請用此 Handle URI 來引用此文件:
http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/50674
完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 鄭如忠 | |
dc.contributor.author | Meng-Wei Wang | en |
dc.contributor.author | 汪孟緯 | zh_TW |
dc.date.accessioned | 2021-06-15T12:52:00Z | - |
dc.date.available | 2021-07-26 | |
dc.date.copyright | 2016-07-26 | |
dc.date.issued | 2016 | |
dc.date.submitted | 2016-07-19 | |
dc.identifier.citation | 1. Ghosh, N. N.; Kiskan, B.; Yagci, Y. Progress in Polymer Science 2007, 32, (11), 1344-1391.
2. Ning, X.; Ishida, H. Journal of Polymer Science Part A: Polymer Chemistry 1994, 32, (6), 1121-1129. 3. Ning, X.; Ishida, H. Journal of Polymer Science Part B: Polymer Physics 1994, 32, (5), 921-927. 4. Kim, S.-K.; Choi, S.-W.; Jeon, W. S.; Park, J. O.; Ko, T.; Chang, H.; Lee, J.-C. Macromolecules 2012, 45, (3), 1438-1446. 5. Liu, C.; Shen, D.; Sebastián, R. M. a.; Marquet, J.; Schönfeld, R. Macromolecules 2011, 44, (12), 4616-4622. 6. Wang, M. W.; Jeng, R. J.; Lin, C. H. Macromolecules 2015, 48, (3), 530-535. 7. Taskin, O. S.; Kiskan, B.; Yagci, Y. Macromolecules 2013, 46, (22), 8773-8778. 8. Chernykh, A.; Agag, T.; Ishida, H. Macromolecules 2009, 42, (14), 5121-5127. 9. Dogan Demir, K.; Kiskan, B.; Yagci, Y. Macromolecules 2011, 44, (7), 1801-1807. 10. Zhang, K.; Zhuang, Q.; Liu, X.; Cai, R.; Yang, G.; Han, Z. RSC Advances 2013, 3, (15), 5261-5270. 11. Wang, C.-F.; Su, Y.-C.; Kuo, S.-W.; Huang, C.-F.; Sheen, Y.-C.; Chang, F.-C. Angewandte Chemie International Edition 2006, 45, (14), 2248-2251. 12. Demir, K. D.; Kiskan, B.; Aydogan, B.; Yagci, Y. Reactive and Functional Polymers 2013, 73, (2), 346-359. 13. Takeichi, T.; Kano, T.; Agag, T. Polymer 2005, 46, (26), 12172-12180. 14. Agag, T.; Takeichi, T. Journal of Polymer Science Part A: Polymer Chemistry 2007, 45, (10), 1878-1888. 15. Chernykh, A.; Liu, J.; Ishida, H. Polymer 2006, 47, (22), 7664-7669. 16. Lin, C. H.; Chang, S. L.; Shen, T. Y.; Shih, Y. S.; Lin, H. T.; Wang, C. F. Polymer Chemistry 2012, 3, (4), 935-945. 17. Holly, F. W.; Cope, A. C. Journal of the American Chemical Society 1944, 66, (11), 1875-1879. 18. Brunovska, Z.; Liu, J. P.; Ishida, H. Macromolecular Chemistry and Physics 1999, 200, (7), 1745-1752. 19. Kenji, O.; Masaaki, O.; Koichi, N. Method for producing thermosetting resin having benzoxazine ring. JP3994970, 2005. 20. Lin, C. H.; Chang, S. L.; Hsieh, C. W.; Lee, H. H. Polymer 2008, 49, (5), 1220-1229. 21. Chang, S. L.; Lin, C. H. Journal of Polymer Science Part A: Polymer Chemistry 2010, 48, (11), 2430-2437. 22. Liu, J.; Agag, T.; Ishida, H. Polymer 2010, 51, (24), 5688-5694. 23. Katagiri, T.; Eguchi, Y. Method for producing thermosetting resin having benzoxazine ring. US7994270 B2, 2010. 24. Marvel, C. S.; Tarköy, N. Journal of the American Chemical Society 1957, 79, (22), 6000-6002. 25. Russell, V. M.; Koenig, J. L.; Low, H. Y.; Ishida, H. Journal of Applied Polymer Science 1998, 70, (7), 1413-1425. 26. Wang, Y.