Development and Experimental Validation of a Dispersity Model for In Silico RAFT Polymerization.
Development and Experimental Validation of a Dispersity Model for In Silico RAFT Polymerization.
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DOI：
10.1021/acs.macromol.2c01798
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发表时间：
2023-02-28
期刊：
影响因子：
5.5
通讯作者：
Warren NJ
中科院分区：
文献类型：
--
作者：
Wilding CYP;Knox ST;Bourne RA;Warren NJ
利用计算技术来预测化学反应的结果正变得越来越普遍，从而减少了优化反应所需的物理实验的数量。在这里，我们调整并结合了聚合动力学模型和摩尔质量分散作为可逆加成碎片链转移（RAFT）溶液聚合转化的函数，包括引入一个考虑终止的新表达式。采用等温条件下的流动反应器对RAFT聚合模型进行了实验验证，并增加了一项以适应停留时间分布的影响。进一步的验证在间歇式反应器中进行，其中先前记录的原位温度监测提供了在更具代表性的间歇条件下对系统进行建模的能力，考虑到缓慢的传热和观察到的放热。该模型还显示了与几个文献中的丙烯酰胺和丙烯酸酯单体在间歇反应器中的RAFT聚合的一致。原则上，该模型不仅为聚合物化学家估计聚合的理想条件提供了一个工具，而且在提供可靠的速率常数估计的情况下，它还可以自动定义初始参数空间，供计算控制的反应器平台进行探索。该模型被编译成一个易于访问的应用程序，以实现几种单体的RAFT聚合模拟。
The exploitation of computational techniques to predict the outcome of chemical reactions is becoming commonplace, enabling a reduction in the number of physical experiments required to optimize a reaction. Here, we adapt and combine models for polymerization kinetics and molar mass dispersity as a function of conversion for reversible addition fragmentation chain transfer (RAFT) solution polymerization, including the introduction of a novel expression accounting for termination. A flow reactor operating under isothermal conditions was used to experimentally validate the models for the RAFT polymerization of dimethyl acrylamide with an additional term to accommodate the effect of residence time distribution. Further validation is conducted in a batch reactor, where a previously recorded in situ temperature monitoring provides the ability to model the system under more representative batch conditions, accounting for slow heat transfer and the observed exotherm. The model also shows agreement with several literature examples of the RAFT polymerization of acrylamide and acrylate monomers in batch reactors. In principle, the model not only provides a tool for polymer chemists to estimate ideal conditions for a polymerization, but it can also automatically define the initial parameter space for exploration by computationally controlled reactor platforms provided a reliable estimation of rate constants is available. The model is compiled into an easily accessible application to enable simulation of RAFT polymerization of several monomers.
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