臺灣博碩士論文加值系統

含偶氮色團( Azobenzene dye )之光致變性高分子，在紫外光照射下(λ~365nm)，會進行反-順( trans-cis photoisomerization )之異構化反應，並可經由照射其他波長之光源或熱行為而進行逆反應，由於其在光學應用，例如在光儲存上，有相當大的潛力，因此在近幾年來受到愈來愈多的重視。
本研究合成十種含偶氮色團與MMA之高分子共聚物，在側鏈尾端偶氮基團的對位上接上不同強度之拉電子基團( -NO2，-CN)，spacer分別為具3或11個碳原子之碳氫鍵，並分別與不同比例之MMA聚合，合成之共聚物為poly(M11NO2-co-MMA)、poly(M3CN-co-MMA) 與poly(M11CN-co-MMA)。產物則先利用NMR、FT-IR與GPC等儀器確定產物之結構，結果顯示共聚合反應確實進行，且產物的分子量在4000以上。本研究並將此十個共聚物分別進行溶液與薄膜之光致變行為測試，實驗的結果發現溶液中在較弱的拉電子基、短的spacer長度與高比例之MMA的條件下，恢復性愈慢，溶劑則以在THF恢復最慢；薄膜中則看不出三種共聚物有明顯的差異。

Optical data storage materials are mainly based on organic molecules. To be suited used as an optical data storage material, molecules has to be photochromic ; i.e., they must be capable of being reversibly switched between two spectroscopically distinct forms by use of light. The photochrome that we have chosen is a substituted azobenzene, which shows a cis-trans isomerization on either a photochemical process or a thermal process. The geometric configuration of the azo bond in azobenzene based compounds can be reversibly switched from trans to cis. The two states have distinct absorption spectra. However, this cis state is thermodynamically unstable with respect to the trans state; therefore a thermal relaxation process occurs even in the dark( at room temperature ). The thermal back-reaction strongly limits the lifetime of the cis state and it should be influenced by the substituent on the azobenzene moiety, temperature and the environment( i.e., solvent type, solvent polarity, type of polymer matrix etc. ).
In this study, azobenzene-based PMMA was synthesize by copolymerization of MMA with azobenzene moiety-tagged MA( methacrylate ). The azobenzene moiety was attached with different electron-withdrawing group( i.e., NO2, CN ),and different spacer length was built between the polymer chain and the azobenzene chromophore. Our results showed that slow back-isomerization( cis to trans )rate was observed in the solution sample when proceeded with weaker electron-withdrawing group, shorter spacer length and lower content of azobenzene-tagged MA. Whereas no significant difference was found when a film sample was used.

中文摘要……………………………………………………………..…Ⅰ
英文摘要………………………………………………………………..Ⅱ
圖目錄…………………………………………………………………Ⅲ
表目錄…………………………………………………………………Ⅳ
壹、緒論…………………………………………………………………1
1-1 前言…………………………………………………………….1
1-2 光致變系統簡介……………………………………………….2
1-2-1 光致變機能性染料簡介……………………………….2
1-2-2 光致變性材料之分類………………………………….4
1-3 機能性染料之發色原理……………………………………...10
1-4 光致變光學之基本原理……………………………………...12
1-5 液晶/染料分子之光驅動機制………………………………..17
1-6 文獻回顧……………………………………………………...18
研究目的..………………………………………………………………21
貳、實驗………………………………………………………………..22
2-1 實驗藥品……………………………………………………...22
2-2 實驗儀器……………………………………………………...23
2-3 合成步驟……………………………………………………...24
2-4 光致變性、光恢復性測試方法………………………………28
參、結果與討論………………………………………………………..30
3-1 共聚物之合成鑑定…………………………………………...30
3-2 光致變性質討論…………………………………….………..35
3-2-1 共聚物之UV吸收光譜………………………………35
3-2-2 共聚物於溶液中之光致變性分析…………………...36
3-2-3 共聚物薄膜之光致變性分析………………………...44
肆、結論………………………………………………………………..45
伍、參考文獻…………………………………………………………..92

1. 大河原信, 黑木宣彥, 北尾梯次郎,“機能性染料化學”., CMC, 昭和56年.
2. E. ter Meer, Annalen, 181, 1, 1876.
3. W. Marckwald, Z. Phys. Chem., 30, 140, 1989.
4. Y. Hirshboerg, Compt. Rend., 231, 903, 1950.
5. Y. Hirshberg,J. Amer. Chem. Soc., 78, 2304, 1956.
6. E. Fischer and Y. Hirshberg, J. Chem. Soc., 4522, 1952.
7. K. Kano, Chem. Lett., 421, 1980.
8. A. Yabe,, Thin Solid Films, 160, 33, 1988.
9. Z. F. Liu, K. Hashimoto and A. Fujishima, Nature, 347, 658, 1990.
10. H. Stobbe, Chem. Ber., 37, 2232, 1904; 38, 3673, 1905.
11. H. G. Heller, C. Chem., F.R.S.C., ”Organic Fatigue-resistant Photochromic Imaging Materials”, IEE Proceeding, Part I :Solid-State Electron Devices, 130 ( 5 ) , pp. 209-211, 1983.
12. R. E. Fox, Final Report on Contract AF41(657)-215. Apr. 1961, AD440226
13. N. Y. C. Chu, Can. J. Chem, 61, 300, 1983
14. S. Kawauchi,H. Yoshida,Bull.Chem. Soc.Jpn., 63, 267, 1990.
15.王明星,“光變色機能性色素之合成及其在高分子材料中性質之研究”, 國立清華大學化學工程研究所博士論文, 1985.
16.錢國坁，”染料化學”，上海交通大學出版社，1988.
17.李文琦, ”改質的spirooxazine光變色色素之合成及其變色性質的研究”, 國立清華大學化學工程研究所碩士論文, 1993.
18. I. Shimizu, H Kokado and E. Inoue, Bull Chem. Soc. Jpn., 42, 1730, 1969.
19. 市村國宏,”光變色性分子”,現代化學,p.28-33,1983年1月.
20. H. Ringsdorf, H. W. Schmidt, Makromol. Chem.185, 1327-1334, 1984.
21.Q. Zhang, T. Ikeda, Y. Nagase, Macromolecules, 32, 3951-3956, 1999.
22.T. Ikeda, S. Tazuke, Macromolecules. 23, 42-48, 1990.
23.O. Tsutsumi, T. Ikeda, Macromolecules, 31, 355-359, 1998.
24. H. Q. Zhang, W. Q. Huang, C. X. Li and B. L. He, Eur . Polym. J. 34, No. 34, 1521-1529, 1998.
25.Y. Imai, K. Naka, Y. Chujo, Macromolecules, 32, 1013-1017, 1999
26. A. Natansohn, P. Rochon, X. Meng, C. Barrett, Macromolecules, 31,1155-1161, 1998.
27.F. L. Labarthet, S. Freeiberg, A. Natansohn, P. Rochon, Macromolecules, 33, 6815-6823, 2000
28. S. Xie, A. Natansohn, P. Rochon, Macromolecules, 27, 1885-1890, 1994.
29. C. Barrett, A. Natansohn, P. Rochon, Macromolecules, 27, 4781-4786, 1994.
30.楊凱能,“偶氮系梳狀側鏈型液晶高分子的光變色性與介電行為研究“, 私立輔仁大學化學研究所碩士論文, 2000.
31.C. H. Ho, K. N. Yang, S. N. Lee, J. Polym. Sci., Polym. Chem., 39, 2296-2307, 2001.