Responsive image
博碩士論文 etd-0617117-104950 詳細資訊
Title page for etd-0617117-104950
論文名稱
Title
合成三官能基聚氧代氮代苯并環己烷之摻氮微孔材料
Synthesis of tri-funtionalized polybenzoxazine based nitrogen-doped microporous carbons
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
80
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2017-07-07
繳交日期
Date of Submission
2017-07-17
關鍵字
Keywords
二氧化碳捕捉、開環聚合反應、聚氧代氮代苯并環己烷、化學活化反應、微孔洞材料
Ring opening polymerization, Chemical activated reaction, Carbon dioxide capture, Microporous materials, Polybenzoxazine
統計
Statistics
本論文已被瀏覽 5670 次,被下載 21
The thesis/dissertation has been browsed 5670 times, has been downloaded 21 times.
中文摘要
本實驗由帶有三羥基的間苯三酚做為起始反應物經由4-硝基氯苯進行取代硝化反應並以鈀碳催化將末端的-NO2還原成-NH2,再將此一級胺分別與苯酚及4-腈基苯酚進行合環反應,合成出兩種末端帶有不同官能基的聚氧代氮代苯并環己烷(以下簡稱 Benzoxazine, BZ),分別為BZPh及BZCN。利用傅立葉轉換紅外光譜儀(FT-IR)、液態核磁共振氫譜(1H NMR)、液態核磁共振碳譜(13C NMR)來鑑定所合成出的兩種BZ化學結構、確認反應是否完全以及是否有反應物沒有純化完全,再以熱微分掃描熱卡計(DSC)、變溫FT-IR來探討BZ的固化行為,並由熱重分析儀(TGA)及動態機械分析儀(DMA)發現帶有腈基(-CN)的BZ在開環聚合後形成的triazine,能夠提升結構的交聯密度而使熱穩定性質也隨之增加。
進一步的將固化後的分子與KOH進行活化反應,得到小於2奈米的微孔洞材料,再利用固態NMR和FT-IR分析鍛燒後材料結構的變化,並從廣角度X光繞射儀(WAXD)觀察出材料的微結構是以六角堆積的方式排列,而利用拉曼光譜(Roman)了解材料鍛燒後因為末端所帶的官能基不同而造成石墨化程度的差異,再以TGA對高溫鍛燒活化後的材料分析因結構的熱穩定性增加而使的在800 oC後的殘留率可達到90%,為了比較化學活化劑對製備微孔結構的影響,因此本實驗也進行了第二種活化劑(ZnCl2)進行活化反應。
除此之外,本實驗在合成BZ分子時利用多官能基反應物來製備網狀型高分子(BPA-BZ、TPPA-BZ),並置於高溫下碳化鍛燒,探討其結構變化、BZ分子的交聯密度及是否形成孔洞,最後以比表面積分析儀(BET)在二氧化碳的環境下進行比表面積及孔徑分布的量測並探討所製備出微孔材料於二氧化碳的捕捉效能。
Abstract
Nitrogen-rich porous carbons were synthesized from new benzoxazine compounds (BZPh and BZCN) directly, which were prepared from two kinds of hydroxyl group (phenol and 4-Cyanophenol), paraformaldehyde and 1,3,5-Tris(4-aminophenoxy)-benzene based on carbonization and KOH activation to use as a capturer for carbon dioxide. NMR and FT-IR were used to prove the chemical structure. We utilized DSC and different temperature FT-IR to discuss the curing behavior of ring opening polymerization. TGA and DMA were used to investigate the thermal properties. The benzoxazine with nitrile-functionalized revealed better thermal properties and improved the physical cross-linking density.
Furthermore, the micropores of BZPh and BZCN were developed by KOH activation also the high temperature physical activation process led to the formation of microporous structure which were characterized using WAXD and BET. Also, Raman spetra was used to represent the graphitic degree of carbons materials. We also compared different activation agents of KOH and ZnCl2 for carbon dioxide capture.
