AbstractThe goal is to present an alternative technique for reactivity ratio estimation in copolymerization. Typically, reactivity ratios are estimated using the instantaneous copolymer composition equation, based on low conversion copolymer composition data. However, using experimental data from the full copolymerization trajectory would, in principle, be more advantageous, and shy away from commonly used restrictive assumptions. Estimation using cumulative copolymerization data and models eliminates the difficulties associated with stopping reactions at low conversion, while one gains to study the full polymerization trajectory. The error‐in‐variables‐model (EVM) method is used for parameter estimation. Two cumulative model forms, the analytical integration of the differential composition equation and the one resulting from the direct numerical integration of this equation, are employed. Using these two types of models improves the reactivity ratio estimation and, in particular, the latter model form is a more reliable and direct method of estimating reactivity ratios. magnified image