臺灣博碩士論文加值系統

在本論文中，合成一系列含光學活性菠酯基(Borneol) 液晶性單體，其核心分子各不相同，分別為偶氮苯(azobenzene)、雙苯(biphenyl)、安息香酸酯(phenyl benzoate)和雙苯酯(biphenyl benzoate)，所合成的液晶性單體具有相同碳鏈間距(spacer)與壓克力系(acrylate)主鏈基團；再利用自由基聚合法合成側鏈型液晶高分子(SCLCP)，聚合出均聚合物與共聚合物，所合成的高分子為液晶高分子或非結晶型高分子。
所合成的化合物與高分子均使用紅外線光譜(FTIR)、質子核磁共振光譜(1HNMR)與元素分析儀(EA)來鑑定其結構，微差掃描熱卡計(DSC)及熱重量分析儀(TGA)對高分子的熱性質分析，偏光顯微鏡(POM)觀察高分子液晶相紋理，紫外光-可見光光譜儀(UV-vis)量測偶氮分子的光物理性質，X-ray繞射鑑定其高分子的微結構排列與GPC量測高分子分子量。
在起始劑5mol%條件下，所合成的高分子之重量平均分子量為6000~10000，分子量分佈在1.3~1.7，均聚合物及共聚合物5wt%熱重損失皆可達400℃以上。含有偶氮苯衍生基之側鏈液晶高分子，在溶液狀態時照射紫外光365nm，偶氮苯基團會發生光化學異構化反應，使的溶液之吸收度λmax下降；在量測動態的UV光譜變化時也發現，在溶劑中，濃度0.1mg/3ml，在10秒內即可到達飽和吸收度。
本研究中，利用偶氮苯分子照光異構化特性應用，將液晶E48、架橋性單體與四種偶氮苯分子均勻混合，製成PDLC液晶薄膜，探討作為光開關應用之可行性。結果顯示，摻混液晶及單體製成PDLC液晶薄膜，確實可藉照射適當波長的UV光，驅動偶氮苯分子發生異構化並藉由偶氮分子構型的改變，影響整體液晶的相變化溫度，其中偶氮分子以末端基團為推電子基的甲氧基團(-OCH3)效果最好。
進一步利用這些化合物，摻混於膽固醇型液晶中。系統在照光10分鐘之後，發現摻混2wt%的偶氮分子，選擇性光反射波長(λmax)會向短波長移動60~110nm，其中以末端含有高立體障礙及光學活性基團的菠酯基效果最好，同時發現，選擇性光反射波長的移動與偶氮分子異構化、偶氮分子旋光性改變和液晶環境的特性有關。

To investigate the steric effects of chiral bornyl groups on the intermolecular interaction and photoisomerization of azobenzene derivatives, a series of monomers derived from azobenzene and biphenyl having end-capped bornyl groups were synthesized. Chiral polyacrylates having bornyl end-capped side chains with four kinds of mesogenic moieties of azobenzene, biphenyl, benzoyloxy biphenyl and phenyl benzoate were prepared.
Compounds and polymers synthesized in this investigation are confirmed by using FTIR, NMR and EA. Thermal properties of polymers were estimated by DSC and TGA. The textures of monomers and polymers were analyzed by crossed polarized microscope. The structures of liquid crystalline polymers were further confirmed by X-ray diffraction analyzer. Photochemical properties of azobenzene compounds were measured by UV-vis photometer. The molecular weights of polymers were evaluated by GPC.
In the presence of 5mol% initiator, the molecular weights of obtained polymers are between 6000 and 10000. Thermal degradation of 5% weight loss of polymers and copolymers was found to be higher than 400℃. The side chain liquid crystal polymer containing azobenzene fragments can undergo photo-isomerization from trans to cis under UV light (365nm) irradiation. The λmax in UV-Vis spectra was found to decrease with UV irradiation time and level off in 10 seconds.
