Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3636
標題: 含形狀記憶效應側鏈型規則樹枝狀聚胺酯之研究
Synthesis and Characterization of Side Chain Dendritic Polyurethanes with Shape-Memory Effect
作者: 游敬翔
Yu, Ching-Shiang
關鍵字: polyurethane
聚胺酯
dendrimer
shape-memory effect
規則樹脂狀聚合物
形狀記憶效應
出版社: 化學工程學系所
引用: 1. W. J. Buchler, J. W. Gilfrich, R. C. Wiley, J. Appl. Phys. 1963, 34, 1475. 2. D. Mantovani, JOM 2000, 10, 36. 3. Z. G. Wei, R. Sandstrom, S. Miyazaki, J. Mater. Sci. 1998, 33, 3743. 4. A. Charlesby, Atomic Radiation and Polymers, Pergamon Press,Oxford, 1960, pp. 198. 5. S. Ota, Radiat. Phys. Chem. 1981, 18, 81. 6. S. Machi, Radiat. Phys. Chem. 1996, 47, 333. 7. V. Skakalova, V. Lukes, M. Breza, Macromol. Chem. Phys. 1997, 198, 3161. 8. Y. Shirai, S. Hayashi, Mitsubishi Tech. Bull. 1988, 184, 1. 9. B. K. Kim, S. Y. Lee, M. Xu, Polymer 1996, 37, 5781. 10. F. Li, X. Zhang, J. Hou, M. Xu, X. Luo, D. Ma, B. K. Kim, J. Appl. Polym. Sci. 1997, 64, 1511. 11. M. Wang, X. Luo, X. Zhang, D. Ma, Polym. Adv. Technol. 1997, 8, 136. 12. B. K. Kim, S. Y. Lee, J. S. Lee, S. H. Baek, Y. J. Choi, J. O. Lee, M. Xu, Polymer 1998, 39, 2803. 13. M. Wang, Z. Lide, J. Polym. Sci. Part B 1999, 37, 101. 14. K. Sakurai, T. Kashiwagi, T. Takahashi, J. Appl. Polym. Sci. 1993, 47, 9370. 15. P. T. Mather, H. G. Jeon, A. Romo-Uribe, Macromolecules 1999, 32,1194. 16. T. Hirai, H. Maruyama, T. Suzuki, S. Hayashi, J. Appl. Polym. Sci. 1992, 45, 1449. 17. Y. Osada, J.-P. Gong, Adv. Mater. 1998, 10, 827. 18. C. Alvarez-Lorenzo, O. Guney, T. Oya, S. Yasuzo, K. Masatoshi, E. Takashi, T. Yukikazu, I. Toru, K. Kenichi, T. Kazunori,W. Guoqiang, A. 19. C.-P. Chen, S. A. Dai, H.-L. Chang, W.-C. Su, R.-J. Jeng, J. Polym. Sci. Part A: Polym. Chem. 2005, 43, 682. 20. G. Oertel, Polyurethane Handbook, Hanser/Gardner Publications Inc., New York, 1993. 21. L. Fambri, A. Penati, J. Kolarik, Polymer 1997, 38, 835. 22. M. D. Lelah, S. L. Cooper, Polyurethanes in Medicine: CRC Press, Florida, 1986. 23. E. Buhleier, W. Wehner,F. Vogtle, Synthesis 1978, 155. 24. D. A.Tomalia, H. Baker, J. Dewald, M. Hall, G. Kallos, S. Martin, J. Roeck, J. Ryder,P. Smith, Polym. J. 1985, 17, 117. 25. Newkome et al. Aldrichimica Acta 1992,25,31. 26. C. J. Hawker, J. M. J. Fre''chet, J. Am. Chem. Soc. 1990, 112, 7638. 27. H. Frauenrath, Prog. Polym. Sci. 2005, 30 , 325. 28. A. D. Schluter, J. P. Rabe, Angew. Chem. Int. Ed. Engl. 2000, 39, 864. 29. D. A. Tomalia, PM Kirchhoff. USP 1987, 4694064. 30. Z. Bo, J. P. Rabe, A. D. Schluter, Angew. Chem. 1999, 111, 2540.; Angew. Chem. Int. Ed. 1999, 38, 2370. 31. I. Goessl, L. Shu, A. D. Schluter, J. P. Rabe, J. Am. Chem. Soc. 2002, 124, 6860. 32. B. Suijkerbuijk, B. KleinGebbink, L. Shu, A. D. Schluter, Macromolecules 2000, 33,4872 33. T. Sato, D. L. Jiang, T. Aida, J. Am. Chem. Soc. 1999, 121, 10658. 34. L. B. Vernon, H. M. Vernon, ‘Producing Molded Articles such as Dentures from Thermoplastic Synthetic Resins’, US Pat. 2234993, 1941. 35. M. Yoshida, R. Langer, A. Lendlein and J. Lahann, Polym. Rev. (Philadelphia), 2006, 46, 347. 36. A. Lendlein, H. Jiang, O. Juenger and R. Langer, Nature (London), 2005, 434, 879. 37. F. Li, A. Perrenoud and R. C. Larock, Polymer, 2001, 42, 10133. 38. F. Li and R. C. Larock, J. Appl. Polym. Sci., 2002, 84, 1533. 