含咵唑-喹咢啉液晶基團之玻璃性柱狀型液晶化合物和1,4-二氮苯及9,10-二氮蒽為核心之盤狀液晶化合物之合成與性質研究

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研究生：	葉俊杉 Chun-Shan Yeh
論文名稱：	含咵唑-喹咢啉液晶基團之玻璃性柱狀型液晶化合物和1,4-二氮苯及9,10-二氮蒽為核心之盤狀液晶化合物之合成與性質研究 Synthesis and Characterization of Glass forming Columnar Liquid Crystals containing Oxadiazole and Biquinoxaline Moietes and Phenzine-,Quino xaline- Derived discatic Liquid Crystals
指導教授：	廖本瑞 Ben-Ruey Liaw
口試委員:	張美濙 Mei-Ying Chang 許應舉 Y.G. Hsu
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2005
畢業學年度：	93
語文別：	中文
論文頁數：	134
中文關鍵詞：	盤狀液晶
外文關鍵詞：	discotic liquid crystals
相關次數：	點閱：305 下載：0
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上一筆

第一系列化合物2,3,2',3'-四{4-[5(3,4,5-三烷氧苯基)-1,3,4-咵唑-2-基]苯基}-6,6'-喹咢啉DBN-3Cn 2,3,2',3'-四{4-[5-(3,4-二烷氧苯基)-1,3,4-咵唑-2-基]苯基}-6,6'-喹咢啉DBN2Cn 2,3,2',3'-四{4-[5(,4-烷氧苯基)-1,3,4-咵唑-2-基]苯基}-6,6'-喹咢啉 DBN1C8 由和1,2-二{4-[5-(3,4,5-三烷氧苯基)-1,3,4-咵唑-2-基]苯基}乙烷-1,2-二酮(1) 1,2-二{4-[5-(3,4-二烷氧苯基)-1,3,4-咵唑-2-基]苯基}乙烷-1,2-二酮(2) 1,2-二{4-[5-(4-烷氧苯基)-1,3,4-咵唑-2-基]苯基}乙烷-1,2-二酮(3)nj縮合反應而成，並在末端位置接上不同長度之烷氧柔軟基(n=3, 5, 6, 8, 10)．這些化合物的分子結構皆經由1H NMR, 13C NMR, FT-IR, AA 及MALD/TOF光譜儀鑑定，並利用DSC, POM 及X-ray繞射鑑定其相變化及液晶相．發現DBN-3C3和DBN-2C3沒有液晶相，而其他DBN-3Cn 和DBN-2Cn (n=4, 5, 6, 8,10)為六角柱狀排列(Col h )．DBN-1C8也沒有液晶相的產生．在DSC第一次冷卻時可發現，DBN-2Cn系列的液晶均向轉移溫度(Ti)的範圍為183~227℃，玻璃轉移溫度(Tg)的範圍為138~154℃．DBN-3Cn系列的液晶均向轉移溫度(Ti)的範圍為151~218℃，玻璃轉移溫度(Tg)的範圍為103~153℃．
第二系列及第三系列中，以兩個不同核心1,4-氮萘及9,10-二氮蒽為主體，2,3-二[3,4-二烷氧苯基]-6,7-[3,4-二烷氧苯基] 1,4-氮萘, 2BN-Cn (n = 4, 6, 7, 8, 9, 10)和2,3,5-四[3,4-二烷氧苯基] 9,10-二氮蒽, N-Cn(n = 5, 6, 8, 9, 10, 11), 側鏈基團為柔軟烷氧基．利用DSC, POM 及X-ray繞射鑑定其相變化及液晶相．利用波長為λ = 1.3332 Å做X-ray繞射實驗，由此波長算出2BN-C10在100℃柱狀矩型晶格的參數為a = 58.10 Å及 b = 30.09 Å，另一方面，N-C5在80℃時，發現在低角度有一根很尖銳的峰。由X-ray照相中，在低角度範圍可發現二個環，比例為1：√3在六角結晶面分別為(100)和(110)，其晶格參數為a ＝ 41.4 Å。

