可逆-失活自由基聚合反應（RDRP）是高分子合成中最普遍運用的技術之一，可用於合成乙烯基聚合物和嵌段共聚物，這類聚合物則廣泛應用於生醫領域。而此方法最大的限制，在於需要使用有毒的金屬錯合物作為調控劑。本研究分為三個章節，前兩個章節探討純有機調控劑，特別是沙洛芬（salophen，第一章）和環庚三烯酮（tropone，第二章）的衍生物，用於醋酸乙烯酯（VAc）、N-乙烯基吡咯烷酮（NVP）和甲基丙烯酸甲酯（MA）等乙烯基單體的自由基聚合中，分子量隨單體轉化率線性增長，並且成功合成嵌段共聚物。研究反應機制的結果顯示，這些有機調控劑會與自由基形成可逆 C–C 鍵並產生休眠物種，透過自由基與休眠物種之間的動態平衡實現調控聚合的能力。第三章則進一步探討嵌段共聚物在可降解水凝膠於生醫領域的應用，此水凝膠展現出可控的溶脹性、可控的降解性、高含水量及良好的皮膚附著性，顯示出其在生醫領域的潛在應用價值。

A reversible-deactivation radical polymerization (RDRP) is a powerful technique in producing vinyl polymers and block copolymers, which are widely used in biomedical applications. Howev-er, the significant limitation in this method is utilization of toxic metal complexes in mediating RDRPs. This research was divided into three parts, including the investigation of new pure or-ganic mediators, specifically derivatives of salophen (Chapter 1) and tropone (Chapter 2), in con-trolling radical polymerizations of vinyl monomers, such as vinyl acetate (VAc), N-vinylpyrrolidone (NVP) and methyl acrylate (MA) with linear molecular weight growth and ena-bling block copolymer formation. The mechanistic studies revealed that organo-mediators form the dormant species through reversible C–C bond. The dynamic equilibrium between active spe-cies and dormant species led to controlled polymerization. The biomedical application of block copolymers was investigated by the study of degradable hydrogels in Chapter 3. The gels were fabricated, and their performances were demonstrated by tunable swelling capacity, high water content, skin adhesion and controllable degradation.

Chapter 1
1. Grubbs, R. B., Nitroxide-mediated radical polymerization: limitations and versatility, Polym. Rev., 2011, 51 (2), 104-137.
2. Sciannamea, V.; Jérôme, R.; Detrembleur, C., In-situ nitroxide-mediated radical polymerization (NMP) processes:  their understanding and optimization, Chem. Rev., 2008, 108 (3), 1104-1126.
3. Nicolas, J.; Guillaneuf, Y.; Lefay, C.; Bertin, D.; Gigmes, D.; Charleux, B., Nitroxide-mediated polymerization, Prog. Polym. Sci., 2013, 38 (1), 63-235.
4. Matyjaszewski, K.; Xia, J., Atom transfer radical polymerization, Chem. Rev., 2001, 101 (9), 2921-2990..
5. Coessens, V.; Pintauer, T.; Matyjaszewski, K., Functional polymers by atom transfer radical polymerization, Prog. Polym. Sci., 2001, 26 (3), 337-377.
6. Wang, J.-S.; Matyjaszewski, K., Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes, J. Am. Chem. Soc., 1995, 117 (20), 5614-5615.
7. Moad, G.; Rizzardo, E.; Thang, S. H., Living radical polymerization by the RAFT process, Aust. J. Chem., 2005, 58 (6), 379-410.
8. D'Agosto, F.; Rieger, J.; Lansalot, M., RAFT-Mediated polymerization-induced self-assembly, Angew. Chem. Int. Ed., 2020, 59 (22), 8368-8392.
9. H Hill, M. R.; Carmean, R. N.; Sumerlin, B. S., Expanding the scope of RAFT polymerization: recent advances and new horizons, Macromolecules, 2015, 48 (16), 5459-5469.
10. Moad, G.; Rizzardo, E.; Thang, S. H., Radical addition–fragmentation chemistry in polymer synthesis, Polymer, 2008, 49 (5), 1079-1131.
11. Yamago, S., Development of organotellurium-mediated and organostibine-mediated living radical polymerization reactions, J. Polym. Sci., 2006, 44 (1), 1-12.
12. David, G.; Boyer, C.; Tonnar, J.; Ameduri, B.; Lacroix-Desmazes, P.; Boutevin, B., Use of iodocompounds in radical polymerization, Chem. Rev., 2006, 106 (9), 3936-3962.
