臺灣博碩士論文加值系統

本篇主要合成含3, 4, 5-烷氧基苯甲酸分子為主體，分成兩系列來探討其合成與研究。系列一為引入雙酚型A環氧樹酯，如SR3、SR350和SR500，形成對稱的化合物結構，[Cn-R3OPhCOOH-SR3] ( n = 14 , 16,18 )；[Cn-R3OPhCOOH-SR350] (n = 18)；[Cn-R3OPhCOOH-SR500] (n =14, 16)，此系列均不具液晶性質，經PXRD推測，其分子排列為六方柱狀型排列。
系列二為引入三乙烯四胺 (TETA)，形成3, 4, 5-烷氧基苯甲酸之直鏈脂肪胺鹽類，[Cn-R3OPhCOO-TETA+(m:1)] (n = 12, 14, 16, m = 1, 2,3, 4, 5)，此系列均具有液晶相，並且呈現寬廣的液晶相範圍，最大溫寬約70℃，但是隨著碳數及3, 4, 5-烷氧基苯甲酸比例的增加，液晶相範圍漸減。由POM判斷液晶相時為層狀排列，進一步經PXRD分析，其分子為傾斜層狀排列，而且隨著溫度增加傾斜角度也隨之增加，證明為SmC液晶相。

Two series of thermotropic compounds with 3,4,5-tris(alkoxyl)benzyl
group as the terminal unit were prepared and their thermal and liquid
crystal properties were examined by powder X-ray diffractometer,
differential scanning calorimeter and on the hot-stage of a
cross-polarizing microscope. Compounds of series I, [Cn-R3OPhCOOHSR3](n = 14, 16, 18), [Cn-R3OPhCOOH-SR350] (n = 18) and [Cn-R3OPhCOOH-SR500] (n = 14, 16), containning bisphenol A functional group moiety as the central spacer, including SR3, SR350, and SR500, formed symmetrical molecular structures,. The compounds of this series weren’t mesogenic and exhibited hexagonal columnar packing
in solid.
The series II of aliphatic ammonium salts, [Cn-R3OPhCOO-TETA+(m:1)] (n = 12, 14, 16, m = 1, 2, 3, 4, 5), were prepared by mixed 3,4,5-tris(alkoxyl)benzoic acid with triethylenetetramine in ratio from 1:1 to 5:1. All compounds of this series exhibited smectic C liquid crystal
(LC) phase, and showed wide temperature ranges about 70°C in the ratio of 1:1 and 20°C in the ratio of 5:1.

中文摘要 ...............................................I
Abstract ............................................ II
目錄 .................................................III
表目錄 .............................................. VII
圖目錄 ............................................... IX
第一章 液晶簡介 .........................................1
1.1 前言 .............................................. 1
1.2 液晶之起源 ......................................... 2
1.3 液晶形成的條件 ...................................... 3
1.4 液晶成的種類 ........................................ 4
1.4.1 依形成方式 .........................................4
1.4.2 依分子形狀 .........................................6
1.5 棒狀液晶之種類 ...................................... 7
1.5.1 向列相液晶(nematic) ...............................7
1.5.2 層列相液晶(smectic) ...............................7
1.5.3 膽固醇相液晶(cholesteric)..........................9
1.6 盤狀液晶 .......................................... 11
1.6.1 盤狀液晶簡介 ..................................... 11
IV
1.6.2 盤狀液晶的合成條件 .................................12
1.6.3 盤狀液晶的種類及排列方式 ............................12
1.7 氫鍵液晶 ........................................... 17
1.8 離子型液晶 ......................................... 19
1.9 金屬液晶 ........................................... 19
1.10 液晶的性質 ........................................ 21
1.11 液晶相之鑑定 ...................................... 23
第二章 3, 4, 5-烷氧基苯甲酸之雙酚A 衍生物之合成與物性研究 .....27
2.1 前言 ............................................... 27
2.2 環氧樹酯簡介 ........................................ 28
2.3 研究動機 ............................................ 29
2.4 文獻回顧 ............................................ 31
2.5 索氏萃取 ............................................ 34
2.6. 實驗流程 ........................................... 35
2.7 實驗步驟 ............................................ 36
2.7.1 3, 4, 5-烷氧基苯甲酸乙酯的合成 .......................36
2.7.2 3, 4, 5-烷氧基苯甲酸的合成 ..........................36
2.7.3 3, 4, 5-烷氧基苯甲酸-雙酚A 衍生物的合成 ...............36
2.8 結果與討論 ........................................... 37
V
2.8.1 鑑定 ...............................................37
2.8.2 偏光顯微鏡&微差式掃描熱分析儀 .........................41
2.8.3 X-ray 粉末繞射 .....................................47
2.8.4 UV 及FL ...........................................49
第三章 3, 4, 5-烷氧基苯甲酸之直鏈脂肪胺鹽之合成與物性研究 ....51
3.1 研究動機 ........................................... 51
3.2 實驗流程 ........................................... 53
3.3 實驗步驟 ........................................... 54
3.3.1 3, 4, 5-烷氧基苯甲酸乙酯的合成 ......................54
3.3.2 3, 4, 5-烷氧基苯甲酸的合成 .........................54
3.3.3 3, 4, 5-烷氧基苯甲酸-TETA 超分子的合成 ..............54
3.4 結果與討論 ......................................... 55
3.4.1 鑑定 .............................................55
3.4.2 液晶相之鑑定 ......................................58
3.4.3 X-ray 粉末繞射 ....................................75
第四章 結論 .............................................97
第五章 實驗部份 ..........................................99
5.1 藥品與儀器 ......................................... 99
5.1.1 藥品(依英文字母排列) ...............................99
5.1.2 溶劑(依英文字母排列) ............................. 101
5.1.3 儀器 ............................................ 102
5.2 實驗合成方法 ....................................... 104
5.2.1 3, 4, 5-烷氧基苯甲酸乙酯的合成 .................... 104
5.2.2 3, 4, 5-烷氧基苯甲酸的合成 ............... .........107
5.2.3 3, 4, 5-烷氧基苯甲酸-雙酚A 衍生物的合成 ............. 112
5.2.4 3, 4, 5-烷氧基苯甲酸-TETA 超分子的合成 .............. 120
第六章 參考文獻 ......................................... 131

