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標題: 自組裝氫鍵尿素超分子合成及研究
Facile Synthesis and Study on Self-Assembly H-bonded Urea Supramolecules
作者: Yi-Syuan Guo
關鍵字: urea;hydrogen bonding;self-assembly;supramolecule;尿素;氫鍵;自組裝;超分子
引用: Reference 1. Weibo Huang, Jiayu Xiang, Ping Lv, Xinmao Li. Study on Mechanical Properties Aging of Spray Pure Polyurea for Hydraulic Concrete Protection [J]. Advanced Materials Research, 2012 ,376:1325-1329(EI) 2. Lehn J-M. Supramolecular Chemistry. 1 ed. Weinheim: Wiley-VCH; 1995 May 1995. 271 p. 3. Lehn, J. M. Proceedings of the National Academy of Sciences of the United States of America 2002, 99, 4763. 4. Otsuka, H. Polymer Journal 2013, 45, 879. 5. Ying, H.; Zhang, Y.; Cheng, J. Nature communications 2014, 5, 3218. 6. Chang, F.-C. Manual of Applied Polymer; Wunan: Taiwan, 2003. 7. Hellbach, H. M., Franz; Towae, Friedrich; BASF A.-G., Fed. Rep. Ger.: 1984; Vol. US 1984-599821. 8. Bohmholdt, G. H., Wilhelm; Kirchner, Peter; Michalczak, Hans Werner In Eur. Pat. Appl.; Huels A.-G.: Germany, 1993. 9. Heitkaemper, P. K., Klaus; Fauss, Rudolf; Findeisen, Kurt; Bayer A.-G., Fed. Rep. Ger: 1983; Vol. US4388238. 10. Thavonekham, B. Synthesis 1997, 1189. 11. Chao-Hsing, L., National Chung Hsing University, 2008. 12. Chun-Ying, H., National Chung Hsing University, 2010. 13. Pan, W.-C., National Chung Hsing University, 2013. 14. Anastas, P.; Eghbali, N. Chem Soc Rev 2010, 39, 301. 15. Binder, W. H.; Bernstorff, S.; Kluger, C.; Petraru, L.; Kunz, M. J. Advanced materials 2005, 17, 2824. 16. Wang Sai, W. B., Duan Junfei, Fang Jianglin, Cheng Dongzhong Progress in Chemistry 2013. 17. Adarsh, N. N. K., D. Krishna; Dastidar, Parthasarathi Tetrahedron 2007, 63. 18. Piepenbrock, M. O.; Lloyd, G. O.; Clarke, N.; Steed, J. W. Chemical communications 2008, 2644. 19. Lloyd, G. O.; Piepenbrock, M.-O. M.; Foster, J. A.; Clarke, N.; Steed, J. W. Soft Matter 2012, 8, 204. 20. Masamichi Yamanaka, T. N., Tomue Nakagawa, Hideyuki Itagaki Tetrahedron Letters 2007, 48, 8990. 21. Lu, C. C.; Su, S. K. Supramolecular Chemistry 2009, 21, 547. 22. Luo Ning, W. D.-N., and Ying Sheng-Kang Macromolecules 1997, 30, 4405. 23. Cheng, C.-C., National Chung Ching University, 2006. 24. Liang Xue, S. D., Zhi Li Macromolecules 2009, 42, 964. 25. A. Tessa ten Cate, D. J. M. v. B., A. J. H. Spiering, Patricia Y. W. Dankers, Rint P. Sijbesma, E. W. Meijer Polymer Preprints 2003, 44(1). 26. Evans, S. D. F., T. M.; Ulman, A Langmuir : the ACS journal of surfaces and colloids 1995, 11.
本研究致力於以有效快速的合成方法製備聚氨酯-尿素超分子,並研究其由氫鍵所導致的自組裝行為。在本實驗中,以4-胺基苯胺(4-aminobenzylamine)為起始原料,與碳酸二苯酯(Diphenyl carbonate)反應之後合成一帶有雙邊苯基的Diphenyl Tolylene-alpha,4-carbamate (4-TABPC),另一則是由反應選擇性控制羰基化反應而保留芳香族胺基的ABPC。4-TABPC可以被運用在熱裂解的研究工作進一步製備帶有反應選擇性的二異氰酸鹽。ABPC則更進一步的運用在合成不同鍊段長度及氫鍵鏈段的聚胺酯-尿素超分子。透過胺基苯酸酯(carbamate)的胺化反應及異氰酸鹽的添加,精準帶有不同數目尿素官能基的聚胺酯-尿素超分子可作為自組裝材料的研究。分子的物理性質及特性能透過結構分析得到進一步的研究。以不同帶有尿素官能基之硬鍊段反應,合成出軟硬鍊段交替的超分子結構,進一步建立尿素官能基與自組裝行為的關係與架構。

In an effort to explore new preparative approach to polyurethane/urea, syntheses of polyurethane-urea supramolecules and their self-assembling behaviors due to their H-bonding interactions have been explored. In the study, 4-aminobenzyl amine (ABA) was used as our starting intermediate to react with diphenyl carbonate (DPC) in making diphenyl tolylene-alpha,4-carbamate (4-TABPC) or 4-aminobenzyl phenyl carbamate (ABPC) selectively through controlled carbonylations. ABPC were then used as our stepping stones to prepare several polyurethane-urea supramolecules of different chain-lengths and H-bonding sites for this study.
Through trans-amination of carbamate groups and addition of isocyanate to the intermediates prepared above, we could rapidly synthesize polyurethane-ureas macromolecules with precise urea-urethane units of two, four or six function groups in the macro-molecular chain terminals, H-S-H, for self-assembling study. Physical and spectral properties of the macromolecules were determined to correlate their self-assembling behaviors with their structures.
It was found that isocyanate-terminated prepolymers made from 2,4-TDI with polycaprolactone diol (PCL diol) of M.W. 2000 or with PCL M.W. triol of 1000 could give the most desirable soft segments with low PDIs and thermal stability. These prepolymers were then reacted with the multi-urea hard-segments at their end groups as supramolecules. Several elastomeric films could then be prepared by physical blending of two low molecular-weights polyurethane-urea macromolecules with complimentary properties.
其他識別: U0005-0602201512341200
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