在此研究中，利用直接芳基化聚合與鈴木偶聯反應合成的噻吩衍生共軛高分子 (PTDMT與PBTDMT)經由皂化反應合成其相對應的鈉鹽高分子以拓展其應用層面，例如鋰離子電池的電極黏著劑與親水有機半導體高分子製成高分子微粒以進行光催化產氫反應。
第一章將簡述此研究的背景知識，著筆於合成方法的反應機制與產生的高分子特性。同時也會簡單介紹其應用面向的背景知識以銜接此研究。
在第二章將討論研究所採用高分子的合成步驟，並將重點放於反應機制與合成策略，同時附上該高分子產物的相關分析以證實其合成的正確性。在後半章節將附上更多該產物光學性質與物理性質的量測結果，並展示該高分子在鋰離子電池與光置產氫應用面的相關數據。
第三章最後總結實驗結論外，也提出未來實驗的構想與設計方向，使此研究更加完備。而在第四章則詳述了實驗的步驟並附上相應的分析結果。

In this work, the thiophene-based conjugated polymers named as poly[3-(2-ethylhexyl) thiophene-alt-2,5-terephthalate (PTDMT) and poly[3,3’-bis(2-ethylhexyl)-2,2’-bithiophene-alt-2,5-terephthalate] (PBTDMT) are synthesized by direct arylation and Suzuki coupling polymerization. The polymers with sodium salt group are obtained via saponification. These polymers are applied to polymer binders in lithium ion batteries (LIBs) and hydrophilic organic semiconductor as polymer dots (Pdots) for photo-catalyzed hydrogen evolution.
In chapter 1, the background of this work is introduced. The detail of synthesis method like direct arylation and Suzuki- Miyaura coupling are described, in the aspect of overview of development, mechanism and characteristic of the produced polymer. The background of the application is mentioned to explain to concept of this work.
Chapter 2 focuses on the synthesis of the conjugated polymers. Particularly, the chapter has more discussion on the reaction mechanism and the strategy of the experiment design. the characterization and analysis data related to the synthesis is displayed. The latter part exhibits the optical and physical properties of these polymers. Importantly, the polymers are applied to the battery binders and photocatalyst for hydrogen evolution; accordingly, the performance of the device and other characterization are shown and discussed.
In chapter 3, the conclusion and future work further summarize the conclusion of this work. In chapter 4, the experimental procedures are elaborated in more detailed description, and the characterization (the NMR and mass spectrum) results are shown in overall.

Chapter 1. Introduction and purpose----------3
1.1 Introduction to conjugated polymers----------3
1.1.1 Overview of conjugated polymers----------3
1.2 Synthesis methods of conjugated polymers----------6
1.2.1 Overview of synthesis methods of conjugated polymers----------6
1.2.2 Direct arylation polymerization----------9
1.2.3 Suzuki-Miyaura coupling reaction----------17
1.3 Applications of conjugated polymers----------20
1.3.1 Conjugated polymer as battery binder for Si-anode lithium ion battery----------20
1.3.2 Conjugated polymer dot as photocatalyst for hydrogen evolution----------22
1.4 Aims of this work----------29
Chapter 2. Synthesis of monomers and polymers----------30
2.1 Introduction----------30
2.2 Synthesis of polymers----------31
2.2.1 Synthesis of PTDMT via direct arylation----------31
2.2.2 Synthesis of PTTPA----------39
2.2.3 Synthesis of PBTDMT via direct arylation----------41
2.2.4 Synthesis of PBTTPA----------48
2.2.5 Synthesis of PTDMT-Linear via Suzuki coupling----------52
2.2.6 Synthesis of PTTPA-Linear----------59
2.2.7 Synthesis of POFDMT via Suzuki coupling----------62
2.2.8 Synthesis of POFTPA----------65
2.3 Characterization and optical properties of the conjugated polymers----------67
2.4 Performance of the conjugated polymers----------72
2.4.1 Conjugated polymer as battery binder in lithium ion battery----------72
2.4.2 Conjugated polymer dot as photocatalyst for hydrogen evolution----------75
Chapter 3 Conclusions and future work----------88
Chapter 4. Experimental section----------89
4.1 General methods----------89
4.2 Synthesis of monomers----------89
4.2.1 Synthesis of 3-(2-ethylhexyl)thiophene (M1)----------89
4.2.2 Synthesis of 3,3’-di(2-ethylhexyl)bithiophene (M2)----------90
4.2.3 Synthesis of dimethyl 2,5-dibromoterephthalate (M3)----------92
4.2.4 Synthesis of 3-(2-ethylhexyl)thiophene-2,5-diboronic acid bis(pinacol) ester (M4)----------92
4.3 Synthesis of polymers----------95
4.3.1 Synthesis of poly[3-(2-ethylhexyl)thiophene-alt-2,5-terephthalate (PTDMT) via direct arylation----------95
4.3.2 Synthesis of poly[3-(2-ethylhexyl)thiophene-alt-2,5-terephthalic acid sodium salt (PTTPA)----------96
4.3.3 Synthesis of poly[3,3’-bis(2-ethylhexyl)-2,2’-bithiophene-alt-2,5-terephthalate] (PBTDMT) via direct arylation----------96
4.3.4 Synthesis of poly[3,3’-bis(2-ethylhexyl)-2,2’-bithiophene-alt-2,5-terephthalic acid sodium salt] (PBTTPA)----------97
4.3.5 Synthesis of poly[3-(2-ethylhexyl)thiophene-alt-2,5-terephthalate (PTDMT-Linear) via Suzuki polymerization.----------98
4.3.6 Synthesis of poly[3-(2-ethylhexyl)thiophene-alt-2,5-terephthalic acid sodium salt (PTTPA-Linear).----------99
4.3.7 Synthesis of poly[9,9-dioctylfluorine-alt-2,5-terephthalate] (POFDMT) via Suzuki coupling----------100
4.3.8 Synthesis of poly[9,9-dioctylfluorine-alt-2,5-terephthalic acid sodium salt] (POFTPA)----------101
4.4 NMR and mass spectra----------102
References----------113

1. C.K. Chiang, C. Fincher Jr, Y.W. Park, A.J. Heeger, H. Shirakawa, E.J. Louis, S.C. Gau, and A.G. MacDiarmid, Phys. Rev. Lett., 1977, 39, 1098.