Compounds 2,3,2',3'-Tetrtakis{4-[5-(3,4,5-tris(alkyloxy)phenyl)-1,3,4
oxadiazol-2-yl]phenyl}-6,6'-biquinoxaline DBN-3Cn ,2,3,2',3'-Tetrtakis
{4-[5-(3,4-bis(alkyloxy)phenyl)-1,3,4-oxadiazol-2-yl]phenyl}-6,6'-biquinoxaline DBN-2Cn , Tetrtakis{4-[5-(4-mono(alkyloxy)phenyl)-1,3,4-oxad
iazol-2-yl]phenyl}-6,6'-biquinoxaline DBN-1C8 are readily synthesized form biphenyl-3,4,3',4'-tetraamine and 1,2-Bis{4-[5-(3,4,5-tris(alkyloxy)
phenyl)-[1,3,4]oxadazol-2-yl]phenyl}ethane-1,2-dione(1),1,2-Bis{4-[5-(3,4,-di(alkyloxy)phenyl)-[1,3,4]oxadazol-2-yl]phenyl}ethane-1,2-dione(2), 1,2-Bis{4-[5-(octyloxyphenyl)-[1,3,4]oxadazol-2-yl]phenyl}ethane-1,2-dione(3), derivatives of diffenent length tails(n=3, 5, 6, 8 and 10),as shown in Scheme Ⅰ.the identities of theses homologs were verified by 1H and 13C NMR spectroscopy, FT-IR spectroscopy, andelemental analysis or M
ALD/TOF mass spectroscopy. The mesogenic behavior of homologs DB
N-3Cn ,DBN-2Cn and DBN-1C8was investigated by a combination of DSC, POM, and variable temperature X-ray-diffraction. The two shor
test homologs DBN-3C3 and DBN2C3 do not exhbit any mesogenic behaviour, whereas compoumds DBN-3Cn and DBN-2Cn wuth flexibe side length (n=4, 5, 6, 8, and10) showed welldefined hexagonal colum
mar mesophases(Col h ). In contrast to the corresponding double- and triple-chain derivatives (DBN-3Cn and DBN-2Cn) the single-chain DBN-1C8 (n=8) is not mesomrphic. The Col h phase of DBN-2Cn exhi
bited isotropic temperature (120~200℃) and glass transition temperature (130~200℃), whereas DBN-3Cn exhibited isotropic temperature (120~
200℃) and glass transition temperature (130~200℃) as determined by DSC on first cooling.

Moreover, two novel homologous series of novel disotic liquid crystals based on the heterocyclic cores of quinoxalin and phenazine- 2,3,6,7-
Tetrakis-(3,4-bis- butyloxy -phenyl)-quinoxaline, 2BN-Cn (n=4, 6, 7, 8, 9, 10) and 2,3,5-tetrakis[3,4-di(alkyloxy)phenyl]phenazines, N-Cn (n=5, 6, 8, 9, 10, 11), where n is the carbon number of peripheral alkyl sidechain
, had been synthesized (SchemeⅣ and SchemeⅤ). Mesomorphic behave
iours were chacterized by DSC, POM and X-ray difftaction. The x-ray diffraction pattern of syncroton radiation (=13332Å) by 2BN-C10(n=10) at 100℃ has reflections that indexed to a rectangular lattice with parameter a=58.10 Å and b=30.09Å, resulting from a disrottion of the lattic. On the other hand, for N-C8(n=8), the diffractogram at 80℃ is dominated by a single sharp peak at low angle, diagonosticod colummar assemblies. The low-angle region of the pattern contained a set of two rings in a reciprocalspacing ratio 1:√3. these maximum are indexed, respectively as the(10) and (11) reflections from the two-dimensinal hexagonal lattice and a lattic constant a=A.

目  錄

中文摘要
英文摘要
誌謝
目錄

List of Scheme
List of Figure
List of Table

第一章   緒論
     1.1  前言……………………………………………………… 1
1.2  液晶簡介……………………………………………….... 2
1.3  液晶分類………………………………………………… 3
1.4  盤狀液晶分子集合狀態及結構………………………… 8
1.5  液晶化合物的化學構成及性質……………  ………… 10
1.6  液晶相之鑑定….…………………………………………13
1.7  研究的動機……………………………………………….16

第二章    實驗
      2.1  藥品………………………………………………………20
      2.2  合成方法…………………………………………………26

第三章    研究結果
      3.1  液晶分子之合成與鑑定……………………..…… ..64
      3.2  液晶相之鑑定與其物性之探討……………….70
      3.3  X-ray之探討…………………………………………….72
      3.4  光學性質之探討………………………………………. .73

第四章    討論……………………………………………………...109

第五章    總結………………………………………………………115

參考資料………………………………………………………………116
List of Scheme

Scheme Ⅰ    The synthesis of DBN3C-n…………………………21
Scheme Ⅱ    The synthesis of DBN2C-n…………………………22
Scheme Ⅲ    The synthesis of DBN1C-n…………………………23
Scheme Ⅳ    The synthesis of 2NB-Cn…………………………...24
Scheme Ⅴ    The synthesis of N-Cn………………………………25