-X.; Ishida, H. Macromolecules 2000, 33, (8), 2839-2847. 27. Ishida, H.; Sanders, D. P. Macromolecules 2000, 33, (22), 8149-8157. 28. Sudo, A.; Kudoh, R.; Nakayama, H.; Arima, K.; Endo, T. Macromolecules 2008, 41, (23), 9030-9034. 29. Chutayothin, P.; Ishida, H. Macromolecules 2010, 43, (10), 4562-4572. 30. Wang, X.; Chen, F.; Gu, Y. Journal of Polymer Science Part A: Polymer Chemistry 2011, 49, (6), 1443-1452. 31. Li, X.; Luo, X.; Liu, M.; Ran, Q.; Gu, Y. Materials Chemistry and Physics 2014, 148, (1–2), 328-334. 32. Santhosh Kumar, K. S.; Reghunadhan Nair, C. P.; Ninan, K. N. European Polymer Journal 2009, 45, (2), 494-502. 33. Kimura, H.; Ohtsuka, K.; Matsumoto, A. Express polym lett 2011, 5, (12), 1113-1122. 34. Li, X.; Gu, Y. Polymer Chemistry 2011, 2, (12), 2778-2781. 35. Lin, C. H.; Huang, S. J.; Wang, P. J.; Lin, H. T.; Dai, S. A. Macromolecules 2012, 45, (18), 7461-7466. 36. Tsai, J.-S.; Lin, C.-H. Journal of Applied Polymer Science 1991, 42, (11), 3045-3050. 37. Nunes, R. W.; Martin, J. R.; Johnson, J. F. Polymer Engineering & Science 1982, 22, (4), 205-228. 38. Kumler, P. L.; Keinath, S. E.; Boyer, R. F. Journal of Macromolecular Science, Part B 1977, 13, (4), 631-646. 39. Schollenberger, C. S.; Dinbergs, K. Journal of Elastomers and Plastics 1979, 11, (1), 58-91. 40. Bersted, B. H.; Anderson, T. G. Journal of Applied Polymer Science 1990, 39, (3), 499-514. 41. Martin, J. R.; Johnson, J. F.; Cooper, A. R. Journal of Macromolecular Science, Part C 1972, 8, (1), 57-199. 42. Vlachopoulos, J.; Hadjis, N.; Hamielec, A. E. Polymer 1978, 19, (1), 115. 43. Dyer, J. R. Applications of absorption spectroscopy of organic compounds, Prentice Hall, Englewood Cliffs, N. J., 1965. 44. Tsuchiya, K.; Endo, T. Journal of Polymer Science Part A: Polymer Chemistry 2014, 52, (5), 699-706. | |
dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/50674 | - |
dc.description.abstract | 本論文透過A-A及B-B聚縮合合成途徑,避免一般曼尼希縮合(Mannich condensation)製程中的副反應發生,成功製備出高分子量的主鏈高分子型氧代氮代苯並環己烷(benzoxazine, Bz)預聚物,P(BF-bapp)-1。另合成三種結構相似、分子量相異之預聚物,探討分子量差異對其固化物物性與微結構之影響。
為探討Bz的開環聚合(ring-opening polymerization, ROP)機制,本論文合成三種不同結構的主鏈高分子型Bz預聚物,分別為雜環上氧及氮原子鄰位(ortho)皆無甲基取代的PBz-0M;雜環上氧原子鄰位受甲基取代的PBz-2M;雜環上氧及氮原子鄰位皆受甲基取代的PBz-6M。透過微差掃描熱分析(DSC)、傅立葉轉換紅外線光譜(FTIR)以及熱性質分析,我們發現,ROP可透過雜環上氮原子的鄰位(ortho)進行,並提出其反應機制進行解釋。 Bz/氰酸酯混膠共聚合反應機制已在多篇文獻中被探討,並有文獻指出Bz開環的結構為混膠中氰酸酯快速三環化的主因。然而,近來我們意外發現將4,4’-oxyaniline/phenol-based Bz (P-oda)以及雙酚A氰酸酯(BACY)以溶劑溶解配置成膠後,靜置於室溫24小時,溶液將形成凝膠(gel)。在此環境下,Bz開環聚合的可能性極低,因此我們認為催化效應來自與Bz本身的結構,本論文將透過Model reaction尋找凝膠化(gelation)之主因,並提出Bz於氰酸酯三環化中之催化機制進行解釋。 | zh_TW |
dc.description.abstract | A main chain-type polybenzoxazine precursor, P(BF-bapp)-1, with high molecular weight (MW) was prepared through a strategy of A-A and B-B polycondensation, avoiding by-reaction that occurred in Mannich condensation. To discuss the effect of the MW of benzoxazine on the properties and microstructure of the resulting thermoset, anthother three structurally similar benzoxazines with difference MW were syntheized in this work.
