以開環歧化聚合法合成具降冰片烯衍生物及間苯乙烯的聚合物之性質與鑑定

簡易檢索 / 詳目顯示

回結果列表

研究生：	蘇家儀 Chia-Yi Su
論文名稱：	以開環歧化聚合法合成具降冰片烯衍生物及間苯乙烯的聚合物之性質與鑑定 Synthesis and Characterization of the Polymers Containing Norbornene Derivatives and m-Phenylenevinylenes by Ring-Opening Metathesis Polymerization
指導教授：	游進陽 Chin-Yang Yu
口試委員:	游進陽 Chin-Yang Yu 羅承慈 Chen-Tsyr Lo 堀江正樹 Masaki Horie
學位類別：	碩士 Master
系所名稱：	工程學院 - 材料科學與工程系 Department of Materials Science and Engineering
論文出版年：	2022
畢業學年度：	110
語文別：	英文
論文頁數：	135
中文關鍵詞：	降冰片烯、間苯乙烯、開環歧化聚合、四苯乙烯、聚集誘導發光
外文關鍵詞：	norbornene, m-phenylenevinylenes, ring-opening metathesis polymerization, tetraphenylethene, aggregation-induced emission
相關次數：	點閱：274 下載：0
分享至:	分享至facebook 分享至twitter

查詢本校圖書館目錄查詢臺灣博碩士論文知識加值系統勘誤回報

本論文主要探討含有降冰片烯衍生物和間苯乙烯之共聚物的合成及性質與鑑定。以開環歧化聚合做為高分子聚合反應，且為了精準地控制聚合物之分子量、重複單元數以及降低其多分散性，選用能快速引發的第三代格拉布催化劑最為起始劑。通過紫外可見吸收光譜和光致發光光譜對共聚物進行分析，表明通過加入間苯乙烯，降冰片烯基共聚物的量子產率顯著提高，且具有四苯乙烯的降冰片烯基聚合物在固態和聚集狀態下表現出高螢光，證明它們具有聚集誘導發光特性。此外，無規共聚物比嵌段共聚物具有更高的量子產率。透過差示掃描量熱儀、熱重分析證明所有聚合物均表現出良好的熱穩定性，利用循環伏安法以及原子力顯微鏡對聚合物薄膜進行電化學性質和形貌之分析。

The aim of this thesis was to synthesize the polymers containing norbornene derivatives and m-phenylenevinylenes by ring-opening metathesis polymerization (ROMP) and their characterization. In this thesis, a fast-initiation ruthenium initiator such as the 3rd generation Grubbs' initiator was chosen to control the molecular weights and narrow polydispersities of the polymers.
By incorporating m-phenylenevinylenes, the quantum yield of norbornene-based copolymers was significantly increased to 16.7–74.5%. The polymers were analyzed by UV-Vis absorption spectroscopy and photoluminescence spectroscopy. Tetraphenylethene (TPE) or fluorinated TPE containing norbornene-based polymers exhibit high emission in the solid and aggregate states demonstrating that they have aggregation induced emission (AIE) characteristics. Additionally, random copolymers have a higher quantum yield than block copolymers. All polymers show good thermal stability with a degradation temperature (Td) of more than 450oC. The energy gaps of the polymers determined by cyclic voltammetry are between 1.77 and 2.08 eV. The morphology of the polymer thin films evaluated using AFM revealed a variety of shapes.