PDLC films were fabricated by a thermal polymerization of the mixture of azobenzene molecules, E48 liquid crystal, and various diacrylate monomers. PDLC films with azobenzene compounds reveal photosensitive Nematic-Isotropic (N-I) phase transition due to photo-convertible trans-cis structure of azobenzene compounds act as an impurity in the liquid crystal domain.
Furthermore, azobenzene derivatives were used as dopants with cholesteric liquid crystal to fabricate a liquid crystal cell. The composite LC cells reveal selective reflecting optical properties. The pitch of the cholesteric cell was verified by UV irradiation due to the photoinduced trans-cis conversion of azobenzene dopants. The optical behavior of the composite cells on UV irradiation and the effects of curing time on thermal stability of composite films were all investigated. Isomerization of azobenzene derivatives due to UV irradiation was confirmed by POM texture study and repeatable image recording.

中文摘要 ---------------------------------------- I
英文摘要 ---------------------------------------- Ⅲ
目錄 -------------------------------------------- Ⅴ
表目錄 ------------------------------------------ Ⅸ
圖目錄 ------------------------------------------ⅩI
Scheme --------------------------------------- ⅩⅤⅡ
符號表 ---------------------------------------ⅩⅤⅢ
第一章 緒論
1-1 前言 -------------------------------------- 1
1-2 偶氮分子光異構化 -------------------------- 2
1-3側鏈型液晶高分子 --------------------------- 5
1-4光學活性基團 ------------------------------- 9
1-5選擇性光反射 ------------------------------ 11
1-6研究動機 ---------------------------------- 12
1-7 參考文獻 --------------------------------- 13
第二章 原理及文獻回顧
2-1 液晶的發現 ------------------------------- 15
2-2 液晶的分類 ------------------------------- 17
2-2-1依液晶成因的分類 ---------------------- 17
2-2-2依液晶分子排列分類 --------------------- 19
2-3 液晶之電學及光學性質 --------------------- 27
2-3-1液晶之電效應 -------------------------- 28
2-3-2液晶之光學效應 ------------------------ 29
2-4液晶高分子概述 ---------------------------- 31
2-5文獻回顧 ---------------------------------- 33
2-5-1偶氮異構化的發現及機構 ---------------- 33
2-5-2偶氮異構化的應用 ---------------------- 35
2-6參考文獻 ---------------------------------- 41
第三章 實驗部分
3-1 實驗儀器與裝置 --------------------------- 43