2. T. Lei, J.-Y. Wang, and J. Pei, Chem. Mater., 2013, 26, 594-603.
3. H. Zhou, L. Yang, and W. You, Macromolecules, 2012, 45, 607-632.
4. A. Facchetti, Mater. Today, 2013, 16, 123-132.
5. G. Barbarella, M. Melucci, and G. Sotgiu, Adv. Mater., 2005, 17, 1581-1593.
6. S.I. Gorelsky, D. Lapointe, and K. Fagnou, J. Am. Chem. Soc., 2008, 130, 10848-10849.
7. A.R. Hajipour, K. Karami, and A. Pirisedigh, Inorganica Chim. Acta, 2011, 370, 531-535.
8. S.I. Gorelsky, Coord. Chem. Rev., 2013, 257, 153-164.
9. Y. Boutadla, D.L. Davies, S.A. Macgregor, and A.I. Poblador-Bahamonde, Dalton Trans., 2009, 5820-5831.
10. J. Oxgaard, W.J. Tenn, R.J. Nielsen, R.A. Periana, and W.A. Goddard, Organometallics, 2007, 26, 1565-1567.
11. J.A. Ashenhurst, Chem. Soc. Rev., 2010, 39, 540-548.
12. A.E. Rudenko and B.C. Thompson, J. Polym. Sci. A, 2015, 53, 135-147.
13. D. Alberico, M.E. Scott, and M. Lautens, Chem. Rev., 2007, 107, 174-238.
14. S. Winstein and T. Traylor, J. Am. Chem. Soc., 1955, 77, 3747-3752.
15. D. Lapointe and K. Fagnou, Chem. Lett., 2010, 39, 1118-1126.
16. H. Bohra and M. Wang, J. Mater. Chem. A, 2017, 5, 11550-11571.
17. J.-R. Pouliot, F. Grenier, J.T. Blaskovits, S. Beaupré, and M. Leclerc, Chem. Rev., 2016, 116, 14225-14274.
18. K. Okamoto, J.B. Housekeeper, F.E. Michael, and C.K. Luscombe, Polym. Chem., 2013, 4, 3499-3506.
19. C. Hawker, R. Lee, and J. Fréchet, J. Am. Chem. Soc., 1991, 113, 4583-4588.
20. A. Suzuki, ChemComm, 2005, 4759-4763.
21. A. Suzuki, J. Organomet. Chem., 2002, 653, 83-90.
22. I. Hussain, J. Capricho, and M.A. Yawer, Adv. Synth. Catal., 2016, 358, 3320-3349.
23. B.H. Lipshutz, T.B. Petersen, and A.R. Abela, Org. Lett., 2008, 10, 1333-1336.
24. C. Len, S. Bruniaux, F. Delbecq, and V. Parmar, Catalysts, 2017, 7, 146.
25. P.K. Nayak, L. Yang, W. Brehm, and P. Adelhelm, Angew. Chem. Int. Ed., 2018, 57, 102-120.
26. M. Li, J. Lu, Z. Chen, and K. Amine, Adv. Mater., 2018, 30, 1800561.
27. G.E. Blomgren, J. Electrochem. Soc., 2017, 164, A5019-A5025.
28. Z. Liu, Q. Yu, Y. Zhao, R. He, M. Xu, S. Feng, S. Li, L. Zhou, and L. Mai, Chem. Soc. Rev., 2019, 48, 285-309.
29. Z.-L. Xu, Y. Gang, M.A. Garakani, S. Abouali, J.-Q. Huang, and J.-K. Kim, J. Mater. Chem. A, 2016, 4, 6098-6106.
30. S.-L. Chou, Y. Pan, J.-Z. Wang, H.-K. Liu, and S.-X. Dou, Phys. Chem. Chem. Phys., 2014, 16, 20347-20359.
31. G. Liu, S. Xun, N. Vukmirovic, X. Song, P. Olalde‐Velasco, H. Zheng, V.S. Battaglia, L. Wang, and W. Yang, Adv. Mater., 2011, 23, 4679-4683.
