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姓名 劉和治(Ho-chih Liu) 查詢紙本館藏 畢業系所 化學學系 論文名稱 無機桿狀液晶之設計與探討
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摘要(中) 摘 要
本論文主要是探討，以benzoxazoles為主要中心core的液晶材料設計與物性。利用NMR來鑑定分子結構，元素分析來測量其純度。此外，並利用熱差掃瞄卡計(DSC)，powder X-ray，偏光顯微鏡，觀察其液晶相變化與分子排列情形。
在系列一之有機液晶分子結構中，我們固定較難合成的2-amino -5-dodecyloxyphenol側鏈碳數(n=12)，只改變另一邊側鏈基碳數，當n=1、4、6、8、10、12與14，具有SmC及N的液晶相。另外，我們也試著改變此有機液晶，將其單邊側鏈基由1根增加為2根及3根，但並沒有液晶相之形成。接著，我們也將此有機液晶分子，試著與金屬Pd配位。結果，我們雖然能成功地與金屬配位，但卻未能形成無機液晶。
將系列一的有機液晶分子結構稍做變化，而形成系列二的配位基。我們仍然固定2-amino-5-dodecyloxyphenol這一邊的側鏈碳數(n=12)。接著，我們將合成出來的配位基4-alkoxybenzoic acid 4-(6-dodecyloxybenzooxazol-2-yl)-3-hydroxyphenyl ester與金屬(M=Zn) 進行配位，得到具有液晶性質之含單金屬無機液晶。接著，我們將配位基與金屬Cu和Pd進行錯合時，並不具有任何液晶相。摘要(英) Abstract
Numerous known examples of hydrocarbon structures, used as core groups exhibiting columnar phases have been reported. However, examples of heterocyclic structures used as core groups are relatively less. The presence of nitrogen, sulfur or oxygen atoms on these heterocyclic rings, which likely introduce a transverse dipole moment often resulted in a change in dielectric anisotropy. The formation of liquid crystallinity in such heterocyclic compounds might be facilitated by weak p - p interaction between these aromatic or heterocyclic rings.
In this work a new type of heterocyclic compounds, 4-alkoxybenzoic acid 4-(6-alkoxy benzoxazol-2-yl)phenyl esters, in which an unsaturated benzoxazole ring was utilized as the rigid core group, were prepared and their mesomorphic properties studied. All compounds were characterized by 1H-, 13C-NMR spectroscopy, powder X-ray diffraction and the mesomorphic properties of these compounds were studied by DSC analysis, optical polarized microscope and powder XRD diffraction. The results indicated that these rod-like compounds exhibited nematic (N) and smectic (SmC) phases. The range of mesophase temperatures was slightly dependent on the ratio of width-to-length (d/l, i.e., aspect ratio) of the molecular shape.關鍵字(中) ★ 桿狀液晶 關鍵字(英) ★ rod liquid crystals 論文目次 目 錄
謝誌..........................................................................................................Ⅰ
中文摘要..................................................................................................Ⅱ
英文摘要..................................................................................................Ⅲ
目錄..........................................................................................................Ⅳ
圖目錄......................................................................................................Ⅶ
表目錄......................................................................................................Ⅸ
附圖目錄..................................................................................................Ⅹ
第一章 緒論...........................................................................................1
1-1 前言.............................................................................................2
1-2 液晶之起源與簡介.....................................................................2
1-3 液晶之分類.................................................................................4
1-3-1 桿狀液晶相...............................................................................6
1-3-2 盤狀液晶相................................................................................11
1-4 無機液晶...................................................................................13
1-5 液晶之物理性質...................................................................14
1-5-1 液晶之異相性…………..………...…………………...………14
1-5-2 介電異相性……………………....….………………...………14
1-5-3 光學異相性…………………..…..….…………...……………15
1-5-4 分子排列規則參數……………..…...……………...…………16
1-5-5 磁化異相性……………………..…..….…………...…………17
1-5-6 黏度............................................................................................18
