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| DC 欄位 | 值 | 語言 |
|---|---|---|
| dc.contributor.advisor | 趙基楊(Chi-Yang Chao) | |
| dc.contributor.author | Po-Hsun Wu | en |
| dc.contributor.author | 吳柏勳 | zh_TW |
| dc.date.accessioned | 2021-06-17T07:03:57Z | - |
| dc.date.available | 2020-01-01 | |
| dc.date.copyright | 2019-08-05 | |
| dc.date.issued | 2019 | |
| dc.date.submitted | 2019-07-29 | |
| dc.identifier.citation | [1.] Daoust, G.; Leclerc, M., 'Structure Property Relationships in Alkoxy-Substituted Polythiophenes.' Macromolecules 1991, 24 (2), 455-459.
[2.] Sheina, E. E.; Khersonsky, S. M.; Jones, E. G.; McCullough, R. D., 'Highly conductive, regioregular alkoxy-functionalized polythiophenes: A new class of stable, low band gap materials.' Chemistry of Materials 2005, 17 (13), 3317-3319. [3.] Yang, Y. L.; Lee, Y. H.; Lee, Y. P.; Chiang, C. J.; Shen, C.; Wu, C. C.; Ohta, Y.; Yokozawa, T.; Dai, C. A., 'Synthesis and characterization of poly(3-hexylthiophene)-poly(3-hexyloxythiophene) random copolymers with tunable band gap via Grignard metathesis polymerization.' Polym Int 2014, 63 (12), 2068-2075. [4.] Huo, L.; Zhou, Y.; Li, Y., 'Alkylthio-substituted polythiophene: absorption and photovoltaic properties.' Macromol Rapid Commun 2009, 30 (11), 925-31. [5.] Wu, X. M.; Chen, T. A.; Rieke, R. D., 'Synthesis of Regioregular Head-to-Tail Poly[3-(Alkylthio)Thiophenes] - a Highly Electroconductive Polymer.' Macromolecules 1995, 28 (6), 2101-2102. [6.] Wu, X.; Chen, T.-A.; Rieke, R. D., 'A Study of Small Band Gap Polymers: Head-to-Tail Regioregular Poly[3-(alkylthio)thiophenes] Prepared by Regioselective Synthesis Using Active Zinc.' Macromolecules 1996, 29 (24), 7671-7677. [7.] Vandeleene, S.; Van den Bergh, K.; Verbiest, T.; Koeckelberghs, G., 'Influence of the polymerization methodology on the regioregularity and chiroptical properties of poly(alkylthiothiophene)s.' Macromolecules 2008, 41 (14), 5123-5131. [8.] Kozycz, L. M.; Gao, D.; Hollinger, J.; Seferos, D. S., 'Donor-Donor Block Copolymers for Ternary Organic Solar Cells.' Macromolecules 2012, 45 (14), 5823-5832. [9.] Maior, R. M. S.; Hinkelmann, K.; Eckert, H.; Wudl, F., 'Synthesis and Characterization of 2 Regiochemically Defined Poly(Dialkylbithiophenes) - a Comparative-Study.' Macromolecules 1990, 23 (5), 1268-1279. [10.] Barbarella, G.; Zambianchi, M.; DiToro, R.; Colonna, M.; Iarossi, D.; Goldoni, F.; Bongini, A., 'Regioselective oligomerization of 3-(alkylsulfanyl)thiophenes with ferric chloride.' J Org Chem 1996, 61 (23), 8285-8292. [11.] Xu, J. M.; Chan, H. S. O.; Ng, S. C.; Chung, T. S., 'Polymers synthesized from (3-alkylthio)thiophenes by the FeCl3 oxidation method.' Synthetic Met 2002, 132 (1), 63-69. [12.] Chung, N. Poly(3-hexylthiothiophene) : precise synthesis, microstructure, and electron-optical properties. National Taiwan University, College of Engineering, 2017. [13.] Di Maria, F.; Olivelli, P.; Gazzano, M.; Zanelli, A.; Biasiucci, M.; Gigli, G.; Gentili, D.; D'Angelo, P.; Cavallini, M.; Barbarella, G., 'A successful chemical strategy to induce oligothiophene self-assembly into fibers with tunable shape and function.' J Am Chem Soc 2011, 133 (22), 8654-61. [14.] Di