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In this thesis, development photochemical or chemical cocatalysts for Cu-catalyzed ATRP is discussed. Chapter 1 introduces the mechanism of ATRP and other important reversibledeactivation radical polymerization (RDRP) methods, which provides fundamental knowledge and the state-of-the-art of research on the development of cocatalysts for ATRP. Chapters 2-8 are research projects that I have worked on during my Ph.D. study, which are divided into three themes: (I) Photochemical Cocatalysts for Cu-Catalyzed ATRP (Chapters 2-5); (II) Chemical Cocatalysts for Cu-Catalyzed ATRP (Chapters 6-7); (III) Applications of Polymerbased Materials (Chapter 8). Both experimental and computational methods were used to study the structure and properties of cocatalysts and related materials. Chapters 2-5 (Theme I) focus on the application of photochemical cocatalysts for Cucatalyzed ATRP and the development of photoactive crosslinked polymer networks. Chapter 2 discusses the synthesis and properties of a photoluminescent polymer prepared via the hydrothermal reaction of polyacrylonitrile (PAN), ht-PLPPAN. Chapter 3 introduces the application of ht-PLPPAN as a photo-cocatalyst in light-mediated Cu-catalyzed ATRP. Different mechanisms under different light irradiations are discussed. Chapter 4 extends the work on PAN to structurally tailored and engineered macromolecular (STEM) networks and discusses the unusual photoluminescence properties of STEM networks containing PAN. Chapter 5 introduces another type of photoluminescent network by immobilizing photoactive iridium (III) complexes onto a commercially available poly(ethylene glycol) (PEG)-based resin, ChemMatrix. Chapters 6-7 (Theme II) focuses on the application of chemical cocatalysts for Cucatalyzed ATRP. In Chapter 6, Cu-catalyzed ATRP using liquid metal micro/nanodroplets as the supplemental activator and reducing agent (SARA) is studied. Chapter 7 extends the application of SARA ATRP to N,N-dimethylacrylamide (DMAA) and less polar organic solvents, as well as the synthesis of block copolymers (BCPs) containing polyethylene and polyacrylamides. Chapter 8 (Theme III) demonstrates the application of BCP-derived nanocarbon materials as fuel cell cathode catalysts. The influence of the composition of the polyacrylonitrile-b-poly(n-butyl acrylate) (PAN-b-PBA) precursor on the nanocarbon properties is discussed. Finally, Chapter 9 provides a summary and future perspectives on the development of cocatalysts for Cu-catalyzed ATRP. Appendices summarized the academic papers published or already submitted during my Ph.D. study, as well as other group activities and related achievements. |