3-2鑑定儀器 ---------------------------------- 43
3-3物性測量儀器 ------------------------------ 44
3-4 藥品 ------------------------------------- 46
3-5合成步驟與結果 ---------------------------- 47
3-5-1 小分子偶氮苯之合成 ------------------ 47
3-5-2含光學活性末端基團之偶氮苯分子之合成 - 49
3-5-3 含光學活性菠酯基單體之合成 ---------- 52
3-5-4 液晶性單體之合成 -------------------- 67
3-6均聚合物高分子和共聚合物高分子的合成------- 68
3-7 材料物性及PDLC薄膜之製作 ----------------- 68
3-7-1 玻片的清洗及空cell的製作 ------------- 69
3-7-2單體與液晶混合液之熱聚合相分離測試 ---- 69
3-8 偶氮苯分子光致變性測試方法 --------------- 69
3-9 光穿透度的測量 --------------------------- 72
3-10 聚合物之SEM量測 ------------------------- 74
第四章 偶氮苯衍生物之合成及特性研究
4-1 前言 ------------------------------------- 76
4-2小分子偶氮苯化合物的合成與鑑定 ------------ 76
4-3含光學活性菠酯基單體之合成與鑑定 ---------- 78
4-4 結論 ------------------------------------- 81
4-5 參考文獻 --------------------------------- 82
第五章 含光學活性菠酯基均聚合物之合成及研究
5-1 前言 ------------------------------------- 93
5-2 高分子之合成與鑑定 ----------------------- 93
5-3高分子熱性質分析 -------------------------- 95
5-4 偶氮光異構化 ----------------------------- 97
5-5 選擇性光反射 ----------------------------- 98
5-6 結論 ------------------------------------- 98
5-7 參考文獻 --------------------------------- 99
第六章 液晶性共聚合物之特性探討
6-1 前言 ------------------------------------ 109
6-2含菠酯基光學活性高分子 ------------------- 109
6-3含光學活性菠酯基偶氮單體成份對共聚合物物性之影響
------------------------------------------- 113
6-4含甲氧基偶氮單體對於共聚合體物性之影響 --- 117
6-5 結論 ------------------------------------ 120
6-6參考文獻 --------------------------------- 121
第七章 小分子偶氮苯化合物應用於PDLC及選擇性光反射之調變
7-1 前言 ------------------------------------ 136
7-2 PDLC光開關應用 -------------------------- 136
7-2-1 PDLC光開關應用原理 ------------------ 136
7-2-2 材料簡介 --------------------------- 137
7-2-3 PDLC配方及製作 --------------------- 138
7-2-4 PDLC薄膜光開關量測方法及定義 ------- 139
7-2-5 PDLC薄膜光開關效果討論 ------------- 140
7-3 選擇性光反射波長的調變 ----------------- 143
7-3-1 簡介-------------------------------- 143
7-3-2 材料、配方及試片製作 -------------- 143
7-3-3 結果與討論 ------------------------ 144
7-4 結論 ------------------------------------ 148
7-5 參考文獻 -------------------------------- 148
第八章 總結 ------------------------------------ 159
著作目錄-----------------------------------------161
自述

1-7 參考文獻
1.Rau, H., “Photochemistry and Photophysics”, Rabek, J. K., Ed, CRCPress, BocaRaton, 1990, 2, 119.