39. K. D. Gall, L. Martin, L. Yiping, F. Dudley, L. Mark and A. Munshi Naseem, Acta Mater., 2002, 50, 5115. 40. Y. G. Liu Ken, L. Dunn Martin and Patrick. McCluskey, Smart Mater. Struct., 2003, 12, 947. 41. 51. A. Matsuda, J. Sato, H. Yasunaga and Y. Osada, Macromolecules, 1994, 27, 7695. 42. W. I. V. Small, M. F. Metzger, T. S. Wilson and D. J. Maitland,IEEE J. Quantum Electron., 2005, 11, 892. 43. W. Lehmann, H. Skupin, C. Tolksdorf, E. Gebhard, R. Zentel, P. Kruger, M. Losche and F. Kremer, Nature (London), 2001, 410, 447. 44. D. L. Thomsen, III, P. Keller, J. Naciri, R. Pink, H. Jeon, D. Shenoy and B. R. Ratna, Macromolecules, 2001, 34, 5868. 45. C. Liu, H. Qin and P. T. Mather, J. Mater. Chem., 2007, 17, 1543. 46. C. Liu and P. T. Mather, Proceedings of the Annual Technical Conference - Society of Plastics Engineers, 60th (Vol. 3), Society of Plastics Engineers, Brookfield, CT, USA, 2002, pp. 2685. 47. H. G. Jeon, P. T. Mather and T. S. Haddad, Polym. Int., 2000, 49,453. 48. V. A. Beloshenko, Y. E. Beygelzimer, A. P. Borzenko and V. N. Varyukhin, Composites, Part A, 2002, 33, 1001. 49. A. Lendlein, S. Kelch, Angew. Chem. Int. Ed. 2002, 41, 2034. 50. C. Liu and P. T. Mather, J. Appl. Med. Polym., 2002, 6, 47. 51. T. H. Tong, ‘Shape Memory Styrene Copolymer’World Pat., 2002059170, 2002. 52. G. Liu, C. Guan, H. Xia, F. Guo, X. Ding and Y. Peng, Macromol. Rapid Commun., 2006, 27, 1100. 53. G. Zhu, G. Liang, Q. Xu and Q. Yu, Gaofenzi Xuebao, 2003, 667. 54. D. A. Chernous, S. V. Shil’ko and Y. M. Pleskachevskii, J. Eng. Phys. Thermophys., 2004, 77, 6. 55. W. G. Reyntjens, F. E. D. Prez and E. J. Goethals, Macromol. Rapid Commun., 1999, 20, 251. 56. M. Irie in Shape memory polymers, ed. K. Otsuka and C. M. ayman, Cambridge University Press, Cambridge, 1998. 57. C. Liu, S. B. Chun, P. T. Mather, L. Zheng, E. H. Haley and E. B. Coughlin, Macromolecules, 2002, 35, 9868. 58. A. Lendlein, A. M. Schmidt and R. Langer, Proc. Natl. Acad. Sci. U. S. A., 2001, 98, 842. 59. C. Liu, I. A. Rousseau and P. T. Mather, Proceedings of First World Congress on Biomimetics and Artificial Muscles, Biomimetics, Albuquerque, New Mexico, 2002. 60. C. Liu and P. T. Mather, Proceedings of the Annual Technical Conference - Society of Plastics Engineers, 61st (Vol. 2), Society of Plastics Engineers, Brookfield, CT, USA, 2003, 1962. 61. C. Min, W. Cui, J. Bei and S. Wang, Polym. Adv. Technol., 2005, 16, 608. 62. T. Ikematsu, Y. Kishimoto and M. Karaushi, ‘Block Copolymer Bumpers With Good Shape Memory’, Jpn. Pat., 02022355, 1990. 63. P. Ping, W. Wang, X. Chen and X. Jing, Biomacromolecules 2005, 6, 587 64. A. Lendlein and R. Langer , Science, 2002, 296, 1673 65. A. Alteheld, Y. Feng, S. Kelch, and A. Lendlein, Angew. Chem. Int. Ed. 2005, 44, 1188. 66. S. P. Rannard, N. J. Davis, J. Am. Chem. Soc. 2000, 122, 11729. 67. 陳衍甫; 國立中興大學化工系碩士論文, 2001. 68. T. T. Thomas, “Ketenes”, P. 38, John Wiley & Sons (1995). 69. I. Yilgor , E. Yilgor , I. G. Guler , T. C. Ward , G. L. Wilkes, Polymer , 2006, 47 , 4105. 70. J. R. Lin and L. W. Chen, Journal of Applied Polymer Science, 1998, 69, 1575. 71. L. T. J. Korley, B. D. Pate, E. L.Thomas , P. T. Hammond, Polymer, 2006, 47, 3073. 72. H. Tan, J. Li, M. Guo, R. Du, X. Xie, Y. Zhong, Q. Fu, Polymer 2005, 46 , 7230. 73. C. Liu, S. B. Chun, P. T. Mather, Macromolecules, 2002, 35, 9868.