1. 松本正一、角田市良 原著, 劉瑞祥 譯, 液晶的基礎與應用, 1996,
國立編譯館。
2. P. J. Collings, M. Hird 原著, 楊怡寬、郭蘭生、鄭殷立 編譯, 液晶化學及物理入門, 2001, 偉明圖書有限公司。
3. R. W. Date, E. F. Iglesias, K. E. Rowe, J. M. Elliott , D. W. Bruce,Dalton Trans., 2003, 10, 1914.
4. I. Dierking, in Textures of liquid crystals, 2003, Wiley-VCH.
5. S. Yagai, S. Kubota, T. Iwashima, K. Kishikawa, T. Nakanishi, T.Karatsu, A. Kitamura, Chem. Eur. J., 2008, 14, 5246.
6. K. Kishikawa, S. Nakahara, Y. Nishikawa, S. Kohmoto, M. Yamamoto,J. Am. Chem. Soc., 2005, 127, 2565.
7. H. Shimura, M. Yoshio, K. Hoshino, T. Mukai, H. Ohno, T. Kato, J.Am. Chem. Soc., 2008, 130, 1759.
8. T. Kato, J. J. M. Frechet, J. Am. Chem. Soc., 1989, 11, 8533.
9. T. Kato, J. J. M. Frechet, Macromolecules, 1989, 22, 3818.
10. T. Kato, O. Ihata, S. Ujiie, M. Tokita, J. Watanabe, Macromolecules, 1998, 31, 3551.
11. S. Mohamed, D. A. Tocher, M. Vickers, P. G. Karamertzanis, S. L.Price, Crystal Growth & Design, 2009, 9, 2881.
12. (a) C. J. Bowals, D. W. Bruce, and K. R. Seddon, Chem. Commun.,1996, 1625. (b) F. Neve, Adv. Mater., 1996, 8, 277. (c) J. D. Holberey,K. R. Seddon, J. Chem. Soc. Dalton Trans., 1999, 2133.
13. M. Yoshio, T. Mukai, H. Ohno, T. Kato, J. Am. Chem. Soc., 2004, 126,994.
14. S. Yagai, S. Kubota, T. Iwashima, K. Kishikawa, T. Nakanishi, T.Karatsu, A. Kitamura, Chem. Eur. J., 2008, 14, 5246.
15. L. Shechter, J. Wynstra, Ind. Eng. Chem., 1956, 48, 86.
16. L. Shechter, J. Wynstra, Ind. Eng. Chem., 1956, 48, 94.
17. A. Kalafi-Nezhad, M. N. Soltani Rad, A.Khoshnood, Synthesis, 2003,16, 2552.
18. C. Monnereau, E. Blart, B. Illien, M. Paris, F. Odobel, J. Phys. Org.Chem., 2005, 18, 1050.
19. X. S. Huang, F. L. Qing, Journal of Fluorine Chemistry, 2008, 129,1076.
20. N. K. Abayasinghe, D. W. Smith, Macromolecules, 2003, 36, 9681.
21. Z. Cheng, B. Ren, H. Shan, X. Liu, Z. Tong, Macromolecules, 2008,41, 2656.
22. N. Canilho, M. Scholl, H. A. Klok, R. Mezzenga, Macromolecules,2007, 40, 8374.
23. H. Shimura, M. Yoshio, K. Hoshino, T. Mukai, H. Ohno, T. Kato, J.Am. Chem. Soc., 2008, 130, 1759.
24. Silverstein 原著, 賀孝雍 譯, 有機化合物之光譜鑑別法 第四版,
1986, 眾光文化事業有限公司。
25. S. I. Muahashi, N. Yoshimura, T. Tsumiyama, T. Kojima, J. Am.Chem. Soc., 1983, 105, 5002.
26. K. A. Wichmann, P. D. W. Boyd, T. Sohnel, G. R.Allen,A. R. J. Phillips, and G. J. S. Cooper, Crystal Growth & Design, 2007, 7, 1844.