Stochastic Modeling of Poly(acrylate) Distributions Obtained by Radical Polymerization under High-Temperature Semi-Batch Starved-Feed Conditions: Investigation of Model Predictions versus Experimental Data,Macromolecular Theory and Simulations

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Stochastic Modeling of Poly(acrylate) Distributions Obtained by Radical Polymerization under High-Temperature Semi-Batch Starved-Feed Conditions: Investigation of Model Predictions versus Experimental Data
Macromolecular Theory and Simulations ( IF 1.8 ) Pub Date : 2021-01-27 , DOI: 10.1002/mats.202000093
Amin Nasresfahani ₁ , Nina Heidarzadeh ₁ , Elizabeth G. Bygott ₁ , Robin A. Hutchinson ₁

Affiliation

Secondary reactions significantly affect acrylate polymerization rates as well as the architecture of polymer produced by high-temperature solution radical polymerization. This impact is amplified under the semi-batch starved-feed policy used to keep monomer concentration low. Thus, the importance of intramolecular chain transfer (backbiting) is significantly increased, generating a tertiary radical center capable of termination, propagation, and scission. In this investigation, a comprehensive stochastic model is formulated to represent results from an experimental study designed to increase the fraction of reactive terminal double bonds (TDB) in the poly(butyl acrylate) product. Model predictions generated using three sets of literature kinetic parameters for backbiting and scission are compared. While each provides reasonable predictions of some reaction characteristics (e.g., free monomer levels, polymer molecular weights, polymer TDB content), none provide an adequate representation of all aspects of the polymerization. It is concluded that other reaction pathways might be needed to represent the system under semi-batch conditions, thus explaining the discrepancies seen among the current parameter estimates.

中文翻译：

高温半间歇饥饿进料条件下自由基聚合获得的聚丙烯酸酯分布的随机模型：模型预测与实验数据的比较

次级反应会显着影响丙烯酸酯的聚合速率以及高温溶液自由基聚合制得的聚合物的结构。在用于保持单体浓度低的半间歇饥饿进料策略下，这种影响被放大了。因此，分子内链转移（回位）的重要性显着增加，从而产生了能够终止，传播和分裂的叔自由基中心。在这项研究中，制定了一个全面的随机模型来代表一项实验研究的结果，该实验旨在提高聚丙烯酸丁酯产品中反应性末端双键（TDB）的比例。比较了使用三组文献动力学参数生成的模型预测结果，以进行咬合和断裂。尽管每个都提供了对某些反应特性（例如，游离单体含量，聚合物分子量，聚合物TDB含量）的合理预测，但没有一个能够充分反映聚合反应的所有方面。结论是，在半间歇条件下可能需要其他反应路径来表示系统，从而解释了当前参数估计值之间的差异。

更新日期：2021-01-27

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