This paper proposes a new method for calculating the monomer reactivity ratios for binary copolymerization based on the terminal model. The original optimization method involves a numerical integration algorithm and an optimization algorithm based on k-nearest neighbour non-parametric regression. The calculation method has been tested on simulated and experimental data sets, at low (<10%), medium (10–35%) and high conversions (>40%), yielding reactivity ratios in a good agreement with the usual methods such as intersection, Fineman–Ross, reverse Fineman–Ross, Kelen–Tüdös, extended Kelen–Tüdös and the error in variable method. The experimental data sets used in this comparative analysis are copolymerization of 2-(N-phthalimido) ethyl acrylate with 1-vinyl-2-pyrolidone for low conversion, copolymerization of isoprene with glycidyl methacrylate for medium conversion and copolymerization of N-isopropylacrylamide with N,N-dimethylacrylamide for high conversion. Also, the possibility to estimate experimental errors from a single experimental data set formed by n experimental data is shown.
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