Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3652
標題: 含胺酯及尿素官能基環型寡聚物之合成、鑑定與開環聚合
Synthesis, identification and ring-opening polymerization of cyclic urethane urea oligomer
作者: 羅偉舜
Lo, Wei-Shun
關鍵字: 環型寡聚物
cyclic oligomer
擬高稀技術
分子間環化反應
聚胺酯
開環聚合反應
pseudo high dilution
intermolecular cyclization
polyurethane urea
ring-opening polymerization
MALDI-ToF mass
出版社: 化學工程學系所
引用: 1. Allcock, H. R.; Lampe, F. W., Comtemporary Polymer Chemistry. 2nd. ed.; Prentice Hall: New. York, 1990. 2. Goodman, I.; Nesbitt, B. F., The structures and reversible polymerization of cyclic oligomers from poly(ethylene terephthalate). Polymer 1960, 1, 384-96. 3. Brunelle, D. J.; Evans, T. L.; Shannon, T. G. Cyclic polycarbonate oligomers from spirobiindane bisphenols. U.S. Patent 4,736,016, 1988. 4. Brunelle, D. J.; Boden, E. P.; Shannon, T. G., Remarkably Selective Formation of Macrocyclic Aromatic Carbonates: Versatile New Intermediates for the Synthesis of Aromatic Polycarbonates. J. Am. Chem. Soc. 1990, 112, 2399-402. 5. Brunelle, D. J.; Shannon, T. G., Preparation and Polymerization of Bisphenol A Cyclic Oligomeric Carbonates. Macromolecules 1991, 24, 3035-44. 6. Brunelle, D. J.; Garbauskas, M. F., Isolation and Spectral and Structural Characterization of Bisphenol A Cyclic Dimer, Trimer, and Tetramer Carbonates. Macromolecules 1993, 26, 2724-29. 7. Gibson, H. W.; Ganguly, S., Synthesis of a novel macrocyclic arylene ether sulfone. Macromolecules 1993, 26, 2408-12. 8. Jiang, H.; Chen, T.; Bo, S., Novel Macrocyclic Precursors of Phenolphthalein Poly(arylene ether ketone) and Poly(arylene ether sulfone): Synthesis and Polymerization. Macromolecules 1997, 30, 7345-47. 9. Teasley, M. F.; Wu, D. Q.; Harlow, R. L., Synthesis, Characterization, and Ring-Opening Polymerization of the Cyclic Oligomers of Poly(Oxy-1,3-phenylenecarbonyl-1,4-phenylene). Macromolecules 1998, 31, 2064-74. 10. Zolotukhin, M. G.; Colquhoun, H. M., Rapid, Uncatalyzed Ring-Opening Polymerization of Individual Macrocyclic Poly(arylene thioether ketone)s under Dynamic Heating Conditions. Macromolecules 2004, 37, 2041-53. 11. Hodge, P.; Ben-Haida, A.; Williams, D. J., Synthesis of a Catechol-Based Poly(ether ether ketone) ("o-PEEK") by Classical Step-Growth Polymerization and by Entropically Driven Ring-Opening Polymerization of Macrocyclic Oligomers. Macromolecules 2006, 39, 6467-72. 12. Schnell, H.; Bottenbruch., L. Production of high molecular weight linear polycarbonate from oligomeric cyclic carbonates. U.S. Patent 3,386,954, 1968. 13. Prochaska., R. J. Aromatic carbonates. U.S. patent 3,274,214, 1966. 14. Moody., L. S. Preparation of aromatic cyclic carbonates. U.S. Patent 3,155,683, 1964. 15. Brunelle, D. J.; Evans, T. L., Semicrystalline Polymers via Ring-Opening Polymerization:Preparation and Polymerization of Alkylene Phthalate Cyclic Oligomers. Macromolecules 1998, 31, 4782-90. 16. Jiang, H.; Chen, T.; Xu, J., Synthesis, Structure, and Ring-Opening Polymerization of Macrocyclic Aromatic Esters: A New Route to High-Performance Polyarylates. Macromolecules 1997, 30, 2839 -42. 17. Fey, T.; Keul, H.; Höcker, H., Ring-Opening Polymerization of the Cyclic Ester Amide Derived from Adipic Anhydride and 1-Amino-5-pentanol. Macromolecules 2003, 36, 3882 -89. 18. Xie, D.; Ji, Q.; Gibson, H. W., Synthesis and Ring-Opening Polymerization of Single-Sized Aromatic Macrocycles for Poly(arylene ether)s. Macromolecules 1997, 30, 4814 -27. 19. Ganguly, S.; Gibson, H. W., Synthesis of a Novel Macrocyclic Arylene Ether Sulfone. Macromolecules 1993, 26, 2408. 20. Hay, A. S.; Ding, Y., Cyclic Aromatic Disulfide Oligomers: Synthesis and Characterization. Macromolecules 1996, 29, 6386-92. 