以開環歧化聚合降冰片烯、四苯乙烯及其衍生物聚合物的合成與表徵

簡易檢索 / 詳目顯示

回結果列表

研究生：	陳冠宇 Kuan-Yu Chen
論文名稱：	以開環歧化聚合降冰片烯、四苯乙烯及其衍生物聚合物的合成與表徵 Synthesis and Characterization of the Polymers Containing Norbornene, Tetraphenylethene, and Tetraphenylethene Derivatives by Ring-Opening Metathesis Polymerization
指導教授：	游進陽 Chin-Yang Yu
口試委員:	施劭儒 Shao-Ju Shih 王丞浩 Cheng-Hao Wang
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：	2023
畢業學年度：	111
語文別：	英文
論文頁數：	120
中文關鍵詞：	降冰片烯、四苯乙烯、硝化四苯乙烯、開環易位聚合、聚集誘導發光
外文關鍵詞：	norbornene, tetraphenylethene, nitrated tetraphenylethene, ring-opening metathesis polymerization, aggregation-induced emission
相關次數：	點閱：373 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

上一筆

本研究重點關注降冰片烯基聚合物的合成和表徵，包括均聚物、二嵌段共聚物和無規共聚物。對含有四苯乙烯或硝化四苯乙烯的降冰片烯進行開環複分解聚合。通過利用三代催化劑並仔細選擇單體，可以有效控制所得聚合物的平均分子量。此外，這種可控聚合過程可以生產具有窄多分散指數的聚合物。由於在降冰片烯上添加了聚集誘導發光之分子，降冰片烯基團連接的四苯乙烯或硝化四苯乙烯聚合物可以在固態和聚集態下表現出強發射，通過紫外-可見吸收光譜和光致發光光譜進行了研究。高分子在聚集狀態下的量子產率也高於在溶液中的量子產率。所有聚合物都表現出優異的熱穩定性，其降解溫度超過 325 ℃ 就證明了這一點。在電化學性能測試中，由於四苯乙烯連續取代基的影響，聚合物的能帶隙變小。形態分析證實了聚合物中球形結構的形成。值得注意的是，這些聚合物對聚集狀態的苯胺表現出優異的靈敏度，檢測限高5×10-6 M。

This study focuses on the synthesis and characterization of norbornene-based polymers including homopolymers and copolymers. The norbornene bases polymers containing tetraphenylethene or nitrated tetraphenylethene carry out ring-opening metathesis polymerization. By utilizing third generation Grubbs’ catalysts and carefully selecting monomers, it is possible to achieve effective control over the average molecular weight of the resulting polymers. In addition, this controlled polymerization process allows for the production of polymers with a narrow polydispersity index. Due to the addition of aggregation-induced emission molecules on norbornene, norbornene group-linked tetraphenylethene or nitrated tetraphenylethene polymers, can exhibit strong emission in solid and aggregated states which was investigated by UV-vis absorption spectroscopy and photoluminescence spectroscopy. The quantum yield of polymers in aggregated state are higher than in solution. All polymers demonstrate excellent thermal stability, as evidenced by their degradation temperatures over 325 ºC. The energy band gap of the polymer becomes smaller due to the influence of the continuous substituents of TPE. The morphological analysis confirms the formation of spherical structures in the polymers. Notably, the polymers demonstrate excellent sensitivity towards aniline in their aggregated state with a remarkable detection limit of 5×10-6 M.