Abstract    II
中文摘要    III
Ackonwledgements    IV
Table of Content    V
List of Figures    IX
List of Schemes    XIII
List of Tables    XV
Chapter 1. Introduction and Aims    1
1 Conjugated polymers    1
2 Polynorbornene    3
3 Aggregation-caused quenching (ACQ)    4
4 Aggregation-induced emission (AIE)    6
4.1 Restriction of intramolecular vibrations (RIV)    8
4.2 Restriction of intramolecular rotations (RIR)    8
5 Ring-opening metathesis polymerization    9
5.1 Overview of ROMP    9
5.2 Catalysts for ROMP    11
6 Copolymers    13
6.1 Block copolymers    13
6.2 Random copolymers    14
6.3 Alternating copolymers    15
6.4 Graft copolymers    15
7 Self-assembly of block copolymers    16
7.1 Introduction to self-assembly of block copolymers    16
7.2 Polymerization-induced self-assembly (PISA)    18
7.3 In Situ nanoparticlization of conjugated polymers    19
8 Aim of Project    20
Chapter 2. Synthesis and Characterization    21
1 General procedures    21
2 Synthesis and characterizations of norbornene-based monomers    22
3 Synthesis and characterizations of dimethoxy-1(1,3),4(1,4)-dibenzenenacyclohexaphane-2,5-diene    35
4 Synthesis and characterizations of polymers    41
4.1 Synthesis of homopolymers    41
4.2 Synthesis of block copolymers    44
4.3 Synthesis of random copolymers    45
4.4 Characterizations of polymers    47
Chapter 3. Properties of Polymers    58
1 Optical properties    58
2 Thermal Properties    68
3 Electrochemical Properties    71
4 Morphology    75
Chapter 4. Conclusion    79
Chapter 5. Experimental Section    80
1 Synthesis of monomers    80
1.1 Synthesis of 5-norbornene-exo-2,3-dicarboxylic anhydride (1)    80
1.2 Synthesis of 5-norbornene-exo-2,3- dicarboximide anhydride (2)    81
1.3 Synthesis of 2-(2-(2-methoxyethoxy)ethoxy)ethyl 4-methylbenzenesulfonate (3)    81
1.4 Synthesis of (2-(p-tolyl)ethene-1,1,2-triyl)tribenzene (4)    82
1.5 Synthesis of (2-(4-(bromomethyl)phenyl)ethene-1,1,2-triyl)tribenzene (5)    83
1.6 Synthesis of 4,4',4''-(2-(p-tolyl)ethene-1,1,2-triyl)tris(fluorobenzene) (6)    84
1.7 Synthesis of 4,4',4''-(2-(4-(bromomethyl)phenyl)ethene-1,1,2-triyl)tris(fluorobenzene) (7)    85
1.8 Synthesis of N- triethylene glycol monomethyl ether-cis-5-norbornene-exo- 2,3-dicarboxylic imid (M1)    86
1.9 Synthesis of 1-(4-methylenephenyl)-1,2,2-triphenylethene substituted 5-norbornene-exo-2,3-dicarboximide anhydride (M2)    87
1.10 Synthesis of 1-(4-methylenephenyl)-1,2,2-(4-fluorophenyl) phenylethene substituted 5-norbornene-exo-2,3-dicarboximide anhydride (M3)    88
1.11 Synthesis of 1,3-phenylenedimethanethiol (8)    89
1.12 Synthesis of 1,4-bis(bromomethyl)-2,5-dimethoxybenzene (9)    90
1.13 Synthesis of Dimethoxy-3,7-dithia-1(1,3),5(1,4)-dibenzenacyclooctaphane (10)    90
1.14 Synthesis of Dimethoxy-1(1,3),4(1,4)-dibenzenacyclohexaphane compound with methyl(phenyl)sulfane (11)    91
1.15 Synthesis of (Methylsulfinyl)benzene compound with 12,15-dimethoxy-1(1,3),4(1,4)-dibenzenacyclohexaphane (12)    92
1.16 Synthesis of Dimethoxy-1(1,3),4(1,4)-dibenzenenacyclohexaphane-2,5-diene (M4)    93
2 Synthesis of Polymers    94
2.1 Synthesis of P1    94
2.2 Synthesis of P2    94
2.3 Synthesis of P3    95
2.4 Synthesis of P4    95
2.5 Synthesis of P5    96
2.6 Synthesis of P6    96
2.7 Synthesis of P7    97
2.8 Synthesis of P8    97
2.9 Synthesis of P9    98
2.10 Synthesis of P10    98
Chapter 6. References    100
Appendix    i
AI. 13C NMR Spectrum    i
AII. MS Spectrum    ix


                                

