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博碩士論文 etd-0626116-031727 詳細資訊
Title page for etd-0626116-031727
論文名稱
Title
合成具有親氟作用力之二苯并[a, c]二氮蔥盤型液晶及其超分子組裝
Synthesis of Fluorophilic Dibenzo[a, c]phenazine Discotic Liquid Crystal and Supermolecular Assembly
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
93
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2016-07-20
繳交日期
Date of Submission
2016-07-26
關鍵字
Keywords
氟烷鏈、液晶性質、盤型液晶、過冷現象、親氟作用力
supercooling, discotic liquid crystal, mesomorphic properties, fluoroalkylated chains, fluorophilic effect
統計
Statistics
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The thesis/dissertation has been browsed 5675 times, has been downloaded 43 times.
中文摘要
本論文中成功合成出具有氟烷鏈修飾的二氮三亞苯盤型液晶。實驗合成分為兩部分,第一部分是將氟烷鏈建構至兒茶酚藉由較快速與簡便的自由基、還原、硝化反應。第二部分則藉由實驗室已發表的1, 2雙酮化合物與氟烷化兒茶酚進行縮合反應而得到產物。接著透過偏光顯微鏡、微差掃描卡計及X光粉末繞射進一步鑑定一系列化合物的液晶性質。數據分析的結果發現具有氟烷鏈取代基的二氮三亞苯化合物其表現優異的液晶性質比起過去醚鏈取代基的二氮三亞苯衍生物,並改變二氮三亞苯另一端醚鏈的長度,發現長醚鏈在降溫過程會產生過冷現象,於室溫下以玻璃態的形式存在,證實氟烷鏈官能基能大幅提高澄清點的溫度,而有效提升液晶相的穩定度。此外,因氟烷鏈使液晶超分子具備親氟作用力,控制超分子排列傾向垂直於基板的管柱型式。
Abstract
We synthesize dibenzo[a,c]phenazine discotic liquid crystal possessing fluoroalkylated side chains. The first synthesis part is catechol modified by fluoroalkylated chains through the following sequence of reactions: (i) radical reaction of but-3-enol with fluoroalkyl iodide (ii) elimination-reduction of the iodo-with DBU (iii) nitration with the fluoroalkylated-oxybenzene. Next part is a condensation of 4,5-diaminobenzenes with tetraalkoxyphenanthrene-9,10-dione. A series of compounds exhibit mesomorphic properties determined by polarized optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray powder diffraction(XRD). The results of data analysis we found that having a fluoroalkyl chain substituted compound improve mesomorphic properties as compare to all the alkoxyl chain substituted triphenylene derivative, and produce supercooling phenomenon on cooling to room temperature formed plastic phase in other long-alkoxyl chains. The fluorophilic effect induced by fluoroalkyl substituted increases the isotropic temperature and effectively enhances the stability of the liquid crystal phase. In addition the supramolecular columnar liquid crystals tend to hometropic alignment.
目次 Table of Contents
中文摘要 ii
英文摘要 iii
圖目錄 vii
表目錄 ix
第一章 緒論 1
1-1 前言 1
1-2液晶介紹 2
1-3液晶的分類---3
1-3-1 依產生液晶相變的原因--- 4
1-3-2 依液晶分子的大小--- 5
1-3-3 依液晶元的形狀 ---7
1.4 液晶之光電特性 ---11
1-5盤狀液晶的應用與價值 ---13
1-6 氟的取代基對於液晶的影響及其文獻回顧 ---15
1-6-1 氟取代基對於有機化合物其性質上的影響 ---16
1-6-2 氟取代基修飾桿型液晶及其影響性 ---19
1-6-3 氟取代基修飾盤型液晶的文獻回顧 ---23
第二章 實驗部分 ---31
2-1 研究動機 ---31
2-2 合成策略 ---32
2-3實驗流程與討論 ---33
2-3-1烷化(alkylation)--- 33
2-3-2 Friedel-Crafts acylation ---33
2-3-3 環化(cyclization)--- 34
2-3-4 Fluorinated side chain – Radical reaction ---36
2-3-5 Fluorinated side chain- elimination/reduction reaction ---36
2-3-6 Fluorinated side chain- Bromination/Substitution of alcohol--- 37
2-3-7 Fluorinated side chain- 氟烷化(fluoroalkylation) ---38
2-3-8 Fluorinated side chain- 硝化(nitration) ---38
2-3-9 Fluorinated side chain- 氫化還原(reduction) ---39
2-3-10縮合反應( Condensation ) ---40
第三章 物性檢測與探討 ----41
3-1 偏光顯微鏡(POM)之觀測 ----42
3-2 微差掃描器(DSC)之檢測 ---47
3-3 變溫X-ray粉末繞射(XRD)之測量 ---50
第四章 總結論 ---55
第五章 實驗部分 ---56
儀器設備 ---56
藥品與溶劑 ---57
過程 ---57
化合物合成條件與檢測資料 ---58
1,2-Bis(alkoxy)benzene (1) ---58
3,3', 4,4'­Tetrakisalkoxybenzil (2) ---60
2,3,6,7-Tetrakis(alkoxy) phenathrene-9,10-dione (3) ---62
5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluoro-3-iodododecan-1-ol (4)--- 64
(E)-5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododec-3-en-1-ol (5) ----65
5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecan-1-ol (6)--- 66
12-bromo-1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluorododecane (7) ---67
5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl 4-methylbenzenesulfonate (8) ---68
1,2-Bis(perfluoroalkoxy)benzene (9)---69
1,2-Bis(perfluoroalkoxy)-4,5-dinitrobenzenes (10)---70
1,2-Bis(perfluoroalkoxy)-4,5-diaminobenzenes (11) ---71
2,3-Bisperfluoroalkoxy-6,7,10,11-tetraalkoxy-1,4- diazatriphenylene (12)---72
參考文獻 ---74
附錄 ---77
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