Table of Content
謝誌    IV
Abstract    V
中文摘要    VI
Table of Content    VII
Chapter 1. Introduction and Aims    1
1 Ring-opening metathesis polymerization (ROMP)    1
1.1 Introduction of ROMP    1
1.2 Catalysts of ROMP    3
2 Introduction to polynorbornene    6
3 Copolymer    7
3.1 Block copolymers    8
3.2 Random copolymers    10
3.3 Alternating copolymers    10
3.4 Graft copolymers    11
4 Self-assembly of block copolymers    11
4.1 Introduction to self-assembly of block copolymers    11
4.2 Polymerization-induced self-assembly (PISA)    15
4.3 In situ nanoparticlization of conjugated polymers (INCP)    16
5 Aggregation-caused quenching (ACQ)    17
6 Aggregation-induced emission (AIE)    21
7 Restriction of intramolecular motions (RIM)    25
8 Aim of project    28
Chapter 2. Synthesis and Characterization    29
1 General procedures    29
1.1 Material    29
1.2 Instrumentation    29
2 Synthesis and characterization of monomers    30
2.1 Synthesis of monomers    30
2.2 Characterization of Monomers    33
3 Synthesis and characterization of polymers    37
3.1 Synthesis of polymers    37
3.2 Characterization of polymers    42
Chapter 3. Properties of Polymers    50
1 Optical properties    50
2 Thermal properties    56
3 Electrochemical properties    59
4 Morphology    63
5 Detection of aniline    69
5.1 Aniline detection in solution    69
5.2 Aniline detection in solid state    74
Chapter 4. Conclusion    77
Chapter 5. Experimental Section    79
1 Synthesis of monomers    79
1.1 Synthesis of 5-norbornene-exo-2,3-dicarboxylic anhydride (1)    79
1.2 Synthesis of 5-norbornene-exo-2,3-dicarboximide anhydride (2)    80
1.3 Synthesis of (2-(p-tolyl)ethene-1,1,2-triyl)tribenzene (4)    81
1.4 Synthesis of (2-(4-(bromomethyl)phenyl)ethene-1,1,2-triyl)tribenzene (5)    82
1.5 Synthesis of 4,4’,4’’-(2-(4-bromomethyl)phenyl)ethene-1,1,2-triyl)tris(nitrobezene) (6)    83
1.6 Synthesis of 1-(4-methylenephenyl)-1,2,2-(4-bromomethyl)phenylethene substituted 5-norbornene-exo-2,3-dicarboximide anhydride (M1)    84
1.7 Synthesis of 1-(4-methylenephenyl)-1,2,2-(4-nitrophenyl) phenylethene substituted 5-norbornene-exo-2,3-dicarboximide anhydride (M2)    85
1.8 Synthesis of 3rd generation Grubbs catalyst (G3)    86
2 Synthesis of polymers    86
2.1 Synthesis of P1    86
2.2 Synthesis of P2    87
2.3 Synthesis of P3    88
2.4 Synthesis of P4    88
2.5 Synthesis of P5    89
2.6 Synthesis of P6    90
References    92
Appendix    i
AI. 1H NMR spectra    i
AII. 13C NMR spectra    v
AIII. MS spectrum    xi


                                

