Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/16812
標題: 含NNO三牙配位基鎂與鋅錯合物之合成、結構解析及催化研究:乳酸交酯開環聚合反應
Synthesis,Characterizaiton and Catalytic Studies of Magnesium and Zinc Complexes Containing NNO-Tridentate Ligands : Their Applications to the Ring-Opening Polymerization of Lactides
作者: 葉建利
Ye, Jian-Li
關鍵字: polylactide;聚乳酸交酯;lactide;racemic lactide;magnesium;zinc;selectivity;ring-opening polymerization;左旋乳酸交酯;外消旋乳酸交酯;鎂;鋅;選擇性;開環聚合
出版社: 化學系所
引用: 1. Fujisato, T; Ikada, Y. Macromo, Symp. 1996,103,73 2. (a)http://www.biodegradable-product.com/downloads.htm .(b) http://www.sony.net/SonyInfo/technology/technology/theme/vegetableplastic_01.html . (c) http://www.sutureexpress.com/covidien-mesh.aspx 3. Drumright, R. E.; Gruber, P. R.; Henton, D. E. AdV. Mater. 2000, 2,1841 4. Uhrich, K. E.; Cannizzaro, S. M.; Langer, R. S.; Shakesheff, K. M. Chem. Rev. 1999, 99, 3181 5. Dorgan, J. R.; Lehermeier, H.; Mang,M. J. Polym. Environ. 2000, 8, 1. 6. Auras, R.; Harte, B.; Selke, S. Macromol. Biosci. 2004, 4, 835 7. Odile, D. C.; Blanca, M. V.; Didier, B. Chem. Rev. 2004, 104, 6147 8. Nomura, N.; Ishii, R.; Yamamoto, Y.; Kondo, T. ChemsEur. J. 2007, 13, 4433 9. Wachsen, K. H. Reichert, R. P. Kriiger, H. Muchb, G. Schulz, Polym. Degrad. Stab. 1997, 55, 225 10. Platel, R. H.; Hodgson, L. M.; Williams,C. K. Polym. Rev. 2008, 48, 11 11. Chamberlain, B. M.; Cheng, M.; Moore, D. R.; Ovitt, T. M.;lobkovsky, E. B.; and Coates, G. W.; J. Am. Chem. Soc. 2001, 123,3229 . 12. Bovey, F. A.; Mirau, P. A. NMR of Polymers; Academic Press:San Diego, 1996. 13. Ouhadi,T;Stevens,C;Teyssie,P.Makromol.Chem.Suppl.1975,1,191. 14. (a)Shiner, V. J. ; Whittaker, D.; Fernadez, V. P. J. Am. Chem. Soc.1963, 85 , 2318.(b) Oliver, J. G.; Phillips, P. K.; Worrall, I. J. J. Inorg. Nucl. Chem. 1969, 31, 1609. (c) Shiner, V. J.; Whittaker, D. J. Am. Chem. Soc. 1969, 91, 394. (d) Kleinschmidy, D. C.; Shiner, V. J.; Whittaker, D. J. Org Chem. 1973, 38, 3384. 15. (a) Ko B,-T, Lin C,-C J. Am. Chem. Soc. 2001, 123, 7973 (b) Hsueh M.-L, Huang B.-H, Wu J, Lin, C.-C Macromolecules 2005, 38, 9482 (c) L Huang B.-H, Ko B.-T, Athar T, Lin C.-C Inorg. Chem. 2006, 45, 7348 (d) Yu T.-L, Huang B,-H, Hung W.-C, Lin C.-C, Wang T.-C, Ho R.-M Polymer, 2007, 48,4401 16. Tang, Z. H.; Chen, X. S.; Hang, Q. Z.; Bian, X. C.; Yang, L. X.; Piao, L. H.; Jing, X. B. J. Polym. Sci. Part A:Polym. Chem. 2003,41,1934 17. (a) Kricheldorf, H. R. Makromol. Chem. 1993, 194, 1665. (b) Ko, B.- T.; Lin, C.-C. J. Am. Chem. Soc. 2001, 123, 7973. (c) Chisholm, M. H.; Lin, C.-C.; Galluccia, J. C.; Ko, B,-T. Dalton Trans. 2003, 406. 18. (a) Dobrzynski, P; Kasperczyk, J; Bero, M; Macromolecules.1999, 32,4735 (b) Darensbourg, D. J.; Choi, W.; Karroonnirun, O.; Bhuvanesh, N. Macromolecules. 