本研究中，成功合成出具有甲基醚側鏈的新型脂環族二酸酐(1R,2R,3S,4S,4aS,5S,6S,7R,8R,8aR,9S,9aR,10R,10aS)-tetramethyl-9,10-dimethoxytetradecahydro-1,4:5,8-dimethanoanthracene-2,3,6,7- tetracarboxylic dianhydride (OMeDA)。本研究也針對合成步驟中的Diels-Alder反應、酮還原反應、Williamson醚合成反應、甲氧基羰基化反應和酸性水解關環反應對於產物結構構型的影響加以討論。並且純化及分離出兩種酮還原後的產物endo-anti-endo-OH (cis化合物3和trans化合物7)，以X-ray單晶繞射佐證化合物的構型。OMeDA二酸酐與五種二胺4, 4’-oxydianiline (ODA)、2, 2’-bis(trifluoromethyl)benzidine (TFMB)、9, 9’-bis (4-aminophenyl) fluorene (FDA)、p-phenylenediamine (PPD)及2, 5(6)-bis(aminomethyl)-bicyclo[2.2.1]heptane (BBH) 以一步法所合成的聚醯亞胺測得熱重損失(T5%)溫度介於386.5 ~ 431.8 ℃。其中OMeDA-ODA、OMeDA-TFMB、OMeDA-FDA聚醯亞胺薄膜展現可撓曲特性，OMeDA-PPD、OMeDA-BBH聚醯亞胺薄膜性質則較脆。OMeDA-ODA、OMeDA-TFMB、OMeDA-FDA的熱膨脹係數(CTE)介於21.6 ~ 42.3 ppm/K；玻璃轉移溫度(Tg)介於400.8 ~ 437.8 ℃；楊氏係數介於2.0 ~ 2.7 GPa；斷裂強度介於55.1 ~ 60.0 MPa。本系列聚醯亞胺在室溫下除了OMeDA-PPD外均展現極佳的溶解度。OMeDA-ODA、OMeDA-TFMB、OMeDA-FDA薄膜的400 nm穿透度(T400)可高達80%以上，並且薄膜的色彩空間CIELAB座標的值為L*=95.04 ~ 96.28, a*=-0.35 ~ -0.93, b*=1.15~ 4.04。

In this study, we successfully synthesize a novel alicyclic dianhydride with methoxy side groups (1R, 2R, 3S, 4S, 4aS, 5S, 6S, 7R, 8R, 8aR, 9S, 9aR, 10R, 10aS)- tetramethyl-9,10-dimethoxytetradecahydro-1,4:5,8-dimethanoanthracene-2,3,6,7-tetracarboxylic dianhydride (OMeDA). The effects of Diels-Alder reaction, ketone reduction, Williamson ether synthesis, methoxycarbonylation, hydrolysis reaction on the structural configuration of the product were also discussed. Also, we purified and separated two ketone-reduced products, endo-anti-endo-OH (cis compound 3 and trans compound 7), while proofing their structures by using X-ray single crystal diffraction.
Polyimides were prepared using OMeDA with five diamines 4, 4-oxydianiline (ODA), 2, 2-bis(trifluoromethyl)benzidine (TFMB), 9, 9'-bis (4-aminophenyl) fluorene (FDA), p-phenylenediamine (PPD) and 2,5(6)-bis(aminomethyl)-bicyclo[2.2.1]heptane (BBH).
The measured thermogravimetric loss (Td5%) temperature ranged from 386.5 to 431.8 °C. Among them, OMeDA-ODA, OMeDA-TFMB, and OMeDA-FDA polyimide films exhibit flexible properties, while OMeDA-PPD and OMeDA-BBH polyimide films are brittle. The coefficient of thermal expansion (CTE) of OMeDA-ODA, OMeDA-TFMB, OMeDA-FDA ranges from 21.6 to 42.3 ppm/K; glass transition temperature (Tg) ranges from 400.8 to 437.8 °C; Young's modulus ranges from 2.0 to 2.7 GPa; tensile strength between 55.1 ~ 60.0 MPa. This series of polyimides show excellent solubility in organic solvents. The 400 nm transmittance (T400) of OMeDA-ODA, OMeDA-TFMB, OMeDA-FDA films can be as high as 80%, and the CIELAB value of the films are L*=95.04 ~ 96.28, a*=-0.35 ~ -0.93, b*=1.15~ 4.04.

