摘要
鈷錯合物在自由基聚合反應發展的歷史中扮演重要的角色。最著名的，莫過於鈷錯合物催化的鍊轉移聚合反應與鈷錯合物調控之可控／活性聚合反應。它們皆是自由基聚合反應中控制高分子分子量與結構的重要方法。本文統整了我們在鈷錯合物於自由基聚合反應中的研究，探討配體結構與鈷錯合物反應活性的關係。我們利用六個苯氧基亞胺（phenoxy imine）配位的鈷錯合物在醋酸乙烯酯的聚合反應，以及另外五種鈷錯合物在丙烯酸甲酯的聚合反應，來檢視配基上官能基的立體阻礙、電子效應、以及鈷錯合物的氧化還原半電位對於鈷錯合物反應活性的影響。在文末我們列舉了理論計算應用在聚合反應的實例，並提出理論計算與實驗結合之後，可控／活性聚合在未來可能的發展。
並列摘要
Cobalt complexes have played an essential role in the development of radical polymerization. Most significantly, the catalytic chain transfer polymerization and the cobalt mediated controlled/ living radical polymerization are both important methods to control the molecular weight and the architecture of polymeric products. Herein, we demonstrated the steric effect of ligand, the electronic effect of ligand, and the influence of redox potential of cobalt complexes to the activity of cobalt complexes in the radical polymerization by the examples of vinyl acetate polymerization with six phenoxy-imine coordinated cobalt complexes and polymerization of methyl acrylate with five cobalt complexes. In the last paragraph, we presented the current application of theoretical calculation in polymer chemistry and proposed the potential of computational modeling to the research of polymer thermodynamics and polymer kinetics in controlled/living radical polymerization.
延伸閱讀
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