臺灣博碩士論文加值系統

本篇論文主要合成具有大立體障礙之希夫鹼(Schiff base)輔助配位基，搭配鈷、鉻和鋅金屬合成錯合物1-6，並對其作一系列之鑑定工作。錯合物1•MeOH和5進一步由X-ray單晶繞射儀鑑定其結構為單核五配位以及單核四配位之結構。利用此系列錯合物對不同環酯類單體進行開環聚合反應。鈷錯合物(1-2)和鉻錯合物(3-4)搭配共催化劑(DMAP)，對酸酐與環氧類單體的共聚合反應具有良好的催化活性以及分子量分佈度的控制性。錯合物1-4搭配Al(OiPr)3對三亞甲基碳酸酯(TMC)的開環聚合反應，能夠有效的改善聚合物分子量的分佈度。鋅錯合物5-6對左旋乳酸交酯之開環聚合反應具有良好的催化活性，以及聚合物分子量的控制性。另外，於催化條件中改變不同比例的單體濃度或是增大苯甲醇的比例，由實驗證明錯合物6具有Living和Immortal之性質。

A series of cobalt, chromium and zinc complexes supported by Schiff base ligands (1-6) with sterically bulky cumyl groups have been synthesized and characterized. X-ray structure of complex 1•MeOH and 5 shows distorted square pyramidal geometry around the cobalt center and distorted tetrahedral geometry around the zinc center, respectively.
Cobalt complexes (1-2) and chromium complexes (3-4) have shown to be efficient initiators for the copolymerization of cyclohexene oxide and succinic anhydride in the presence of DMAP as a cocatalyst. Ring-opening polymerization of TMC with complexes 1-4 and Al(OiPr)3 effectively improve the polydispersity of PTMC. In addition, complexes 5-6 are also efficient initiators for the ring-opening polymerization of L-LA. Experimental results reveal that complex 6 have living and immortal properties for the ring-opening polymerization.

第一章 緒論 1
1-1　前言 1
1-2　環保材料 2
1-3開環聚合與共聚合反應(Ring-Opening Polymerization and Copolymerization)的介紹 5
1-4　催化劑的研發與設計 7
1-5　聚合反應之歷史文獻 9
第二章　實驗部分 28
2-1　鑑定儀器 28
2-2 藥品與溶劑處理 30
2-3　操作技巧 33
2-4　配位基之合成 36
2-5　錯合物之合成 40
2-6　催化劑於開環聚合反應上之應用 46
第三章 結果與討論 49
3-1　配位基及錯合物1-6之合成與光譜研究 49
3-2　錯合物之晶體解析 58
3-3　催化劑於開環聚合反應上的應用 64
第四章 結論 81
參考文獻 83
附錄 87
1.錯合物1•MeOH晶體資料 87
2.錯合物5晶體資料 100

