The State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, 200433, China.
Macromol Rapid Commun. 2020 Apr;41(7):e1900640. doi: 10.1002/marc.201900640. Epub 2020 Feb 5.
The results of polymer synthesis via visible light (blue light λ = 465 nm) and a Pd-catalyzed Mizoroki-Heck coupling reaction at ambient temperature are reported. The kinetic study demonstrates that the polymerization rate is faster under light irradiation than that in the dark, affording larger molecular weight of polymer product in the former. A mechanistic study using F NMR indicates that light can activate the oxidative addition step, increasing the rate of formation of the oxidative addition intermediate. The present work not only reveals a new mechanism of light's effect on Mizoroki-Heck coupling reaction in the absence of sensitizer, but also represents the first example of its application in step-growth polymerization.
本文报道了在可见光(蓝光 λ = 465nm)照射下和 Pd 催化的 Mizoroki-Heck 偶联反应条件下的聚合物合成结果。动力学研究表明,聚合速率在光照下比在黑暗中更快,前者得到的聚合物产物的分子量更大。使用 19 F NMR 的机理研究表明,光可以激活氧化加成步骤,增加氧化加成中间体形成的速率。本工作不仅揭示了在没有敏化剂的情况下光对 Mizoroki-Heck 偶联反应的影响的新机制,而且也是其在逐步聚合中应用的首例。