1. Liaw, D.-J.; Wang, K.-L.; Huang, Y.-C.; Lee, K.-R.; Lai, J.-Y.; Ha, C.-S., Advanced polyimide materials: Syntheses, physical properties and applications. Progress in Polymer Science 2012, 37 (7), 907-974.
2. Guo, Y.-Z.; Song, H.-W.; Zhai, L.; Liu, J.-G.; Yang, S., Synthesis and characterization of novel semi-alicyclic polyimides from methyl-substituted tetralin dianhydride and aromatic diamines. Polymer Journal 2012, 44 (7), 718-723.
3. Lee, L. T. C.; Pearce, E. M.; Hirsch, S. S., Novel aliphatic polymers containing imide ring. I. Polyspiroimide based on methanetetraacetic acid. Journal of Polymer Science Part A-1: Polymer Chemistry 1971, 9 (11), 3169-3174.
4. Mathews, A. S.; Kim, I.; Ha, C.-S., Synthesis, characterization, and properties of fully aliphatic polyimides and their derivatives for microelectronics and optoelectronics applications. Macromolecular Research 2007, 15 (2), 114-128.
5. Tapaswi, P. K.; Ha, C.-S., Recent Trends on Transparent Colorless Polyimides with Balanced Thermal and Optical Properties: Design and Synthesis. Macromolecular Chemistry and Physics 2019, 220 (3), 1800313.
6. Zhuang, Y.; Seong, J. G.; Lee, Y. M., Polyimides containing aliphatic/alicyclic segments in the main chains. Progress in Polymer Science 2019, 92, 35-88.
7. Hasegawa, M., Development of Solution-Processable, Optically Transparent Polyimides with Ultra-Low Linear Coefficients of Thermal Expansion. Polymers 2017, 9 (10), 520.
8. Hasegawa, M.; Hirano, D.; Fujii, M.; Haga, M.; Takezawa, E.; Yamaguchi, S.; Ishikawa, A.; Kagayama, T., Solution-processable colorless polyimides derived from hydrogenated pyromellitic dianhydride with controlled steric structure. Journal of Polymer Science Part A: Polymer Chemistry 2013, 51 (3), 575-592.
9. Hasegawa, M.; Horie, K., Photophysics, photochemistry, and optical properties of polyimides. Progress in Polymer Science 2001, 26, 259-335.
10. Ni, H.-j.; Liu, J.-g.; Wang, Z.-h.; Yang, S.-y., A review on colorless and optically transparent polyimide films: Chemistry, process and engineering applications. Journal of Industrial and Engineering Chemistry 2015, 28, 16-27.
11. Itamura, S.; Yamada, M.; Tamura, S.; Matsumoto, T.; Kurosaki, T., Soluble polyimides with polyalicyclic structure. 1. Polyimides from bicyclo[2.2.2]oct-7-ene-2-exo,3-exo,5-exo,6-exo-tetracarboxylic 2,3:5,6-dianhydrides. Macromolecules 1993, 26 (14), 3490-3493.
12. Matsumoto, T.; Kurosaki, T., Soluble and Colorless Polyimides from Bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic 2,3:5,6-Dianhydrides. Macromolecules 1997, 30 (4), 993-1000.
13. Yamada, M.; Kusama, M.; Matsumoto, T.; Kurosaki, T., Synthesis of bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic 2,3:5,6-dianhydrides. The Journal of Organic Chemistry 1992, 57 (22), 6075-6077.
14. Kusama, M.; Matsumoto, T.; Kurosaki, T., Soluble Polyimides with Polyalicyclic Structure.3. Polyimides from (4arH,8acH)-Decahydro-1t,4t:5c,8c-dimethanonaphthalene- 2t,3t,6c,7c-tetracarboxylic 2,3:6,7-Dianhydride. Macromolecules 1994, 27 (5), 1117-1123.
15. Matsumoto, T., Nonaromatic Polyimides Derived from Cycloaliphatic Monomers. Macromolecules 1999, 32 (15), 4933-4939.
16. 木村, 亮.; 松本, 利., 無色透明な耐熱高分子―シクロペンタノンビススピロノルボルナン構造を有する脂環式ポリイミド. 高分子論文集 2011, 68 (3), 127-131.