[1] N. K, C. S. Rout, Rsc Adv. 2021, 11, 5659.
[2] S. B. Mdluli, M. E. Ramoroka, S. T. Yussuf, K. D. Modibane, V. S. John-Denk, E. I. Iwuoha, Polymers 2022, 14, 716.
[3] M. M. Nahid, E. Gann, L. Thomsen, C. R. McNeill, Eur. Polym. J. 2016, 81, 532.
[4] S. Gunes, H. Neugebauer, N. S. Sariciftci, Chem. Rev. 2007, 107, 1324.
[5] O. Ostroverkhova, Chem. Rev. 2016, 116, 13279.
[6] M. V. Bermeshev, P. P. Chapala, Prog. Polym. Sci. 2018, 84, 1.
[7] S. Varlas, S. B. Lawrenson, L. A. Arkinstall, R. K. O’Reilly, J. C. Foster, Prog. Polym. Sci. 2020, 107, 101278.
[8] R. Hoffmann, R. B. Woodward, J. Am. Chem. Soc. 2002, 87, 4388.
[9] J. Sauer, Angew. Chem. Int. Ed. 1967, 6, 16.
[10] M. L. Gringolts, Y. I. Denisova, G. A. Shandryuk, L. B. Krentsel, A. D. Litmanovich, E. S. Finkelshtein, Y. V. Kudryavtsev, Rsc Adv. 2015, 5, 316.
[11] F. Blank, C. Janiak, Coord. Chem. Rev. 2009, 253, 827.
[12] J. D. Rule, J. S. Moore, Macromolecules 2002, 35, 7878.
[13] K.-H. Yoon, K. O. Kim, M. Schaefer, D. Y. Yoon, Polymer 2012, 53, 2290.
[14] Z. Zhao, C. Y. K. Chan, S. Chen, C. Deng, J. W. Y. Lam, C. K. W. Jim, Y. Hong, P. Lu, Z. Chang, X. Chen, P. Lu, H. S. Kwok, H. Qiu, B. Z. Tang, J. Mater. Chem. A 2012, 22, 4527.
[15] T. Förster, Angew. Chem. Int. Ed. 1969, 8, 333.
[16] M. H. Chua, K. W. Shah, H. Zhou, J. Xu, Molecules 2019, 24, 2711.
[17] J. Mei, Y. Hong, J. W. Y. Lam, A. Qin, Y. Tang, B. Z. Tang, Adv. Mater. 2014, 26, 5429.
[18] M. Gao, B. Z. Tang, ACS Sens. 2017, 2, 1382.
[19] Y. Hong, J. W. Lam, B. Z. Tang, Chem. Comm. 2009, 4332.
[20] Y. Dong, J. W. Y. Lam, A. Qin, J. Liu, Z. Li, B. Z. Tang, J. Sun, H. S. Kwok, Appl. Phys. Lett. 2007, 91, 011111.
[21] M. Chen, L. Li, H. Nie, J. Tong, L. Yan, B. Xu, J. Z. Sun, W. Tian, Z. Zhao, A. Qin, B. Z. Tang, Chem. Sci. 2015, 6, 1932.
[22] C.-K. Lim, S. Kim, I. C. Kwon, C.-H. Ahn, S. Y. Park, Chem. Mater. 2009, 21, 5819.
[23] J. Chen, C. C. W. Law, J. W. Y. Lam, Y. Dong, S. M. F. Lo, I. D. Williams, D. Zhu, B. Z. Tang, Chem. Mater. 2003, 15, 1535.
[24] Y. Zang, Y. Li, B. Li, H. Li, Y. Yang, Rsc Adv. 2015, 5, 38690.
[25] S. Riebe, C. Vallet, F. Van Der Vight, D. Gonzalez-Abradelo, C. Wölper, C. A. Strassert, G. Jansen, S. Knauer, J. Voskuhl, Chem. Eur. J. 2017, 23, 13660.
[26] K. Li, Y. Lin, C. Lu, Chem. Asian J. 2019, 14, 715.
[27] J. Luo, Z. Xie, J. W. Y. Lam, L. Cheng, B. Z. Tang, H. Chen, C. Qiu, H. S. Kwok, X. Zhan, Y. Liu, D. Zhu, Chem. Commun. 2001, 1740.
[28] R. Zhang, X. Huang, C. Chen, R. T. K. Kwok, J. W. Y. Lam, B. Z. Tang, Mater. Sci. Eng. R Rep. 2021, 146.
[29] T. P. M. Goumans, A. W. Ehlers, K. Lammertsma, Organometallics 2005, 24, 3200.
[30] C. W. Bielawski, R. H. Grubbs, Prog. Polym. Sci. 2007, 32, 1.
[31] J. Suriboot, H. Bazzi, D. Bergbreiter, Polymers 2016, 8, 140.
[32] H.-K. Lee, T.-L. Choi, ACS Macro Lett. 2018, 7, 531.
