鈷調控自由基聚合反應是一種活性自由基聚合反應。其是少數能有效的控制乙烯基酯單體類的活性自由基聚合反應。這份研究聚焦在鈷調控自由基聚合反應並能分成三個部分。在第一章我們利用鍊延伸反應來驗證三種鈷錯合物在醋酸乙烯酯的聚合反應中是經由何種路徑。同時，我們也測量了不同鈷錯合物在六十度下對丙烯酸甲酯進行活性聚合反應時的平衡常數與該鈷錯合物的半波電位之間的關係。接著我們提出了一個反應模型去描述等能量交換反應的控制機制，並輔以模擬與實驗的數據佐證。最後我們應用鈷調控自由基聚合反應合成了聚丙烯酸與聚乙烯醇的嵌段共聚物並將它製作成膜。我們發現他有良好的力學與吸水性質。

Cobalt mediated radical polymerization (CMRP) is a living radical polymerization method, which has been recognized as one of the most efficient way to control the polymerization of vinyl esters. This research was divided into three parts. In the first chapter we demonstrated the different controlling pathway by applying three cobalt complex in the polymerization of vinyl acetate (VAc). Also the correlation between equilibrium constant and the redox potential of the complexes was established. Next, one of the controlling pathway in CMRP, degenerative transfer (DT), was studied. We build a model to describe the DT mechanism. The model was further proven by both simulation and experimental data. In the last part, CMRP was applied to obtain hydrophilic poly(acrylic acid)-b-poly(vinyl alcohol) block copolymer. The materials were studied by thermal analysis and mechanical characterization.

Abstract 1
摘要.....1
Abstract.....2
謝誌.....3
List of Publications.....4
Background.....5
Chapter 1. The Mechanism and Thermodynamic Studies of CMRP: Different Control Mechanisms Demonstrated by CoII(TMP), CoII(salen*), and CoII(acac)2 Mediated Polymerization and The Correlation of Reduction Potential, Equilibrium Constant, and Control Mechanism.....9
Supporting Information-Chapter 1.....33
Chapter 2. Mechanism Study of Degenerative Transfer via Observing the Distribution of Living Chains by Cobalt Mediated Radical Polymerization.....50
Supporting Information - Chapter 2.....60
Chapter 3. Highly Stretchable Free Standing Poly(acrylic acid)-b-Poly(vinyl alcohol) Membranes Obtained from Cobalt Mediated Radical Polymerization.....67
Supporing Information-Chapter 3.....93
Summary and Future Perspective.....104

Background:
1. Wayland, B. B.; Basickes, L.; Mukerjee, S.; Wei, M.; Fryd, M., Macromolecules, 1997, 30 (26), 8109-8112.
2. Debuigne, A.; Caille, J.-R.; Jérôme, R., Angewandte Chemie, 2005, 117 (7), 1125-1128.
3. Liao, C.-M.; Hsu, C.-C.; Wang, F.-S.; Wayland, B. B.; Peng, C.-H., Polymer Chemistry, 2013, 4 (10), 3098-3104.

Chapter 1:
1. Matyjaszewski, K., Macromolecules, 2012, 45 (10), 4015-4039.
2. Moad, G.; Rizzardo, E.; Thang, S. H., Aust J Chem, 2012, 65 (8), 985-1076.
3. Nicolas, J.; Guillaneuf, Y.; Lefay, C.; Bertin, D.; Gigmes, D.; Charleux, B., Prog Polym Sci, 2013, 38 (1), 63-235.
4. Destarac, M., Macromol React Eng, 2010, 4 (3-4), 165-179.
5. Rosler, A.; Vandermeulen, G. W. M.; Klok, H. A., Adv Drug Deliver Rev, 2012, 64, 270-279.
6. Siegwart, D. J.; Oh, J. K.; Matyjaszewski, K., Prog Polym Sci, 2012, 37 (1), 18-37.
7. Xu, F. J.; Yang, W. T., Progress in Polymer Science, 2011, 36 (9), 1099-1131.
8. Zhang, Q.; Ko, N. R.; Oh, J. K., Chem Commun, 2012, 48 (61), 7542-7552.
9. Debuigne, A.; Caille, J. R.; Jerome, R., Angew Chem Int Edit, 2005, 44 (7), 1101-1104.
10. Debuigne, A.; Poli, R.; Jerome, C.; Jerome, R.; Detrembleur, C., Prog Polym Sci, 2009, 34 (3), 211-239.
11. Wayland, B. B.; Poszmik, G.; Mukerjee, S. L.; Fryd, M., J Am Chem Soc, 1994, 116 (17), 7943-7944.
12. Liao, C. M.; Hsu, C. C.; Wang, F. S.; Wayland, B. B.; Peng, C. H., Polymer Chemistry, 2013, 4 (10), 3098-3104.
13. Fu, R.; Fu, G. D., Polymer Chemistry, 2011, 2 (3), 465-475.
14. Huber, A.; Muller, L.; Elias, H.; Klement, R.; Valko, M., European Journal of Inorganic Chemistry, 2005, (8), 1459-1467.
