Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/96277
標題: Zinc complexes Bearing (Pyridinyl / Pyrazolyl / Oxazolinyl)-Indolate ligands: Synthesis, Characterization and Application in Ring-Opening Polymerization of L-Lactide
具(吡啶/吡唑/呃唑啉)吲哚配位基之鋅金屬錯合物:合成、鑑定及其對左旋乳酸交酯在開環聚合反應之應用
作者: Chun-Wei Yang
楊峻維
關鍵字: 開環聚合;聚乳酸;鋅金屬;吲哚;ROP;lactide;Zinc;indole
引用: 1. (a) https://www.etsy.com/listing/103964997/weatherbeels-listing (b) http://blog.yam.com/bomba/article/32022064 (c) http://theanthroposea.blogspot.tw/ (d) http://news.ltn.com.tw/news/society/breakingnews/1748034 (e) http://info.ep.hc360.com/2008/04/17111352895.shtml (f) https://www.1688.com/pic/-D3F1C3D7D1C0C7A9.html (g) http://blog.xuite.net/zhang690817/twblog/ (h) http://sincianati.pixnet.net/blog (i) http://www.omschina.net/communion/keyan/2006/0822/1892.html (j) http://www.rensheng2.com/1620000/1612368.shtml (k) https://www.flickr.com/photos/gergtreble/4278598285/ 2. S. Mecking, Angew. Chem. Int. Ed. 2004, 43, 1078 3. E.T.H. Vink, K. R. Ra'bago, D. A. Glassner, P. R. Gruber, Polymer Degradation and Stability, 2003, 80, 403–419 4. (a) D. W. Hutmacher, Biomaterials, 2000, 21, 2529-2543; (b) R. S. Narins, L. Baumann, F. S. Brandt, S. Fagien, S. Glazer, N. J. Lowe, G. D. Monheit, M. I. Rendon, R. J. Rohrich, and W. P. Werschler, J. AM. ACAD. DERMATOL., 2010, 62(3), 449-462; (c) K.T. Nguyen, S. H. Sua, A. Shenga, D. Wawrob, N. D. Schwadeb, C. F. Brouse, P. E. Greilich, L. Tang, R. C. Eberhart, Biomaterials, 2003, 24, 5191-5201 5. (a) E. F. Connor, G. W. Nyce, A. Möck, and J. L. Hendrick. J. Am. Chem. Soc., 2002, 124, 914-915.; (b) S. Matsumura, K. Mabuchi, and K. Toshima. Macromol. Rapid Commun., 1997, 18, 477-482. 6. C. M. Silvernail, L. J. Yao, L. M. R. Hill, M. A. Hillmyer and W. B. Tolman, Inorg. Chem., 2007, 46, 6565-6574. 7. (a) H. R. Kricheldorf, M. Berl, N. Scharnagl. Macromolecules, 1988, 21, 286-293.; (b) P. Dubois, C. Jacobs, R. Jérôme, P. Tessié. Macromolecules, 1991, 24, 2266-2270. 8. C. M. Silvernail, L. J. Yao, L. M. R. Hill, M. A. Hillmyer and W. B. Tolman, Inorg. Chem., 2007, 46, 6565-6574. 9. W.-A. Ma, and Z.-X. Wang. Dalton Trans., 2011, 40, 1778-1786. 10. M. H. Chisholm, J. C. Gallucci, C. Krempner. Polyhedron, 2007, 26, 4436-4444. 11. B. M. Chamberlain, M. Cheng, D. R. Moore, T. M. Ovitt, E. B. Lobkovsky, and G. W. Coates. J. Am. Chem. Soc., 2001, 123, 3229-3238. 12. P. Piromjitpong, P. Ratanapanee, W. Thumrongpatanaraks, P. Kongsaeree, and K. Phomphrai. Dalton Trans., 2012, 41, 12704-12710. 13. O. Degee, P. Dubois, S. Jacobsen. S. G. Fritz, Jerome. R. J. Polym. Sci., Polym. Chem., 1999, 37, 2413-2420. 14. A. Kowalski, A. Duda, and S. Penczek. Macromolecules, 1998, 31, 2114-2122. 15. G. Schwach, J. Coudane, R. Engel, and M. Vert. Polymer International 1988, 46, 177-182. 16. A. P. Dove, V. C. Gibson, E. L. Marshall, A. J. P.White and D. J. Williams, Dalton Trans., 2004, 570-578. 17. (a) M. H. Chisholm, J. Gallucci and K. Phomphrai, Inorg. Chem., 2005, 44, 8004. (b) M. H. Chisholm, N. W. Eilerts, J. C. Huffman, S. S. Iyer, M. Pacold, and K. Phomphrai, J. Am. Chem. Soc., 2000, 122, 11845; (c) M. H. Chisholm, J. C. Gallucci and K. Phomphrai, Inorg. Chem., 2004, 43, 6717. 18. X. Xu, Y. Chen, G. Zou, Z. Mac and G. Li, J. Organomet. Chem., 2010, 695, 1155. 19. (a) C.-T. Chen, C.-Y. Chan, C.-A. Huang, M.-T. Chen and K.-F. Peng, Dalton Trans., 2007, 4073-4078; (b) M.-T. Chen and C.-T. Chen, Dalton Trans., 2011, 40, 12886-12894; (c) M.-T. Chen, P.-J. Chang, C.-A. Huang, K.-F. Peng and C.-T. Chen, Dalton Trans., 2009, 41, 9068–9074; (d) C.-T. Chen, H.-J. Weng, M.-T. Chen, C.-A. Huang and K.-F. Peng, Eur. J. Inorg. Chem., 2009, 2129-2135; (e) K.-F. Peng and C.-T. Chen, Dalton Trans., 2009, 9800-9806. 20. (a) K.-F. Peng, Y. Chen, and C.-T. Chen. Dalton Trans., 2015, 44, 9610–9619.; (b) C.-T. Chen, D.-H. Lin and K.-F. Peng, Polymers, 2015, 7, 1954-1964. 21. Y. Kim, G. K. Jnaneshwara, and J. G. Verkade, Inorg. Chem., 2003, 42(5), 1437-1447. 22. G. Xiao, B. Yan, R. Ma, W. J. Jin, X. Q. Lu, L. Q. Ding, C. Zeng, L. L. Chen and F. Bao, Polym. Chem., 2011, 2, 659-664. 23. K. D-.Pressing, J. H. Lehr, M. E. Pratt, L. N. Dawe, A. A. Sarjeantc and C. M. Kozak, Dalton Trans., 2015, 44, 12365-12375. 24. Z.-R. Dai, C.-F. Yin, C. Wang, J.-C. Wu, Chin. Chem. Lett., 2016, 27(11), 1649-1654. 25. A. Dobbs. J. Org. Chem., 2001, 66, 638-641. 26. (a) S. Kotha, M. Saifuddin and V. R. Aswar, Org. Biomol. Chem., 2016, 14, 9868–9873; (b) S. Yokozawa, N. Ohneda, K. Muramatsu, T. Okamoto, H. Odajima, T. Ikawa, J.-I. Sugiyama, M. Fujita, T. Sawairi, H. Egami, Y. Hamashima, M. Egid and S. Akai, RSC Adv., 2015, 5, 10204-10210. 27. H. Wolfle, H. Kopacka, K. Wurst, P. P. Pflugl, B. Bildstein, J. Organomet. Chem., 2009, 694, 2493-2512. 28. (a) W.-K. Chu, L. T.-L. Lo, S.-M. Yiu, C.-C. Ko, J. Organomet. Chem., 2011, 696, 3223-3230; (b) D. Zhao, D. L. Hughes, D. R. Bender, A. M. DeMarco, and P. J. Reider, J. Org. Chem., 1991, 56, 3001-3006 29. M. S. Mudadu, A. Singh, and R. P. Thummel, J. Organomet. Chem. 2006, 71, 7611-7617 30. J. C. Antilla, J. M. Baskin, T. E. Barder, and S. L. Buchwald, J. Org. Chem. 2004, 69, 5578-5587 31. E. Djurendić, S. D. Vujašković, M. Sakač, J. Ajduković, A. Gaković, V. Kojić, G. Bogdanović, O. Klisurić, and K. P. Gašia, ARKIVOC, 2011, (ii), 83-102. 32. (a) H. Cox, C. Norris, G. Wu, J. Guan, S. Hessey and A. J. Stace, Dalton Trans., 2011, 40, 11200-11210; (b) C. Dowling, V. J. Murphy, and G. Parkin, Inorg. Chem., 1996, 35, 2415-2420. 33. 國立中興大學化學研究所林登濠碩士學位論文
摘要: 
The pyridinyl-indolate ligand precursors L1H-L4H, L7H and L8H, pyrazolyl-indolate ligand precursor L5H and oxazolinyl-indolate ligand precursor L6H were synthesized. Treatment of ligand precursors with 0.6 equivalent of ¬¬ZnEt2 in toluene affords zinc complexes 57-64. All these compounds were characterized by NMR spectroscopy and elemental analysis. The molecular structures of 59, 62- 63 were determined by single-crystal X-ray diffraction techniques. Complexes 57-63 show catalytic activities and molecular weight controllability for the ring-opening polymerization of L-Lactide in the presence of 9-anthracenemethanol in molten lactide at 130℃. Complex 59 also exhibited both 'living' and 'immortal' characters. End group analysis of the polymer and reaction mechanism were characterized by 1H NMR spectra and ESI-MS spectra.