[33] C. W. Bielawski, R. H. Grubbs, Angew. Chem. Int. Ed. 2000, 39, 2903.
[34] A. Leitgeb, J. Wappel, C. Slugovc, Polymer 2010, 51, 2927.
[35] S. Sutthasupa, M. Shiotsuki, F. Sanda, Polym J. 2010, 42, 905.
[36] D. J. Walsh, S. H. Lau, M. G. Hyatt, D. Guironnet, J. Am. Chem. Soc. 2017, 139, 13644.
[37] P. Samaddar, A. Deep, K.-H. Kim, Chem. Eng. J. 2018, 342, 71.
[38] W. Zheng, Z.-G. Wang, Macromolecules 1995, 28, 7215.
[39] S. Wu, C. Bubeck, Macromolecules 2013, 46, 3512.
[40] W. Hu, V. B. F. Mathot, R. G. Alamo, H. Gao, X. Chen, "Crystallization of Statistical Copolymers", Springer International Publishing, 2016, p. 1.
[41] L. Li, K. Raghupathi, C. Song, P. Prasad, S. Thayumanavan, Chem. Commun. 2014, 50, 13417.
[42] J. Huang, S. R. Turner, Polymer 2017, 116, 572.
[43] K. Nishimori, M. Ouchi, Chem. Commun. 2020, 56, 3473.
[44] A. Bhattacharya, Prog. Polym. Sci. 2004, 29, 767.
[45] W. Wang, W. Wang, H. Li, X. Lu, J. Chen, N.-G. Kang, Q. Zhang, J. Mays, Ind. Eng. Chem. Res. 2015, 54, 1292.
[46] S. Creutz, J. van Stam, F. C. De Schryver, R. Jérôme, Macromolecules 1998, 31, 681.
[47] H. Shinoda, P. J. Miller, K. Matyjaszewski, Macromolecules 2001, 34, 3186.
[48] J. K. Kim, S. Y. Yang, Y. Lee, Y. Kim, Prog. Polym. Sci. 2010, 35, 1325.
[49] W.-N. He, J.-T. Xu, Prog. Polym. Sci. 2012, 37, 1350.
[50] T. N. Hoheisel, K. Hur, U. B. Wiesner, Prog. Polym. Sci. 2015, 40, 3.
[51] G. I. Peterson, S. Yang, T.-L. Choi, Polym. Chem. 2021, 12, 1393.
[52] Y. Sha, M. A. Rahman, T. Zhu, Y. Cha, C. W. McAlister, C. Tang, Chem. Sci. 2019, 10, 9782.
[53] M. J. Derry, L. A. Fielding, S. P. Armes, Prog. Polym. Sci. 2016, 52, 1.
[54] J. Wan, B. Fan, S. H. Thang, Chem. Sci. 2022, 13, 4192.
[55] S. Sahoo, Y. D. Gordievskaya, K. Bauri, A. A. Gavrilov, E. Y. Kramarenko, P. De, Macromolecules 2022, 55, 1139.
[56] S. L. Canning, G. N. Smith, S. P. Armes, Macromolecules 2016, 49, 1985.
[57] S. Shin, K.-Y. Yoon, T.-L. Choi, Macromolecules 2015, 48, 1390.
[58] I.-H. Lee, P. Amaladass, I. Choi, V. W. Bergmann, S. A. L. Weber, T.-L. Choi, Polym. Chem. 2016, 7, 1422.
[59] V. Lapinte, J.-C. Brosse, L. Fontaine, Macromol. Chem. Phys. 2004, 205, 824.
[60] M. Banerjee, S. J. Emond, S. V. Lindeman, R. Rathore, J. Org. Chem. 2007, 72, 8054.
[61] M. Ephritikhine, Chem. Commun. 1998, 2549.
[62] H. Zhang, Y. Nie, J. Miao, D. Zhang, Y. Li, G. Liu, G. Sun, X. Jiang, J. Mater. Chem. C 2019, 7, 3306.
[63] M. P. Aldred, C. Li, G.-F. Zhang, W.-L. Gong, A. D. Q. Li, Y. Dai, D. Ma, M.-Q. Zhu, J. Mater. Chem. A 2012, 22.
[64] C.-J. Liu, C.-C. Wang, D.-L. Kuo, C.-Y. Yu, Polymer 2019, 181, 121770.
[65] L. Liao, Y. Pang, L. Ding, F. E. Karasz, Macromolecules 2004, 37, 3970.
[66] C.-Y. Yu, M. L. Turner, Angew. Chem. Int. Ed. 2006, 118, 7961.

全文公開日期 2024/09/26 (校內網路)
全文公開日期本全文未授權公開 (校外網路)
全文公開日期 2120/09/26 (國家圖書館：臺灣博碩士論文系統)

簡易檢索 / 詳目顯示

相關論文