32. J. Zhao, X. Yang, Y. Yao, Y. Gao, Y. Sui, B. Zou, H. Ehrenberg, G. Chen, and F. Du, Adv. Sci., 2018, 5, 1700768.
33. A. Züttel, A. Remhof, A. Borgschulte, and O. Friedrichs, Philos. Trans. Royal Soc. A, 2010, 368, 3329-3342.
34. G. Marbán and T. Valdés-Solís, Int. J. Hydrog. Energy, 2007, 32, 1625-1637.
35. L. Barelli, G. Bidini, F. Gallorini, and S. Servili, Energy (Oxf.), 2008, 33, 554-570.
36. S. Hammes-Schiffer, Acc. Chem. Res., 2009, 42, 1881-1889.
37. X. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin, J.M. Carlsson, K. Domen, and M. Antonietti, Nat. Mater., 2009, 8, 76.
38. L. Wang, R. Fernández‐Terán, L. Zhang, D.L. Fernandes, L. Tian, H. Chen, and H. Tian, Angew. Chem. Int. Ed., 2016, 55, 12306-12310.
39. C. Wu and D.T. Chiu, Angew. Chem. Int. Ed., 2013, 52, 3086-3109.
40. D. Chen, I.-C. Wu, Z. Liu, Y. Tang, H. Chen, J. Yu, C. Wu, and D.T. Chiu, Chem. Sci., 2017, 8, 3390-3398.
41. T. Kietzke, D. Neher, K. Landfester, R. Montenegro, R. Güntner, and U. Scherf, Nat. Mater., 2003, 2, 408.
42. C. Wu, C. Szymanski, and J. McNeill, Langmuir, 2006, 22, 2956-2960.
43. R.C. Evans, J. Mater. Chem. C, 2013, 1, 4190-4200.
44. J. Chen, D. Wang, A. Turshatov, R. Muñoz-Espí, U. Ziener, K. Koynov, and K. Landfester, Polym. Chem., 2013, 4, 773-781.
45. J. Kuwabara, K. Yamazaki, T. Yamagata, W. Tsuchida, and T. Kanbara, Polym. Chem., 2015, 6, 891-895.
46. A.E. Rudenko and B.C. Thompson, Macromolecules, 2015, 48, 569-575.
47. K. Masui, H. Ikegami, and A. Mori, J. Am. Chem. Soc., 2004, 126, 5074-5075.
48. Q. Liao, Y. Wang, M.A. Uddin, J. Chen, H. Guo, S. Shi, Y. Wang, H.Y. Woo, and X. Guo, ACS Macro Lett., 2018, 7, 519-524.
49. S. Vegiraju, B.C. Chang, P. Priyanka, D.Y. Huang, K.Y. Wu, L.H. Li, W.C. Chang, Y.Y. Lai, S.H. Hong, and B.C. Yu, Adv. Mater., 2017, 29, 1702414.
50. M.A. Oberli and S.L. Buchwald, Org. Lett., 2012, 14, 4606-4609.
51. M. Liu, Y. Chen, C. Zhang, C. Li, W. Li, and Z. Bo, Polym. Chem., 2013, 4, 895-899.
52. A. Dhanabalan, J. Van Dongen, J. Van Duren, H. Janssen, P. Van Hal, and R. Janssen, Macromolecules, 2001, 34, 2495-2501.
53. K.H. Hendriks, W. Li, G.l.H. Heintges, G.W. van Pruissen, M.M. Wienk, and R.A. Janssen, J. Am. Chem. Soc., 2014, 136, 11128-11133.
54. B. Liu, W.-L. Yu, Y.-H. Lai, and W. Huang, Chem. Mater., 2001, 13, 1984-1991.
55. F. Lombeck, F. Marx, K. Strassel, S. Kunz, C. Lienert, H. Komber, R. Friend, and M. Sommer, Polym. Chem., 2017, 8, 4738-4745.
56. H.-Y. Liu, P.-J. Wu, S.-Y. Kuo, C.-P. Chen, E.-H. Chang, C.-Y. Wu, and Y.-H. Chan, J. Am. Chem. Soc., 2015, 137, 10420-10429.
57. P.B. Pati, G. Damas, L. Tian, D.L. Fernandes, L. Zhang, I.B. Pehlivan, T. Edvinsson, C.M. Araujo, and H. Tian, Energy Environ. Sci., 2017, 10, 1372-1376.