Please use this identifier to cite or link to this item:
標題: 合成與鑑定具NNO-三牙配位基之鋁錯合物及其在左旋乳酸交酯和環己內酯開環聚合反應上之研究
Synthesis of Aluminum Complexes Supported by NNO-Tridentate Ketiminate Ligands and Their Application in the Ring-Opening Polymerization of L-Lactide and ε-Caprolactone
作者: 蘇育主
Su, Yu-Chu
關鍵字: Aluminum;鋁;R.O.P.;lactide;caprolactone;開環聚合;左旋乳酸交酯;環己內酯
出版社: 化學系所
引用: 1. 行政院環境保護署 2. Huang, L.; Zhuang, X.; Hu, J.; Lang, L.; Zhang, P.; Wang, Y.; Chen, X.; Wei, Y.; Jing, X. Biomacromolecules 2008, 9, 850–858. 3. Vink, E. T. H.; Rabago, K. R.; Glassner, D. A.; Gruber, P. R. Polym. Degrad. Stab. 2003, 80, 403–419. 4. Gupta, A. P.; Kumar, V. Eur. Polym. J. 2007, 43, 4053–4074. 5. Place, E. S.; George, J. H.; Williams, C. K.; Stevens, M. M. Chem. Soc. Rev. 2009, 38, 1139–1151. 6. Eva M. Martin del Valle, Miguel A. Galan and Ruben G. Carbonell Ind. Eng. Chem. Res., 2009, 48 (5), pp 2475–2486. 7. 8. Odile, D. C.; Blanca, M. V.; Didier, B. Chem. Rev. 2004, 104, 6147-6176. 9. (a) Chisholm, M.-H.; Lin, C.-C.; Gallucci, J.-C.; Ko, B. -T. Dalton Trans. 2003, 406. (b) Hsueh, M.-L.; Huang, B.-H.; Wu, J.; Lin, C.-C. Macromolecules 2005, 38, 9482. (c) 2009年蔡岳軒碩士論文. 10. (a) Shueh, M.-L.; Wang,Y. -S.; Huang, B.-H.; Kuo, C.-Y. ; Lin,C.-C. Macromolecules 2004, 37, 5155–5162. (b) Yu,T.-L.; Wu, C. -C.; Chen,C. -C.; Huang, B.-H. ; Wu, J.; Lin, C.-C. Polymer 2005, 46, 5909. (c) Tang, H.-Y.; Chen, H.-Y.; Huang, J.-H.; Lin, C.-C. Macromolecules 2007, 40, 8855. (d) Wu, J.; Chen, Y.-Z.; Hung, W.-C.; Lin, C.-C. Organometallics 2008, 27, 4970. (e) Huang, Y.; Hung, W.-C.; Liao, M.-Y.; Tsai, T.-E.; Peng, Y.-L.; Lin,C.-C. J. Polym. Sci., Part A: Polym. Chem. 2009, 47, 2318. (f) Jessie D. Monegan , Scott D. Bunge, Inorg. Chem. 2009, 48 , 3248. 11. (a) Chisholm, M. H.; Gallucci, J. C.; Phomphrai, K. Chem. Commun. 2003, 48. (b) M. S. Hill and P. B. Hitchcock, Chem. Commun. 2003, 1758. (c) Chisholm, M. H.; Gallucci, J. C.; Phomphrai, K. Inorg. Chem. 2004, 43, 6717. (d) Darensbourg, D. J.; Choi, W.; Richers, C. P. Macromolecules 2007, 40, 3521.(e) Darensbourg, D. J.; Choi, W.; Karroonnirun, O.; Bhuvanesh, N. Macromolecules 2008, 41, 3493. 12. (a) Aubrecht, K. B.; Hillmyer, M. A.; Tolman, W. B. Macromolecules 2002, 35, 644. (c) Amsden, B.; Wang, S.; Wyss, U. Biomacromolecules 2004, 5, 1399. (d) Nimitsiriwat, N.; Marshall, E. L.; Gibson, V. C.; Elsegood, M. R. J.; Dale, S. H. J. Am. Chem. Soc. 2004, 126, 13598. (d) Wu, J.; Huang, B.-H.; Hsueh, M.-L.; Lai, S.-L; Lin, C.-C. Polymer 2005, 46, 9784. 13. (a) Takeda, N.; Inoue, S. Makromol. Chem.1978, 119, 1377 (b) Kuroki, M.; Watanabe, T.; Aida, T. ; Inoue, S. J. Am. Chem. SOC. 1991, 113, 5903.(c) Dubois, P.; Jacobs, C.; Jerome, R.; Teyssie, P. Macromolecules 1991, 24, 2266.(d) Spassky, N.; Wisniewski, M.; Pluta, C.; Le Borgne, A. Macromol. Chem. Phys. 1996, 197, 2627. (e) Ko, B. -T.; Lin, C. -C. Macromolecules 1999, 32, 8296. (f) Ovitt, T. M.; Coates, G. W., J. Am. Chem. Soc. 1999, 121, 4072. (g) Ovitt, T. M.; Coates, G. W., J. Polym. Sci., Polym. Chem., 2000, 38, 4686–4692. (h) Ovitt, T. M.; Coates, G. W. J. Am. Chem. Soc. 2002, 124, 1316–1326. (i) Huang, C.-H.; Wang, F.-C.; Ko, B.-T.; Yu, T. L.; Lin, C.-C. Macromolecules 2001, 34, 356–361. (j) Liu Y-C; Ko B.-T ; Lin C.