List of Figure

Fig.1-1    Schematic representation of Nematic…….…………….4
Fig.1-2    Schematicrepresentationof Cholesteric………………...5
Fig.1-3    Schmatic representation of Smectic………………..…..5
Fig.1-4    Schematic representation of smectic mesophases……...7
Fig.1-5    ubclassification of discotic liquid crystalls according to molecular agregation…………………..…………….8
Fig.1-6    Characterization of discotic liquid crystals……………. 9
Fig.1-7    Characterization of discotic liquid crystals……………. 9
Fig.1-8    Characterization discotic liquid crystalls……. ……..… .11
Fig.1-9    Characterization discotic liquid crystalls……. ……..… .12
Fig.1-10   Characterization discotic liquid crystalls……. ……..… .19
Fig.3.1-1  MS ofompound1,2-Bis{4-[5-(3,4,5-tris(pentyloxy)
phenyl)-[1,3,4]oxadazol-2-yl]phenyl}ethane
-1,2-dion.......………………………………………….....44
Fig.3.1-2  IRspectrumofcompound1,2-Bis{4-[5-(3,4,5-tris(pentyloxy)
phenyl)-[1,3,4]oxadazol-2-yl]phenyl}ethane-1,2-dione…..45
Fig.3.1-3  MS of compound2,3,2',3'-Tetrtakis{4-[5-(3,4,5-tris(pentyloxy)
phenyl)-1,3,4-oxadiazol- 2-yl]phenyl}-6,6'-biquinoxaline...46
Fig.3.1-4   1H MNR of compound2,3,2',3'-Tetrtakis{4-[5-(3,4,5-tris
(pentyloxy)phenyl)-1,3,4-oxadiazol-2-yl]phenyl}-6,6'
-biquinoxaline……………………………………………47
Fig.3.1-5   13C MNR of compound2,3,2',3'-Tetrtakis{4-[5-(3,4,5-tris
(pentyloxy)phenyl)-1,3,4-oxadiazol-2-yl]phenyl}-6,6'-
biquinoxaline……………………………………………48
Fig.3.1-6  IR of compound2,3,2',3'-Tetrtakis{4-[5-(3,4,5-tris
(pentyloxy)phenyl)-1,3,4-oxadiazol- 2-yl]phenyl}-6,6'-
biquinoxaline……………………………………………..49
Fig.3.1-7  MS of compound 1,2-bis{4-[5-3,4-bis(pentyloxy)phenyl ]
-[1,3,4]oxadazol-2-yl}phenyl}ethane-1,2-dione…………50
Fig.3.1-8  IR of compound  1,2-bis{4-[5-3,4-bis(pentyloxy)phenyl ]
-[1,3,4]oxadazol-2-yl}phenyl}ethane-1,2-dione…………51
Fig.3.1-9  IR of compound 3,4-di(pentyloxy) phenylboronic acid
…………………………………………………………..52
Fig.3.1-10  IR of compound4',5'-Dinitro-3,4,3'',4''-tetrakis-octyloxy-
[ 1,1';2',1'']terphenyl………………………..…………..53
Fig.3.1-11  MS of compound 2,3,6,7-Tetrakis-(3,4-bis- butyloxy -phenyl)-quinoxaline……………………………………54
Fig.3.1-12   1H NMR of compound 2,3,6,7-Tetrakis-(3,4-bis- butyloxy -phenyl)-quinoxaline……………………………………55
Fig.3.1-13   13C NMR of compound 2,3,6,7-Tetrakis-(3,4-bis- butyloxy -phenyl)-quinoxaline……………………………………..56
Fig.3.1-14  IR of compound 2,3,6,7-Tetrakis-(3,4-bis- butyloxy -phenyl)-quinoxaline…………………………………..57
Fig.3.1-15  IR of compound 2,3,5,6-Tetrakis-(3,4-dimethoxy
-phenyl)-pyrazine………………………………………..58
Fig.3.1-16  IR of compound 2,3,5,6-Tetrakis-(3,4-dimethoxy
-phenyl)-pyrazine…………………………………………59
Fig.3.1-17  MS of compound 2,3,5,6-Tetrakis-(3,4-bis-pentyloxy
-phenyl)-pyrazine……………………………………... ..60
Fig.3.1-18   1H NMR of compound2,3,5,6-Tetrakis-(3,4-bis-pentyl
oxy-phenyl)-pyrazine…………………………………...61
Fig.3.1-19  13C NMR of compound 2,3,5,6-Tetrakis-(3,4-bis-Penty
loxy-phenyl)-pyrazine…………………………………..62
Fig.3.2-1   DSC thermograms for DBN3C4………………………….76
Fig.3.2-2   DSC thermograms for DBN3C5…………………………..76
Fig.3.2-3   DSC thermograms for DBN3C6…………………………..77
Fig.3.2-4   DSC thermograms forDBN3C10……..…………………...77
Fig.3.2-5   Polarized optical micrograph of DBN3Cn，cooled from the isotropicphase……………………………………..…….78
Fig.3.2-6   DSC thermograms for DBN2C4…………………………..80
Fig.3.2-7   DSC thermograms forDBN2C5…………………………80
Fig.3.2-8   DSC thermograms for DBN2C6…...................................81
Fig.3.2-9   DSC thermograms for DBN2C8…………………………81
Fig.3.2-10  DSC thermograms for DBN2C10………………………..82
Fig.3.2-11  Polarized optical micrograph of DBN2Cn，cooled from the isotropic phase………………………………………….83
Fig 3.2-12  DSC thermograms for 2NB-C6…………………………..85
Fig 3.2-13  DSC thermograms for 2NB-C7…………………………..85
Fig 3.2-14  DSC thermograms for 2NB-C8…………………………...86
Fig 3.2-15  DSC thermograms for 2NB-C9…………………………...86
Fig.3.2-16  Polarized optical micrograph of 2NB-Cn，cooled from the isotropic phase……………………………………………..87
Fig 3.2-17  DSC thermograms for N-C5………………………………89
Fig 3.2-18  DSC thermograms for N-C6………………………………89
Fig 3.2-19  DSC thermograms for N-C8………………………………90
Fig 3.2-20  DSC thermograms for N-C9………………………………90
Fig 3.2-21  DSC thermograms for N-C10……………………………..91
Fig 3.2-22  DSC thermograms for N-C11……………………………..91
Fig.3.2-16  Polarized optical micrograph of N-Cn，cooled from the isotropic phase……………………………………………..92

