Ab initio study of acrylate polymerization reactions: methyl methacrylate and methyl acrylate propagation.
Ab initio study of acrylate polymerization reactions: methyl methacrylate and methyl acrylate propagation.
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丙烯酸酯聚合反应的从头算研究：甲基丙烯酸甲酯和丙烯酸甲酯增长。
DOI：
10.1021/jp800643a
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发表时间：
2008
期刊：
影响因子：
--
通讯作者：
L. Broadbelt
中科院分区：
文献类型：
--
作者：
Xinrui Yu;J. Pfaendtner;L. Broadbelt
用量子化学和过渡态理论计算了甲基丙烯酸甲酯和甲基丙烯酸甲酯自由基扩散的动力学参数。用多重密度泛函理论(DFT)方法计算了反应的活化能，发现MPWB1K/6-31G(d，p)的计算结果与实验数据符合得很好。为了得到与实验数据最符合的动力学参数值，采用一维内旋翼模型对低频进行处理。通过考察单体、二聚体和三聚体自由基对甲基丙烯酸甲酯和丙烯酸甲酯的加成反应，探讨了链长效应。结果表明，单体中三聚自由基加成的值与实验值最接近。用连续描述的单体作为溶剂计算的动力学参数与真空计算的结果没有显著差异。
The kinetic parameters of the free radical propagation of methyl methacrylate and methyl acrylate have been calculated using quantum chemistry and transition state theory. Multiple density functional theory (DFT) methods were used to calculate the activation energy, and it was found that MPWB1K/6-31G(d,p) yields results that are in very good agreement with experimental data. To obtain values of the kinetic parameters that were in the best agreement with experimental data, low frequencies were treated using a one-dimensional internal rotor model. Chain length effects were also explored by examining addition reactions of monomeric, dimeric, and trimeric radicals to monomer for both methyl methacrylate and methyl acrylate. The results show that the values for the addition of the trimeric radical to monomer are closest to experimental data. The kinetic parameters that were calculated using a continuum description of the monomer as a solvent were not significantly different from the vacuum results.