2. Neporent, B.S., Stolbova,O.V., Opt. Spectrosc, 1961, 10, 146.
3. Neporent, B. S., Stolbova, O. V., Opt.Spectrosc, 1963, 14, 331.
4. Makushenko, A. M., Neporent, B. S., Stolbova, O. V., Opt. Spectrosc, 1971, 31, 295.
5. Makushenko, A. M., Neporent, B. S., Stolbova,O.V., Opt.Spectrosc, 1971, 31, 397.
6. Todorov, T., Nikolova, L., Tomova, N., Appl.Opt, 1984, 23, 4309.
7. Eich, M., Wendorff, J., Makromol.Chem, 1987, 8, 467.
8. Eich, M., Wendorff, J., Reck, B., Ringsdorf, H., Makromol. Chem., 1987, 8, 59.
9. Ichimura, K., Suzuki, Y., Seki, T., Hosoki, A., Aoki, K., Langmuir, 1988, 4, 1214.
10. 松本正一、角田市良合著，劉瑞祥譯，“液晶之基礎與應用”國立編譯館出版。
11. Finkelmann, H., Naegel, D., Rinsdorf, H., Makromol. Chem, 1979, 180, 803.
12. Shibaev, V. P., Polym. Commun., 1983, 24, 364.
13. Irie, M., Chem. Rev., 2000, 100, 1683.
14. Bouteiller, L. P., Barny, L., Liq. Cryst., 1996, 21, 157.
15. Stegemeyer, H., Guest Ed., “ Liquid Crystals”, 1994, p. 116.
16. Bobrovsky, A. Y., Boiko, N. I., Shibaev, V. P., Liq. Cryst., 2001, 28, 919.
17. Bobrovsky, A. Y., Boiko, N. I., Shibaev, V. P., Liq. Cryst., 1999, 26, 1749.
18. Berkovic, G., Krongauz, V., Weiss, V., Chem. Rev., 2000, 100, 1741.
19. Hattori, H., Uryu, T., Liq. Cryst., 1999, 26, 1085.
20. Wu, Y., Demachi, Y., Tsutsumi, O., Kanazawa, A., Shiono, T., Ikeda, T., Macromolecules., 1998, 31, 349.
2-6 參考文獻
1. 松本正一、角田市良合著，劉瑞祥譯，“液晶之基礎與應用”國立編譯館出版。
2. 蔡宗岳，“含光學活性單體PSCT 液晶顯示元件之光電特性研究”國立成功大學化工研究所碩士論文，(1999)。
3. Reinitzer, F., Monatsh., Chem, 1888, 9, 421.
4. Lehmann, O. Z., Phys. Chem, 1889, 4, 462.
5. Friedel, G., Ann. Physique, 1922, 273.
6. 賴耿陽，”液晶製法與應用”，復漢出版社，民國86 年2 月再版。
7. Stegemeyer, H., Guest Ed., “ Liquid Crystals”, 1994.
8. 蔡月娥， “雙官能機單體間隙長度對PSCT 液晶顯示器光電特性效應之研究” 國立成功大學化工研究所碩士論文，(2000)。
9. 呂子琦，” 2(S)-[2(S)-甲基己氧基]丙酸之合成及含其之液晶化合物”國立高雄師範大學化學研究所碩士論文，(1999)。
10. 王素誼，”光異構性偶氮型液晶之合成及其光電特性探討”國立成功大學化工研究所碩士論文，(2002)。
11. McMillian, W. L., Phys. Rev. A., 1973, 8, 1921.
12. Meyer, R.B., “Paper presented at the 5th International Liquld Crystals Conference”, Stockholm, June, 1974.
13. Wulf, A., Phys. Rev., 1975, A-11, 365.
14. Alberty, R. A., “Physical chemistry”, Chap. 14, John Wiley & Son, N. Y., 1987.
15. Neporent, B. S., Stolbova, O. V., Opt.Spectrosc, 1963, 14, 331.
16. Makushenko, A. M., Neporent, B. S., Stolbova,O.V., Opt.Spectrosc, 1971, 31, 397.
17. Todorov, T., Nikolova, L., Tomova, N., Appl.Opt, 1984, 23, 4309.
18. Eich, M., Wendorff, J., Reck, B., Ringsdorf, H., Makromol. Chem., 1987, 8, 59.
19. Ichimura, K., Suzuki, Y., Seki, T., Hosoki, A., Aoki, K., Langmuir, 1988, 4, 1214.
20. Ichimura, K., Chem. Rev., 2000, 1847.