成功製備吡啶吲哚配位基前驅物L1H-L4H、L7H、L8H、吡唑吲哚配位基前驅物L5H、呃唑啉吲哚配位基前驅物L6H,並與0.6當量二乙基鋅試劑在甲苯溶劑中反應,可以成功合成單核雙取代基之鋅金屬錯合物57-64。合成之鋅金屬錯合物,利用核磁共振光譜以及元素分析儀數據進行鑑定,經由X-ray單晶繞射儀確定了鋅金屬錯合物59、61-63的分子結構。將鋅金屬錯合物57-63在130℃,熔融態下,於外加9-蒽甲醇的條件下,對左旋乳酸交酯進行開環聚合反應,皆有良好的催化活性與分子量控制性,且鋅金屬錯合物59具有Living和Immortal性質。催化所得之聚合物利用電噴霧電離質譜儀以及核磁共振氫光譜進行尾端官能基鑑定,並推測其催化反應機制。
URI: http://hdl.handle.net/11455/96277
Rights: 同意授權瀏覽/列印電子全文服務,2020-07-13起公開。
Appears in Collections:化學系所

Files in This Item:
File Description SizeFormat Existing users please Login
nchu-106-7104051082-1.pdf6.47 MBAdobe PDFThis file is only available in the university internal network    Request a copy
Show full item record
 

Google ScholarTM

Check


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