Predictive Tool for Design and Analysis of ARGET ATRP Grafting Reactions

Abstract

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 sur...