21. Natansohn, A., Rochon, P., Chem. Rev., 2002, 102, 4139.
22. Eich, M.,Wendorff, J., Makromol.Chem., 1987, 8, 467.
23. Tredgold, R.H., Allen, R. A., Hodges,P., Khoshdel, E., J. Phys. D:Appl.Phys., 1987, 20, 1385.
24. Wiesner, U.,Antonietti, M., Boeffel, C., Spiess, H. W., Makromol. Chem.,1990, 191, 2133.
25. Hvilsted, S., Andruzzi, F., Ramanujam, P. S., Opt. Letters, 1992, 17, 1234.
26. Natansohn, A., Rochon, P., Pezolet, M., Audet, P., Brown, D., To, S., Macromolecules, 1994, 27, 2580.
27. Natansohn, A., Rochon, P., Gosselin, J., Xie, S., Macromolecules, 1992, 25, 2268.
28. Rochon, P., Bissonnette, D., Natansohn, A., Xie, S., Appl. Opt., 1993, 32, 7277.
4-5 參考文獻
1. Morrison Boyd, “Organic Chemistry 6th”, Prentice-Hall International Edition, U.S.A., 1992.
2. 王素誼，”光異構性偶氮型液晶之合成及其光電特性探討”國立成功大學化工研究所碩士論文，(2002)。
3. 松本正一、角田市良合著，劉瑞祥譯，“液晶之基礎與應用”國立編譯館出版。
4. D. demus, J. Goodby, G. W. Gray, H. W. Spiess, V. Vill, ”Handbook of Liquid crystals”, Vol 2a, 2b, Wiley-VCH, 1998.
5. A. Y. Bobrovsky, N. I. Boiko, V. P. Shibaev, Liq. Cryst., 1999, 26, 1749.
6. C.B McARDLE, “Side chain liquid crystal polymers”, Wiley-VCH, (1989)
7. H. Stegemeyer, Guest Ed. “Liquid crystal”, Steinkopff Darmstadat, Springer New York, (1994)
8. H. Hattori, T. Uryu, Liq. Cryst., 1999, 26, 1085.
9. H. K. Lee, K. Doi, H. Harada, O. Tsutsumi, A. Kanazawa, T. Shiono, T. Ikeda, J. Phys. Chem. B, Vol. 104, 7023 (2000).
10. S. Xie, A. Natansohn, P. Rochon, Chem. Mater. Vol. 5, 403 (1993).
5-7 參考文獻
1. Bobrovsky, A. Y., Boiko, N. I., Shibaev, V. P., Liq. Cryst., 2001, 28, 919.
2. Hattori, H., Uryu, T., Liq. Cryst., 1999, 26, 1085.
3. Natansohn, A., Rochon, P., Chem. Rev., 2002, 102, 4139.
4. 王素誼，”光異構性偶氮型液晶之合成及其光電特性探討”國立成功大學化工研究所碩士論文
5. Imrie, C. T., Karasz, F. E., Attard, G. S., Macromolecules, 1994, 27, 1578-1585.
6. Shibaev, V. P., Kozlovsky, M., Beresnev, L., Blinov, L., PlateÁ, N., Polym. Bull, 1984, 12, 299-311.
7. Scherowsky, G., Schliwa, A., Springer, J., Ku¨ hnpast, K., Trapp, W., Liq. Cryst, 1989, 5, 1281-1288.
8. Bobrovsky, A. Y., Boiko, N. I., Shibaev, V. P., Polym. Sci. A., 1998, 40, 232-245.
9. Bobrovsky, A. Yu., Boiko, N. I., Shibaev, V. P., L iq. Cryst, 1999, 26, 1749-1766.
10. 湯宏東，“含環氧基鐵電性液晶體的合成及性質研究”國立成功大學化工研究所碩士論文，(1998)。
11. Wu, Y., Ikeda, T., Zhag, Q., Adv. Mater., 1999, 11, 300-308.
12. Shibaev, V. P., Kostromin, S. G., Ivanov, S. A., J. Polym. Sci. A., 1997, 39, 118-132.
13. Berg, R. H., Hvilsted, S., Ramanujam, P. S., Nature, 1996, 383, 505-513.
14. Abe, J., Hasegawa, M., Matsushima, H., Shirai, Y., Nemoto, N., Nagase, Y., Takamiya, N., Macromolecules, 1995, 28, 2938.
