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研究生: 陳姿穎
Zih-ying Chen
論文名稱: 不同莫爾比的雙馬來醯亞胺/巴比妥酸之反應動力學研究
Reaction Kinetics for Bismaleimide and Barbituric Acid with different molar ratios
指導教授: 陳崇賢
Chorng-Shyan Chern
口試委員: 黃延吉
Yan-Jyi Huang
許榮木
Jung-mu Shu
學位類別: 碩士
Master
系所名稱: 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年: 2014
畢業學年度: 102
語文別: 中文
論文頁數: 54
中文關鍵詞: 麥克加成反應自由基聚合反應雙馬來醯亞胺巴比妥酸
外文關鍵詞: Michael addition, Free radical polymerization, Bismaleimide, Barbituric Acid
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  • 本研究主要研究在不同莫爾比下,使用雙馬來醯亞胺(N,N’-bismaleimide-4,4-diphenylmethane, BMI)與巴比妥酸(Barbituric acid, BTA)進行聚合反應之反應動力學,進而討論不同莫爾比對反應速率的影響,以及同時存在的麥克加成反應(Michael addition)和自由基聚合反應(Free radical polymerization)兩種反應速率的競爭。利用不同的莫爾比分別為BMI/BTA((1/1 (mol/mol))、BMI/BTA((2/1 (mol/mol))和BMI/BTA((4/1 (mol/mol))(固含量:20.46%),進行反應動力學之研究。
    使用微分式掃描熱量分析儀(DSC),在373K∼403K反應一小時得到反應放熱數據,將實驗所得數據利用Matlab數學軟體分析推倒公式,模擬出之 "k" ‾ 和 ("k" _"i" ) ‾ 再利用Arrhenius方程式計算BMI/BTA反應之活化能 "E" ‾ 和 ("E" _"i" ) ‾ 。


    This work studied the kinetics of N,N’-bismaleimide-4,4-diphenylmethane (BMI) polymerization with Barbituric acid (BTA) with different molar ratios. This polymerization was governed by the competitive Michael addition reaction and free radical polymerization. The system of BMI/BTA = 1/1 (mol/mol)、BMI/BTA = 2/1 (mol/mol) and BMI/BTA = 4/1 (mol/mol) (in the temperature range 373K~403K) were chosen in this work.
    To obtain the reaction of kinetic data, then analyze the data using the proposed reaction model.

    摘要 I Abstract II 致謝 III 目錄 IV 圖目錄 VI 表目錄 IX 第一章 緒論 1 1.1 雙馬來醯亞胺高分子(Bismaleimide based polymers) 1 1.2 巴比妥酸(Barbituric acid) 2 1.3 研究動機 4 第二章 文獻回顧 5 2.1 雙馬來醯亞胺聚合反應類型 5 2.1.1 麥克加成反應(Michael addition) 5 2.1.2 自由基聚合反應(Free radical polymerization) 7 2.2 巴比妥酸及其衍生物 10 2.2.1巴比妥酸 10 2.2.2 巴比妥酸的互變異構與氫鍵 10 2.2.3 巴比妥酸衍生物 12 第三章 實驗藥品、儀器與步驟 13 3.1 實驗藥品 13 3.2 實驗儀器 15 3.3 實驗步驟 16 3.3.1 不同莫爾比之實驗設置及樣品配置 16 3.3.2 反應轉化率 17 3.3.3 BMI/BTA聚合反應之動力學模式建立 17 第四章 結果與討論 26 4.1 不同莫爾比之體積莫爾濃度 26 4.2 不同莫爾比之BMI不飽和雙鍵與BTA活性氫的聚合反應 27 4.3 不同莫爾比之轉化率分析 30 4.4 反應動力學模擬建立與分析 35 4.5 符合不同莫爾比之反應動力學反應速率及活化能探討 37 第五章 結論 46 參考文獻 48 附錄 52