1.L. Huang, X. Zhuang, J. Hu, L. Lang, P. Zhang, Y. Wang, X. Chen, Y. Wei, X. Jing, Biomacromolecules 2008, 9, 850.
2.A. P. Gupta, V. Kumar, Eur. Polym. J. 2007, 43, 4053.
3.E. T. H. Vink, K. R. Rabago, D. A. Glassner, P. R. Gruber, Polym. Degrad. Stab. 2003, 80, 403.
4.http://www.ctajn.com.cn
5.E. S. Place, J. H. George, C. K. Williams, M. M. Stevens, Chem. Soc. Rev. 2009, 38, 1139.
6.http://www.yuancailiao.net/trade/offerdetail-3057855.aspx
7.T. Fujisato, Y. Ikada, Macromo, Symp., 1996, 103, 73.
8.(a) J. C. Bogaert, P. Coszach, Macromol. Symp., 2000, 153, 287. (b) M. Vert, Macromol. Symp., 2000, 153, 333. (c) R. A. Jain, Biomaterials, 2000, 21, 2475. (d) S. K. Ritter, Chem. Eng. News., 2002, 80, 26.
9.D. J. Darensbourg, R. R. Poland, and C. Escobedo, Macromolecules, 2012, 45, 2242-2248.
10.(a) B. T. Ko, C. C. Lin, J. Am. Chem. Soc. 2001, 123, 7973. (b) M. H. Chisholm, C. C. Lin, J. C. Gallucci, B. T. Ko, Dalton Trans. 2003, 406. (c) M. L. Hsueh, B. H. Huang, J. Wu, C. C. Lin, Macromolecules 2005, 38, 9482.
11.(a) H. R. Kricheldorf, Makromol. Chem. 1993, 194, 1665. (b) B. T. Ko, C. C. Lin, J. Am. Chem. Soc. 2001, 123, 7973. (c) M. L. Shueh, Y. S. Wang, B. H. Huang, C. Y. Kuo, C. C. Lin, Macromolecules 2004, 37, 5155. (d) T. L. Yu, C. C. Wu, C. C. Chen, B. H. Huang, J. Wu, C. C. Lin, Polymer 2005, 46, 5909. (e) J. Wu, Y. Z. Chen, W. C. Hung, C. C. Lin, Organometallics 2008, 27, 4970.
12.(a) H. Urayama, T. Kanamori, K. Fukushima, Y. Kimura, Polymer, 2003, 44, 5635. (b) O. D. Cabaret, B. M. Vaca, D. Bourissou, Chem. Rev. 2004, 104, 6147. (c) J. C. Wu, T. L. Yu, C. T. Chen, C. C. Lin, Coord. Chem. Rev. 2006, 250, 602. (d) H. M. Ye, J. Xu, J. Freudenthal, B. J. Kahr, Am. Chem. Soc., 2011, 133, 13848.
13.(a) M. H. Chisholm, J. C. Gallucci, K. Phomphrai, Chem. Commun. 2003, 48. (b) M. S. Hill, P. B. Hitchcock, Chem. Commun. 2003, 1758. (c) D. J. Darensbourg, W. Choi, O. Karroonnirun, N. Bhuvanesh, Macromolecules,2008, 41, 3493.
14.(a) H. R. Kricheldorf, M. V. Sumbbl, I. K. Saunders, Macromolecules 1991, 24, 1944. (b) K. B. Aubrecht, M. A. Hillmyer, W. B. Tolman, Macromolecules 2002, 35, 644. (c) N. Nimitsiriwat, E. L. Marshall, V. C. Gibson, M. R. J. Elsegood, S. H. Dale, J. Am. Chem. Soc. 2004, 126, 13598. (d) J. Wu, B. H. Huang, M. L. Hsueh, S. L. Lai, C. C. Lin, Polymer 2005, 46, 9784.
15.(a) O. D. Cabaret, B. M. Vaca, D. Bourissou , Chem. Rev. 2004, 104, 6147-6176. (b)J. Wu, T. L. Yu, C. T. Chen, C. C. Lin, Coord. Chem. Rev., 2006, 250, 602-626. (c) N. Nomura, R. Ishii, Y. Yamamoto, T. Kondo, Chem. Eur. J., 2007, 13, 4433-4451. (d) D. J. Darensbourg, Chem. Rev., 2007, 107, 2388-2410. (e) C. M. Thomas, Chem. Soc. Rev., 2010, 39, 165-173. (f) G. Q. Chen, M. K. Patel, Chem. Rev., 2012, 112, 2082-2099.
16.M. H. Chisholm, J. C. Gallucci, H. Zhen, Inorg. Chem. 2001, 40, 5051.
17.D. Pappalardo, L. Annunziata, C. Pellecchias, Macromolecules 2009,42, 6056.
18.H. Y. Chen, H. Y. Tang, C. C. Lin, Macromolecules 2006, 39, 3745.
19.C. Robert, F. Montigny, C. M. Thomas, Nat. Commun. 2011, doi:10.1038/ncomms1596.
20.A. M. DiCiccio, G. W. Coates, J. Am. Chem. Soc. 2011, 133, 10724-10727.
21.(a) S. Huijser, E. H. Nejad, R. Sablong, C. d. Jong, C. E. Koning, R. Duchateau, Macromolecules, 2011, 44, 1132-1139. (b) E. H. Nejad, A. Paoniasari, C. E. Koning, R. Duchateau, Polym. Chem., 2012,3, 1308-1313. (c) E. H. Nejad, C. G. W. van Melis, T. J. Vermeer, C. E. Koning, R. Duchateau, Macromolecules, 2012, 45, 1770-1776.
22.J. Yang, Y. Yu, Q. Li, Y. Li, A. Cao, Journal of Polymer Science: Part A: Polymer Chemistry, 2005, 43, 373-384.
23.D. J. Darensbourg, P. Ganguly, D. Billodeaux, Macromolecules, 2005, 38, 5406-5410.
24.D. J. Darensbourg, A. I. Moncada, Macromolecules, 2009, 42, 4063-4070.
25.T. M. Ovitt, G. W. Coates, J. Am.Chem. Soc. 2002, 124, 1316.
26.N. Nomura, R. Ishii, M. Akakura, K. Aoi, J. Am. Chem. Soc. 2002,124, 5938.
27.H. L. Chen, S. Dutta, P.Y.Huang, C. C. Lin, Organometallics, 2012, 31, 2016.
28.H. Ajiro, K. L. Peretti, E. B. Lobkovsky, G. W. Coates, Dalton Trans., 2009, 8828-8830.
29. J. Welby, L. N. Rusere, J. M. Tanski, L. A. Tyler, Inorganica Chimica Acta, 2009, 362, 1405-1411.
30. M. Helou, O. Miserque, J. M. Brusson, J. F. Carpentier, S. M. Guillaume, Chem. Eur. J. 2008, 14, 8772-8775.
31. M. Save, M. Schappacher, A. Soum, Macromol. Chem. Phys. 2002, 203, 889.
32. D. J. Darensbourg, P. Ganguly, D. Billodeaux, Macromolecules 2005, 38, 5406-5410.
33. S. Inoue, J. Polym. Sci., Part A: Polym. Chem. 2000, 38, 2861.