[1] S. B. Lawrenson, S. Varlas, L. A. Arkinstall, R. K. O’Reilly, and J. C. Foster, Prog. Polym. Sci. 2020, 107, 101278.
[2] A. R. Hlil, J. Balogh, S. Moncho, H. L. Su, R. Tuba, E. N. Brothers, M. Al-Hashimi, and H. S. Bazzi, J. Polym. Sci. 2017, 55, 3137.
[3] I. Choinopoulos, Polymer, 2019, 11, 298.
[4] W. C. P. Tsang, K. C. Hultzsch, J. B. Alexander, P. J. Bonitatebus, R. R. Schrock, and A. H. Hoveyda, J. Am. Chem. Soc. 2003, 125, 2652.
[5] G. C. Bazan, J. H. Oskam, H. N. Cho, L. Y. Park, and R. R. Schrock, J. Am. Chem. Soc. 1991, 113, 6899.
[6] R. R. Schrock, G. C. Bazan, H. N. Cho, and V. C. Gibson, Macromolecules, 1991, 24, 4495.
[7] R. H. Grubbs, and S. T. Nguyen, J. Am. Chem. Soc. 1993, 115, 9858.
[8] R. H. Grubbs, and C. W. Bielawski, Angew. Chem. Int. Ed. 2000, 39, 2903.
[9] S. Demel, S. Riegler, K. Wewerka, W. Schoefberger, C. Slugovc, and F. Stelzer, Inorganica Chim. Acta, 2003, 345, 363.
[10] V. C. Gibson, D. A. Robson, R. G. Davies, and M. North, Macromolecules, 1999, 32, 6371.
[11] J. C. Lee, A. Song, K. A. Parker, and N. S. Sampson, J. Am. Chem. Soc. 2010, 132, 10513.
[12] D. J. Walsh, S. H. Lau, M. G. Hyatt, and D. Guironnet, J. Am. Chem. Soc. 2017, 139, 13644.
[13] J. D. Rule, and J. S. Moore, Macromolecules, 2002, 35, 7878.
[14] E. S. Finkelshtein, and M. V. Bermeshev, Journal of Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 2018, 1, 39.
[15] M. Carratu, R. Troiano, S. Pragliola, A. C. Boccia, and F. Grisi, Eur. Polym. J. 2022, 167, 111065.
[16] A. Demonceau, L. Delaude, and A. F. Noels, Macromolecules, 1999, 32, 2091.
[17] J. D. Rule, and J. S. Moore, Macromolecules, 2002, 35, 7878.
[18] N. Hanania, N. Eghbarieh, A. Zamir, M. Nassir, T. Stein, and A. Masarwa, J. Am. Chem. Soc. 2021, 143, 6211.
[19] A. Deep. P. Samaddar, and K. H. Kim, Chem. Eng. J. 2018, 342, 71.
[20] M. Khimani, H. Patel, V. Patel, P. Parekh, and R. L. Vekariya, Original Paper, 2020, 77, 5783.
[21] Z. G. Wang, and W. Zheng, Macromolecules, 1995, 28, 7215.
[22] C. Bubeck, and S. Wu, Macromolecules, 2013, 46, 3512.
[23] M. Ouchi, and K. Nishimori, Chem. Commun. 2020, 56, 3473.
[24] W. Hu, V. B. F. Mathot, R. G. Alamo, H. Gao, and X. Chen, , Adv. Polym. Sci. 2016, 276, 1.
[25] P. J. Miller, H. Shinoda, and K. Matyjaszewski, Macromolecules, 2001, 34, 3186.
[26] A. Bhattacharya, Prog. Polym. Sci. 2004, 29, 767.
[27] W. Wang, W. Wang, H. Li, X. Lu, J. Chen, N. G. Kang, Q. Zhang, and J. Mays, Ind. Eng. Chem. Res. 2015, 54, 1292.
[28] F. S. Bates, and M. W. Masten, Macromolecules, 1996, 29, 1091.
[29] S. Y. Yang, J. K. Kim, Y. Lee, and Y. Kim, Prog. Polym. Sci. 35, 1325.
[30] R. Nistico, Beilstein J. Nanotechnol. 2018, 9, 2332.
[31] S. Y. Yang, J. K. Kim, Y. Lee, and Y. Kim, Prog. Polym. Sci. 2010, 35, 1325.
[32] F. S. Bates, Science, 1991, 251, 898.
[33] Y. Mai, and A. Eisenberg, Chem. Soc. Rev. 2012, 41, 5969.
[34] F. S. Bates, and G. H. Fredrickson, Phys. Today, 1999, 52, 32.