Fig.3.3-1   X-ray diffraction pattern of DBN3C5 at 150℃…………..94
Fig.3.3-2   X-ray diffraction pattern of DBN3C5 at 100℃………..…94
Fig.3.3-3   X-ray diffraction pattern of 2NB-10C at 100℃…………..95
Fig.3.3-4   X-ray diffraction pattern of 2NB-10C at 80℃….……..….95
Fig.3.3-5   X-ray diffraction pattern of 2NB-7C at 100℃……………96
Fig 3.3-6   X-ray diffraction pattern of 2NB-4C at 100℃……………96
Fig 3.3-7   X-ray diffraction pattern of N8C at 30℃…………………97
Fig 3.3-8   X-ray diffraction pattern of N8C at 80℃…………………97
Fig.3.4-1   Absorption and photoluminescent spectra of DBN3C4…..99
Fig.3.4-2   Absorption and photoluminescent spectra of DBN3C10...100
Fig.3.4-3   Absorption and photoluminescent spectra of DBN2C4….101
Fig.3.4-4   Absorption and photoluminescent spectra of DBN2C10...102
Fig.3.4-5   Absorption and photoluminescent spectra of 2NB-4C…..103
Fig 3.4-6   Absorption and photoluminescent spectra of 2NB-10C....104
Fig 3.4-7   Absorption and photoluminescent spectra of N-C5……...105
Fig 3.4-8   Absorption and photoluminescent spectra of N-C8……..106
Fig.4-1    Dependence of the transition temperture(Ti,Tg) on n, the number of carbons on alkoxy group of for the series of discotic liquid crystalline DBN3Cn(n=4,5,6,8,10) ………111
Fig.4-2    Dependence of the transition temperture(Ti,Tg) on n, the
number of carbonson alkoxy group of for the series of
discotic liquid crystallineBDN2Cn(n=4,5,6,8,10) …….…112
Fig.4-3    Dependence of the transition temperture(Ti,Tm,Tc) on n,
the number of carbons on alkoxy group of for the series of discotic liquid crystalline 2NB-Cn (n=4,6,7,8,9,10) …….113
Fig.4-4    Dependence of the transition temperture(Ti,ΔH) on n, the
number of carbons on alkoxy group of for the series of discotic liquid crystallineNCn(n=5,6,8,9,10,11)……..…...114

List of Table

Table 3.2-1  Thermal transitions and thermodynamic parameters of DBN3C-n……………………………………………...75
Table 3.2-2  Thermal transitions and thermodynamic parameters of
              DBN2C-n………………………………………………79
Table 3.2-3  Thermal transitions and thermodynamic parameters of
            2BN-Cn………………………………………………...84
Table 3.2-4  Thermal transitions and thermodynamic parameters of
            N-Cn……………………………………………………88
Table 3.3-1  The X-ray by 2BN-Cn has reflection that indexed to
arectangular lattice with a and b(λ=1.3332&Aring;)…………...93
Table 3.4-1  Photoluminescent and absorption of DBN3Cn…………..98
Table 3.4-2  Photoluminescent and absorption of DBN2Cn…………..98
Table 3.4-3  Photoluminescent and absorption of 2NB-nC…………..103
Table 3.4-4  Photoluminescent and absorption of 2NB-nC…………..106

                                

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