活性/可控自由基聚合反應成功被應用在N-乙烯基吡咯烷酮的聚合反應，在本研究當中，成功合成出N,N-Bis(4-diethylaminosalicylidene)ethylene-diaminocobalt(II) (CoII(salen-NEt2))鈷金屬錯化合物作為調控劑，在40 ºC的純水中利用2,2'-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride(VA-044)作為引發劑調控N-乙烯基吡咯烷酮的聚合反應，使分子量與轉化率成線性關係，分子量增長到37500，分子量分布係數介於1.2到1.3之間，並且利用優化過後的聚合反應條件拓展到其他單體的聚合反應，包含丙烯酸2-羥乙酯（HEA），N，N-二甲基丙烯醯胺（DMA）與丙烯酸（AA）。最終使用合成出來的PDMA短鏈在水中進行鏈增長反應，應證了良好的尾端官能基活性。

Controlled radical polymerization of N-vinylpyrrolidone (NVP) in water mediated by cobalt complex is reported. In this article, cobalt-mediated radical polymerization (CMRP) was successfully accomplished with N,N-Bis(4-diethylaminosalicylidene)ethylene-diaminocobalt(II) (CoII(salen-NEt2)) as mediator and VA-044 as the radical initiator at 40 ºC. Linear relationship of molecular weight and conversion was observed in water with molecular weights (MW) as high as 37500 and relatively narrow molecular weight distributions (PDI = 1.2−1.3). Furthermore, the monomer scope has grown to include Acrylic acid(AA), 2-hydroxyethyl acrylate(HEA), N,N-Dimethylacrylamide(DMA). Chain extension of the synthesized PDMA macroinitiator with DMA in water showed a clear shift in MWs, which indicated high retention of chain end functionality.

摘要 i
Abstract ii
謝誌 iii
目錄 iv
圖目錄 vii
表目錄 xv
式目錄 xvi
第一章 緒論 1
1.1傳統自由基聚合反應 1
1.2 活性自由基聚合反應 3
1.3 鈷配位化合物自由基聚合（Cobalt-mediated radical polymerization,CMRP） 6
1.4 共軛單體(conjugated monomers)與非共軛單體(unconjugated monomers) 9
1.5水相鈷金屬錯合物調控活性自由基聚合 (Cobalt-mediated radical polymerization in aqueous phase) 10
1.6 N-乙烯基吡咯烷酮水相單體聚合發展與困難 11
1.7研究動機 12
第二章 以鈷金屬錯合物作為調控劑催化水溶性單體之活性自由基聚合反應 14
2.1 實驗設計 14
2.2 N-乙烯基吡咯烷酮(NVP)之水相活性自由基聚合 16
2.2.1 以水溶性CoII(salen-NEt2)調控 N-乙烯基吡咯烷酮聚合反應 16
2.2.2結論 20
2.3 溫度與酸鹼值對鈷錯合物的影響 21
2.3.1 水溶性CoII(salen-NEt2)在高溫與酸性環境下反應 21
2.3.2 結論 26
2.4 N-乙烯基吡咯烷酮(NVP)在低溫時之水相活性自由基聚合 27
2.4.1 在低溫時以水溶性CoII(salen-NEt2)調控N-乙烯基吡咯烷酮聚合反應 27
2.4.2 結論 32
2.5 丙烯酸羥乙酯之水相活性自由基聚合 33
2.5.1 以水溶性Co(salen-NEt2)調控丙烯酸羥乙酯聚合反應 33
2.5.2 結論 41
2.6 N,N-二甲基丙烯醯胺之水相活性自由基聚合 42
2.6.1 以水溶性Co(salen-NEt2)調控N,N-二甲基丙烯醯胺聚合反應 42
2.6.2 結論 48
2.7 丙烯酸之活性自由基聚之活性自由基聚合 49
2.7.1 以水溶性CoII(salen-NEt2)聚合丙烯酸 49
2.7.2結論 51
2.8 寡聚物鏈增長反應 52
第三章 實驗步驟及儀器鑑定 55
3.1 原料、藥劑 55
3.2 儀器 56
3.3 一般聚合實驗步驟 58
3.4 甲基化聚丙烯酸 58
3.5 5-Chloromethyl-2-hydroxybenzaldehyde之合成步驟 59
3.6 5-Diethylaminomethylsalicylaldehyde之合成步驟 60
3.7 Salen-NEt2之合成步驟 61
3.8 CoII(salen-NEt2)之合成步驟 62
第四章 附錄 63
附錄 1. 5-Chloromethyl-2-hydroxybenzaldehyde之1H NMR光譜圖。 63
附錄 2. 5-Chloromethyl-2-hydroxybenzaldehyde之13C NMR光譜圖。 63