13. Uegaki, H.; Kotani, Y.; Kamigaito, M.; Sawamoto, M., Nickel-mediated living radical polymerization of methyl methacrylate, Macromolecules, 1997, 30 (8), 2249-2253.
14. Li, P.; Qiu, K.-Y., Nickel-mediated living radical polymerization of styrene in conjunction with tetraethylthiuram disulfide, Polymer, 2002, 43 (22), 5873-5877.
15. dens, I.; Degée, P.; Haddleton, D. M.; Dubois, P., Reactivity ratios in conventional and nickel-mediated radical copolymerization of methyl methacrylate and functionalized methacrylate monomers, Eur. Polym. J., 2005, 41 (10), 2255-2263.
16. Debuigne, A.; Poli, R.; Jérôme, C.; Jérôme, R.; Detrembleur, C., Overview of cobalt-mediated radical polymerization: Roots, state of the art and future prospects. Progress in Polymer Science 2009, 34 (3), 211-239.
17. Debuigne, A.; Caille, J.-R.; Jérôme, R., Highly efficient cobalt-mediated radical polymerization of vinyl acetate, Angew. Chem. Int. Ed., 2005, 44 (7), 1101-1104.
18. Benchaphanthawee, W.; Peng, C.-H., Organo-cobalt complexes in reversible-deactivation radical polymerization, Chem. Rec., 2021, 21 (12), 3628-3647.
19. Stoffelbach, F.; Haddleton, D. M.; Poli, R., Controlled radical polymerization of alkyl acrylates and styrene using a half-sandwich molybdenum(III) complex containing diazadiene ligands, Eur. Polym. J., 2003, 39 (11), 2099-2105.
20. Braunecker, W. A.; Brown, W. C.; Morelli, B. C.; Tang, W.; Poli, R.; Matyjaszewski, K., Origin of activity in Cu-, Ru-, and Os-mediated radical polymerization, Macromolecules, 2007, 40 (24), 8576-8585.
21. Poli, R.; Allan, L. E. N.; Shaver, M. P., Iron-mediated reversible deactivation controlled radical polymerization, Prog. Polym. Sci., 2014, 39 (10), 1827-1845.
22. Teodorescu, M.; Gaynor, S. G.; Matyjaszewski, K., Halide anions as ligands in iron-mediated atom transfer radical polymerization, Macromolecules, 2000, 33 (7), 2335-2339.
23. Rossi, B.; Prosperini, S.; Pastori, N.; Clerici, A.; Punta, C., New advances in titanium-mediated free radical reactions, Molecules, 2012, 17 (12), 14700-14732.
24. Asandei, A. D.; Moran, I. W.; Saha, G.; Chen, Y., Titanium-mediated living radical styrene polymerizations. VI. Cp2TiCl-catalyzed initiation by epoxide radical ring opening: effect of the reducing agents, temperature, and titanium/epoxide and titanium/zinc ratios, J. Polym. Sci. 2006, 44 (7), 2156-2165.
25. Champouret, Y.; MacLeod, K. C.; Smith, K. M.; Patrick, B. O.; Poli, R., Controlled radical polymerization of vinyl acetate with cyclopentadienyl chromium β-diketiminate complexes: ATRP vs OMRP, Organometallics, 2010, 29 (14), 3125-3132.
26. Champouret, Y.; MacLeod, K. C.; Baisch, U.; Patrick, B. O.; Smith, K. M.; Poli, R., Cyclopentadienyl chromium β-diketiminate complexes: initiators, ligand steric effects, and deactivation processes in the controlled radical polymerization of vinyl acetate, Organometallics, 2010, 29 (1), 167-176.
27. Shaver, M. P.; Hanhan, M. E.; Jones, M. R., Controlled radical polymerization of vinyl acetate mediated by a vanadium complex, Chem. Commun. 2010, 46 (12), 2127-2129.
28. Perry, M. R.; Allan, L. E. N.; Decken, A.; Shaver, M. P., Organometallic mediated radical polymerization of vinyl acetate using bis(imino)pyridine vanadium trichloride complexes, Dalton Trans., 2013, 42 (25), 9157-9165.
29. Chang, C.-W.; Jen, Y.-Y.; Tang, S.-C.; Zhang, P.; Chen, C.; Peng, C.-H., Reversible-deactivation radical polymerization of vinyl acetate mediated by tralen, an organomediator, Polym. Chem., 2021, 12 (36), 5159-5167.
30. Subramaniam, P.; Jeevi Esther Rathnakumari, R.; Janet Sylvia Jaba Rose, J., Importance of ground state stabilization in the oxovanadium(IV)-salophen mediated reactions of phenylsulfinylacetic acids by hydrogen peroxide – non-linear hammett correlation, Polyhedron, 2016, 117, 496-503.
