화학공학소재연구정보센터
Macromolecules, Vol.50, No.20, 7930-7939, 2017
Predictive Tool for Design and Analysis of ARGET ATRP Grafting Reactions
Solving a comprehensive, yet simple, reaction model for describing the activators regenerated by electron transfer (ARGET)-atom transfer radical polymerization (ATRP) reaction cascade, we show that the molar ratios of transition metal catalyst to initiator and reducing agent to catalyst are critical parameters in the ARGET ATRP mechanism, with optimal values on the order of 0.1:1 and 10:1, respectively. The model also predicts an optimal molar ratio of reducing agent to initiator of 1:1. The ARGET ATRP reaction cascade is extremely complex with many adjustable species concentrations and reaction parameters. The effect of varying any of these parameters on the resulting temporal conversion trajectory of the polymerization is not straightforward. This analysis greatly simplifies the process allowing one to select the proper conditions to optimize the reaction and could save much effort, time and money. These results have severe implications when grafting polymer chains from surfaces, since the amount of surface-bound initiator is very low relative to the amount of catalyst. This suggests adding a sacrificial initiator to the reaction solution when grafting from surfaces is necessary to prevent loss of control on the polymerization. The most viable parameter for both increasing the polymerization rate and maintaining maximum attainable conversion for the ARGET ATRP system is to increase the reaction temperature. For broad use, the model was developed in MATLAB to predict conversion versus time behavior in the ARGET ATRP reaction cascade using an inexpensive ligand. Utilizing known rate constants and pre-exponential factors to the Arrhenius equations from the literature, the model was able to predict published experimental data for the methyl methacrylate (MMA), styrene (St), and glycidyl methacrylate (GMA) monomers at various temperatures. The main assumptions of the model are that termination reactions occur through radical coupling only and the propagation and termination reaction rates are chain length independent. The resulting model is shown to be very accurate, especially at conversions of 0.4 and lower. Sensitivity analyses were performed on the ARGET ATRP mechanism using MMA as a model monomer to identify key reaction parameters to ensure successful controlled polymerization.