Surface-Dependent Kinetics of Cu(0)-Wire-Catalyzed Single-Electron Transfer Living Radical Polymerization of Methyl Acrylate in DMSO at 25 °C
Surface-Dependent Kinetics of Cu(0)-Wire-Catalyzed Single-Electron Transfer Living Radical Polymerization of Methyl Acrylate in DMSO at 25 °C
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DOI：
10.1021/ma8028562
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发表时间：
2009-04-14
期刊：
影响因子：
5.5
通讯作者：
Percec, Virgil
中科院分区：
文献类型：
--
作者：
Nguyen, Nga H.;Rosen, Brad M.;Percec, Virgil
通过动力学实验分析了Cu（0）线尺寸对Cu（0）线/Me-6-TREN催化的丙烯酸甲酯（MA）非均相单电子转移活性自由基聚合（SET-LRP）的影响。将这些动力学结果与Cu（0）粉末/Me-6-TREN催化的SET-LRP的动力学结果进行了比较。线和粉末都产生完美的SET-LRP，在生长物种Lip中具有一级聚合速率，转化率为100%。尽管如此，Cu（0）线实验证明SET-LRP具有更大的完善性，允许准确测定非均相Cu（0）催化剂的外部速率级（维斯表面积）和从线尺寸准确预测k（p）（app）。Cu（0）线还表现出比Cu（0）粉末显著更大的分子量分布控制。更容易的催化剂制备、处理、可预测性、可调谐性、简单的回收/再循环以及增强的分子量分布控制的综合优势使得Cu（0）-线催化的SET-LRP成为合成定制聚丙烯酸酯的理想方法。
The effect of Cu(0) wire dimensions Oil the Cu(0) wire/Me-6-TREN-catalyzed heterogeneous single-electron transfer living radical polymerization (SET-LRP) of methyl acrylate (MA) initiated with methyl 2-bromopropionate (MBP) in DMSO at 25 degrees C was analyzed by kinetic experiments. These kinetic results were compared with those of Cu(0) powder/Me-6-TREN-catalyzed SET-LRP. Both wire and powder produce perfect SET-LRP with a first-order rate of polymerization in growing species Lip to 100% conversion. Nevertheless, Cu(0) wire experiments demonstrated SET-LRP with greater perfection, allowing for the accurate determination of the external rate order (vis-a-vis Surface area) for heterogeneous Cu(0) catalyst and accurate prediction of k(p)(app) from wire dimension. Cu(0) wire also exhibited a significantly greater control of molecular weight distribution than Cu(0) powder. The combined advantages of easier catalyst preparation, handling, predictability, tunability, simple recovery/recycling, and enhanced control of molecular weight distribution make Cu(0)-wire-catalyzed SET-LRP the ideal methodology for the synthesis of tailored polyacrylates.