31. Santos, I. C.; Vilas-Boas, M.; Piedade, M. F. M.; Freire, C.; Duarte, M. T.; de Castro, B., Electrochemical and x-ray studies of nickel(II) schiff base complexes derived from salicylaldehyde: structural effects of bridge substituents on the stabilisation of the +3 oxidation state, Polyhedron, 2000, 19 (6), 655-664.
32. Destarac, M., Industrial development of reversible-deactivation radical polymerization: is the induction period over?, Polym. Chem., 2018, 9 (40), 4947-4967.
33. Zhao, G.; Yang, Y.; Zhang, C.; Song, Y.; Li, Y., The theoretical study of excited-state intramolecular proton transfer of N, N,-bis (salicylidene)-(2-(3″4′-diaminophenyl) benzothiazole), J. Lumin., 2021, 230, 117741-117751.
34. Duarte, L. G. T. A.; Germino, J. C.; Berbigier, J. F.; Barboza, C. A.; Faleiros, M. M.; de Alencar Simoni, D.; Galante, M. T.; de Holanda, M. S.; Rodembusch, F. S.; Atvars, T. D. Z., White-light generation from all-solution-processed OLEDs using a benzothiazole–salophen derivative reactive to the ESIPT process, Phys. Chem. Chem. Phys., 2019, 21 (3), 1172-1182.
35. Guliashvili, T.; Percec, V., A comparative computational study of the homolytic and heterolytic bond dissociation energies involved in the activation step of ATRP and SET-LRP of vinyl monomers, J. Polym. Sci., 2007, 45 (9), 1607-1618.

Chapter 2
1. Corrigan, N.; Jung, K.; Moad, G.; Hawker, C. J.; Matyjaszewski, K.; Boyer, C., Reversible-deactivation radical polymerization (controlled/living radical polymerization): from discovery to materials design and applications. Prog. Polym. Sci. 2020, 111, 101311.
2. Pan, X.; Tasdelen, M. A.; Laun, J.; Junkers, T.; Yagci, Y.; Matyjaszewski, K., Photomediated controlled radical polymerization. Prog. Polym. Sci. 2016, 62, 73-125.
3. Braunecker, W. A.; Matyjaszewski, K., Controlled/living radical polymerization: features, developments, and perspectives. Prog. Polym. Sci. 2007, 32 (1), 93-146.
4. Ouchi, M.; Sawamoto, M., Sequence-controlled polymers via reversible-deactivation radical polymerization. Polym. J. 2018, 50 (1), 83-94.
5. Bagheri, A.; Fellows, C. M.; Boyer, C., Reversible deactivation radical polymerization: from polymer network synthesis to 3D printing. Adv. Sci. 2021, 8 (5), 2003701.
6. Zhao, Y.; Ma, M.; Lin, X.; Chen, M., Photoorganocatalyzed divergent reversible-deactivation radical polymerization towards linear and branched fluoropolymers. Angew. Chem. Int. Ed. 2020, 59 (48), 21470-21474.
7. Li, W.; Matyjaszewski, K.; Albrecht, K.; Möller, M., Reactive surfactants for polymeric nanocapsules via interfacially confined miniemulsion ATRP. Macromolecules 2009, 42 (21), 8228-8233.
8. Li, W.; Matyjaszewski, K., Cationic surface-active monomers as reactive surfactants for AGET emulsion ATRP of N-butyl methacrylate. Macromolecules 2011, 44 (14), 5578-5585.
9. Zehm, D.; Laschewsky, A.; Gradzielski, M.; Prévost, S.; Liang, H.; Rabe, J. P.; Schweins, R.; Gummel, J., Amphiphilic Dual brush block copolymers as “Giant Surfactants” and their aqueous self-assembly. Langmuir 2010, 26 (5), 3145-3155.
10. Thomson, M. E.; Manley, A.-M.; Ness, J. S.; Schmidt, S. C.; Cunningham, M. F., Nitroxide-mediated surfactant-free emulsion polymerization of N-butyl methacrylate with a small amount of styrene. Macromolecules 2010, 43 (19), 7958-7963.
11. Gallagher, J. J.; Hillmyer, M. A.; Reineke, T. M., Acrylic triblock copolymers incorporating isosorbide for pressure sensitive adhesives. ACS Sustainable Chem. Eng. 2016, 4 (6), 3379-3387.
12. Wang, S.; Shuai, L.; Saha, B.; Vlachos, D. G.; Epps, T. H., From tree to tape: direct synthesis of pressure sensitive adhesives from depolymerized raw lignocellulosic biomass. ACS Cent. Sci. 2018, 4 (6), 701-708.