1-6 研究動機....................................................................................18
1-6-1 系列一與系列二........................................................................19
第二章 實驗部分..................................................................................20
2-1 實驗藥品....................................................................................22
2-2 儀器設備....................................................................................23
2-3 實驗流程....................................................................................27
2-3-1 系列一之實驗流程....................................................................27
2-3-2 系列二之實驗流程....................................................................28
2-4 實驗步驟....................................................................................29
2-4-1 4-Alkoxybenzoic acid 4-(6-dodecyloxybenzoxazol-2-yl)phenyl esters系列之合成...................................................................29
2-4-1-1 3-Dodecyloxy-phenol合成.....................................................29
2-4-1-2 5-Dodecyloxy-2-nitrophenol之合成......................................30
2-4-1-3 2-Amino-5-dodecyloxyphenol之合成...................................30
2-4-1-4 p-Alkoxybenzoicacids之合成...............................................31
2-4-1-5 4-(p-n-Alkoxybenzoyloxy)benzaldehydes之合成.................31
2-4-1-6 4-Alkoxybenzoic acid 4-[4-dodecyloxy-2-hydroxy
phenylimino)methyl]phenyl ester之合成..............................32
2-4-1-7 4-Alkoxybenzoic acid 4-(6-dodecyloxybenzoxazol -2-yl)phenyl esters……………..………………………........33
2-4-1-8 2-(3,4-Bis-dodecyloxy-phenyl)-6-dodecyloxy-benzoxazol....37
2-4-1-9 6-Tetradecyloxy-2-(3,4,5-tris-tetradecyloxy-phenyl)- benzoxazole……………………………………………....…38
2-4-2 Bis[4-alkoxy-benzoic acid 4-(6-dodecyloxy-benzoxazol- 2-yl)-3-hydroxy-phenyl ester]metal系列之合成..................39
2-4-2-1 4-(p-n-Alkoxybenzoyloxy)salicylaldehydes之合成.............39
2-4-2-2 4-Alkoxy-benzoic acid 4-[(4-dodecyloxy-2-hydroxy-
phenylimino)methyl]-3-hydroxy-phenyl ester之合成..........39
2-4-2-3 4-Alkoxybenzoic acid 4-(6-dodecyloxy-benzoxazol -2-yl)-3-hydroxy-phenyl esters 之合成…………...........…..40
2-4-2-4 Bis[4-alkoxy-benzoicacid4-(6-dodecyloxy -benzoxazol-2-yl)-3-hydroxy-phenyl ester]metal之合成.....44
第三章 結果與討論..............................................................................48
3-1 系列一....................................................................................50
3-1-1 化合物合成反應機制之探討................................................51
3-1-2 NMR之鑑定..........................................................................55
3-1-3 液晶相的形式與範圍之鑑定................................................55
3-1-4 其它性質之探討....................................................................60
3-2 系列二....................................................................................66
3-2-1 配位基液晶相之討論............................................................66
3-2-2 錯合物液晶相之討論............................................................67
3-2-3 與其他不同金屬配位............................................................71
3-3 結論........................................................................................74
3-3-1 系列一....................................................................................74
3-3-2 系列二....................................................................................74
參考資料..................................................................................................75
圖 目 錄
圖1. 液晶相為介於固相與液相間之一個相……………………….....3
圖2. 液相型液晶……...........................................................................4
圖3. 液相型液晶之聚集方式................................................................5
圖4. 熱向性液晶……………………………………………………......5
