本研究探討 Phenoxy-imine配位之鈷錯合物調控的自由基聚合反應，其配位基結構與 salen*結構相似，且具有與 CoII(acac)2一樣的四面體構型。設計一系列具有不同官能基的 Phenoxy-imine配位之鈷錯合物，進行有機鈷金屬錯合物調控自由基聚合反應 (Cobalt-mediated radical polymerization；CMRP)。發現控制劑對醋酸乙烯酯聚合反應控制效果會隨著配位基的立體阻礙增加、推電子性減少而上升；反之，則會使聚合反應偏向鏈轉移聚合反應。以催化劑 1a的控制效果最佳，但在60 oC下的分子量偏差相當大，因此優化反應條件，發現當降低溫度時能使分子量偏差程度降低，並且在 0 oC時，幾乎完全符合理論分子量。在醋酸乙烯酯鏈轉移聚合反應中，此系列以催化劑 2b的表現最為出色，並且比CoII(dmgBF2)2(H2O)2的鏈轉移常數 (CT)更大。CoII(dmgBF2)2(H2O)2為工業上常用於調控甲基丙烯酸甲酯的鏈轉移試劑。並且以 1H NMR證明聚醋酸乙烯酯上的末端雙鍵，並利用聚醋酸乙烯酯作為巨型單體進行聚合，用以計算末端烯官能基比例。此系列催化劑可經由改變配位基官能基而變換醋酸乙烯酯的聚合反應機制，期許能將可控聚合及鏈轉移聚合結合。

Organo-cobalt complexes have demonstrated unique properties in the mediation of radical polymerizations such as catalytic chain transfer polymerization (CCTP) of methacrylates and reversible deactivation radical polymerization (RDRP) of unconjugated monomers vinyl acetate (VAc). A series of CoII phenoxy-imine complexes mediated radical polymerization of vinyl acetate is reported. The catalyst with bulkier structure will have better control performance. The increasing of electron donating property of phenoxy-imine ligand and decreasing of steric property near CoII could both switch the polymerization mechanism from RDRP to CCTP. VAc polymerization mediated by catalyst 1a and 3a are C/LRP and catalyst 1a has better result. Lower temperature will decrease Mn deviation and experimental Mn are match with theory Mn at 0 oC with TPO as initiator. In CCTP of VAc, catalyst 2b has best performance in this series catalysts and has larger catalytic chain transfer constant (CT) than CoII(dmgBF2)2(H2O)2 which is best known catalytic chain transfer agent in methyl methacrylate (MMA) polymerization. Also, chain-end double bond has been characterized by 1H NMR and chain-end functionality was evaluated by using PVAc as the monomer to run free radical polymerization. The switch of polymerization mechanisms between RDRP and CCTP could be achieved by changing property of phenoxy-imine ligand, demonstrating the potential of this system to combine CCTP and RDRP techniques.

摘要 I
Abstract II
謝誌 III
目錄 IV
圖目錄 VII
表目錄 XVIII
式目錄 XXII
第一章 緒論 (Introduction) 1
1-1 自由基聚合反應 2
1-2 可控/活性自由基聚合 6
1-2-1 原子轉移自由基聚合反應 8
1-2-2 可逆加成-斷裂鏈轉移聚合反應 10
1-2-3 氮氧自由基聚合反應 13
1-2-4 有機鈷金屬錯合物調控自由基聚合反應 14
1-3 鏈轉移聚合反應 23
1-4 研究目的及動機 28
第二章 實驗與鑑定 (Experimental section and characterization of cobalt complexes) 29
2-1 實驗 30
2-1-1 化學藥品 30
2-1-2 儀器 31
2-1-3 聚合反應 32
2-2 Phenoxy-imine及 Phenoxy-imine配位之鈷錯合物合成 34