Maria, F.; Gazzano, M.; Zanelli, A.; Gigli, G.; Loiudice, A.; Rizzo, A.; Biasiucci, M.; Salatelli, E.; D’ Angelo, P.; Barbarella, G., 'Synthesis and Photovoltaic Properties of Regioregular Head-to-Head Substituted Thiophene Hexadecamers.' Macromolecules 2012, 45 (20), 8284-8291. [15.] Ruiz, J. P.; Gieselman, M. B.; Nayak, K.; Marynick, D. S.; Reynolds, J. R., 'The Effect of Structural Modification on the Physical and Electronic-Properties of Polythiophenes.' Synthetic Met 1989, 28 (1-2), C481-C486. [16.] Ruiz, J. P.; Nayak, K.; Marynick, D. S.; Reynolds, J. R., 'Soluble Ethylmercapto-Substituted Polythiophenes.' Macromolecules 1989, 22 (3), 1231-1238. [17.] Sorensen, A. R.; Overgaard, L.; Johannsen, I., 'Reactivity of 2,5-Dithienyl-Pyrroles and Thiophenes.' Synthetic Met 1993, 55 (2-3), 1626-1631. [18.] Mccullough, R. D.; Tristramnagle, S.; Williams, S. P.; Lowe, R. D.; Jayaraman, M., 'Synthesis and Physical-Properties of Self-Orienting Head-to-Tail Poly(3-Alkylthiophenes) - New Insights on Structure-Property Relationships in Conducting Polymers.' Abstr Pap Am Chem S 1993, 206, 271-Orgn. [19.] Boucher, D. S.; Barrett, H. P.; Kennedy, W. J., 'Spectroscopic characterization of P3HT/SWNT composites synthesized using in situ GRIM methods: Improved polymer ordering via nanoscaffolding.' Abstr Pap Am Chem S 2014, 247. [20.] Presto, D.; Song, V.; Boucher, D., 'P3HT/graphene composites synthesized using In situ GRIM methods.' J Polym Sci Pol Phys 2017, 55 (1), 60-76. [21.] Goldoni, F.; Iarossi, D.; Mucci, A.; Schenetti, L.; Zambianchi, M., 'Synthesis and characterization of poly[3-(butylthio)thiophene]: A regioregular head-to-tail polymer.' J Mater Chem 1997, 7 (4), 593-596. [22.] Peeters, H.; Couturon, P.; Vandeleene, S.; Moerman, D.; Leclere, P.; Lazzaroni, R.; De Cat, I.; De Feyter, S.; Koeckelberghs, G., 'Influence of the regioregularity on the chiral supramolecular organization of poly(3-alkylsulfanylthiophene)s.' Rsc Advances 2013, 3 (10), 3342-3351. [23.] Roncali, J., 'Conjugated Poly(Thiophenes) - Synthesis, Functionalization, and Applications.' Chem Rev 1992, 92 (4), 711-738. [24.] Mccullough, R. D.; Lowe, R. D.; Jayaraman, M.; Anderson, D. L., 'Design, Synthesis, and Control of Conducting Polymer Architectures - Structurally Homogeneous Poly(3-Alkylthiophenes).' J Org Chem 1993, 58 (4), 904-912. [25.] Kozycz, L. M.; Gao, D.; Seferos, D. S., 'Compositional Influence on the Regioregularity and Device Parameters of a Conjugated Statistical Copolymer.' Macromolecules 2013, 46 (3), 613-621. [26.] Loewe, R. S.; Ewbank, P. C.; Liu, J. S.; Zhai, L.; McCullough, R. D., 'Regioregular, head-to-tail coupled poly(3-alkylthiophenes) made easy by the GRIM method: Investigation of the reaction and the origin of regioselectivity.' Macromolecules 2001, 34 (13), 4324-4333. [27.] Pal, B.; Yen, W. C.; Yang, J. S.; Su, W. F., 'Substituent effect on the optoelectronic properties of alternating fluorene-thiophene copolymers.' Macromolecules 2007, 40 (23), 8189-8194. [28.] Lanzi, M.; Di-Nicola, F. P.; Livi, M.; Paganin, L.; Cappelli, F.; Pierini, F., 'Synthesis and characterization of conjugated polymers for the obtainment of conductive patterns through laser tracing.' J Mater Sci 2013, 48 (11), 3877-3893. [29.] Di Maria, F.; Biasiucci, M.; Di Nicola, F. P.; Fabiano, E.; Zanelli, A.; Gazzano, M.; Salatelli, E.; Lanzi, M.; Della Sala, F.; Gigli, G.; Barbarella, G., 'Nanoscale Characterization and Unexpected Photovoltaic Behavior of Low Band Gap Sulfur-Overrich-Thiophene/Benzothiadiazole Decamers and Polymers.' J Phys Chem C 2015, 119 (49), 27200-27211. [30.] Chen, S. A.; Tsai, C. C., 'Structure Properties of Conjugated Conductive Polymers .2. 