    1. T. Pascal, R. Mercier, B. Sillion, “New semi-interpenetrating polymeric networks from linear polyimides and thermosetting bismaleimides. 1: Synthesis and characterization of starting components”, Polymer, 30, 739 (1989).
    2. C. S. Wang, C. H. Lin, “Synthesis and properties of phosphorus containing copoly(bismaleimide)”, Polymer, 40, 5665 (1999)
    3. P. Mison, B. Sillion, “Thermosetting Oligomers Containing Maleimides and Nadimides End-Groups”, Adv Polym Sci, 140, 137 (1999).
    4. Z. D. Xiang, F. R. Jones, “Thermal degradation of an end-capped bismaleimide resin matrix (PMR-15) composite reinforced with pan-based carbon fibres”, Compos Sci Technol, 47, 209 (1993).
    5. A. von. Baeyer, “Untersuchungen uber die Harsauregrouppe”, Ann. Chem. Pharm. 127, 199 (1863)
    6. V. H. Bredereck, B. Fohlisch, R. Franz, “Uber CH-aktive polymerisationsinitiatoren. XIII. Mitt. Polymerisationen und polymerisationsinitiatoren”, Makromol Chem, 92,70 (1996)
    7. J. P. Pan, G. Y. Shiau, S. S. Lin, K. M. Chen, “Effect of Barbituric Acid on the Self-Polymerization Reaction of Bismaleimides”, J.Appl. Polym. Sci., 45,103 (1992)
    8. R. Christian, “Solvents and Solvent Effects in Organic Chemistry”, Wiley-VCH, Weinheim/English, 2003.
    9. L. R. Dix, J. R. Ebdon, N. J. Flint, P. Hodge and R. O’dell, “Chain extension and crosslinking of telechelic oligomers”, Eur. Polym. J., 31, 647 (1995).
    10. M. F. Grenier-Loustalot and L. D. Cunha, “Influence of steric hindrance on the reactivity and kinetics of molten-state radical polymerization of binary bismaleimide—diamine systems”, Polymer, 39, 1799 (1998).
    11. Z. Shen, J. R. Schlup and L. T. Fan, “Synthesis and characterization of leather impregnated with bismaleimide (BMI)”, J. Appl. Polym. Sci., 69, 1019 (1998).
    12. X. Zhang, F. S. Du, Z. C. Li and F. M. Li, “Bismaleimides Having Electron-Donating Chromophore Moieties: A New Approach toward monitoring the Process of Curing Based on their Fluorescence Behavior”, Macromol. Rapid Commun., 22,983 (2001).
    13. Y. L. Liu, S. H. Tsai, C. S. Wu and R. J. Jeng, “Preparation and characterization of hyperbranched polyaspartimides from bismaleimides and triamines”, J. Polym. Sci. Part A: Polym. Chem., 42, 5921 (2004).
    14. M. Sava and C. V. Grigoras, “Bismaleimide monomers and polymers with ester and ether units. Synthesis and properties”, J. Macromolecular Sci Part A: Pure and Applied Chemistry, 42, 1095 (2005).
    15. E.D. Bergman, D. Ginsburg, R. Pappo, “The Michael reaction”, Organic Reaction, 10, 556 (1959).
    16. R. D. Little, M. R. Masjedizadeh, O. Wallquist, J. I. McLoughlin, “The intramolecular Michael reaction”, Organic Reaction, 47, 315 (1995).
    17. M. E. Jung, “Stabilized nucleophiles with electron deficient alkenes and alkynes”, B.M. Trost (Ed.), Comprehensive organic synthesis, Pergamon, Oxford (1991).
    18. A. J. “Michael, Ueber die addition von natriumacetessig- und natriummalonsaureathern zu den aethern ungesattigter sauren”, Prakt Chem, 35, 349 (1887).
    19. R. Connor, W.R. McClellan, “The Michael condensation. V. The influence of the experimental conditions and the structure of the acceptor upon the condensation”, J Org Chem, 3, 570 (1938).
    20. L. Kurti, B. Czako, “Strategic Applications of Named Reactions in Organic Synthesis”, 286 (2005)
    21. B. D. Mather, K. Viswanathan, K. M. Miller, T. E. Long, “Michael Addition Reactions in Macromolecular Design for Emerging Technologies”, Prog. Polym. Sci., 31, 487 (2006)
    22. N. F. Albertson, “Alkylation with Non-ketonic Mannich Bases. Aminothiazoles and Pyrrole", J. Am. Chem Soc., 70, 669 (1948).
    23. L. G. Wade, Organic Chemistry 5th Ed. Mechanism supplements origina, 319 (2002).
    24. M. Brown and T. C. Sandreczki, “Cross-linking reactions in maleimide and bis(maleimide) polymers. An ESR study”, Macromolecules, 23,100 (1990).
    25. J. V. Crivello, D. A. Conlon, and S. T. Rice, “Bismaleimide-bisvinylether copolymers: A new class of thermosetting resins”, Polym. Bull., 13, 409 (1985).
    26. N. TSUBOKAWA, N. SHIBATA, and Y. SONE, ”Radical Polymerization of Methyl Methacrylate Initiated by an Enolizable Ketone-Carbon Black System”, J Polym Sci, 21, 425 (1983).
    27. Heng-Lei Su, Jung-Mu Hsu, Jing-Pin Pan, Tsung-Hsiung Wang, Chorng-Shyan Chern, ”Effects of Solvent Basicity on Free Radical Polymerizations of N,N’-bismaleimide-4,4’-diphenylmethane Initiated by Barbituric Acid”, J. Appl. Polym. Sci., 117, 596 (2010).
    28. 劉文英,藥物分析,北京:人民衛生出版社,pp 112-130,2007。
    29. 曾昭瓊,《有機化學》第四版上冊,北京:高等教育出版社,2005。
    30. W. O. Foye, T. L. Lemke, D. A. Williams, Principles of Medicinal Chemistry 4th Ed., pp 88-180 (1995).
    31. Baeyer., ”Untersuchungen uber die Harnsauregruppe”, Annalen der Chemie und Pharmacie, 131, 291 (1864).
    32. Heng-Lei Su, Jung-Mu Hsu, Jing-Pin Pan, Tsung-Hsiung Wang, Fu-En Yu, Chorng-Shyan Chern, ”Kinetic and structural studies of the polymerization of N,N′-bismaleimide-4,4′-diphenylmethane with barbituric acid”, Polym. Eng. Sci., 51, 1188 (2011)
    33. Fu-En Yu, Hao-Yeh Lee, Jung-Mu Hsu, Jing-Pin Pan, Tsung-Hsiung Wang, Chorng-Shyan Chern, ”Kinetics of polymerization of N,N’-bismaleimide-4,4’-diphenylmethane with Barbituric acid”, J. Taiwan Inst. Chem. Eng., accept (Jun, 3 2014)

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