2008, 41, 3493.(c) Chisholm, M.; Galluccia, J. C.; Phomphrai, K. Inorg. Chem. 2004, 43 ,6717. 19. (a) O’Keefe, B. J.; Hillmyer, M. A.; Tolman, W. B. Dalton Trans. 2001, 2215. (b) Cabaret, O.D.; Vaca, B.M.; Bourissou, D. Chem. Rev. 2004, 104, 6147. (c) Wu, J.-C.; Yu, T.-L.; Chen, C.-T; Lin, C.-C. Coord. Chem. Rev. 2006, 250, 602. 20. (a) Nimitsiriwat, N.; Marshall, E. L.; Gibson, V. C.; Elsegood, M.R. J.; Dale, S. H. J. Am. Chem. Soc. 2004, 126, 13598. (b) Dove, A. P.; Gibson, V. C.; Marshall, E. L.; Rzepa, H. S.; White, A. J. P.; Williams, D. J. J. Am. Chem. Soc. 2006, 128, 9834.(c) Nimitsiriwat, N.; Gibson, V. C.; Marshall, E. L.; White, A. J. P.; Dale, S. H.; Elsegood, M. R. J. Dalton Trans. 2007, 4464 21. Peckermann, I.; Kapelski, A.; Spaniol, T.P.; Okuda, J. Inorg Chem. 2009, 48,5526 22. Ma, H.; Spaniol, T. P.; Okuda, J. Angew. Chem., Int. Ed. 2006, 45, 7818. 23. Ajellal, N.; Lyubov, D. M.; Sinenkov. M. A.; Fukin, G. K.; Cherkasov, A. V.; Thomas, C. M.; Carpentier, J.F.; Trifonov, A. A. Chem. Eur. J. 2008, 14, 5440 24. (a) Chmura, A. J.; Davidson, M. G.; Jones, M. D.; Lunn, M. D.; Mahon,M. F.; Johnson, A. F.; Khunkamchoo, P.; Roberts, S. L.; Wong, S. S. F. Macromolecules 2006, 39, 7250. (b) Zelikoff, A. L.; Kopilov, J.; Goldberg, I.; Coates, G. W.; Kol, M.Chem. Commun. 2009, 6804. (c) Gendler, S.; Segal, S.; Goldberg, I.; Goldschmidt, Z.; Kol, M. Inorg.Chem. 2006, 45, 4783. 25. (a)Ning, Y.; Zhang, Y.; Rodriguez-Delgado, A.; Chen, E Y. -X. Organometallics 2008, 27, 5632.(b)Ning, Y.; Chen, E. Y.-X. J. Am. Chem.Soc. 2008, 130, 2463 26. Chmura, A. J.; Davidson, M. G.; Frankis, C. J.; Jones, M. D.; Lunn, M. D. Chem. Commun. 2008, 1293. 27. Xue, M.; Jiao R; Zhang, Y.; Yao, Y.; Shen, Q. ; Eur. J. Inorg. Chem. 2009, 4118 28. Wang, J.; Yao, Y.; Zhang, Y.; Shen, Q. Inorg Chem.2009, 48,744 29. (a) Kricheldorf, H. R.; Sumbbl, M. V.; Saunders, I. K. Macromolecules 1991, 24, 1944. (b) Aubrecht, K. B.; Hillmyer, M. A.; Tolman, W. B. Macromolecules 2002, 35, 644. (c) Amsden, B.; Wang, S.; Wyss, U. Biomacromolecules 2004, 5, 1399. 30. Chamberlain, B. M.; Cheng, M.; Moore, D. R.; Ovitt, T. M.;lobkovsky, E. B.; and Coates, G. W.; J. Am. Chem. Soc. 2001, 123, 3229. 31. Chisholm, M. H.;Gallucci, J.;Phomphrai, K. Inorg. Chem. 2002, 41, 2785 32. Marshall, E. L.;Gibson, V. C.; Rzepa, H. S. J. Am. Chem. Soc. 2005, 127, 6048 33. Nimitsiriwat, N; Gibson, V. C.; Marshall, E. L.; Elsegood, M. R. J. Inorg. Chem. 2008, 47, 5417 34. Williams, C. K.; Breyfogle, L. E.; Choi, S. K.; Nam, W.; Young, V. G.; Hillmyer, M. A.; Tolman, W. B. J. Am. Chem. Soc. 2003, 125, 11350. 