附錄 3. Diethylaminomethylsalicylaldehyde之1H NMR光譜圖。 64
附錄 4. Diethylaminomethylsalicylaldehyde之13C NMR光譜圖。 64
附錄 5. Salen-NEt2之1H NMR光譜圖。 65
附錄 6. Salen-NEt2之13C NMR光譜圖。 65
附錄 7. Co(Salen-NEt2)之1H NMR光譜圖。 66
附錄 8. Co(Salen-NEt2)之UV-Vis光譜圖。 66
附錄 9. Co(Salen-NEt2)質譜圖。 67
附錄10. CoII(salen-NEt2)與V-501反應隨時間變化H1NMR圖譜(D2O)。反應條件為[CoII(salen-NEt2)]/[V-501]=1/10在60 ºC下，[CoII(salen-NEt2)]=0.00668 M。 67
附錄11. CoII(salen-NEt2)在60 ºC下與CH3COOH反應隨時間變化H1NMR圖譜(D2O)。反應條件為[CoII(salen-NEt2)]/[CH3COOH]=1/1.85在60 ºC下，[CoII(salen-NEt2)]=0.00668 M。 68
參考文獻 69

1. Braunecker, W. A.; Matyjaszewski, K., Prog. Polym. Sci. 2007, 32, 93-146.
2. Cunningham, M. F., Prog. Polym. Sci. 2008, 33, 365-398.
3. Georges, M. K.; Veregin, R. P.; Karzmaier, P. M.; Hamer, G. K., Macromolecules 1993, 26, 2987-2988.
4. Kamigaito, M.; Ando, T.; Sawamoto, M.; Higashimura, T., Chem. Rev. 2001, 101, 3689-3746.
5. Kato, M.; Kamigaito, M.; Sawamoto, M.; Higashimura, T., Macromolecules 1995, 28, 1721-1723.
6. Matyjaszewski, K.; Xia, J., Chem. Rev. 2001, 101, 2921-2990.
7. Moad, G.; Rizzardo, E.; Thang, S. H., Aust. J. Chem. 2005, 58, 379-410.
8. Moad, G.; Rizzardo, E.; Thang, S. H., Aust. J. Chem. 2009, 58, 1402-1472.
9. Moad, G.; Rizzardo, E.; Thang, S. H., Aust. J. Chem. 2012, 65, 985-1076.
10. Ouchi, M.; Terashima, T.; Sawamoto, M., Chem. Rev. 2009, 109, 4963-5050.
11. Liao, C.-M.; Hsu, C.-C.; Wang, F.-S.; Wayland, B.; Peng, C.-H., Polym. Chem. 2013, 4, 3098-3104.
12. Percec, V.; Barboiu, B., Macromolecules 1995, 28, 7970-7972.
13. Perrier, S.; Takolpuckdee, P., J. Polym. Sci. Pol. Chem. 2005, 43, 5347-5393.
14. Rosen, B. M.; Percec, V., Chem. Rev. 2009, 109, 5069-5119.
15. Wang, J. S.; Matyjaszewski, K., J. Am. Chem. Soc. 1995, 117, 5614-5615.
16. Yamago, S.; Iida, K.; Yoshida, J.-I., J. Am. Chem. Soc. 2002, 124, 2874-2875.
17. Gao, H.; Matyjaszewski, K., Prog. Polym. Sci. 2009, 34, 317-350.
18. Chen, H.-Y.; Lahann, J.-I., Langmuir 2010, 27, 34-48.
19. Siegwart, D. J.; Oh, J. K.; Matyjaszewski, K., Prog. Polym. Sci. 2012, 37, 18-37. 
20. Wu, D.; Xu, F.; Sun, B.; Fu, R.; He, H.; Matyjaszewski, K., Chem. Rev. 2012, 112, 3959-4015.
21. Matyjaszewski, K.; Tsarevsky, N. V., Nat. Chem 2009, 1, 276-288.
22. Matyjaszewski, K., Macromolecules 2012, 45, 4015-4039.
23. Chiefari, J.; Chong, Y.; Ercole, F.; Krstina, J.; Jeffery, J.; Le, T. P.; Mayadunne, R. T.; Meijs, G. F.; Moad, C. L.; Moad, G., Macromolecules 1998, 31, 5559-5562.
