為了研究掌性效應影響掌性嵌段共聚物其自組裝的普遍相行為，故設計並合成含聚環己烷基乙交酯之新型掌性嵌段共聚物(聚甲基丙烯酸苄-聚右旋環己烷基乙交酯)。分子層級與鏈層級的掌性可分別由圓二色光譜及振動圓二色光譜來驗證，且含聚環己烷基乙交酯的掌性嵌段共聚物利用掌性嵌段之分子內作用力可得到單一旋性的聚環己烷基乙交酯，其分子內作用力可藉由在振動圓二色光譜中羰基的耦合作用來驗證。利用掌性嵌段之分子間作用力，含聚環己烷基乙交酯之掌性嵌段共聚物可自組裝形成螺旋結構，顯示掌性效應於嵌段共聚物中在自組裝行為上的影響。在此值得注意的是，因掌性聚環己烷基乙交酯具有較大的螺旋旋轉能力，螺旋結構的介穩定性會受到顯著之影響，故含掌性聚環己烷基乙交酯之嵌段共聚物可自組裝形成較聚苯乙烯-聚左旋乳酸系統更穩定的螺旋態。在含掌性聚環己烷基乙交酯之嵌段共聚物中所觀察到之相行為可與定向自洽場理論模擬之結果相符合。此外，根據理論預測掌性聚環己烷基乙交酯可能具有類似液晶的行為表現，分子鏈間具有特定取向之排列，可藉由醚基在振動圓二色光譜的吸收波段之訊號來驗證。上述結果皆可與定向自洽場理論之模擬結果相互呼應。

Here, we aim to investigate the universal behaviors of the chirality effect on the self-assembly of chiral block copolymers (BCPs*). A new type of chiral block polymer (BCP*), poly(cyclohexylglycolide) (PCG)-containing block copolymer (BCP) (i.e., poly(benzyl methacrylate)-b-poly(D-cyclohexylglycolide) (PBnMA-PDCG)), are designed and synthesized. On the basis of the molecular chirality and conformational chirality of the chiral PCGs identified by circular dichroism and vibrational circular dichroism spectra, respectively, exclusively handedness of PCG polymer chains in the enantiomeric BCPs* can be found due to intramolecular chiral interaction of chiral entities as evidenced by coupling of carbonyl group (C=O) in VCD spectra. By taking advantage of intermolecular chiral interaction which could be observed by vibration of C-O-C in VCD spectra, the self-assembly of the PCG-containing BCP* gives the formation of helical phase (H*), suggesting the chirality effect on BCP self-assembly. Most interestingly, with the high twisting power, the metastability of forming H* can be significantly affected, resulting in the tendency to give H* with higher thermodynamic stability. The observed phase behaviors of the PCG-containing BCP*s are in line with theoretical prediction based on chiral orientational self-consistent field theory. Also, the self-assembly of chiral orientational self-consistent field theory at which the chiral PCG behaves like mesogenic liquid crystal, giving the nematic texture with specific twisting direction as evidenced by the mirror-imaged VCD signals of C-O-C vibration.

摘要..................................................................I
Abstract.............................................................II
致謝................................................................III
Contents.............................................................IV
Figures Captions.....................................................VI
Tables Captions.....................................................XII
Chapter 1 Introduction................................................1
1.1 Self-Assembly and Supramolecular Chemistry........................1
1.2 Self-Assembly of Block Copolymers (BCPs) .........................5
1.3 Chirality ........................................................6
1.4 New Phases in Chiral Block Copolymers (BCPs*).....................8
1.5 Circular Dichroism and Vibrational Circular Dichroism............14
1.6 Circular Dichroism and Vibrational Circular Dichroism for Chiral Polymers and Block Copolymers........................................20
1.7 Chirality in Liquid Crystal..............................................................26
1.8 Orientational Self-Consistent Field Theory.......................28
Chapter 2 Objectives.................................................32
Chapter 3 Experimental Section.......................................34
3.1 Materials........................................................34
3.2 Preparation of Bulk Samples......................................36
3.3 Preparation of Polymer Thin-film Sample..........................36
3.4 Characterization and Instrumentation.............................36
Chapter 4 Results and Discussion.....................................40
4.1 Synthesis and characterization of Poly(cyclohexylglycolide)-Containing Homopolymers and Block Copolymers.........................40
4.2 Configurational and Conformaitonal Chirality in Poly(cyclohexyl glycolide) Homopolymers and Poly(cyclohexylglycolide)-Containing Block Copolymers...........................................................47
4.3 Universal Behaviors of Chirality Effect on BCP Self-Assembly..52
4.4 Intermolecular Chiral Interaction of Chiral PCGs.................60
Chapter 5 Conclusions and Prospective................................68
Chapter 6 References.................................................70

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