[35] C. I. Huang, and T. P. Lodge, Macromolecules, 1998, 31, 3556.
[36] M. W. Matsen, and M. Schick, Phys. Rev. Lett. 1994, 72, 2660.
[37] L. Wu, Q. Wang, J. Wang, and L. Wang, Prog. Polym. Sci. 2017, 29, 435.
[38] G. W. Wang, and B. Y. Shi, Acta Polym. Sin. 2022, 53, 15.
[39] G. N. Smith, S. L. Canning, and S. P. Armes, Macromolecules, 2016, 49, 1985.
[40] S. Yang, E. H. Kang, S. Y. Yu, J. Kim, and T. L. Choi, J. Polym. Sci., Part A: Polym Chem. 2017, 55, 2851.
[41] I. H. Lee, K. Y. Yoon, K. O. Kim, J. Jang, E. Lee, and T. L. Choi, J. Am. Chem. Soc. 2012, 134, 14291.
[42] S. Shin, K. Y. Yoon, Y. J. Kim, I. Kim, E. Lee, and T. L. Choi, Macromol. Rapid Commun. 2015, 36, 1069.
[43] C. Qin, Y. Li, Q. Li, C. Yan, and L. Cao, Chin. Chem. Lett. 2021, 32, 3531.
[44] Z. Zhao, S. Chen, J. W. Y. Lam, Z. Wang, P. Lu, F. Mahtab, H. H. Y. Sung, I. D. Williams, Y. Ma, H. S. Kwok, and B. Z. Tang, J. Mater. Chem. 2011, 21, 7210.
[45] 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, and B. Z. Tang, J. Mater. Chem. A. 2012, 22, 4527.
[46] J. W. Y. Lam, B. Z. Tang, and Y. Hong, Chem. Soc. Rev. 2011, 40, 5361.
[47] Z. Xie, J. Luo, J. W. Y. Lam, L. Cheng, H. Chen, C. Qiu, X. Zhan, H. S. Kwok, Y. Liu, D. Zhu, and B. Z. Tang, Chem. Commun. 2001, 1740.
[48] Y. Hong, J. Mei, J. W. Y. Lam, A. Qin, Y. Tang, and B. Z. Tang, Adv. Mater. 2014, 26, 5429.
[49] Y. Hong, J. Mei, J. W. Y. Lam, A. Qin, Y. Tang, and B. Z. Tang, Adv. Mater. 2014, 26, 5225.
[50] J. Ma, Z. Wang, C. Li, and H. Zhang, Biosensors, 2023, 13, 159.
[51] X. Zhang, H. Liu, G. Zhuang, S. Yang, and P. Du, Nat. Commun. 2022, 13. 3543.
[52] N. Xie, N. L. C. Leung, W. Yuan, Y. Liu, Q. Wu, Q. Peng, Q. Miao, J. W. Y. Lam, and B. Z. Tang, Chem. Eur. J. 2014, 47, 15349.
[53] N. Xie, N. L. Leung, W. Yuan, Y. Liu, Q. Wu, Q. Peng, Q. Miao, J. W. Y. Lam, and B. Z. Tang, Chem. Eur. J. 2014, 20, 15353.
[54] E. R. Jimenez, and H. Rodriguez, J. Mater. Sci. 2020, 55, 1366.
[55] M. C. Kloetzel, Org. React. 1948, 4. 1.
[56] K. H. Yoon, K. O. Kim, M. Schaefer, and D. Y. Yoon, Polymer, 2012, 53, 2290.
[57] M. Banerjee, S. J. Emond, S. V. Lindeman, and R. Rathore, J. Org. Chem. 2007, 72, 8054.
[58] J. Aw, F. Widjaja, Y. Ding, J. Mu, L. Yang, and B. Xing, Chem. Commun. 2017, 53, 3330.
[59] C. Li, M. P. Aldred, G. Zhang, W. Gong, A. D. Q. Li, Y. Dai, D. Ma, and M. Q. Zhu, J. Mater. Chem. 2012, 22, 7515.
[60] V. R. Desai, A. H. Sidarai, S. M. Hunagund, M. Basanagouda, and J. S. Kadadevarmath, J. Solut. Chem. 2017, 46, 1328.
[61] D. S. Guo, B. P. Jiang, and Y. Liu, J. Org. Chem. 2011, 76, 6101.
[62] C. Vaughns, Stern-Volmer Quenching of Conjugated Polymers in School of Chemistry & Biochemistry, Georgia Instutite of Technology, United States of America 2007.

全文公開日期 2028/08/02 (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 2028/08/02 (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