15. Lin, Y. C.; Hsieh, Y. L.; Lin, Y. D.; Peng, C. H., Macromolecules, 2014, 47 (21), 7362-7369.
16. Langlotz, B. K.; Fillol, J. L.; Gross, J. H.; Wadepohl, H.; Gade, L. H., Chem-Eur J, 2008, 14 (33), 10267-10279.
17. Wang, B. Q.; Zhuang, Y.; Luo, X. X.; Xu, S. S.; Zhou, X. Z., Macromolecules, 2003, 36 (26), 9684-9686.
18. Kermagoret, A.; Debuigne, A.; Jerome, C.; Detrembleur, C., Nat Chem, 2014, 6 (3), 179-187.
19. Chi-How, P.; Shan, L.; Bradford, B. W., Formation, Dissociation, and Radical Exchange of Organo-Cobalt Complexes in Mediating Living Radical Polymerization. In Controlled/Living Radical Polymerization: Progress in RAFT, DT, NMP & OMRP, American Chemical Society: 2009; Vol. 1024, pp 115-129.
20. Averill, D. F.; Broman, R. F., Inorg Chem, 1978, 17 (12), 3389-3394.
21. Kihnbotulinski, M.; Meunier, B., Inorg Chem, 1988, 27 (1), 209-210.
22. Peng, C.-H.; Li, S.; Wayland, B. B., Journal of the Chinese Chemical Society, 2009, 56 (2), 219-233.
23. Maria, S.; Kaneyoshi, H.; Matyjaszewski, K.; Poli, R., Chemistry – A European Journal, 2007, 13 (9), 2480-2492.
24. Debuigne, A.; Champouret, Y.; Jerome, R.; Poli, R.; Detrembleur, C., Chem-Eur J, 2008, 14 (13), 4046-4059.
25. Moad, G.; Rizzardo, E.; Solomon, D. H.; Beckwith, A. L. J., Polym Bull, 1992, 29 (6), 647-652.
26. Li, S.; Bruin, B. d.; Peng, C.-H.; Fryd, M.; Wayland, B. B., J Am Chem Soc, 2008, 130 (40), 13373-13381.
27. Wayland, B. B.; Peng, C. H.; Fu, X. F.; Lu, Z.; Fryd, M., Macromolecules, 2006, 39 (24), 8219-8222.
28. Matyjaszewski, K.; Gobelt, B.; Paik, H. J.; Horwitz, C. P., Macromolecules, 2001, 34 (3), 430-440.
29. Tang, W.; Matyjaszewski, K., Macromolecules, 2006, 39 (15), 4953-4959.
30. Hurtgen, M.; Debuigne, A.; Jérôme, C.; Detrembleur, C., Macromolecules, 2010, 43 (2), 886-894.
31. Cepria´, G.; Castillo, J. R., Journal of Applied Electrochemistry, 1998, 28 (1), 65-70.
32. Peng, C.-H.; Li, S.; Wayland, B. B., Inorg Chem, 2009, 48 (11), 5039-5046.

Chapter 2:
1. Szwarc, M., Nature, 1956, 178 (4543), 1168-1169.
2. WEBSTER, O. W., Science, 1991, 251 (4996), 887-893.
3. Bielawski, C. W.; Grubbs, R. H., Progress in Polymer Science, 2007, 32 (1), 1-29.
4. Coessens, V.; Pintauer, T.; Matyjaszewski, K., Progress in Polymer Science, 2001, 26 (3), 337-377.
5. Hadjichristidis, N.; Iatrou, H.; Pitsikalis, M.; Mays, J., Progress in Polymer Science, 2006, 31 (12), 1068-1132.
6. Higashihara, T.; Hayashi, M.; Hirao, A., Progress in Polymer Science, 2011, 36 (3), 323-375.
7. Xu, F. J.; Yang, W. T., Progress in Polymer Science, 2011, 36 (9), 1099-1131.
8. Braunecker, W. A.; Matyjaszewski, K., Progress in Polymer Science, 2007, 32 (1), 93-146.
9. Moad, G.; Rizzardo, E.; Thang, S. H., Australian Journal of Chemistry, 2009, 62 (11), 1402-1472.
10. Debuigne, A.; Poli, R.; Jérôme, C.; Jérôme, R.; Detrembleur, C., Progress in Polymer Science, 2009, 34 (3), 211-239.
11. Nicolas, J.; Guillaneuf, Y.; Lefay, C.; Bertin, D.; Gigmes, D.; Charleux, B., Progress in Polymer Science, 2013, 38 (1), 63-235.
