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Solvent Effects on Acrylate k(p) in Organic Media: A Response

机译:溶剂对有机介质中丙烯酸酯k(p)的影响:回应

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摘要

Radical propagation rate is adequately understood in the light of fundamental kinetic theory. Differences in bulk and solution k(p) are primarily of entropic origin, with the effects depending on the differences in polarity and size of monomer and solvent molecules, respectively. Experimental data for the propagation rate coefficient of secondary acrylate radicals demonstrate that bulk and solution-in-toluene k(p) exhibit distinctly different behavior. Bulk k(p) is clearly enhanced in passing from methyl acrylate (MA) to dodecyl acrylate (DA), whereas solution-in-toluene k(p) is approximately constant with a slight tendency to decrease from MA to DA. This k(p) behavior has also been found in a recent study, in which it has, however, been concluded that k(p) in solution of toluene (and of butyl acetate) displays a similar behavior to bulk. This surprising and inadequate conclusion requires the present comment and rectification to be made.
机译:根据基本动力学理论,充分理解了自由基传播速率。体积和溶液k(p)的差异主要来自熵,其影响分别取决于单体和溶剂分子的极性和大小的差异。仲丙烯酸酯自由基传播速率系数的实验数据表明,本体和甲苯溶液中的k(p)表现出明显不同的行为。从丙烯酸甲酯(MA)到十二烷基丙烯酸酯(DA)的体积k(p)明显增强,而甲苯溶液中的k(p)大致恒定,从MA到DA略有下降趋势。在最近的一项研究中也发现了这种 k(p) 行为,然而,在该研究中得出的结论是,甲苯(和乙酸丁酯)溶液中的 k(p) 表现出与本体相似的行为。这一令人惊讶和不充分的结论需要作出本评论和纠正。

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