Modeling and Observer-Based Monitoring of RAFT Homopolymerization Reactions
Modeling and Observer-Based Monitoring of RAFT Homopolymerization Reactions
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DOI：
10.3390/pr7100768
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发表时间：
2019-10-01
期刊：
影响因子：
3.5
通讯作者：
Kravaris, Costas
中科院分区：
文献类型：
--
作者：
Lathrop, Patrick M.;Duan, Zhaoyang;Kravaris, Costas
本文采用多速率多时滞观测器对甲基丙烯酸甲酯(MMA)的可逆加成-断裂链转移(RAFT)聚合反应进行了建模和监控。首先，为了对模型中的RAFT反应速率系数和引发剂效率进行拟合，利用小规模(400毫升)回流反应的原位核磁共振实验数据对模型进行了验证。拟合的模型准确地预测了大规模反应的聚合物性质，但在反应后期略有不一致。基于该模型，设计了一种多速率多时滞观测器，该观测器与采样间预测器和纯滞后补偿器相耦合，以考虑具有非恒定时延的异步多速率测量。该多速率多时滞观测器在几次采样后表现出良好的收敛特性，并与基于实验测量的后期反应时间的实际数据吻合较好。
Reversible addition-fragmentation chain-transfer (RAFT) polymerization of methyl methacrylate (MMA) is modeled and monitored using a multi-rate multi-delay observer in this work. First, to fit the RAFT reaction rate coefficients and the initiator efficiency in the model, in situ 1H nuclear magnetic resonance (NMR) experimental data from small-scale (400 mL) reflux reactions is then used to validate the fitted model. The fitted model accurately predicts the polymer properties of the large-scale reactions with slight discordance at late reaction times. Based on the fitted model, a multi-rate multi-delay observer coupled with an inter-sample predictor and dead time compensator is designed, to account for the asynchronous multi-rate measurements with non-constant delays. The multi-rate multi-delay observer shows perfect convergence after a few sampling times when tested against the fitted model, and is in fair agreement with the real data at late reaction times when implemented based on the experimental measurements.