To discuss the mechanism of ring-opening polymerization (ROP) of benzoxazine, three polybenzoxazine precursors were prepared. Among the polybenzoxazine precursors, free ortho positions to the O and N of oxazine are available for PBz-0M. The ortho positions to the O of oxazine are blocked by methyl group for PBz-2M. The ortho positions to the O and N of oxazine are blocked by methyl group for PBz-6M. According to DSC, IR, and thermal analysis, we found that the ROP of PBz-2M can be carried out through free ortho positions to the N of oxazine. A reaction mechanism was proposed to explain the polymerization in this work. Blends of cyanate ester and benzoxazine have been independently studied by several researchers, some of them suggest that the rapid trimerization of cyanate ester in the blend is related to the ring-opened structure of benzoxazine. Recently, we unexpectedly observe that gelation occurred in solution of P-oda/BACY blend after 24 h at room temperature. However, the possibility of ring-opening polymerization for benzoxazine at room temperature is rare. Therefore, it is highly likely that the catalytic effect results from the benzoxazine itself. We tried to find the reason of gelation through model reaction in this work, and proposed a catalytic mechanism of benzoxazine for the trimerization of cyanate ester. | en |
dc.description.provenance | Made available in DSpace on 2021-06-15T12:52:00Z (GMT). No. of bitstreams: 1 ntu-105-D02549002-1.pdf: 3174910 bytes, checksum: 0268f75919c0570e97e729642fd6d2a5 (MD5) Previous issue date: 2016 | en |
dc.description.tableofcontents | 中文摘要 i
Abstract ii 目錄 iv Scheme目錄 vi 圖目錄 viii 表目錄 ix 第一章 緒論 1 第二章 原理與文獻回顧 4 2.1 氧代氮代苯并環己烷(Benzoxazine, Bz)合成文獻 4 2.2 主鏈高分子型氧代氮代苯并環己烷(Benzoxazine, Bz)合成文獻 7 2.3 氧代氮代苯并環己烷(Benzoxazine, Bz)開環聚合文獻 11 2.4 氰酸酯/氧代氮代苯并環己烷(Benzoxazine, Bz)混膠文獻 17 第三章 實驗內容 23 3.1 實驗藥品與溶劑 23 3.2 實驗儀器 24 3.3 實驗規劃 26 3.4 實驗步驟 29 3.4.1 單體(1)合成 29 3.4.2 主鏈高分子型Bz預聚物P(BF-bapp)-1 30 3.4.3主鏈高分子型Bz預聚物P(BF-bapp)-2 31 3.4.4 寡聚物型Bz預聚物P(BF-bapp)-3 32 3.4.5單體型Bz預聚物P-bapp 33 3.4.6 預聚物P(BF-bapp)-1, P(BF-bapp)-2以及P(BF-bapp)-3固化程序 34 3.4.7 預聚物P-bapp固化程序 34 3.4.8 高分子型預聚物PBz-0M合成 35 3.4.9 高分子型預聚物PBz-2M合成 35 3.4.10 高分子型預聚物PBz-6M合成 35 3.4.11 薄膜製備程序 35 3.4.12 P-oda合成 36 第四章 結果與討論 37 4.1 Bz預聚物分子量(Molecular weight, MW)差異對固化物之影響 37 4.1.1 Bz合成探討與結構鑑定 37 4.1.2 Bz預聚物之DSC分析 40 4.1.3 固化物熱性質 41 4.1.4 固化物機械性質 44 4.1.5 固化物折射率與介電性質 45 4.2 Bz開環聚合機制探討 47 4.2.1 PBz-0M、PBz-2M以及PBz-6M結構鑑定 47 4.2.2 微差掃描熱卡計(DSC)分析 48 4.2.3 微結構分析 49 4.2.4 熱性質分析 51 4.2.5 熱穩定性分析 53 4.2.6 機制探討 54 4.3 Bz催化氰酸酯三環化之催化機制探討 56 4.3.1 Bz/BACY凝膠化現象觀察 56 4.3.2 Model reaction 59 4.3.3 催化機制探討 62 第五章 結論 64 第六章 參考文獻 66 第七章 研究成果列表 69 (A) 國外期刊 69 (B) 國內期刊 70 (C) 專書 70 (D) 專利 70 | |
dc.language.iso | zh-TW | |
dc.title | 氧代氮代苯并環己烷:合成改善、機制及其固化物微結構之研究 | zh_TW |
dc.title | Benzoxazine: Synthetic Modification, Mechanism, and Microstructure of Its Resulting Thermoset | en |
dc.type | Thesis | |
dc.date.schoolyear | 104-2 | |
dc.description.degree | 博士 | |
dc.contributor.coadvisor | 林慶炫 | |
dc.contributor.oralexamcommittee | 童世煌,邱文英,丁維和 | |
dc.subject.keyword | 氧代氮代苯并環己烷,聚縮合,分子量,開環聚合機制,氰酸酯,凝膠化,催化機制, | zh_TW |
dc.subject.keyword | benzoxazine,polycondensation,molecular weight,cyanate ester,gelation,catalytic mechanism, | en |
dc.relation.page | 70 | |
dc.identifier.doi | 10.6342/NTU201601072 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2016-07-20 | |
dc.contributor.author-college | 工學院 | zh_TW |
dc.contributor.author-dept | 高分子科學與工程學研究所 | zh_TW |
顯示於系所單位: | 高分子科學與工程學研究所 |
文件中的檔案:
檔案 | 大小 | 格式 | |
---|---|---|---|
ntu-105-1.pdf 目前未授權公開取用 | 3.1 MB | Adobe PDF |
系統中的文件,除了特別指名其著作權條款之外,均受到著作權保護,並且保留所有的權利。