3-Ether-Substituted Polythiophenes and Poly(4-Methylthiophene)S.' Macromolecules 1993, 26 (9), 2234-2239. [31.] Kong, R.; Xiao, Z.; Xie, F. Y.; Jiang, J. X.; Ding, L. M., 'A D-A copolymer donor containing an alkylthio-substituted thieno[3,2-b]thiophene unit.' New J Chem 2017, 41 (8), 2895-2898. [32.] Jiang, B. Y.; Vegiraju, S.; Chiang, A. S. T.; Chen, M. C.; Liu, C. L., 'Low-voltage-driven organic phototransistors based on a solution-processed organic semiconductor channel and high k hybrid gate dielectric.' J Mater Chem C 2017, 5 (38), 9838-9842. [33.] Li, H.; Dailey, J.; Kale, T.; Besar, K.; Koehler, K.; Katz, H. E., 'Sensitive and Selective NO2 Sensing Based on Alkyl- and Alkylthio-Thiophene Polymer Conductance and Conductance Ratio Changes from Differential Chemical Doping.' Acs Appl Mater Inter 2017, 9 (24), 20501-20507. [34.] Wang, J.-j. The Synthesis and Characterization of 3-Tetradecanylsulfanylthiophene Based Soluble Thieno[3,2-b]thiophene (DSTTT) Derivatives as Organic Thin Film Transistor (OTFT) Application. National Central University, 2013. [35.] Yokoyama, A.; Miyakoshi, R.; Yokozawa, T., 'Chain-growth polymerization for poly(3-hexylthiophene) with a defined molecular weight and a low polydispersity.' Macromolecules 2004, 37 (4), 1169-1171. [36.] Willot, P.; Koeckelberghs, G., 'Evidence for Catalyst Association in the Catalyst Transfer Polymerization of Thieno[3,2-b]thiophene.' Macromolecules 2014, 47 (24), 8548-8555. | |
| dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/72700 | - |
| dc.description.abstract | Poly-(3-alkylthiothiophene)s (P3ATTs) 為3號位置有一硫烷側鍊之噻吩共軛高分子。因其在硫烷基之硫原子相較於廣被研究的P3AT之烷基集團(CH2)有較小的凡德瓦半徑，P3ATTs將提共更好的主鍊共平面性以提高有效的共軛長度與分子間堆疊而進一步地提高載子遷移率。另外，硫烷基的π-拉電子特性將會降低其最高占據分子軌域（HOMO）和最低未占分子軌域（LUMO）能帶以提高其電化學穩定性與降低其能帶隙。
近期我們團隊研製出一新單體與對應之GRIM聚合反應以合成高立體規則性之poly(3-hexylthiothiophene) (P3HTT)。我們將此新方法學視為一擬活聚合法以提供較好的分子量控制。但其仍有許多問題尚未被解釋，包含其未被確定的聚合反應機制以及含有3-butylthiothiophene (3BTT)單體而導致的低純度P3HTT聚合物。在本篇論文中我們導入修正後的3HTT合成方法學以致出高純度之3HTT單體以利後續的高立體規則性P3HTT聚合反應機制探討。另外，我們也製備出高純度之3BTT與3-(2-ethylhexylthio)thiophene (32EHTT)以供其不同烷基測鍊對其相對應知P3ATT聚合物之物理性質探討。 | zh_TW |
| dc.description.abstract | Poly-(3-alkylthiothiophene)s (P3ATTs) are conjugated polymers possessing alkylthio side chain at 3-position of the polythiophene backbone. Because of the smaller VDW diameter of sulfur in the alkylthio side chain in comparison with the methylene group (CH2) of the alkyl side chain of the well-studied P3ATs, P3ATTs generally exhibit better backbone coplanarity, leading to elongated effective conjugation length and well-organized interchain packing to improve charge carrier mobility. Additionally, the π-electron withdrawing character of sulfur would lower both HOMO and LUMO levels to promote the electrochemical stability and to decrease the electronic band gap.
