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 ∆

G

TS

. Finally

the kinetic characteristics 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.