A mathematical model to describe the emulsion polymerization kinetics of co- and ter-polymerizations is developed. The model uses the well-known pseudo-homopolymerization approach together with recently developed models for radical entry and desorption in order to monitor crucial kinetic variables such as conversion and latex composition. The model includes a series of unknown parameters related to monomer-specific gel-effect coefficients, that are needed to compute the bimolecular termination reaction rates. The unknown parameters are determined through extensive calibration of the model on literature data for homo- and co-polymerizations of n-butyl acrylate (n-BA) and methyl methacrylate (MMA). The so-obtained predictive model is then applied to the modelling of the ter-polymerization of n-BA and MMA with 2-hydroxyethyl methacrylate (2-HEMA) with sodium persulphate (SPR) as initiator: predictions for the time-evolution of particle size and conversion are in excellent agreement with experimental measurements using Dynamic Light Scattering (DLS) and Gas Chromatography (GC), upon tuning the gel-effect coefficient related to 2-HEMA. The developed model is used to quantify the surfactant surface coverage of the particles as well as the total concentration of counterions in the system throughout the entire polymerization process. This key information provides a way to rationalize and control the coagulation behavior during the whole polymerization process.

中文翻译：

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种子乳液共聚合和三元聚合中聚合物反应动力学和凝聚行为的预测模型

建立了描述共聚和三聚的乳液聚合动力学的数学模型。该模型使用众所周知的拟均聚方法以及最近开发的自由基进入和解吸模型，以监测关键的动力学变量，例如转化率和胶乳组成。该模型包括一系列与单体特异性凝胶效应系数有关的未知参数，这些参数是计算双分子终止反应速率所必需的。未知参数是通过在文献数据中对丙烯酸正丁酯的均聚和共聚的模型进行广泛校准而确定的（n-BA）和甲基丙烯酸甲酯（MMA）。然后将如此获得的预测模型应用于以过硫酸钠（SPR）为引发剂的甲基丙烯酸2-羟乙酯（2-HEMA）与正丁烯酸（2-HEMA）引发的n -BA和MMA的三元聚合建模：预测粒子的时间演化调整与2-HEMA相关的凝胶效应系数后，其大小和转化率与使用动态光散射（DLS）和气相色谱（GC）进行的实验测量非常吻合。所开发的模型用于量化颗粒的表面活性剂表面覆盖率以及整个聚合过程中系统中抗衡离子的总浓度。此关键信息提供了在整个聚合过程中合理化和控制混凝行为的方法。