35. Chen, H.-Y.; Tang, H. Y.; Lin, C.-C. Macromolecules 2006, 39, 3745. 36. Yu, R.-C.; Hung, C.-H.; Huang, J.-H.; Lee, H.-Y.; Chen. J.-T. Inorg. Chem. 2002, 41, 6450. 37. Doherty, S.; Errington, R. J.; Housley, N.; Clegg, W. Organometallics 2004, 23, 2382 38. Lee, W.-Y.; Hsieh, H.-H.; Hsieh, C.-C.; Lee, H.-M.; Lee, G.-H.; Huang, J.-H.; Wu, T.-C.; Chuang S.-H. J. Organomet. Chem. 2007, 692, 1131. 39. Tang, H.-Y.; Chen, H.-Y.; Huang, J.-H.; Lin, C.-C. Macromolecules 2007, 40, 8855. 40. Hung, W.-C.; Huang, Y.; Lin, C.-C. J. Polym. Sci ., Part A: Polym. Chem. 2008, 46, 6466. 41. Huang, Y.; Hung, W.-C.; Peng, Y.-L.; Lin, C.-C. J. Polym. Sci ., Part A: Polym. Chem. 2009, 47, 2318. 42. 2009年蔡宗恩碩士論文 43. Save, M.; Schappacher, M.; Soum, A. Macromol. Chem. Phys. 2002, 203, 889. 44. F. H. Allen; O. Kennard; D. G. Watson; L. Brammer; A. G. Orpen; J. Chem. Soc., Perkin Trans. 1987, 2 ,S1 45. Bunten, K. A.; Chen, L.; Fernandez, A. L. ; Poe, A. J. Coord. Chem. Rev. 2002, 233-234 , 41 46. (a) A. Kowalski, A. Duda , S. Penczek, Macromolecules, 2000, 33, 1964 (b) Chen, H.-Y; Zhang J.; Lin, C.-C.; Reibenspies J. H.; Miller S. A. Green Chem., 2007. 9, 1038
摘要: 
合成4種不同取代基修飾之N N O三牙烯胺酮配位基(NNO-tridentate ketiminate ligand),分別與二乙基鋅或二正丁基鎂搭配苯甲醇合成一系列7個以苄氧基為架橋五配位的鋅、鎂雙核(dimeric)錯合物,並且得到錯合物[(L4)Mg(μ-OBn)] 2(4a)、[(L1)Zn(μ-OBn)]2(1b)和[(L2)Zn(μ-OBn)]2(2b)三者之晶體結構。由開環聚合反應結果顯示,鋅、鎂錯合物( [LZn(μ-OBn)]2、[LMg(μ-OBn)]2 )對左旋乳酸交酯的開環聚合反應皆有極佳效果,可控制其分子量且分子量分佈度狹窄,而在對外消旋乳酸交酯之開環聚合反應上,則發現鎂錯合物有較高選擇性。根據錯合物[(L1)Mg(μ-OBn)]2(1a)動力學研究,在開環聚合反應中整個速率反應式為-d[LA]/dt = kp[LA]2[1a]1.77。

Seven metal benzylalkoxides ,containging NNO-tridentate ketoiminate ligands [L2M2(μ-OBn)2] (L=L1-H-L4-H, M = Mg or Zn) have been synthesized and characterized. X-ray crystal structural studies of [(L4)Mg(μ-OBn)] 2(4a)、[(L1)Zn(μ-OBn)]2(1b) and[(L2)Zn(μ-OBn)]2(2b) reveal these complexes are dinuclear species with the geometry around metal center is penta-coordinated bridging through the benzylalkoxy oxygen atoms in the solid structure.
The activities and stereoselectivities of these seven complexes toward the ring-opening polymerization of L-lactide and rac-lactide have been investigated. Polymerization of L-lactide initiated by these seven metal benzyloxides proceeds rapidly with good molecular weight control and yields polymer with very narrow molecular weight distribution. Experimental results show that among these metal benzylalkoxides, complexes 1a-4a all exhibit high stereoselectivity with Pr above 80 % and complex 1a possesses the highest activity and stereoselectivity.
URI: http://hdl.handle.net/11455/16812
其他識別: U0005-2106201021250300
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