In this research, we increased the functional group of the reactants to prepare the network polybenzoxazine (BPA-BZ and TPPA-BZ), after curing and carbonization the materials with properties of surface area and pore structure possess the potential to the CO2 capture performance.
目次 Table of Contents
論文審定書 i
論文公開授權書 ii
摘要 iii
Abstract iv
目錄 v
表目錄 viii
圖目錄 ix
第一章 緒論 1
1-1 前言 1
1-2研究動機 1
第二章 理論介紹與文獻回顧 2
2-1聚氧代氮代苯并環己烷(Polybenzoxazine)介紹 2
2-2吸附理論 4
2-3二氧化碳的捕捉 6
第三章 實驗步驟 8
3-1 實驗方法及流程 8
3-2 實驗藥品 9
3-3 合成步驟 10
3-3-1 1,3,5-Tris(4-aminophenoxy)benzene之合成 10
3-3-2 Benzoxazine單體(BZPh)之合成 11
3-3-3 Benzoxazine單體(BZCN)之合成 11
3-3-4 Benzoxazine之開環聚合、高溫鍛燒碳化及KOH活化 13
3-3-5 以ZnCl2活化BZCN之碳材 13
3-3-6 Bisphenol A-Benzoxazine(BPA-BZ)之合成 14
3-3-7 Bisphenol A-Benzoxazine(BPA-BZ)之開環聚合 14
3-3-8 Trisphenol PA-Benzoxazine(TPPA-BZ)之合成 15
3-3-9 Trisphenol PA-Benzoxazine(TPPA-BZ)之開環聚合、碳化 15
3-4 實驗儀器 17
3-4-1 核磁共振光譜儀 (NMR, Nuclear Magnetic Resonance, 型號:JEOL ECZ600R) 17
3-4-2 傅立葉轉換紅外光譜儀 (FT-IR, Fourier Transform Infrared Spectrometer, 型號:Bruker Tensor-27) 18
3-4-3 熱重分析儀 (TGA, Thermal Gravimetric Analyzer, 型號:TA Q-50) 18
3-4-4 熱微分掃描卡計 (DSC, Differential Scanning Calorimetry, 型號:TA Q-20) 19
3-4-5 動態機械分析儀 (DMA, Dynamic Mechanical Spectrometer, 型號:Perkin Elmer DMA8000) 19
3-4-6 拉曼光譜 (Raman Spetrum, 型號:HORIBA HR800) 20
3-4-7 X光光電子能譜儀 (X-ray photoelectron spectroscopy, XPS, 型號:PHI 5000 VersaProbe) 20
3-4-8 廣角度X光繞射儀 (Wide Angle X-ray Diffraction, WAXD, 型號:NSRRC BL17A1) 21
3-4-9 穿透式電子顯微鏡 (TEM, Transmission Electron Microscope, 型號:JEOL-2100) 21
3-4-10 比表面積分析儀 ( BET, Specific Surface Area& Pore Size Distribution Analyzer, 型號:ASAP 2020 ) 22
第四章 結果與討論 23
4-1 1,3,5-Tris(4-nitrophenoxy)benzene與1,3,5-Tris(4-amino- phenoxy)benzene結構鑑定分析 23