12. Matyjaszewski, K.; Xia, J., Chemical Reviews, 2001, 101 (9), 2921-2990.
13. Debuigne, A.; Caille, J.-R.; Jérôme, R., Angewandte Chemie, 2005, 117 (7), 1125-1128.
14. Peng, C.-H.; Scricco, J.; Li, S.; Fryd, M.; Wayland, B. B., Macromolecules, 2008, 41 (7), 2368-2373.
15. Liao, C.-M.; Hsu, C.-C.; Wang, F.-S.; Wayland, B. B.; Peng, C.-H., Polymer Chemistry, 2013, 4 (10), 3098-3104.
16. Kermagoret, A.; Debuigne, A.; Jérôme, C.; Detrembleur, C., Nat Chem, 2014, 6 (3), 179-187.
17. Debuigne, A.; Willet, N.; Jérôme, R.; Detrembleur, C., Macromolecules, 2007, 40 (20), 7111-7118.
18. Debuigne, A.; Warnant, J.; Jérôme, R.; Voets, I.; de Keizer, A.; Cohen Stuart, M. A.; Detrembleur, C., Macromolecules, 2008, 41 (7), 2353-2360.
19. Wang, F.-S.; Yang, T.-Y.; Hsu, C.-C.; Chen, Y.-J.; Li, M.-H.; Hsu, Y.-J.; Chuang, M.-C.; Peng, C.-H., Macromolecular Chemistry and Physics, 2016, 217 (3), 422-432.

Chapter 3:
1. Hawker, C. J.; Bosman, A. W.; Harth, E., Chemical Reviews, 2001, 101 (12), 3661-3688.
2. Nicolas, J.; Guillaneuf, Y.; Lefay, C.; Bertin, D.; Gigmes, D.; Charleux, B., Progress in Polymer Science, 2013, 38 (1), 63-235.
3. Matyjaszewski, K.; Xia, J., Chemical Reviews, 2001, 101 (9), 2921-2990.
4. Börner, H. G.; Beers, K.; Matyjaszewski, K.; Sheiko, S. S.; Möller, M., Macromolecules, 2001, 34 (13), 4375-4383.
5. 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 (16), 5559-5562.
6. Mayadunne, R. T. A.; Rizzardo, E.; Chiefari, J.; Krstina, J.; Moad, G.; Postma, A.; Thang, S. H., Macromolecules, 2000, 33 (2), 243-245.
7. Perrier, S.; Takolpuckdee, P., Journal of Polymer Science Part A: Polymer Chemistry, 2005, 43 (22), 5347-5393.
8. Jacquin, M.; Muller, P.; Lizarraga, G.; Bauer, C.; Cottet, H.; Théodoly, O., Macromolecules, 2007, 40 (8), 2672-2682.
9. Yamago, S., Journal of Polymer Science Part A: Polymer Chemistry, 2006, 44 (1), 1-12.
10. Yusa, S.-i.; Yamago, S.; Sugahara, M.; Morikawa, S.; Yamamoto, T.; Morishima, Y., Macromolecules, 2007, 40 (16), 5907-5915.
11. Koumura, K.; Satoh, K.; Kamigaito, M.; Okamoto, Y., Macromolecules, 2006, 39 (12), 4054-4061.
12. Lacroix-Desmazes, P.; Severac, R.; Boutevin, B., Macromolecules, 2005, 38 (15), 6299-6309.
13. Debuigne, A.; Poli, R.; Jérôme, C.; Jérôme, R.; Detrembleur, C., Progress in Polymer Science, 2009, 34 (3), 211-239.
14. Peng, C.-H.; Yang, T.-Y.; Zhao, Y.; Fu, X., Organic & Biomolecular Chemistry, 2014, 12 (43), 8580-8587.
15. Ge, Z.; Liu, S., Chemical Society Reviews, 2013, 42 (17), 7289-7325.
16. Kataoka, K.; Harada, A.; Nagasaki, Y., Advanced Drug Delivery Reviews, 2001, 47 (1), 113-131.
17. Nunns, A.; Gwyther, J.; Manners, I., Polymer, 2013, 54 (4), 1269-1284.
18. Bates, C. M.; Maher, M. J.; Janes, D. W.; Ellison, C. J.; Willson, C. G., Macromolecules, 2014, 47 (1), 2-12.
19. Peinemann, K.-V.; Abetz, V.; Simon, P. F. W., Nat Mater, 2007, 6 (12), 992-996.
20. Stuparu, M. C.; Khan, A.; Hawker, C. J., Polymer Chemistry, 2012, 3 (11), 3033-3044.
21. DeMerlis, C. C.; Schoneker, D. R., Food and Chemical Toxicology, 2003, 41 (3), 319-326.
22. Watase, M.; Nishinari, K.; Nambu, M., Cryo-Lett, 1983, 4 (3), 197-200.
23. Wan, W. K.; Campbell, G.; Zhang, Z. F.; Hui, A. J.; Boughner, D. R., Journal of Biomedical Materials Research, 2002, 63 (6), 854-861.
