首页|Effect of solvent on the initiation mechanism of living anionic polymerization of styrene:A computational study

Effect of solvent on the initiation mechanism of living anionic polymerization of styrene:A computational study

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For living anionic polymerization(LAP),solvent has a great influence on both reaction mechanism and kinetics.In this work,by using the classical butyl lithium-styrene polymerization as a model system,the effect of solvent on the mechanism and kinetics of LAP was revealed through a strategy combining density functional theory(DFT)calculations and kinetic modeling.In terms of mechanism,it is found that the stronger the solvent polarity,the more electrons transfer from initiator to solvent through detailed energy decomposition analysis of electrostatic interactions between initiator and solvent molecules.Furthermore,we also found that the stronger the solvent polarity,the higher the monomer initiation energy barrier and the smaller the initiation rate coefficient.Counterintuitively,initiation is more favorable at lower temperatures based on the calculated results of △GTS.Finally,the kinetic character-istics in different solvents were further examined by kinetic modeling.It is found that in benzene and n-pentane,the polymerization rate exhibits first-order kinetics.While,slow initiation and fast propagation were observed in tetrahydrofuran(THF)due to the slow free ion formation rate,leading to a deviation from first-order kinetics.

Living anionic polymerizationSolvent effectReaction kineticsComputational chemistryMathematical modelingKinetic modeling

Shen Li、Yin-Ning Zhou、Zhong-Xin Liu、Zheng-Hong Luo

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School of Chemical Engineering and Technology,Hainan University,Haikou 570228,China

Department of Chemical Engineering,School of Chemistry and Chemical Engineering,State Key Laboratory of Metal Matrix Composites,Shanghai Jiao Tong University,Shanghai 200240,China

National Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaCenter for highperformance Computing at Shanghai Jiao Tong University

U21A2031322222807

2024

10.1016/j.cjche.2024.01.007

中国化学工程学报(英文版)
中国化工学会

中国化学工程学报(英文版)

CSTPCDEI
影响因子：0.818
ISSN：1004-9541
年,卷(期)：2024.69(5)
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