17. Matsumoto, T.; Ishiguro, E.; Nakagawa, S.; Kimura, R., Alicyclic Polyimides Derived from Alkanone Bis-spironorbornanetetracarboxylic Dianhydrides. Journal of Photopolymer Science and Technology 2013, 26 (3), 361-365.
18. Oka.T.; Kohama, Y. N., M.; Hisano, N.; Iwamoto, K.; Hiroysu, K.; Katasura, R.; Yasuda, S., Polyimide precursor, polyimide, polyimide film, substrate, and tetracarboxylic acid dianhydride used for producing polyimide. WO2017209197A1 2017.
19. 田伏, 岩.; 谷村, 昇.; 小田, 良., 付加環化でえられる脂環テトラカルボン酸類からのポリイミドの生成. 工業化学雑誌 1964, 67 (7), 1084-1086.
20. Suzuki, H.; Abe, T.; Takaishi, K.; Narita, M.; Hamada, F., The synthesis and X-ray structure of 1,2,3,4-cyclobutane tetracarboxylic dianhydride and the preparation of a new type of polyimide showing excellent transparency and heat resistance. Journal of Polymer Science Part A: Polymer Chemistry 2000, 38 (1), 108-116.
21. Carruthers, J. C., W.; Coldham, I., Modern methods of organic synthesis. 4th ed. Cambridge University Press 2004, p189.
22. James, D. E.; Stille, J. K., The palladium(II) catalyzed olefin carbonylation reaction. Mechanisms and synthetic utility. Journal of the American Chemical Society 1976, 98 (7), 1810-1823.
23. 王建淳. 脂環族二酸酐與其聚醯亞胺之合成技術開發. 國立臺灣科技大學, 台北市, 2017.
24. Hamed, O.; El-Qisairi, A.; Henry, P. M., Palladium(II)-Catalyzed Oxidation of Aldehydes and Ketones. 1. Carbonylation of Ketones with Carbon Monoxide Catalyzed by Palladium(II) Chloride in Methanol. The Journal of Organic Chemistry 2001, 66 (1), 180-185.
25. 李祥榕. 新型含酮基脂環族二酸酐及其聚醯亞胺之合成. 國立臺灣科技大學, 台北市, 2020.
26. 陳志堅, 李祥榮, 鍾凱城, Polyimides, ketone-containing alicyclic dianhydrides and applications thereof. US17/383782 2021.
27. Thierry Granier, A. H., Jerzy A. Bajgrowicz, Bicyclo[3,3,1]nonanes and bicyclo[3,3,1]nonenes and their use as flavour or fragrance ingredient. WO2005070860A1 2005.
28. Menczel, J. D. P., R. B. , Thermal analysis of polymers: fundamentals and applications. John Wiley & Sons 2009, p322.
29. Matsumoto, T.; Ishiguro, E.; Komatsu, S., Low Temperature Film-fabrication of Hardly Soluble Alicyclic Polyimides with High Tg by A Combined Chemical and Thermal Imidization Method. Journal of Photopolymer Science and Technology 2014, 27, 167-171.
30. 徐寧霜. 脂環族二酸酐與聚醯亞胺之合成與表徵. 國立臺灣科技大學, 台北市, 2019.
31. Hasegawa, M.; Horiuchi, M.; Kumakura, K.; Koyama, J., Colorless polyimides with low coefficient of thermal expansion derived from alkyl-substituted cyclobutanetetracarboxylic dianhydrides. Polymer International 2014, 63 (3), 486-500.
32. Zhai, L.; Yang, S.; Fan, L., Preparation and characterization of highly transparent and colorless semi-aromatic polyimide films derived from alicyclic dianhydride and aromatic diamines. Polymer 2012, 53 (16), 3529-3539.
33. Hasegawa, M.; Fujii, M.; Ishii, J.; Yamaguchi, S.; Takezawa, E.; Kagayama, T.; Ishikawa, A., Colorless polyimides derived from 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride, self-orientation behavior during solution casting, and their optoelectronic applications. Polymer 2014, 55 (18), 4693-4708.
34. Dong, L.; Sun, H.-S.; Wang, J.-T.; Lee, W.-Y.; Chen, W.-C., Fluorene based donor-acceptor polymer electrets for nonvolatile organic transistor memory device applications. Journal of Polymer Science Part A: Polymer Chemistry 2015, 53 (4), 602-614.