基于Monte Carlo方法的聚苯硫醚聚合反应动力学建模

doi:10.11949/0438-1157.20190127

摘要/Abstract

摘要：

根据聚苯硫醚（PPS）聚合机理及过程分析并通过合理假设，提出了基于Monte Carlo方法的PPS聚合反应动力学模型。利用文献数据对模型参数进行了拟合回归，结果表明动力学模型计算值与相应的实验数据符合良好，并且模型外推预测与相同条件的实验接近，两者偏差小于2%；通过模型对反应物配比的影响进行模拟计算，结果与文献值相符合。最后，通过建立工业PPS聚合反应器模型对工业生产过程进行了模拟计算，结果表明PPS生产过程宜采用多釜串联的方式。相关研究结果可对PPS聚合反应动力学建模和工业过程的设计和优化提供理论依据。

关键词: 聚苯硫醚, Monte Carlo, 动力学建模, 聚合反应

Abstract:

Based on the polymerization mechanism and process analysis of polyphenylene sulfide (PPS) and reasonable assumptions, a kinetic model of PPS polymerization based on Monte Carlo method was proposed. The fitting regression of the model parameters was performed through literature data, and the results show that the calculated value based on the kinetic model is in good agreement with the corresponding experimental data, and the extrapolation prediction based on the model is consistent with experiments, with the deviation less than 2%. The effect of the reactants ratio on the polymerization reaction was calculated based on kinetic model, and the results is in accordance with the literature value. Finally, by establishing the reactor model of industrial PPS polymerization, the industrial production process was simulated, and the results show that the tanks-in-series mode should be adopted for this process. The relevant results in this work will provide theoretical basis to the kinetic modeling of PPS polymerization reaction and the design and optimization of industrial PPS production.

Key words: polyphenylee sulfnide, Monte Carlo, kinetic modeling, polymerization reaction

中图分类号:

TQ 316.3

文帅, 王德坤, 孙伟振, 赵玲. 基于Monte Carlo方法的聚苯硫醚聚合反应动力学建模[J]. 化工学报, 2019, 70(10): 3976-3984.

Shuai WEN, Dekun WANG, Weizhen SUN, Ling ZHAO. Kinetic modeling of polyphenylene sulfide polymerization reaction based on Monte Carlo method[J]. CIESC Journal, 2019, 70(10): 3976-3984.

图/表 6

图1 反应程度P随时间的变化

Fig.1 Extent of reaction P with time

图2 平均分子质量随时间的变化

Fig.2 Average molecular mass M n with time

图3 聚合物分子量分布随反应时间的变化（模拟计算）(温度：190℃；压力：0.2 MPa；反应物配比 n p - D C B ∶ n N a 2 S =1∶0.94)

Fig.3 Calculated values of polymer molecular weight distribution at different reaction time

图4 物料配比对反应程度的影响（模拟计算）（温度：190℃；压力：0.2 MPa；反应时间：600 min）

Fig.4 Calculated results for effect of reaction material ratio on reaction degree P (temperature: 190℃; pressure: 0.2 MPa; reaction time: 600 min)

图5 不同反应物配比下600 min时聚合物分子量分布（模拟计算）（温度：190℃；压力：0.2 MPa）

Fig.5 Calculated values of polymer molecular weight distribution at 600 min for different reactants ratios (temperature: 190℃; pressure: 0.2 MPa)

表1 三釜串联出口转化率随停留时间变化的计算值

Table 1 Calculated values of change of outlet conversion with residence time for three-tanks-in-series

单釜停留时间/h	釜一出口p-DCB转化率/x ₁	釜二出口p-DCB转化率/x ₂	釜三出口p-DCB转化率/x ₃
0.5	0.29	0.42	0.55
1.0	0.38	0.55	0.68
1.5	0.46	0.68	0.78
2.0	0.51	0.71	0.82
2.5	0.55	0.76	0.85
3.0	0.58	0.83	0.88
3.4	0.61	0.88	0.90

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