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研究生： 韋伊卡
Widharyanti, Ika Dyah
論文名稱： 含ODOPB基液晶性酯化合物及其包容錯體之合成 及特性探討
Synthesis and Characterization of Liquid Crystalline Esters Containing ODOPB Group and its Inclusion Complexes
指導教授： 劉瑞祥
Liu, Jui-Hsiang
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2011
畢業學年度： 99
語文別： 英文
論文頁數： 88
中文關鍵詞： 液晶 、包容錯體 、自組裝 、耐燃劑
外文關鍵詞： liquid crystal, phosphaphenanthrene, inclusion complex, self-assembly
相關次數： 點閱：58  下載：1 
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    • 本研究合成兩系列含ODOPB結構之光致變性熱向型液晶分子，分子結構設計上，導入含有不同長碳鏈的烷鏈，及使含有偶氮苯及[1, 2, 3]-triazole基團。利用即合反應(click chemistry)將aromatic phenolic azide及alkyl propargyl ether合成三氮二烯五員雜環(heterocyclic triazole core)。由熱分析結果顯示，所合成的液晶分子在升、降溫過程皆呈現層列型液晶相。由於DOPO耐燃基團之導入，殘餘灰份(char yield)隨著含磷基團比例之增加而增加。此外，本研究亦利用二次作用力，將所合成的液晶分子與β-環糊精(β-cyclodextrin)形成主-客型包容錯體(inclusion complexes, IC)。藉由TGA、DSC與UV-vis光譜儀分別觀察單體與包容錯體(IC)的熱裂解溫度、結晶及相轉移溫度的改變與最大吸收波長藍位移現象等。包容錯體之自我組裝、以及所形成之微結構體，均有詳細討論。

    Two series of structurally isomeric thermotropic liquid crystalline esters (TLCEs) containing 2-(6-oxide-6H-dibenz(c,e)(1,2)oxaphosphorin-6-yl)-1,4-dihydroxy phenylene (ODOPB) with photochromic azobenzene and [1,2,3]-triazole ring at the terminal positions were synthesized and characterized. Heterocyclic triazole core was introduced into the target compound through click chemistry between aromatic phenolic azide and alkyl propargyl ethers. Introducing of the highly conjugated DOPO group onto side chain leads to the formation of enantiotropic smectic phase on heating and cooling cycles. The liquid crystalline phases were further confirmed using differential scanning calorimetric investigations. In addition, the synthesized liquid crystalline esters have a high char yield values. The result is ascribed to the existence of the flame retardant DOPO unit. To synthesize inclusion complexes (ICs), β-cyclodextrin (β-CD) was threaded onto TLCEs. Physicochemical evidences show the degradation temperature for the evaporation of water molecules within the β-CD cavities, differences in crystallinity/transition temperatures, remarkable blue shift in λmax/λemis, and reasonable morphology changes from nanoball-like structure to nanorod-like structure were investigated. Self-assembly and the morphologies of synthesized ICs were further studied.

    Contents Abstract I 中文摘要 II Acknowledgements III Contents IV List of Tables VII List of Figures VIII List of Schemes XI Chapter 1 Introduction 1 1.1 Introduction 1 1.2 Research Motivation 4 Chapter 2 General Introduction and Theoretical Background 6 2.1 Introduction of liquid crystals 6 2.1.1 Thermotropic liquid crystals 8 2.1.1.1 Nematic 9 2.1.1.2 Smectic 10 2.1.1.3 Cholesteric 11 2.1.1.4 Discotic 12 2.1.2 Lyotropic liquid crystals 13 2.1.3 Anisotropies of liquid crystals 13 2.1.3.1 Birefringence of liquid crystals 13 2.1.3.2 Dielectric properties of liquid crystals 14 2.1.4 Identification of liquid crystal phases 16 2.1.5 Basic molecular structure of rodic liquid crystals 17 2.1.6 Photochromism in Liquid Crystals 20 2.1.7 Phosphorus containing Liquid Crystal 23 2.1.8 Application of liquid crystals 24 2.2 Self-Assembly 26 2.2.1 Future and present application 27 2.3 Cyclodextrin 28 2.3.1 Properties of Cyclodextrins 28 2.3.2 Cyclodextrin application in industries 31 2.3.3 Cyclodextrin inclusion complex 33 2.3.3.1 Fabrication of Cyclodextrins Inclusion Complexes 34 2.3.4 Application of cyclodextrin inclusion complexes 35 2.3.5 Cyclodextrin based supramolecular self-assembly 36 Chapter 3 Experiment Section 41 3.1 Materials 41 3.2 Measurements 42 3.3 Synthesis of liquid crystal compounds 44 3.4 Synthesis of Inclusion Complexes with β-Cyclodextrin 49 Chapter 4 Results and Discussion 51 4.1 Synthesis of Novel Liquid Crystals 51 4.2 Mesomorphic and Thermal properties of Liquid Crystals57 4.2.1 POM analysis 57 4.2.2 DSC analysis 60 4.2.3 TGA analysis 63 4.3 Photochemical properties 65 4.4 Preparation of β-Cyclodextrin-LC Inclusion Complexes 67 4.5 Characterization of Inclusion Complexes 68 4.5.1 FTIR spectroscopy 68 4.5.2 1H-NMR spectroscopy 70 4.5.3 Thermal Analysis 73 4.5.4 Photochemical analysis 75 4.5.5 Morphology 77 Chapter 5 Conclusions 82 References 83

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