24. Schmedlen, R. H.; Masters, K. S.; West, J. L., Biomaterials, 2002, 23 (22), 4325-4332.
25. Burczak, K.; Gamian, E.; Kochman, A., Biomaterials, 1996, 17 (24), 2351-2356.
26. Millon, L. E.; Wan, W. K., Journal of Biomedical Materials Research Part B: Applied Biomaterials, 2006, 79B (2), 245-253.
27. Tang, X.; Alavi, S., Carbohydrate Polymers, 2011, 85 (1), 7-16.
28. Musetti, A.; Paderni, K.; Fabbri, P.; Pulvirenti, A.; Al-Moghazy, M.; Fava, P., Journal of Food Science, 2014, 79 (4), E577-E582.
29. Baker, M. I.; Walsh, S. P.; Schwartz, Z.; Boyan, B. D., Journal of Biomedical Materials Research Part B: Applied Biomaterials, 2012, 100B (5), 1451-1457.
30. Kobayashi, M.; Chang, Y.-S.; Oka, M., Biomaterials, 2005, 26 (16), 3243-3248.
31. Debuigne, A.; Caille, J.-R.; Jérôme, R., Angewandte Chemie, 2005, 117 (7), 1125-1128.
32. Peng, C.-H.; Scricco, J.; Li, S.; Fryd, M.; Wayland, B. B., Macromolecules, 2008, 41 (7), 2368-2373.
33. Liao, C.-M.; Hsu, C.-C.; Wang, F.-S.; Wayland, B. B.; Peng, C.-H., Polymer Chemistry, 2013, 4 (10), 3098-3104.
34. Morin, A. N.; Detrembleur, C.; Jérôme, C.; De Tullio, P.; Poli, R.; Debuigne, A., Macromolecules, 2013, 46 (11), 4303-4312.
35. Hsu, C.-S.; Yang, T.-Y.; Peng, C.-H., Polymer Chemistry, 2014, 5 (12), 3867-3875.
36. Debuigne, A.; Warnant, J.; Jérôme, R.; Voets, I.; de Keizer, A.; Cohen Stuart, M. A.; Detrembleur, C., Macromolecules, 2008, 41 (7), 2353-2360.
37. Wagner, R. W.; Lawrence, D. S.; Lindsey, J. S., Tetrahedron Letters, 1987, 28 (27), 3069-3070.
38. Candau, F.; François, J.; Benoit, H., Polymer, 1974, 15 (10), 626-630.
39. Dong, H.; Hou, T.; Zhao, Y.; Fu, X.; Li, Y., Computational and Theoretical Chemistry, 2012, 1001, 51-59.
40. Li, S.; Bruin, B. d.; Peng, C.-H.; Fryd, M.; Wayland, B. B., Journal of the American Chemical Society, 2008, 130 (40), 13373-13381.
41. Wang, F.-S.; Yang, T.-Y.; Hsu, C.-C.; Chen, Y.-J.; Li, M.-H.; Hsu, Y.-J.; Chuang, M.-C.; Peng, C.-H., Macromolecular Chemistry and Physics, 2016, 217 (3), 422-432.
42. Chuang, W.-Y.; Young, T.-H.; Yao, C.-H.; Chiu, W.-Y., Biomaterials, 1999, 20 (16), 1479-1487.
43. Wu, G. M.; Lin, S. J.; Yang, C. C., Journal of Membrane Science, 2006, 275 (1–2), 127-133.
44. Gilman, J. W.; VanderHart, D. L.; Kashiwagi, T., Thermal Decomposition Chemistry of Poly(vinyl alcohol). In Fire and Polymers II, American Chemical Society: 1995; Vol. 599, pp 161-185.
45. Holland, B. J.; Hay, J. N., Polymer, 2001, 42 (16), 6775-6783.
46. Maurer, J. J.; Eustace, D. J.; Ratcliffe, C. T., Macromolecules, 1987, 20 (1), 196-202.
47. Lattimer, R. P., Journal of Analytical and Applied Pyrolysis, 2003, 68–69, 3-14.
48. Lee, H.; Mensire, R.; Cohen, R. E.; Rubner, M. F., Macromolecules, 2012, 45 (1), 347-355.