Abstract: Two opposing explanations to significant rate retardation in dithioester-mediated polymerization with reversible addition fragmentation chain transfer process(RAFT),e.g: slow fragmentation of intermediate radicals (Model A),and cross termination between intermediates and growing radicals (Model B),had been proposed by Davis and Monteiro independently. In this paper,a comparison of simulation results of Model A and Model B with experiment results was presented. The simulated results show that the intermediate concentration of Model A is much higher than that of experiments,while Model B gives a rather high polymerization rate than experiments with large concentration of dithioesters. The reaction model was better fitted,in light of kinetics,intermediate concentration and distribution of molecular weight,to experimental data when both cross termination and slow fragmentation were taken into account.

Key words: RAFT process, Intermediate radical, Cross termination, Monte Carlo simulation