2-2-1 配位基前驅物的合成 34
2-2-2 配位基 (phenoxy-imine)的合成 35
2-2-3 Phenoxy-imine配位之鈷錯合物 (CoII(phenoxy-imine)2)的合成 38
2-3 Phenoxy-imine配位之鈷錯合物 (CoII(phenoxy-imine)2)之鑑定 40
2-3-1 電化學分析 40
2-3-2 紫外光-可見光吸收光譜 42
2-3-3 電子順磁共振光譜 46
2-3-4 超導磁性測量 47
2-3-5 晶體 X-ray 49
第三章 Phenoxy-imine配位之鈷錯合物 (CoII(phenoxy-imine)2)調控可控/活性自由基聚合反應 (The research of control/living radical polymerization mediated by bis(phenoxy-imine) CoII complexes) 56
3-1 Phenoxy-imine配位之鈷錯合物 (CoII(phenoxy-imine)2)調控醋酸乙烯酯聚合反應 57
3-2 催化劑 1a調控醋酸乙烯酯聚合反應之優化 86
3-3 Phenoxy-imine 配位之鈷錯合物 (CoII(phenoxy-imine)2)調控甲基丙烯酸甲酯及苯乙烯之聚合反應 97
3-4 結論 104
第四章 Phenoxy-imine配位之鈷錯合物調控鏈轉移聚合反應 (The research of catalytic chain transfer reaction for bis(phenoxy-imine) CoII complexes) 106
4-1 Phenoxy-imine 配位之鈷錯合物調控之醋酸乙烯酯鏈轉移聚合反應 107
4-2 Phenoxy-imine 配位之鈷錯合物調控甲基丙烯酸甲酯鏈轉移聚合反應 115
4-3 Phenoxy-imine 配位之鈷錯合物調控醋酸乙烯酯鏈轉移聚合末端官能基鑑定 117
4-4 結論 121
第五章 附錄 123
引用文獻 182

1. Stevens, M. P., Polymer Chemistry An Introduction. New York Oxford, 1999.
2. Georges, M. K.; Veregin, R. P. N.; Kazmaier, P. M.; Hamer, G. K., Macromolecules 1993, 26, 2987-2988.
3. Kamigaito, M.; Ando, T.; Sawamoto, M., Chem. Rev. 2001, 101, 3689-3746.
4. Matyjaszewski, K.; Xia, J., Chem. Rev. 2001, 101, 2921-2990.
5. Moad, G.; Rizzardo, E.; Thang, S. H., Aust. J. Chem. 2005, 58, 379-410.
6. Yamago, S.; Iida, K.; Yoshida, J.-i., J. Am. Chem. Soc. 2002, 124, 2874-2875.
7. Braunecker, W. A.; Matyjaszewski, K., Prog. Polym. Sci. 2007, 32, 93-146.
8. Cunningham, M., Prog. Polym. Sci. 2008, 33, 365-398.
9. Liao, C.-M.; Hsu, C.-C.; Wang, F.-S.; Wayland, B. B.; Peng, C.-H., Polym. Chem. 2013, 4, 3098-3104.
10. Moad, G.; Rizzardo, E.; Thang, S. H., Aust. J. Chem. 2012, 65, 985-1076.
11. Ouchi, M.; Terashima, T.; Sawamoto, M., Chem. Rev. 2009, 109, 4963-5050.
12. Perrier, S.; Takolpuckdee, P., J. Polym. Sci., Part A: Polym. Chem. 2005, 43, 5347-5393.
13. Rosen, B. M.; Percec, V., Chem. Rev. 2009, 109, 5069-5119.
14. Szwarc, M., Nature 1956, 178, 1168.
15. Gao, H.; Matyjaszewski, K., Prog. Polym. Sci. 2009, 34, 317-350.
16. Matyjaszewski, K., Macromolecules 2012, 45, 4015-4039.
17. Percec, V.; Barboiu, B., Macromolecules 1995, 28, 7970-7972.
18. Siegwart, D. J.; Oh, J. K.; Matyjaszewski, K., Prog. Polym. Sci. 2012, 37, 18-37.
19. Chiefari, J.; Chong, Y. K.; Ercole, F.; Krstina, J.; Jeffery, J.; Le, T. P. T.; Mayadunne, R. T. A.; Meijs, G. F.; Moad, C. L.; Moad, G.; Rizzardo, E.; Thang, S. H., Macromolecules 1998, 31, 5559-5562.
