有機金屬錯合物在開環與可控/活性自由基聚合的應用

Development of Organometallic Complexes for Ring-opening and Controlled / Living Radical Polymerization

謝宜良(Hsieh, Yi Liang)

指導教授 ： 彭之皓

國立清華大學/理學院/化學系/博士(2015年)

https://doi.org/10.6843/NTHU.2015.00092

摘要

Cobalt complexes mediated radical polymerization (CMRP) and ring-opening polymerization (ROP) are the most tools of modern controlled / living polymerization. CMRP is recognized by its unique control efficiency to vinyl acetate (VAc), which shows important applications in materials science and medical biology but can hardly be controlled by other living radical polymerization (LRP) methods. ROP is the major technique to synthesize biocompatible and biodegradable polyesters materials with low polydispersity (PDI = Mw/Mn) and well-controlled molecular weight. Initiators or catalysts used in ring-opening polymerization are required to have a high reactivity, negligible toxicity, low cost, and capability to lead a high degree of polymerization. In this regard, this thesis describes new organometallic complexes that focus on the mediate vinyl olefins and cyclic esters monomers, which were successfully achieve by CMRP and ROP systems. Building various copolymers with different components are also effectively synthesized through CMRP and ROP methods. For better understanding, I divided this thesis into four chapters. The chapter 1 to 3 describe about ROP catalyzed / initiated by newly metal complexes and discuss steric and electronic effect on ligands. In addition, the stereoselectivity of rac-lactide polymerization is the important topic in Al complexes system. Last chapter illustrate about polymerization of various vinyl olefins and block copolymer synthesis mediated by cobalt bipyridine-bisphenolate complex (CoII(BpyBph)).

關鍵字

開環聚合反應 ； 可控自由基聚合反應 ； 聚酯類高分子

並列摘要

Cobalt complexes mediated radical polymerization (CMRP) and ring-opening polymerization (ROP) are the most tools of modern controlled / living polymerization. CMRP is recognized by its unique control efficiency to vinyl acetate (VAc), which shows important applications in materials science and medical biology but can hardly be controlled by other living radical polymerization (LRP) methods. ROP is the major technique to synthesize biocompatible and biodegradable polyesters materials with low polydispersity (PDI = Mw/Mn) and well-controlled molecular weight. Initiators or catalysts used in ring-opening polymerization are required to have a high reactivity, negligible toxicity, low cost, and capability to lead a high degree of polymerization. In this regard, this thesis describes new organometallic complexes that focus on the mediate vinyl olefins and cyclic esters monomers, which were successfully achieve by CMRP and ROP systems. Building various copolymers with different components are also effectively synthesized through CMRP and ROP methods. For better understanding, I divided this thesis into four chapters. The chapter 1 to 3 describe about ROP catalyzed / initiated by newly metal complexes and discuss steric and electronic effect on ligands. In addition, the stereoselectivity of rac-lactide polymerization is the important topic in Al complexes system. Last chapter illustrate about polymerization of various vinyl olefins and block copolymer synthesis mediated by cobalt bipyridine-bisphenolate complex (CoII(BpyBph)).

參考文獻

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