4-2 BZCN與BZPh分析研究 26
4-2-1 BZCN與BZPh結構鑑定分析 26
4-2-2 BZCN與BZPh交聯性質與熱穩定性分析 31
4-3 BZCN與BZPh高溫鍛燒後分析 37
4-3-1 微孔BZCN及BZPh之結構探討 37
4-3-2 微孔BZCN及BZPh之比表面積儀(BET)分析 45
4-4BZCN-ZC之分析研究 48
4-4-1 BZCN-ZC之比表面積儀(BET)分析 48
4-5 BPA-BZ之分析研究 51
4-5-1 BPA-BZ之結構鑑定 51
4-5-2 BPA-BZ之交聯性質分析 53
4-5-3 BPA-BZ開環聚合及碳化後結構變化與熱穩定性分析 55
4-5-4 BPA-BZ之比表面積儀(BET)分析 58
4-6 TPPA-BZ之分析研究 60
4-6-1 TPPA-BZ之結構鑑定 60
4-6-2 TPPA-BZ之交聯性質分析 62
4-6-3 TPPA-BZ開環聚合及碳化後結構變化與熱穩定性分析 64
4-6-3 TPPA-BZ之比表面積儀(BET)分析 65
第五章 結論 67
第六章 參考文獻 68
參考文獻 References
1. Venna, S. R. and Carreon, M. A. J. Am. Chem. Soc., 2010, 132, 76.
2. Choi, S.; Gray, M. M. L. and Jones, C. W. ChemSusChem., 2011, 4, 628.
3. Rochelle, G. T. Science, 2009, 325, 1652.
4. Rao, A. B. and Rubin, E. S. Environ. Sci. Technol., 2002, 36, 4467.
5. Adeniran, B.; Masika, E. and Mokaya, R. J. Mater. Chem. A, 2014, 2, 14696.
6. Taskin, O. S.; Kiskan, B.; Aksu, A.; Balkis, N.; Weber, J. and Yagci, Y. Chem. Eur. J. 2014, 20, 10953.
7. Wan, L.; Wang, J.; Xie, L.; Sun, Y.; and Li, K. ACS Appl. Mater. Interfaces, 2014, 6, 15583.
8. Hao, G. P.; Li, W.C.; Qian, D.; Wang, G. H.; Zhang, W. P.; Zhang, T.; Wang, A. Q.; Schuth, F.; Bongard, H. J.; and Lu, A. H. J. Am. Chem. Soc. 2011, 133, 11378.
9. Wan, L.; Wang, J.; Xie, L.; Sun, Y. and Li, K. Nanoscale, 2015, 7, 6534.
10. Ania, C. O.; Khomenko, V.; Raymundo-Pinero, E.; Parra, J. B. and Beguin, F. Angew. Chem.,Int. Ed. 2007, 17, 1828.
11. Hall, P. J.; Mirzaeian, M.; Fletcher, S. I.; Sillars, F. B.; Rennie, A. J. R.; Shitta-Bey, G. O.; Wilson, G.; Cruden, A. and Carter, R. Energy Environ. Sci. 2010, 3, 1238.
12. Hulicova-Jurcakova, D.; Puziy, A. M.; Poddubnaya, O. I.; Suárez-García, F.; Tascón, J. M. D. and Lu, G. Q. J. Am. Chem. Soc. 2009, 131, 5026.