20. Moad, G.; Rizzardo, E.; Thang, S. H., Aust. J. Chem. 2009, 62, 1402-1472.
21. Hawker, C. J.; Bosman, A. W.; Harth, E., Chem. Rev. 2001, 101, 3661-3688.
22. Debuigne, A.; Caille, J. R.; Jérôme, R., Angew. Chem., Int. Ed. 2005, 117, 1125-1128.
23. Peng, C.-H.; Scricco, J.; Li, S.; Fryd, M.; Wayland, B. B., Macromolecules 2008, 41, 2368-2373.
24. Kato, M.; Kamigaito, M.; Sawamoto, M.; Higashimura, T., Macromolecules 1995, 28, 1721-1723.
25. Wang, J.-S.; Matyjaszewski, K., J. Am. Chem. Soc. 1995, 117, 5614-5615.
26. Pitto, V.; Voit Brigitte, I.; Loontjens Ton, J. A.; van Benthem Rolf, A. T. M., Macromol. Chem. Phys. 2004, 205, 2346-2355.
27. Yin, M.; Habicher, W. D.; Voit, B., Polymer 2005, 46, 3215-3222.
28. Zhang, L.; Miao, J.; Cheng, Z.; Zhu, X., Macromol. Rapid Commun. 2010, 31, 275-280.
29. Wayland, B. B.; Poszmik, G.; Mukerjee, S. L.; Fryd, M., J. Am. Chem. Soc. 1994, 116, 7943-7944.
30. Debuigne, A.; Michaux, C.; Jérôme, C.; Jérôme, R.; Poli, R.; Detrembleur, C., Chem.-Eur. J. 2008, 14, 7623-7637.
31. Li, S.; Bruin, B. d.; Peng, C.-H.; Fryd, M.; Wayland, B. B., J. Am. Chem. Soc. 2008, 130, 13373-13381.
32. Wayland, B. B.; Peng, C.-H.; Fu, X.; Lu, Z.; Fryd, M., Macromolecules 2006, 39, 8219-8222.
33. Debuigne, A.; Morin Aurélie, N.; Kermagoret, A.; Piette, Y.; Detrembleur, C.; Jérôme, C.; Poli, R., Chem.-Eur. J. 2012, 18, 12834-12844.
34. Hsu, C.-S.; Yang, T.-Y.; Peng, C.-H., Polym. Chem. 2014, 5, 3867-3875.
35. Kermagoret, A.; Debuigne, A.; Jérôme, C.; Detrembleur, C., Nat. Chem. 2014, 6, 179.
36. Tokunaga, M.; Larrow, J. F.; Kakiuchi, F.; Jacobsen, E. N., Science 1997, 277, 936.
37. Sherwood, R. K.; Kent, C. L.; Patrick, B. O.; McNeil, W. S., Chem. Commun. 2010, 46, 2456-2458.
38. Taylor, H. S.; Jones, W. H., J. Am. Chem. Soc. 1930, 52, 1111-1121.
39. Flory, P. J., J. Am. Chem. Soc. 1937, 59, 241-253.
40. Gridnev, A., J. Polym. Sci., Part A: Polym. Chem. 2000, 38, 1753-1766.
41. Bakac, A.; Espenson, J. H., J. Am. Chem. Soc. 1984, 106, 5197-5202.
42. Debuigne, A.; Poli, R.; Jérôme, C.; Jérôme, R.; Detrembleur, C., Prog. Polym. Sci. 2009, 34, 211-239.
43. Heuts, J. P. A.; Smeets, N. M. B., Polym. Chem. 2011, 2, 2407-2423.
44. Roberts, G. E.; Barner-Kowollik, C.; Davis, T. P.; Heuts, J. P. A., Macromolecules 2003, 36, 1054-1062.
45. Gridnev, A. A.; Ittel, S. D., Chem. Rev. 2001, 101, 3611-3660.
46. Mayo, F. R., J. Am. Chem. Soc. 1943, 65, 2324-2329.
47. Chiang, L.; Allan, L. E. N.; Alcantara, J.; Wang, M. C. P.; Storr, T.; Shaver, M. P., Dalton Trans. 2014, 43, 4295-4304.
48. 黃鵑, 國立清華大學碩士論文, 2016.
49. Bain, G. A.; Berry, J. F., J. Chem. Educ. 2008, 85, 532.
50. Alexanian, E. J.; Hartwig, J. F., J. Am. Chem. Soc. 2008, 130, 15627-15635.
51. 李家齊, 國立清華大學碩士論文, 2017.
52. 許鎮守, 國立清華大學碩士論文, 2013.
53. Bellan, E. V.; Thevenin, L.; Gayet, F.; Fliedel, C.; Poli, R., ACS Macro Lett. 2017, 6, 959-962.