Kinetics and Modeling of Solution ARGET ATRP of Styrene, Butyl Acrylate, and Methyl Methacrylate

This work reports a kinetic model for the activator-regenerated-by-electron-transfer atom-transfer radical polymerization (ARGET ATRP) and its verification by the experimental data of solution ARGET ATRP of styrene, methyl methacrylate, and butyl arylate from literatures. The effects of ATRP equilibrium constant K and apparent reducing rate coefficient k(r) on the ARGET ATRP kinetics are investigated. A highly active initiation/catalyst system with a large K results in a poor control of the polymerization while an increased k(r) promotes the polymerization rate but the formation of dead polymer chains. Reducing agent with a moderate k(r) gives good control over ARGET ATRP. It is not feasible to use a moderate catalyst system for the ARGET ATRP of highly active monomers.

这项工作报道了一种电子转移活化剂再生原子转移自由基聚合（ARGET ATRP）的动力学模型，并通过文献中苯乙烯、甲基丙烯酸甲酯和丙烯酸丁酯的溶液ARGET ATRP实验数据对其进行了验证。研究了原子转移自由基聚合平衡常数\(K\)和表观还原速率系数\(k(r)\)对ARGET ATRP动力学的影响。具有较大\(K\)的高活性引发/催化体系会导致聚合控制不佳，而\(k(r)\)增大虽会提高聚合速率，但会形成死聚物链。具有适中\(k(r)\)的还原剂能对ARGET ATRP实现良好控制。对于高活性单体的ARGET ATRP，使用适中的催化体系是不可行的。