Atom transfer radical copolymerization kinetics

Starting from the basic radical mechanism of atom transfer radical polymerization (ATRP), simple expressions are derived for the description of atom transfer radical copolymerization kinetics. It is shown that kinetic parameters are interchangeable between atom transfer and conventional free-radical copolymerization, which is important for two reasons. Firstly, it enables the prediction of the average equilibrium constant (and hence average rate of polymerization) in an ATRP system with two monomers if the corresponding conventional kinetic parameters are known. Secondly, it enables the determination of the relative fractions of propagating radicals by a detailed ATRP study.