13. Noppalit, S.; Simula, A.; Billon, L.; Asua, J. M., Paving the way to sustainable waterborne pressure-sensitive adhesives using terpene-based triblock copolymers. ACS Sustainable Chem. Eng. 2019, 7 (21), 17990-17998.
14. Ebeling, B.; Vana, P., RAFT-Polymers with single and multiple trithiocarbonate groups as uniform gold-nanoparticle coatings. Macromolecules 2013, 46 (12), 4862-4871.
15. Zhang, Z.; Corrigan, N.; Boyer, C., A photoinduced dual-wavelength approach for 3D printing and self-healing of thermosetting materials. Angew. Chem. Int. Ed. 2022, 61 (11), e202114111.
16. Singh, R.; Rhee, H.-W., Controlled polymerization for lithium-ion batteries. Energy Storage Mater. 2022, 52, 598-636.
17. Yang, K.; Huang, X.; Huang, Y.; Xie, L.; Jiang, P., Fluoro-polymer@BaTiO3 Hybrid nanoparticles prepared via RAFT polymerization: toward ferroelectric polymer nanocomposites with high dielectric constant and low dielectric loss for energy storage application. Chem. Mater. 2013, 25 (11), 2327-2338.
18. O'Brien, C.; Ignaszak, A., Polymer-grafted-carbon assembled via an electrochemically-aided atom transfer radical polymerization: Towards improved energy storage electrode. Electrochem. Commun. 2022, 135, 107198.
19. Boyer, C.; Bulmus, V.; Davis, T. P.; Ladmiral, V.; Liu, J.; Perrier, S., Bioapplications of RAFT polymerization. Chem. Rev. 2009, 109 (11), 5402-5436.
20. Grubbs, R. B., Nitroxide-mediated radical polymerization: limitations and versatility. Polym. Rev. 2011, 51 (2), 104-137.
21. Sciannamea, V.; Jérôme, R.; Detrembleur, C., In-situ nitroxide-mediated radical polymerization (NMP) processes:  their understanding and optimization. Chem. Rev. 2008, 108 (3), 1104-1126.
22. Nicolas, J.; Guillaneuf, Y.; Lefay, C.; Bertin, D.; Gigmes, D.; Charleux, B., Nitroxide-mediated polymerization. Prog. Polym. Sci. 2013, 38 (1), 63-235.
23. Matyjaszewski, K.; Xia, J., Atom transfer radical polymerization. Chem. Rev. 2001, 101 (9), 2921-2990.
24. Coessens, V.; Pintauer, T.; Matyjaszewski, K., Functional polymers by atom transfer radical polymerization. Prog. Polym. Sci. 2001, 26 (3), 337-377.
25. Wang, J.-S.; Matyjaszewski, K., Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes. J. Am. Chem. Soc. 1995, 117 (20), 5614-5615.
26. Moad, G.; Rizzardo, E.; Thang, S. H., Living radical polymerization by the RAFT process. Aust. J. Chem. 2005, 58 (6), 379-410.
27. D'Agosto, F.; Rieger, J.; Lansalot, M., RAFT-Mediated polymerization-induced self-assembly. Angew. Chem. Int. Ed. 2020, 59 (22), 8368-8392.
28. Hill, M. R.; Carmean, R. N.; Sumerlin, B. S., Expanding the scope of RAFT polymerization: recent advances and new horizons. Macromolecules 2015, 48 (16), 5459-5469.
29. Moad, G.; Rizzardo, E.; Thang, S. H., Radical addition–fragmentation chemistry in polymer synthesis. Polymer 2008, 49 (5), 1079-1131.
30. Yamago, S., Precision Polymer synthesis by degenerative transfer controlled/living radical polymerization using organotellurium, organostibine, and organobismuthine chain-transfer agents. Chem. Rev. 2009, 109 (11), 5051-5068.
31. David, G.; Boyer, C.; Tonnar, J.; Ameduri, B.; Lacroix-Desmazes, P.; Boutevin, B., Use of iodocompounds in radical polymerization. Chem. Rev. 2006, 106 (9), 3936-3962.
32. Uegaki, H.; Kotani, Y.; Kamigaito, M.; Sawamoto, M., Nickel-mediated living radical polymerization of methyl methacrylate. Macromolecules 1997, 30 (8), 2249-2253.
33. Li, P.; Qiu, K.-Y., Nickel-mediated living radical polymerization of styrene in conjunction with tetraethylthiuram disulfide. Polymer 2002, 43 (22), 5873-5877.