圖5. 桿狀液晶的分子結構....................................................................6
圖6. 向列型(a)、層列型(b)、(c)、(d)與(e)液晶分子排列......9
圖7. 左圖為膽固醇型液晶，右圖為光學活性向列型液晶……..……11
圖8. 盤狀液晶之堆疊方式……………………………………………12
圖9. Colh之細部排列…….……………………………….………….13
圖10. 含benzooxazole結構的分子…………………………….…….19
圖11. 系列一之有機液晶分子結構………………………………….19
圖12. 系列二的配位基……………………………………………….19
圖13. 系列二的無機液晶分子結構………………………………….20
圖14. 偏光顯微鏡判斷液晶相紋路之規則………..…………………25
圖15. 系列一之實驗流程…………………………………………….27
圖16. 系列二之實驗流程…………………………………………….28
圖17. 系列一化合物之之柱狀圖………………………….………….56
圖18. 結晶相的粉末繞射圖…………………………………………..57
圖19. 液晶相的粉末繞射圖…………………………………………..57
圖20. 有機液晶之光學紋理圖………………………………………..58
圖21. 有機液晶(n=12)之FAB-MS質譜圖….………………………60
圖22. 化合物UV-Vis absorption光譜……………………..…………62
圖23. 有機液晶的螢光放射(PL)光譜………………….……..………63
圖24. 配位基之液晶相範圍柱狀圖………………..…………..……..67
圖25. Zn金屬錯合物其液晶相的範圍柱狀圖………………………69
圖26. 無機液晶之光學紋理圖n=1(N相，177℃)………......………70
圖27. 無機液晶之光學紋理圖n=1(SmC相，90℃)...........................70
圖28. 銅錯合物之EPR圖…………………………………………….72
圖29. 鋅錯合物之EPR圖…………………………………………….72
表 目 錄
表1. 實驗之化學藥品……....................................................................22
表2. 為系列一化合物之熱焓值數據整理............................................55
表3. 有機液晶之d-spacing值...............................................................58
表4. 有機液晶之元素分析(EA)............................................................59
表5. 為兩結晶相(DSC)之數據……....………………………....…….60
表6. 為兩結晶相之元素分析(EA)........................................................61
表7. Pd錯合物(DSC)之數據…………....…......……….……….……61
表8. 化合物之螢光量子產率整理表…………...……….……………64
表9. 為系列二之配位基熱分析(DSC)數據.........................................66
表10. 系列二Zn金屬錯合物之熱分析(DSC)數據...............................68
表11. 系列二Cu, Pd金屬錯合物之熱分析(DSC)數據.......................71
表12. 無機液晶之元素分析(EA).........................................................73
表13. 為兩銅錯合物之元素分析(EA).................................................73
附 圖 目 錄
附圖1. 3-Tetradecyloxyphenol之1H NMR圖譜...................................1
附圖2. 3-Tetradecyloxyyphenol之13C NMR圖譜................................2
附圖3. 5-Tetradecyloxyphenol-2-nitrophenols之1H NMR圖譜..........3
附圖4. 5-Tetradecyloxyphenol-2-nitrophenols之13C NMR圖譜.........4
附圖5. p-Decyloxybenzoic acids之1H NMR圖譜...............................5
附圖6. p-Decyloxybenzoic acids之13C NMR圖譜............................ 6
附圖7. 4-(p-n-Decyloxybenzoyloxy)benzaldehydes之1H NMR圖譜..7
附圖8. 4-(p-n-Decyloxybenzoyloxy)benzaldehydes之13C NMR圖譜.8
附圖9. 4-Decyloxybenzoic acid 4-(6-alkoxybenzoxazol-2-yl)phenyl esters之1H NMR圖譜...............................................................9
附圖10. 4-Decyloxybenzoic acid 4-(6-alkoxybenzoxazol-2-yl)phenyl esters之13C NMR圖譜............................................................10
附圖11. 4-Decyloxybenzoic acid 4-(6-dodecyloxybenzoxazol-2-yl) phenyl esters之DSC圖譜.........................................................11
附圖12. 4-(p-n-Decyloxybenzoyloxy)salicylaldehydes之1H NMR.......12
附圖13. 4-(p-n-Decyloxybenzoyloxy)salicylaldehydes之13C NMR......13
附圖14. 4-Decyloxybenzoic acid 4-[(4- dodecyloxy-2-hydroxy- phenylimino)methyl]-3-hydroxyphenyl esters之1H NMR圖譜..............................................................................................14
附圖15. 4-Decyloxybenzoic acid 4-[(4-dodecyloxy-2-hydroxyph enylimino)methyl]-3-hydroxyphenyl esters之13C NMR.........15
附圖16. 4-Decyloxybenzoic acid 4-(6-dodecyloxybenzoxazol-2-yl) -3-hydroxyphenyl esters之1H NMR圖譜...............................16
附圖17. 4-Decyloxybenzoic acid 4-(6-dodecyloxybenzoxazol-2-yl) -3-hydroxyphenyl esters之13C NMR圖譜..............................17
附圖18. 4-Decyloxybenzoic acid 4-(6-dodecyloxybenzoxazol-2-yl) -3-hydroxyphenyl esters之DSC圖譜.....................................18
附圖19. Bis[4-Decyloxybenzoic acid 4-(6-dodecyloxybenzoxazol-2-yl) -3-hydroxyphenyl ester]zinc(II)之DSC圖譜......................19參考文獻 參考文獻
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