摘要: 智慧型材料是能感覺到外部刺激、自我診斷和應答的一種新功能性材料。最著名的智慧型材料是形狀記憶材料,它能被區分成三個類型(1)金屬合金,(2)陶瓷材料,(3)高分子。然而,因為高分子材料的低成本、製程容易,以及輕易修改的最佳優勢。樹枝狀高分子則具有獨特,精確和完美的奈米結構,以致於在各個領域包括藥劑的傳遞、自我組裝系統、光電材料、催化劑等特別有用。 基於此,我們發展一個熱應答的側鏈型規則樹枝狀polyurethane系統。在追求發展具有形狀記憶效能的奈米尺寸polyurethane上,朝著兩方面邁進:(1)線性的polyurethane:硬段區塊由methylene di-p-phenyl diisocynate (MDI) 和diethylene glycol (DEG)所構成,而軟段區塊由Tone ployol 0260 (Mn=3000)所構成。(2)製備側鏈型樹枝狀polyurethane:利用polyurethane/malonamide樹枝狀分子作為鏈延長劑來改質線性的polyurethane。 藉由導入不同代數的dendrimer,運用其分子與分子間的作用力,例如氫鍵、偶極作用力以及凡得瓦力等,來補強其硬鏈段的物理性質。為了探討不同代數dendrimer以及軟硬鏈段比例的影響,我們利用DSC和拉力測試分析材料熱性質及機械性質。此外,軟硬鏈段相分離情形可藉由AFM來分析其特徵。 在形狀記憶測試方面,隨著dendrimer的導入及代數的增加,可得到具有優良形狀回復能力的PU材料,其回復率可由85% 提升至100%,且形狀回復能在3秒內完成。藉由DSC及AFM分析可得知其材料具備軟硬鏈段輕微相混合。因此在分子間作用力及軟硬鏈段輕微相混合的雙重作用下,因而提升材料的形狀回復能力,於機械強度測試中發現,導入一代dendrimer的PU材料,其機械性質最佳,斷裂延伸率最大可達700%,抗張強度可達18.8Mpa。因此在本實驗中已成功製備出具優良形狀記憶效應之側鏈型規則樹枝狀PU材料。
Intelligent material is a new functional material which can sense external stimulus and respond to it, and self-diagnose. The most famous intelligent material is shape-memory material which can be divided into three types (1) metal alloy (2) ceramic material (3) polymer. Moreover, the polymeric material attracts most attention because of its low cost, ease of processing, and facile modification. Dendrimers are nanostructures with specific, precise and predictable physical properties (lower intrinsic viscosity and higher solubility). This makes them especially useful for various areas including drug delivery, self-assembly systems, electro-optical materials, catalysts, etc. Herein, we focus on a thermo-responsive side chain dendritic polyurethane system. The pursuit of developing nano-scaled polyurethanes with shape memory effect is approached in two aspects: (1) linear polyurethane: hard domain consists of methylene di-p-phenyl diisocynate (MDI) and diethylene glycol (DEG) and Tone polyol 0260 (Mn=3000) is used as soft domain. (2) side chain dendritic polyurethane : Employing a polyurea/malonamide dendrons as chain extender to modify traditional linear polyurethanes. By embedding different generations of dendrimers in polyurethanes, the physical properties will be enhanced because of the presence of interactions such as hydrogen bonding, dipole-dipole interactions and van Der Waals forces. To probe into the influences of different generation dendritic diols and hard segment/soft segment ratios, we utilized DSC and tensile measurement to examine thermal properties and mechanical properties, respectively. In addition, phase separation was characterized by AFM. In shape-memory test, the dendritic polyurethanes possessed great recovery ability because of the presence of embedded dendrimers. After incorporation of the dendritic structures, the recovery ratio could improve from 85% to 100%, and the primary shape was fully recovered within 3 second. It was found that somewhat phase-mixed morphology was present in the dendritic polyurethanes by the study of DSC and AFM. These phase-mixed materials would further improve recovery capacity under strong molecular interactions. It is important to note that the polyurethane consisting of generation one dendrimer possessed the better mechanical properties. The elongation at break was up to 700% and the tensile strength reached as high as 18.8Mpa. Hence, novel side chain dendritic polyurethanes with excellent shape-memory effect have been successfully developed in this work.
URI: http://hdl.handle.net/11455/3636
其他識別: U0005-2208200709510400
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-2208200709510400
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