15. Walba, D. M., Xiao, L., Keller, P., Shao, R., Link, D., Clark, N., Pure appl. Chem., 1999, 71, 2117-2128.
6-6 參考文獻
1. Shibaev, V. P., Kozlovsky, M., Beresnev, L., Blinov, L., PlateÁ, N., Polym. Bull, 1984, 12, 299-311.
2. Shibaev, V. P., Kostromin, S. G., Ivanov, S. A., Polym. Sci. A., 1997, 39, 118-132.
3. Bobrovsky, A. Y., Boiko, N. I., Shibaev, V. P., Liq. Cryst., 2001, 28, 919.
4. Wu, Y., Mamiya, J. I., Kanazawa, A., Shiono, T., Ikeda, T., Zhang, Q., Macromolecules, 1999, 32, 8829-8835.
5. Kurihara, S., Yoneyama, D., Nonaka, T., Chem. Mater., 2001, 13, 2807-2812.
6. Kurihara, S., Sakamoto, A., Yoneyama, D., Nonaka, T., Macromolecules, 1999, 32, 6493-6498.
7. Wu, Y., Ikeda, T., Zhag, Q., Adv. Mater., 1999, 11, 300-308.
8. Hattori, H., Uryu, T., Liq. Cryst., 1999, 26, 1085.
9. Wu, Y., Demachi, Y., Tsutsumi, O., Kanazawa, A., Shiono, T., Ikeda, T., Macromolecules, 1998, 31, 349.
10. Ikeda, T., Tsutsumi O., Science, 1995, 268, 1873.
11. Natansohn, A., Rochon, P., Chem. Rev., 2002, 102, 4139.
12. 王素誼，”光異構性偶氮型液晶之合成及其光電特性探討” 國立成功大學化工研究所碩士論文。
13. Stegemeyer, H., Guest Ed., “ Liquid Crystals”, 1994, 116.
14. Ichimura, K., Suzuki, Y., Seki, T., Hosoki, A., Aoki, K., Langmuir, 1988, 4, 1214.
15. Ichimura, K., Chem. Rev., 2000, 1847.
16. 蔡福人， “含菠酯光學活性高分子之合成及其物性探討與其在光學分割上之應用研究”，國立成功大學博士論文，2000。
7-5 參考文獻
1. Ikeda, T., Sasaki, T., Ichimura, K., Nature, 1993, 361, 428.
2. Montgomery, G. P., Smith, G. W., Vaz, A. A., Shibaev, V. P., Liquid crystalline and mesomorphic polymers, Berlin: Springer, 1994, chap.5., 149.
3. Doane, J. W., In: Bahadur B, editor. Liquid crystal: applications and uses, Singapore: World Scientific, 1990, chap. 14, 361.
4. Kurihara, S., Nomiyama, S., Nonaka, T., Chem. Mater., 2001, 13, 1992-1997.
5. Lee, H. K., Doi, K., Kanazawa, A., Shiono, T., Ikeda, T., Fujisawa, T., Aizawa, M., Lee, B., Polymer, 2000, 41, 1757-1763.
6. Lee, H. K., Kanazawa, A., Shiono, T., Ikeda, T., Chem. Mater., 1998, 10, 1402-1407.
7. Lee, H. K., Kanazawa, A., Shiono, T., Ikeda, T., Fujisawa, T., Aizawa, M., Lee, B., J. Appl. Phys., 1999, 86, 5927-5934.
8. Bouteiller, L., Barny, P. L., Liq. Cryst., 1996, 21, 157-174.
9. Rajaram, C. V., Hudson, S. D., Chien, L. C., Chem. Mater., 1996, 8, 2451-2460.
10. Lee, H. K., Doi, K., Harada, H., Tsutsumi, O., Kanazawa, A., Shiono, T., Ikeda, T., J. Phys. Chem. B., 2000, 104, 7023-7028.
11. 楊博智，”含硝基偶氮苯衍生基光敏性液晶高分子之合成及特性探討”國立成功大學化工研究所碩士論文，(2003)。
12. Tsutsumi, O., Kitsunai, T., Macromolecules, 1998, 355.
13. Liang, Z., Ming, H., Zhang, Q., J. Appl. Phys., 2001, 90, 5866.
14. Wu, Y., Zhang, Q., Ikeda, T., Adv. Mater., 1999, 11, 300.
15. Ichimura, K., Chem. Rev., 2000, 1847.
16. Kürschner, K., Strohriegl, P., Liq. Cryst., 2000, 27, 1595.
17. Bouas-Laurent, H., Dürr, H., Pure Appl. Chem., 2001, 73, 639.
18. Bobrovsky, A. Y., Boiko, N. I., Shibaev, V. P., Liq. Cryst., 1999, 26,1749.
19. 松本正一、角田市良合著，劉瑞祥譯，“液晶之基礎與應用”國立編譯館出版。
20. 王素誼，”光異構性偶氮型液晶之合成及其光電特性探討”國立成功大學化工研究所碩士論文，(2002)。