34. Ydens, I.; Degée, P.; Haddleton, D. M.; Dubois, P., Reactivity ratios in conventional and nickel-mediated radical copolymerization of methyl methacrylate and functionalized methacrylate monomers. European Polym. J. 2005, 41 (10), 2255-2263.
35. Debuigne, A.; Poli, R.; Jérôme, C.; Jérôme, R.; Detrembleur, C., Overview of cobalt-mediated radical polymerization: roots, state of the art and future prospects. Prog. Polym. Sci. 2009, 34 (3), 211-239.
36. Debuigne, A.; Caille, J.-R.; Jérôme, R., Highly efficient cobalt-mediated radical polymerization of vinyl acetate. Angew. Chem. Int. Ed. 2005, 44 (7), 1101-1104.
37. Benchaphanthawee, W.; Peng, C.-H., Organo-cobalt complexes in reversible-deactivation radical polymerization. Chem. Rec. 2021, 21 (12), 3628-3647.
38. Stoffelbach, F.; Haddleton, D. M.; Poli, R., Controlled radical polymerization of alkyl acrylates and styrene using a half-sandwich molybdenum(III) complex containing diazadiene ligands. European Polym. J. 2003, 39 (11), 2099-2105.
39. Braunecker, W. A.; Brown, W. C.; Morelli, B. C.; Tang, W.; Poli, R.; Matyjaszewski, K., Origin of activity in Cu-, Ru-, and Os-mediated radical polymerization. Macromolecules 2007, 40 (24), 8576-8585.
40. Poli, R.; Allan, L. E. N.; Shaver, M. P., Iron-mediated reversible deactivation controlled radical polymerization. Prog. Polym. Sci. 2014, 39 (10), 1827-1845.
41. Teodorescu, M.; Gaynor, S. G.; Matyjaszewski, K., Halide anions as ligands in iron-mediated atom transfer radical polymerization. Macromolecules 2000, 33 (7), 2335-2339.
42. Rossi, B.; Prosperini, S.; Pastori, N.; Clerici, A.; Punta, C., New advances in titanium-mediated free radical reactions. Molecules 2012, 17 (12), 14700-14732.
43. Asandei, A. D.; Moran, I. W.; Saha, G.; Chen, Y., Titanium-mediated living radical styrene polymerizations. VI. Cp2TiCl-catalyzed initiation by epoxide radical ring opening: effect of the reducing agents, temperature, and titanium/epoxide and titanium/zinc ratios. J. Polym. Sci. 2006, 44 (7), 2156-2165.
44. Champouret, Y.; MacLeod, K. C.; Smith, K. M.; Patrick, B. O.; Poli, R., Controlled radical polymerization of vinyl acetate with cyclopentadienyl chromium β-diketiminate complexes: ATRP vs OMRP. Organometallics 2010, 29 (14), 3125-3132.
45. Champouret, Y.; MacLeod, K. C.; Baisch, U.; Patrick, B. O.; Smith, K. M.; Poli, R., Cyclopentadienyl chromium β-diketiminate complexes: initiators, ligand steric effects, and deactivation processes in the controlled radical polymerization of vinyl acetate. Organometallics 2010, 29 (1), 167-176.
46. Shaver, M. P.; Hanhan, M. E.; Jones, M. R., Controlled radical polymerization of vinyl acetate mediated by a vanadium complex. Chem. Commun. 2010, 46 (12), 2127-2129.
47. Perry, M. R.; Allan, L. E. N.; Decken, A.; Shaver, M. P., Organometallic mediated radical polymerization of vinyl acetate using bis(imino)pyridine vanadium trichloride complexes. Dalton Trans. 2013, 42 (25), 9157-9165.
48. Chang, C.-W.; Jen, Y.-Y.; Tang, S.-C.; Zhang, P.; Chen, C.; Peng, C.-H., Reversible-deactivation radical polymerization of vinyl acetate mediated by tralen, an organomediator. Polym. Chem. 2021, 12 (36), 5159-5167.
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Chapter 3
1. Yan, X.; Sun, T.; Song, Y.; Peng, W.; Xu, Y.; Luo, G.; Li, M.; Chen, S.; Fang, W.-W.; Dong, L.; Xuan, S.; He, T.; Cao, B.; Lu, Y., In situ thermal-responsive magnetic hydrogel for multidisciplinary therapy of hepatocellular carcinoma. Nano Lett. 2022, 22 (6), 2251-2260.
2. Park, J. S.; Park, J. W.; Ruckenstein, E., Thermal and dynamic mechanical analysis of PVA/MC blend hydrogels. Polymer 2001, 42 (9), 4271-4280.
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