• atom transfer radical polymerization (ATRP);
  • copolymerization;
  • kinetics (polym.);
  • polymer synthesis and characterization


In controlled/living radical copolymerization (atom transfer radical copolymerization in this study) and in any other living chain-growth copolymerization, the possible preferential addition of one of the comonomers onto the (macro)initiator-derived (macro)radical can affect the copolymer composition, especially at low conversion; this results in inaccurate comonomer reactivity ratio estimation by the classic approach. A new general approach is introduced in this article, which allowed us to exclude the influence of the possible preferential addition of one of the comonomers onto the (macro)initiator-derived (macro)radical on the copolymer composition at any conversion. According to this approach, copolymer chain grown during time t (t ≠ 0) is considered to be, in fact, the macroinitiator terminated with one of the comonomers under study, which will further grow during the time interval Δt′ = t′ − t [where any reaction time t′ is considered to be grater than reaction time t, i.e. t′ > t] from a comonomer mixture with composition of f(t) [where f(t) is the molar ratio of comonomer i to comonomer j in the comonomer mixture] at time t. In such a situation, it is possible to obtain individual comonomer conversions [xit′) and xjt′)], the overall comonomer conversion [xovt′)], and the cumulative average copolymer composition for the copolymer formed during Δt′, from which more accurate comonomer reactivity ratios can be calculated by the various low- or high-conversion methods, depending on the overall comonomer conversion. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011