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研究生： 陳政緯
Jeng-Wei Chen
論文名稱： 硝酸銨和苯并-18-冠-6醚1:1共晶化合物的篩選、製備、燃燒速率及其溶解
Screening, Manufacturing, Burning Characteristics, and Dissolution of 1:1 Co-crystal of Ammonium Nitrate-Benzo-18-crown-6
指導教授： 李度
Tu Lee
口試委員:
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程與材料工程學系
Department of Chemical & Materials Engineering
畢業學年度： 99
語文別： 英文
論文頁數： 153
中文關鍵詞： 相轉換 、低溫熱微差掃描分析儀 、燃燒特性 、共晶化合物 、苯并18冠6醚 、硝酸銨
外文關鍵詞： Ammonium nitrate (AN), Bezno-18-crown-6 (B18C6)
相關次數： 點閱：15  下載：0 
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    • 結晶工程已發展出以自組裝現有分子產生新型固體而不需破壞或形成共價鍵的方法。以共晶化合物來量身訂做材料特性，已激發許多研究人員在結晶工程領域的興趣。
    冠醚是超分子化學的代表之一。不僅是廣泛用在超分子化學和結晶工程中作為不同類型陽離子如水合氫離子(H3O+)、銨離子(NH_4^+)的主體而且也能藉由形成氫鍵和鹼金屬/過渡金屬離子和氫化陽離子形成穩定的錯合物。不同的冠醚有不同的分子孔洞大小且大部分可和特定陽離子有緊密鍵結。本論文中，硝酸銨被選用希望能改變其晶貌並希望誘導出新的具有特殊物理化學性質的同質異構物。
    首先，利用23種有機溶劑篩選的方式，有關構形IV 硝酸銨的溶解度(solubility)、多形性(polymorphism)、結晶度(crystallinity)、晶貌(crystal habit)以及多晶形表(Form Space)的資料被完整收集。其次，基於硝酸銨和冠醚的多晶形表，利用反溶劑法可生成一新的1:1硝酸銨—苯并18冠6醚共晶化合物。分析工具，如LTDSC, TGA, FT-IR, OM, PXRD, SXD被用來了解其超分子結構和確定其分子間的化學劑量比。同時，也進行1:1硝酸銨—苯并18冠6醚共晶化合物的球型結晶研究。最後進行此共晶化合物的燃燒速率、溶解度和溶解速率的測量以便了解其性質。

    Crystal engineering had developed a manner that it applied self-assembly of existing molecules to generate a new solid without the need to break or form covalent bonds. Cocrystals have excited the interest of many researchers in the crystal engineering field as a way to tailor-make material properties.
    Crown ethers are one of the symbols of supermolecular chemistry. This is not only because of their extensive utilization in supermolecular chemistry and crystal engineering as hosts for variety of cationic species such as hydronium ion (H3O+), ammonium ion (NH_4^+) but also because crown ethers are able to form stable complexes with alkali or transition-metal ions and hydrogenate cations via hydrogen bonding. The different crown ethers have different cavity szies and can be chosen to bind most strongly with a given cation. In this thesis, ammonium nitrate was selected in order to change the crystal habit and to hopefully induce new polymorph of AN which possessed special physicochemical properties.
    Firstly, engineering data of solubility, polymorphism, crystallinity, crystal habit and Form Space by solvent screening for Form IV ammonium nitrate (AN) was established. Secondly, a new cocrystal of AN and benzo-18-crown-6 (B18C6) was found by antisolvent method based on Form Space of AN and crown ether. Analytical tools such as LTDSC, TGA, FT-IR, OM, PXRD, SXD were used for understanding the supramolecular architectures and to ensure the stoichiometry of cocrystal. In the mean time, a spherical crystallization study for 1:1 cocrystal of AN-B18C6 was carried out based on Form Space of AN and B18C6. Finally, 1:1 cocrystal of AN-B18C6 was manufactured for burning characteristic, solubility and dissolution rate measurement to understand its properties.