24. Hawker, C. J.; Bosman, A. W.; Harth, E., Chem. Rev. 2001, 101, 3661-3688.
25. Debuigne, A.; Caille, J. R.; Jerome, R., Angew. Chem. 2005, 117, 1125-1128.
26. Peng, C. H.; Scricco, J.; Li, S.; Fryd, M.; Wayland, B. B., Macromolecules 2008, 41, 2368-2373.
27. Wayland, B. B.; Poszmik, G.; Mukerjee, S. L.; Fryd, M.,. J. Am. Chem. Soc. 1994, 116 (17), 7943-7944.
28. B.M. Rosen, V. Percec, Chem. Rev. 109 (2009) 5069–5119.
29. Wang, J-S; Matyjaszewski, K. J. Am. Chem. Soc. 1995, 117: 5614–5615.
30. Kato, M; Kamigaito, M; Sawamoto, M; Higashimura, T. Macromolecules. 1995, 28: 1721–1723
31. Burdyńska, J; Cho, H-Y.; Mueller L, and Matyjaszewski K., Macromolecules. 2016, 49(23): 8838–8847.
31. O'Reilly, E. J.; Dennany, L.; Griffith, D.; Moser, F.; Keyes, T. E.; Forster, R. J., Phys. Chem. Chem. Phys. 2011, 13 (15), 7095-7101.
32. Reggelin, M.; Doerr, S.; Klussmann, M.; Schultz, M.; Holbach, M., Proceedings of the National Academy of Sciences of the United States of America 2004, 101 (15), 5461-6.
33. Ott, C.; Ulbricht, C.; Hoogenboom, R.; Schubert, U. S., Macromol. Rapid Commun. 2012, 33 (6-7), 556-561.
34. Housni, A.; Zhao, Y., Langmuir 2010, 26 (15), 12933-12939.
35. Peeler, J. C.; Woodman, B. F.; Averick, S.; Miyake-Stoner, S. J.; Stokes, A. L.; Hess, K. R.; Matyjaszewski, K.; Mehl, R. A., J. Am. Chem. Soc. 2010, 132 (39), 13575-13577.
36. Chiefari, J.; Chong Y. K.; Ercole, F.; Krstina, J.; Jeffery, J.; Tam, P.; Le, T.; Roshan, T. A.; Mayadunne, Gordon F.; Meijs, Catherine L. ;Moad, G. , Rizzardo, E.;Thang, S-H., Macromolecules, 1998, 31 (16), pp 5559–5562
37. B.B. Wayland,; G. Poszmik.; S.L. Mukerjee,; M. Fryd,; J. Am. Chem. Soc. 1994, 116,7943–7944.
38. H.H. Arvanitopoulos.; L.D.; Greuel M.P., Polym Prep. 1994, 35, 549–550.
39. Min, K.; Matyjaszewski, K., Cent. Eur. J. Chem. 2009, 7(4), 657–674.
40. Bian, C.; Y-N Zhou.; J-K Guo.; and Z-H Luo, Macromolecules.
41. Emily A.; Hoff, Brooks A.; Abel, Chase A.; Tretbar, Charles L.; McCormick,; Derek L. Patton, Polym. Chem., 2013, 00, 1‐3.
42. Peng C-H.; Fryd M; B.B. Wayland, Macromolecules 2007, 40, 6814-6819
43. Coupillaud, P.; Fèvre, M.; A-L Wirotius.; Aissou, K.; Fleury, G.; Debuigne, A., Detrembleur, C.;Mecerreyes, D.; Vignoll,e J.; Taton, D., Macromol. Rapid Commun. 2014, 35, 422−430
44. Laura, E.N.; Allan, Mitchell, R.; Perry, Michael, P.; Shaver., Prog. Polym. Sci. 2012, 37,127–156.
45. Chaduc I.; Crepet A.; Boyron O.; Charleux B.; D’Agosto F.; Lansalot M., Macromolecules, 2013, 46, 6013−6023.
46. Aymeric, G.; Stephane Mazieres D.; Wilson, J.; Destarac, M., Polym. Chem., 2012, 3, 81–84.
47. Nakabayashi, K.; Mori, H., Eur Polym, 2013, 49, 2808–2838 2809.
48. Lu, X.; Gong, S.; Meng, L.,; Li, C.; Yang, S.; Zhang L., Polymer. 2007, 48, 2835-2842