-C Macromolecules 2001, 34, 6196–6201. (k) Wu, J.; Pan, X.; Tang, N.; Lin, C. -C. Eur. Polym. J. 2007, 43, 5040–5046. (l) Nonsee Nimitsiriwat, Vernon C. Gibson, Edward L. Marshall and Mark R. J. Elsegood, Inorg. Chem. 2008, 47, 5417. 14. (a) Kricheldorf, H. R.; Lee, S.-R.; Bush, S. Macromolecules 1996, 29, 1375.(b) Kricheldorf, H. R. Macromol. Symp. 2000, 153, 55.(c) Chisholm, M. H.; Delbridge, E. E. New J. Chem. 2003, 27, 1177.(d) Grafov, A.; Vuorinen, S.; Repo, T.; Kemell, M.; Nieger, M.; Leskela, M. Eur. Polym. J. 2008, 44, 3797. 15. (a) Nomura, N.; Ishii, R.; Yamamoto, Y.; Kondo, T. Chem. Eur. J. 2007, 13, 4433.(b) Tina M. Ovitt ; Geoffrey W. Coates J. Am. Chem. Soc. 2002, 124, 1316. 16. Ouhadi, T.; Stevens, C.; Teyssie, P. Makromol. Chem. Suppl. 1975, 1, 191. 17. Alton J. Banks. J. Chem. Educ., 1992, 69 (1),18. 18. Zhang, C.; Wang Z.-X. J. Organomet. Chem. 2008, 693, 3151. 19. Kuo-Fu Peng and Chi-Tien Chen Dalton Trans., 2009, 9800. 20. Chamberlain, B. M.; Cheng, M.; Moore, D. R.; Ovitt, T. M.; Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc. 2001, 123, 3229. 21. Yu, R. -C.; Hung,C. H.; Huang, J. H.; Lee, H. Y.; Chen, J. T. Inorg. Chem. 2002, 41, 6450. 22. Chisholm, M. H.; Gallucci,J. C.; Zhen, H.; Huffman,J. C. Inorg. Chem. 2001, 40, 5051. 23. Daniela Pappalardo, Liana Annunziata, and Claudio Pellecchias, Macromolecules 2009, 42, 6056. 24. (a) Iwasa, N.; Katao, S.; Liu, J.; Fujiki, M.; Furukawa, Y.;Nomura, K. Organometallics 2009, 28 (7), 2179–2187. (b) Iwasa, N.; Fujiki, M.; Nomura, K. J. Mol. Catal. A 2008, 292, 67–75. (c) Liu, J.; Iwasa, N.; Nomura, K. Dalton Trans. 2008, 3978–3988. (d) Iwasa, N.; Liu, J.; Nomura, K. Catal. Commun. 2008, 9, 1148–1152. 25. Huang,-Y.; Hung, W.-C.; Peng, Y.-L.; Lin, C.-C. J. Polym. Sci., Part A: Polym. Chem. 2009, 47, 2318. 26. Save, M.; Schappacher, M.; Soum, A. Macromol. Chem. Phys. 2002, 203, 889. 27. Dr. Inoue J. Polym. Sci., Part A: Polym. Chem. 2000, 38, 2861.
本篇論文主要合成一系列具有NNO-三牙配位基之鋁金屬錯合物,並且透過NMR、MS、IR和EA鑑定其結構。錯合物2、4、5、6與7更進一步由X-ray單晶繞射儀證實其結構為單核五配位之錯合物。此一系列金屬鋁錯合物在外加苯甲醇的條件下對於左旋乳酸交酯以及環己內酯之開環聚合反應均具有良好的催化活性,並且對於聚合物分子量有良好的控制性,分子量分佈於狹窄範圍內。於催化條件中改變不同比例的單體濃度抑或是增大苯甲醇的比例,由實驗結果皆可證明此系列錯合物具有Living 和Immortal之性質。經由動力學實驗發現,不同對位取代基之錯合物對於環己內酯開環聚合反應速率上的差異,並且透過動力學公式推測錯合物對環己內酯進行催化時屬於二級反應,反應速率式可表示為 -d[CL]/dt= kobs[CL]2。

A series of aluminum complexes [LAlMe2] (L=L1H~L8H) supported by NNO-tridentate ketiminate ligands were synthesized. These complexes have been fully characterized by 1H and 13C NMR as well as elemental analysis. X-ray structure determination of complexes 2、4、5、6 and 7, show that all of these complexes are mononuclear species and the geometry around aluminum center is penta-coordinated.
All of these complexes have shown to be efficient initiators for the ring-opening polymerization of L-lactide and ε-caprolactone in the presence of benzyl alcohol, yielding polymers with good molecular weight control and narrow polydispersity. Experimental results reveal that these complexes have immortal and living properties for the ring-opening polymerization.
The polymerization kinetics of the complexes were also studied, and the experimental results demonstrate the reaction rate is depending on the substituents on ligands with -d[CL]/dt= kobs[CL]2.
其他識別: U0005-2206201122253500
Appears in Collections:化學系所

Show full item record

Google ScholarTM


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