b-poly(tert-butyl methacrylate) (αAdDVB-b-tBMA) and poly(β-adamantyl-divinylbenzene)-b-poly(2-vinylpyridine) (βAdDVB-b-2VP). The as-cast films of both copolymers were found to exhibit metastable distorted morphologies and prolonged annealing above the glass transition temperatures were required to attain the thermodynamically equilibrium microphase-separated structures. The small angle X-ray scattering (SAXS) profile of the annealed αAdDVB8.8k-b-tBMA4.6k (with the weight fraction of the tBMA coil block of 0.34) could be fitted satisfactorily by the Percus-Yevick model of cylindrical domains, showing the lack of long-range order in the microphase-separated structure. The real-space observation of the morphology by transmission electron microscope (TEM) suggested that the diblock copolymer exhibited a bicontinuous disordered network morphology.
For the βAdDVB-b-2VP systems, the two samples with the P2VP block volume fraction of 0.41 and 0.69 were found to display ill-defined morphology in the as-cast state. The metastable structure transformed into well-ordered lamellar morphology upon thermal annealing above the glass transition temperature of βAdDVB block. βAdDVB11.6k-b-2VP7k further exhibited a morphological transformation from lamellae to hexagonally packed cylinders upon annealing at 260°C for more than 6 hours. The transient structures, including undulated lamellae and mesh structure, in the transition process were identified by TEM. An asymmetric phase diagram arising from the large disparity in conformational rigidity of βAdDVB-b-2VP was proposed.
Strikingly, a smaller-length-scale mesomorphic structure arising from the self-assembly of the adamantayl block was revealed by the combination of the SAXS results and polarized optical microscopy (POM). The smaller-length-scale structure in αAdDVB8.8k-b-tBMA4.6k and βAdDVB7k-b-2VP14.2k developed lamellar order upon prolonged annealing. Consequently, the adamantane-containing diblock copolymers constitute a special system displaying hierarchical structure with two distinct length scales: the larger-length-scale structure arose from the microphase separation between the adamantyl block and the coil block, and the smaller-length-scale structure was associated with the formation of a lamellar mesophase by the adamantyl block within its microdomain.

Abstract I
摘要 III
Table of Contents IV
List of Tables VI
List of Figures VII
Chapter 1 Introduction 1
1-1 Introduction to Block Copolymer 1
1-2 Phase Behavior of Diblock Copolymer 3
1-3 Classification of Diblock Copolymers According to Conformational
Characteristics 11
1‐3‐1 Coil‐Coil Diblock Copolymers 11
1‐3‐2 Rod‐Coil Diblock Copolymers 11
1‐3‐3 Liquid Crystalline Diblock Copolymers 16
1-4 Introduction to Adamantyl Block Copolymer 24
1-5 Motivation and Objective of the Study 26
Chapter 2 Experimental section 27
2-1 Materials 27
2-2 Sample Preparation 29
2-3 Characterization 30
2‐3‐1 Thermogravimetric Analysis (TGA) Measurements 30
2‐3‐2 Differential Scanning Calorimetry (DSC) Measurements 30
2‐3‐3 Small Angle and Wide Angle X‐ray Scattering (SWAXS) Measurements 30
2‐3‐4 Transmission Electron Microscope (TEM) Observation 31
2‐3‐5 Polarized Optical Microscope (POM) Observation 32
Chapter 3 Results and Discussions 33
3-1 Thermal Properties of the Adamantyl Diblock Copolymers 33
3-2 Microphase-separated Structures of the Adamantyl Diblock Copolymers 37
3‐2‐1 Structure of αAdDVB8.8k‐b‐tBMA4.6k 37
3‐2‐2 Phase behavior and self‐assembled structure of βAdDVB‐b‐2VP 42
3-3 A Smaller-lengthscale-structure Formed by the Adamantyl Block 56
3-4 An Intermediate-Lengthscale Structure of Adamantyl Homopolymer and Diblock Copolymers 63
Chapter 4 Conclusions 70
Reference 72

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