Recently, our research group developed a new monomer and the corresponding GRIM polymerization procedure to synthesize highly regioregular poly(3-hexylthiothiophene) (P3HTT). The new methodology was expected to be pseudo-living so that good molecular weight control could be achieved. However, several issues are still wait to be solved, including the unclear and testified polymerization mechanism, as well as the existence of 3-butylthiothiophene (3BTT) monomer resulting in impure P3HTTs. In this work, we adopted a modified methodology to synthesize pure 3HTT monomers, enabling the studies in the polymerization mechanism and high purity and high regioregularity of P3HTTs. 3BTT and 3-(2-ethylhexylthio)thiophene (32EHTT) are also prepared in high purity to investigate the effect of side group on the physical properties of the resulting P3ATTs. | en |
| dc.description.provenance | Made available in DSpace on 2021-06-17T07:03:57Z (GMT). No. of bitstreams: 1 ntu-108-R04527041-1.pdf: 4800320 bytes, checksum: 6b5908898a48fc505d2b4bdb7588a3e3 (MD5) Previous issue date: 2019 | en |
| dc.description.tableofcontents | 口試委員會審定書 I
致謝 II 中文摘要 IV Abstract V Table of Contents VI Figures Index IX Table Index XIII Chapter 1. Introduction 1 1.1 Background 1 1.2 Motivation and Research Scope 4 Chapter 2. Literature Review 7 2.1 Synthesis of P3ATTs 7 2.1.1 Electrochemical Polymerization 8 2.1.2 Rieke’s Active Zinc Coupling 9 2.1.3 FeCl3 Oxidative Coupling 11 2.1.4 Modified McCullough Method 13 2.1.5 Grignard metathesis (GRIM) method 15 2.2 Synthesis of 3ATTs 17 2.2.1 Usage of Alkyl disulfides 17 2.2.2 Usage of 3-methoxythiophene 18 2.2.3 Applying the sulfur element 19 2.3 Physical properties of P3ATTs 21 2.3.1 Optical and electrical properties of P3ATTs 22 2.3.2 Thermal analysis and Crystalline behaviors of P3ATTs 29 Chapter 3. Experimental Method 33 3.1 Materials 33 3.2 Experimental instruments 36 3.3 Synthetic Routes 37 3.3.1 Synthesis of 3-mercaptothiophene (2s) 38 3.3.2 Synthesis of 3-alkylthiothiophene (2a) 39 3.3.3 Synthesis of 3-butylthiothiophene (2a) 40 3.3.4 Synthesis of 2-bromo-alkylthiothiophene (3) 41 3.3.5 Synthesis of 2-bromo-5-iodo-alkylthiothiophene (4) 42 3.3.6 Polymerization of P3ATTs 43 Chapter 4. Results and Discussions 45 4.1 Synthesis strategies 45 4.2 Monomer synthesis and Characterization 48 4.2.1 Synthesis of 3-butylthiothiophene (3BTT) 48 4.2.2 Synthesis of 3-alkylthiothiophenes: 3HTT and 32EHTT 50 4.2.3 Synthesis of 2-bromo-3-alkylthiothiophenes 57 4.2.4 Synthesis of 2-bromo-5-iodo-3-alkylthiothiophenes 61 4.3 Polymer synthesis: GRIM polymerization 65 4.3.1 Characterization of regioregularities in P3HTTs 68 4.3.2 Optical properties of P3HTTs 70 4.3.3 Crystalline behaviors of P3HTTs 73 Chapter 5. Conclusions 76 Appendix 77 References 83 | |
| dc.language.iso | en | |
| dc.subject | 共軛高分子 | zh_TW |
| dc.subject | 聚3-烷基?吩 | zh_TW |
| dc.subject | 聚3-硫烷基?吩 | zh_TW |
| dc.subject | GRIM 聚合法 | zh_TW |
| dc.subject | 立體規則性 | zh_TW |
| dc.subject | Poly(3-alkylthiophenes) | en |
| dc.subject | Poly(3-alkythiothiophenes) | en |
| dc.subject | GRIM Polymerization | en |
| dc.subject | Regioregularity | en |
| dc.subject | Conjugated polymer | en |
| dc.title | 含硫烷側鏈之３－烷基噻吩：單體與其聚合物合成與研究 | zh_TW |
| dc.title | 3-alkylthiothiophene : From Monomers to Polymers | en |
| dc.type | Thesis | |
| dc.date.schoolyear | 107-2 | |
| dc.description.degree | 碩士 | |
| dc.contributor.oralexamcommittee | 陳錦地,陳銘洲,戴子安 | |
| dc.subject.keyword | 共軛高分子,聚3-烷基?吩,聚3-硫烷基?吩,GRIM 聚合法,立體規則性, | zh_TW |
| dc.subject.keyword | Conjugated polymer,Poly(3-alkylthiophenes),Poly(3-alkythiothiophenes),GRIM Polymerization,Regioregularity, | en |
| dc.relation.page | 87 | |
| dc.identifier.doi | 10.6342/NTU201901360 | |
| dc.rights.note | 有償授權 | |
| dc.date.accepted | 2019-07-30 | |
| dc.contributor.author-college | 工學院 | zh_TW |
| dc.contributor.author-dept | 材料科學與工程學研究所 | zh_TW |
| 顯示於系所單位： | 材料科學與工程學系 | |
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