21. Jacobson, H.; Beckman, C. O., Intramolecular Reaction in Polycondensations II.Ring-Chain Equilibrium in Polydecamethylene Adipate. The Journal of Chemical Physics 1950, 18, 1607-12. 22. Jacobson, H.; Stockmayer, W. H., Intramolecular Reaction in Polycondensations. I. The Theory of Linear Systems. The Journal of Chemical Physics 1950, 18, 1600-06. 23. Hodge, P.; Kamau, S. D., Cyclo-depolymerisations of polyurethanes to give macrocyclic oligomers: entropically driven ring-opening polymerisations of the macrocyclic oligomers produced. Reactive & Functional Polymers 2004, 60, 55-64. 24. Ercolani, G.; Mandohi, L.; Mencarelli, P., Kinetic Treatment of Irreversible Cyclooligomerization of Bifunctional Chains and Its Relevance to the Synthesis of Many-Memebered Rings. Macromolecules 1988, 21, 1241-46. 25. Kirby, A. J., Effective molarities for intramolecular reactions. 1980, 17, 183. 26. Mandolini, L. A., Intramolecular reactions of chain molecules. Adv. Phys. Org. Chem. 1986, 22, 1. 27. Ra¨der, H. J.; Schrepp, W., MALDI-TOF mass spectrometry in the analysis of synthetic polymers. Acta Polymerica 1998, 49, p 272-93. 28. Okamoto, K., MALDI Mass Spectrometry of Synthetic Polymers. R&D Reviews of Toyota CRDL 2006, 41, 29. 29. Kusan, J.; Keul, H.; Hocker, H., Cationic Ring-Opening Polymerization of Tetramethylene Urethane. Macromolecules 2001, 34, 389-95. 30. Hodge, P.; Colquhoun, H. M., Recent work on entropically-driven ring-opening polymerizations: some potential applications. Polym. Adv. Technol. 2005, 16, 84-94. 31. 鄭智嘉; 戴憲弘. 新穎反應型的環狀高分子中間體:巨環型聚丙烯醚二亞胺之合成、反應及應用. 國立中興大學化工所碩士論文, 2006. 32. Takeichi, T.; Ujiie, K., High performance poly(urethane-imide) prepared by introducing imide blocks into the polyurethane backbone. Polymer 2005, 46, 11225-31. 33. Bohme, F.; Kunert, C., Polymeric and Macrocyclic Ureas Based on Meta-Substituted Aromatic Diamines. Macromolecules 2002, 35, 4233-37.
摘要: 本研究藉由2,4-甲苯二異氰酸鹽(2,4-toluene diisocyanate,2,4-TDI)與分子量700的聚丙烯醚二元醇(poly(oxypropylene),PPG700)以2.2:1的比例,成功合成產率達76%以上之單鏈段雙異氰酸鹽末端基的線型預聚物(2,2’-TDI700)。並在擬高稀(pseudo high dilution)的反應環境下,與乙二胺(ethylene diamine,EDA)進行雙分子環合反應,製備得含胺酯與尿素基的環型寡聚物EDA700,經丙酮(acetone)分離純化後,重量產率可達50%。 藉由末端官能基分析與分子量的探討,以及模式反應的設計將寡聚物NMR圖譜做進一步解析,達到環型結構的鑑定。並在開環聚合反應中,利用溫度,溶劑,催化劑等不同條件的測試,以建立此種含胺酯與尿素基的環型寡聚物之開環聚合反應技術。
In this study, 2,2'-diisocyanate terminated TDI700 was obtained by reaction of 2,4-TDI and Mw.700 poly(oxypropylene) at a ratio of 2.2:1. GPC analysis showed us a good yield of low chain extended 2,2'-TDI700 around 76%. In the model compound study, chemical shifts in the urethane and urea group derived from 2,4-TDI were clearly identified and widely used in our research. Followed by reacting with ethylene diamine(EDA) at a pseudo high dilution condition, the ring closure of diisocyanate group on 2,2'-TDI700 was achieved with repeating unit of 1~2. The purified structure of cyclization product, EDA700, was confirmed by FTIR, NMR, MALDI-ToF mass analysis. However ,the GPC analysis of EDA700 did not agree with the mass analysis. By several indirect evidences, cyclic compound is considered to form aggregates. In the ring opening polymerization of EDA700, effects of catalysts and temperature were studied. An unexpected release of EDA molecular during the reaction restricted the growth of molecular weight. The highest polymeric product was synthesized without any catalyst at 180℃ for 6 hours and showed only up to 8 repeating units with polydispersity of 1.31 in GPC analysis.
URI: http://hdl.handle.net/11455/3652
其他識別: U0005-2708200711264000
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-2708200711264000
Appears in Collections:化學工程學系所

文件中的檔案:

取得全文請前往華藝線上圖書館



Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.