    Table of contents 摘要 i Abstract ii Acknowledgement iv Table of contents v List of Tables ix List of Figures x Chapter 1 Executive Summary 1 1.1 Introduction 1 1.2 Brief Introduction of Ammonium Nitrate 9 1.3 Conceptual Framework 12 Chapter 2 Analytical Instruments 19 2.1 Introduction 19 2.2 Thermal Analysis Methods 22 2.2.1 Low Temperature Differential Scanning Calorimetry (LT-DSC) 22 2.2.2 Thermogravimetric Analysis (TGA) 24 2.3 Crystallographic Analysis Method 26 2.3.1 Single-Crystal X-ray Diffractometer 26 2.3.2 Powder X-ray Diffraction (PXRD) 29 2.4 Spectroscopic Analytical Method 32 2.4.1 Fourier Transform Infrared (FT-IR) Spectroscopy 32 2.5 Microscopic Method 35 2.5.1 Optical Microscopy (OM) 35 2.5.2 Polarized Optical Microscopy (POM) 36 2.6 Low Vacuum Scanning Electron Microscopy (LVSEM) 37 2.7 Process Control Technology 40 2.7.1 Conductivity Meter 40 2.7.2 Strand Burner 42 2.8 Conclusion 44 Chapter 3 Solubility, Polymorphism, Crystal habit and Crystallinity of Ammonium Nitrate (AN) by Initial Solvent Screening 49 3.1 Introduction 49 3.1.1 Ammonium nitrate 50 3.1.2 Solubility 56 3.1.3 Polymorphism 57 3.1.4 Crystal Habits 59 3.1.5 Crystallinity 60 3.2 Materials 61 3.2.1 Ammonium Nitrate 61 3.2.2 Solvents 62 3.3 Experimental Methods 66 3.3.1 Initial Solvent Screening. 66 3.3.1.1 Temperature Cooling Method 67 3.3.2 Instrumental Analysis 67 3.3.2.1 Low Temperature Differential Scanning Calorimetry (LT-DSC) 67 3.3.2.2 Thermogravimetric Analysis (TGA) 68 3.3.2.3 Powder X-ray Diffractometry (PXRD) 69 3.3.2.4 Fourier Transform Infrared (FT-IR) Spectroscopy 69 3.3.2.5 Optical Microscopy (OM) 69 3.4 Results and Discussion 71 3.4.1 Solubility 71 3.4.2 Polymorphism 78 3.4.3Crystal Habits 80 3.4.4 Crystallinity 82 3.5 Conclusions 83 Chapter 4 Cocrystal of AN and B18C6 and its spherical agglomerate 91 4.1 Introduction 91 4.1.1 Antisolvent method 94 4.1.2 Spherical Crystallization 96 4.1.3 Gas generator propellant 97 4.2 Materials 101 4.2.1 Ammonium Nitrate and Crown Ether 101 4.2.2 Solvents 102 4.3 Experimental Section 103 4.3.1 Selection of solvent combination 103 4.3.2 Screening by antisolvent method 103 4.3.3 Spherical crystallization of AN+B18C6+EtOH+MTBE+H2O 108 4.3.4 Measurement of micromeritic and mechanical properties 110 4.3.5 Dissolution rate measurement 111 4.3.6 Burning rate measurement 113 4.3.7 Instrumental Analysis 114 4.3.7.1 Low Temperature Differential Scanning Calorimetry (LTDSC) 114 4.3.7.2 Thermogravimetric Analysis (TGA) 115 4.3.7.3 Powder X-ray Diffractometry (PXRD) 115 4.3.7.4 Fourier Transform Infrared (FT-IR) Spectroscopy 116 4.3.7.5 Optical Microscopy (OM) 116 4.3.7.6 Low Vacuum Scanning Electron Microscopy (LVSEM) 117 4.3.7.7 Orbital shaker 117 4.3.7.8 Digital Camera (DC) 117 4.4 Results and Discussion 118 4.4.1 Solvent Screening 118 4.4.2 Cocrystal of AN and B18C6 121 4.4.4 SEM Photomicrographs of Spherical Surface 130 4.4.5 Single Crystal X-ray Diffraction (SXD) 133 4.4.5 Burning characteristics 140 4.4.6 Observation of smoke 142 4.4.7 Solubility and dissolution rate 144 4.5 Conclusions 146 Chapter 5 Conclusions and Future Work 151 5.1 Conclusions 151 5.2 Future Work 153

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