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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical Study of Chain Transfer to Solvent Reactions of Alkyl Acrylates
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Theoretical Study of Chain Transfer to Solvent Reactions of Alkyl Acrylates

机译：链转移对丙烯酸烷基酯溶剂反应的理论研究

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This computational and theoretical study deals with chain transfer to solvent (CTS) reactions of methyl acrylate (MA), ethyl acrylate (EA), and n-butyl acrylate (n-BA) self-initiated homopolymerization in solvents such as butanol (polar, protic), methyl ethyl ketone (MEK) (polar, aprotic), and p-xylene (nonpolar). The results indicate that abstraction of a hydrogen atom from the methylene group next to the oxygen atom in n-butanol, from the methylene group in MEK, and from a methyl group in p-xylene by a live polymer chain are the most likely mechanisms of CTS reactions in MA, EA, and n-BA. Energy barriers and molecular geometries of reactants, products, and transition states are predicted. The sensitivity of the predictions to three hybrid functionals (B3LYP, X3LYP, and M06-2X) and three different basis sets (6-31G(d,p), 6-311G(d), and 6-311G(d,p)) is investigated. Among n-butanol, sec-butanol, and tertbutanol, tert-butanol has the highest CTS energy barrier and the lowest rate constant. Although the application of the conductorlike screening model (COSMO) does not affect the predicted CTS kinetic parameter values, the application of the polarizable continuum model (PCM) results in higher CTS energy barriers. This increase in the predicted CTS energy barriers is larger for butanol and MEK than for p-xylene. The higher rate constants of chain transfer to n-butanol reactions compared to those of chain transfer to MEK and p-xylene reactions suggest the higher CTS reactivity of n-butanol.
机译：这项计算和理论研究涉及丙烯酸丁酯（MA），丙烯酸乙酯（EA）和丙烯酸正丁酯（n-BA）在溶剂（例如丁醇（极性），质子），甲基乙基酮（MEK）（极性，非质子）和对二甲苯（非极性）。结果表明，通过活性聚合物链从正丁醇中次于氧原子的亚甲基，MEK中的亚甲基和对二甲苯中的甲基夺取氢原子是最可能的机理。 MA，EA和n-BA中的CTS反应。可以预测反应物，产物和过渡态的能垒和分子几何形状。预测对三种混合功能（B3LYP，X3LYP和M06-2X）和三种不同基集（6-31G（d，p），6-311G（d）和6-311G（d，p）的敏感性）进行调查。在正丁醇，仲丁醇和叔丁醇中，叔丁醇具有最高的CTS能垒和最低的速率常数。尽管类似导体的筛查模型（COSMO）的应用不会影响CTS动力学参数的预测值，但可极化连续体模型（PCM）的应用会导致更高的CTS能垒。与对二甲苯相比，丁醇和MEK的预计CTS能垒的增加更大。与向MEK和对二甲苯反应的链转移相比，向正丁醇反应的链转移的速率常数更高，表明正丁醇的CTS反应性更高。

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