13. Holly, F. W. and Cope, A. C. J. Am. Chem. Soc. 1944, 166, 1875.
14. Zhang,Q.; Yang, P.; Deng, Y.; Zhang, C.; Zhu, R. and Gu, Y. RSC Adv., 2015, 5, 103203.
15. Ishida, H. and Agag, T. Handbook of Polybenzoxazine Resins, Elsevier, Amsterdam 2011, 1, 3.
16. Turpin, E. T.; Thranem, D. T.; U. S. Pat. 1988, 4, 719, 253.
17. Ning, X.; Ishida, H.; J. Polym. Sci. A Polym. Chem. 1994, 32, 1121.
18. Bruke, W. J.; J. Am. Chem. Soc. 1949, 71, 609.
19. Agag, T. and Takeichi, T. Macromolecules, 2003, 36, 6010.
20. Kim, H. J.; Brunovska, Z. and Ishida, H. Polymer, 1999, 40, 6565.
21. Cao, G. P.; Chen, W. J.; Wei, J. J.; Li, W. T. and Liu, X. B. Polym. Lett., 2007, 1, 512.
22. Chaisuwan, T. and Ishida, H. J. Appl. Polym. Sci., 2006, 101, 548.
23. Bruke, W. J. J. Am. Chem. Soc. 1949, 71, 609.
24. Wang, Y. X.; Ishida, H. Polymer, 1999, 40, 4563.
25. Ning, X. and Ishida, H. J. Polym. Sci. A Polym. Chem. 1994, 32, 1121.

26. Ishida, H. and Agag, T. Handbook of Polybenzoxazine Resins, Elsevier, Amsterdam 2011, 1, 4.
27. 近藤精一,時關達雄,安部郁夫著,李國希譯,吸附科學,化學工業出版社,2006。
28. Tien, C. NewYork, Butterworths, Boston, 1994, IUPAC.
29. Thommes, M.; Kaneko, K.; Neimark, A. V.; Olivier, J. P. ; Rodriguez-Reinoso, F.; Rouquerol, J. and Sing, K. S. W. Pure Appl. Chem. 2015.
30. Wang, Q.; Luo, J.; Zhong, Z. and Borgna, A. Energy Environ. Sci., 2011, 4, 42.
31. Yu, K. M. K.; Curcic, I.; Gabriel, J. and Tsang, S. C. E. ChemSusChem, 2008, 1, 893.
32. Liang, C.D.; Li, Z. J. S. Angew. Chem. Int. Ed. 2008, 47, 3696.
33. Lu, A. H.; Schuth, F. Adv. Mater. 2006, 18, 1793.
34. Wahby, A.; Ramos‐Fernández, J. M.; Martínez‐Escandell, M.; Sepúlveda‐Escribano, A.; Silvestre‐Albero, J.; Rodríguez-Reinoso, F. ChemSusChem, 2010, 3, 974.
35. Pevida, C.; Drage, T. C. Carbon, 2008, 1464.
36. Lohe, M. R.; Rose, M.; Kaskel, S. Chem. Commun. 2009, 6056.
37. Lin, R. C.; Mohamed, M. G.; Hsu, K. C.; Wu, J. Y.; Jheng, Y. R. and Kuo, S. W. RSC Adv., 2016, 6, 10683.
38. Brun, N.; Garcı’a-Gonza’lez, C. A.; Smirnova, I.; Titirici, M. M. RSC Adv., 2013, 3,17088.
39. Wang, Q.; Yan, J.; Wang, Y.; Ning, G.; Fan, Z.; Wei, T.; Cheng, J.; Zhang, M.; Jing, X. Carbon, 2013, 209.
40. Nandi, M.; Okada, K.; Dutta, A.; Bhaumik, A.; Maruyama, J.; Derks, D. and Uyama, H. Chem. Commun., 2012, 48, 10283.
41. Liu, L.; Deng, Q. F.; Hou, X. X. and Yuan, Z. Y. J. Mater. Chem., 2012, 22, 15540.
42. Gomes, R. and Bhaumik, A. RSC Adv., 2016, 6, 28047.
43. Gomes, R.; Bhanja, P. and Bhaumik, A. Chem. Commun., 2015, 51, 10050.
44. Saleh, M.; Chandra, V.; Kemp, K. C. and Kim, K. S. Nanotechnology, 2013, 24, 255702
45. Wang, J. and Kaskel, S. J. Mater. Chem., 2012, 22, 23710.
46. Ma, Y Waste Biomass Valoriz., 2016, 1-11.
電子全文 Fulltext
本電子全文僅授權使用者為學術研究之目的,進行個人非營利性質之檢索、閱讀、列印。請遵守中華民國著作權法之相關規定,切勿任意重製、散佈、改作、轉貼、播送,以免觸法。
論文使用權限 Thesis access permission:自定論文開放時間 user define
開放時間 Available:
校內 Campus: 已公開 available
校外 Off-campus: 已公開 available


紙本論文 Printed copies
紙本論文的公開資訊在102學年度以後相對較為完整。如果需要查詢101學年度以前的紙本論文公開資訊,請聯繫圖資處紙本論文服務櫃台。如有不便之處敬請見諒。
開放時間 available 已公開 available

QR Code