導電高分子 (conjugated conductive polymers, CPs) 的相關研究是近年來最受矚目的研究領域之一，其中聚噻吩由於其具有高導電性、易合成、熱穩定性及特殊的光學性質等優點，可以有效的應用在非常多的領域中，因此被廣泛的研究。然而傳統上使用過渡金屬催化劑進行催化聚合會導致增加成本及造成金屬殘留等不利因素，故發展不含金屬的聚合方法是當今各國學者努力的方向。
以往常見的鹵素離去基在進行酸催化聚合反應時會放出酸度較強的鹵化氫，額外啟動新的聚合鏈造成高分子鏈長度縮短、PDI增大等負面影響。本篇論文首先探討於含烷氧側鏈噻吩上甲氧基化的反應機制，並成功地提升產物的產率，優化條件下產率能達80 %，接著透過將含烷氧側鏈噻吩上的鹵素離去基替換成中性的甲氧基離去基，並以本實驗室開發的質子酸 (Brønsted acid) 催化聚合法進行聚合，可以得到高平均分子量 (Mn = 8000) 並維持低PDI (< 2)。
最後將甲氧基離去基應用於EDOT單元體的酸催化聚合上，意外地得到黃褐色可溶於一般有機溶劑 (二氯甲烷、四氫呋喃) 的PEDOT寡聚物，經MALDI-TOF分析證實為PEDOT的四聚物及五聚物，並透過和其他含烷氧側鏈的噻吩單體進行共聚合來提升其溶解度。

Conjugated conductive polymers are recently one of the highly interesting research fields. Among conjugated conductive polymer, polythiophenes have numerous applications due to its high conductivity, easy processability, thermal stability and unique optical characteristics. However, it would encounter some problems for polymerization of polythiophenes with traditional transition metal catalyst, such as high cost and residue of metal impurities. Therefore, development of metal-free polymerization is now the hot research direction.
The acid-induced polymerization of 2-substituted thiophene having halide on the leaving group would release acidic hydrogen halide, which could initiate many new polymer chains continuously leading to shorter polymer length and higher PDI value. In this dissertation, firstly, we have optimized reaction condition of methoxylation on alkoxythiophenes, raising yield up to 80 %. Secondly, we studied the effect of neutral methoxy leaving group on the acid-induced polymerization of alkoxythiophenes by using Brønsted acid catalyst. Comparing to traditional halide leaving group, it can get much higher average molecular weight (Mn = 8000) and, meanwhile, maintain lower PDI value (< 2). Finally, we applied neutral methoxy leaving group to synthesize PEDOT. A brown yellow, organic solvent soluble PEODT oligomer is obtained. Furthermore, we have also conducted the copolymerization between the PEDOT oligomers and alkoxythiophenes, trying to enhance its solubility.

(1) Shirakawa, H.; Louis, E. J.; MacDiarmid, A. G.; Chiang, C. K.; Heeger, A. J. J. Chem. Soc., Chem, Commun. 1977, 578.
(2) McCullough, R. D. Adv. Mater. 1998, 10, 93.
(3) Ocampo, C.; Armelin, E.; Liesa, F.; Alemán, C.; Ramis, X.; Iribarren, J. I. Prog. Org. Coat. 2005, 53, 217.
(4) Shirakawa, H.; Ikeda, S. Polym. J. 1971, 2, 231.
(5) Sharma, P. S.; Pietrzyk-Le, A.; D’Souza, F.; Kutner, W. Anal. Bioanal. Chem. 2012, 402, 3177.
(6) Dai, L. In Intelligent Macromolecules for Smart Devices: From Materials Synthesis to Device Applications; Springer London: London, 2004, p 1.
(7) Das, T. K.; Prusty, S. Polym.-Plast. Technol. 2012, 51, 1487.
(8) Pinto, N. J.; Jr., A. T. J.; MacDiarmid, A. G.; Mueller, C. H.; Theofylaktos, N.; Robinson, D. C.; Miranda, F. A. Appl. Phys. Lett. 2003, 83, 4244.
(9) Qi, P.; Javey, A.; Rolandi, M.; Wang, Q.; Yenilmez, E.; Dai, H. J. Am. Chem. Soc. 2004, 126, 11774.
(10) Boroumand, F. A.; Fry, P. W.; Lidzey, D. G. Nano Lett. 2005, 5, 67.
(11) Grimsdale, A. C.; Leok Chan, K.; Martin, R. E.; Jokisz, P. G.; Holmes, A. B. Chem. Rev. 2009, 109, 897.
