In this study, we combined the kinetic measurement and the computational simulation to build a kinetic model for the hybridization of cobalt-mediated radical polymerization (CMRP) and atom transfer radical polymerization (ATRP), which is a novel method for the one-pot synthesis of block copolymers of less activated monomers and more activated monomers, such as PVAc-b-PMMA and PVAc-b-PSty. The rate constants of the two most important reactions for PVAc radical, the dissociation of PVAc-Co^III(acac)₂ and the deactivation with Cu^II(PMDETA)Br₂, have been evaluated at 40 °C as 4.99 × 10^–3 s^–1 and 4.19 × 10⁶ M^–1 s^–1, respectively. These two kinetic parameters associated with other rate constants allowed us to build a quantitative model that can simulate the polymerization behavior observed in the hybridization of CMRP and ATRP and thus rationalize the mechanism more precisely.

中文翻译：

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聚合物动力学的计算辅助研究：钴介导的自由基聚合和原子转移自由基聚合的杂交机理

在这项研究中，我们将动力学测量和计算仿真相结合，建立了钴介导的自由基聚合（CMRP）和原子转移自由基聚合（ATRP）杂交的动力学模型，这是一种一锅合成的新方法较少活化的单体和较高活化的单体，例如PVAc- b- PMMA和PVAc- b- PSty的嵌段共聚物。对PVAc自由基的两个最重要反应的速率常数，即PVAc-Co ^III（acac）₂的解离和Cu ^II（PMDETA）Br ₂的失活，已在40°C下评估为4.99×10 ^–3 s ^–1和4.19×10 ⁶ M^–1 s ^–1。这两个动力学参数与其他速率常数相关联，使我们能够建立一个定量模型，该模型可以模拟在CMRP和ATRP杂交中观察到的聚合行为，从而更精确地合理化机理。