(12) Gallon, B. J.; Kojima, R. W.; Kaner, R. B.; Diaconescu, P. L. Angew. Chem. Int. Edit. 2007, 46, 7251.
(13) Xiong, S.; Wang, Q.; Xia, H. Synthetic Met. 2004, 146, 37.
(14) Houarner-Rassin, C.; Blart, E.; Buvat, P.; Odobel, F. Photoch. Photobio. Sci. 2008, 7, 789.
(15) Ghosh, A.; Lee, Y. H. ChemSusChem 2012, 5, 480.
(16) Abidian, M. R.; Ludwig, K. A.; Marzullo, T. C.; Martin, D. C.; Kipke, D. R. Adv. Mater. 2009, 21, 3764.
(17) Otero, T. F.; Cortes, M. T. Chem. Commun. 2004, 284.
(18) Yin, J.; Zhao, X.; Xia, X.; Xiang, L.; Qiao, Y. Polymer 2008, 49, 4413.
(19) Sarkar, N.; Sahoo, G.; Das, R.; Prusty, G.; Sahu, D.; Swain, S. K. Ind. Eng. Chem. Res. 2016, 55, 2921.
(20) Yamamoto, T.; Sanechika, K.; Yamamoto, A. J. Polym. Sci., Polym. Lett. Ed. 1980, 18, 9.
(21) Lin, J. W. P.; Dudek, L. P. J. Polym. Sci., Polym. Lett. Ed. 1980, 18, 2869.
(22) Osaka, I.; McCullough, R. D. Accounts Chem. Res. 2008, 41, 1202.
(23) Loewe, R. S.; Ewbank, P. C.; Liu, J.; Zhai, L.; McCullough, R. D. Macromolecules 2001, 34, 4324.
(24) Chen, T.-A.; Wu, X.; Rieke, R. D. J. Am. Chem. Soc. 1995, 117, 233.
(25) Bonillo, B.; Swager, T. M. J. Am. Chem. Soc. 2012, 134, 18916.
(26) Balasubramanian, A.; Ku, T.-C.; Shih, H.-P.; Suman, A.; Lin, H.-J.; Shih, T.-W.; Han, C.-C. Polym. Chem. 2014, 5, 5928.
(27) 郭芳伶 碩士論文 清華大學 2015.
(28) Sperotto, E.; van Klink, G. P. M.; van Koten, G.; de Vries, J. G. Dalton T. 2010, 39, 10338.
(29) Krause, N. Modern Organocopper Chemistry John Wiley&Sons, 2002.
(30) Cohen, T.; Wood, J.; Dietz, A. G. Tetrahedron Lett. 1974, 15, 3555.
(31) 夏聖捷 碩士論文 清華大學 2016.
(32) Keegstra, M. A.; Peters, T. H. A.; Brandsma, L. Tetrahedron 1992, 48, 3633.
(33) Ebert, G. W.; Rieke, R. D. J. Org. Chem. 1988, 53, 4482.
(34) Whitesides, G. M.; Sadowski, J. S.; Lilburn, J. J. Am. Chem. Soc. 1974, 96, 2829.
(35) Håkansson, M.; Lopes, C.; Jagner, S. Organometallics 1998, 17, 210.
(36) Guo, Y.; Ji, S.-Z.; Chen, C.; Liu, H.-W.; Zhao, J.-H.; Zheng, Y.-L.; Ji, Y.-F. Res. Chem. Intermediat. 2015, 41, 8651.
(37) Aalten, H. L.; van Koten, G.; Grove, D. M.; Kuilman, T.; Piekstra, O. G.; Hulshof, L. A.; Sheldon, R. A. Tetrahedron 1989, 45, 5565.
(38) Cheng, B.; Yi, H.; He, C.; Liu, C.; Lei, A. Organometallics 2015, 34, 206.
(39) Mansour, M.; Giacovazzi, R.; Ouali, A.; Taillefer, M.; Jutand, A. Chem. Commun. 2008, 6051.
(40) Franc, G.; Jutand, A. Dalton T. 2010, 39, 7873.
(41) Kirchmeyer, S.; Reuter, K. J. Mater. Chem. 2005, 15, 2077.
(42) Kumar, A.; Reynolds, J. R. Macromolecules 1996, 29, 7629.
(43) Tran-Van, F.; Garreau, S.; Louarn, G.; Froyer, G.; Chevrot, C. J. Mater. Chem. 2001, 11, 1378.
(44) Chen, S.; Lu, B.; Duan, X.; Xu, J. J. Polym. Sci. Pol. Chem. 2012, 50, 1967.