Accurate Determination of Reactivity Ratios for Copolymerization Reactions with Reversible Propagation Mechanisms

22 January 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


An understanding of monomer sequence is required to predict and engineer the properties of copolymers. Typically, comonomer sequence is inferred or determined from reactivity ratios, which are measured through copolymerization experiments. The accurate determination of reactivity ratios from copolymerizations where one or both monomers undergo reversible propagation, however, has been complicated by difficulty in solving the underlying population balance equations, the presence of myriad copolymer equations in the literature derived under varying assumptions and simplifications, and lack of an easy to fit integrated model. Here, we rectify and assert the consistency between previously reported copolymer equations of disparate form, introduce a new method to explicitly solve the underlying population balance equations, and perform stochastic copolymerization simulations to evaluate the ability of these three methods to produce consistent comonomer consumption predictions and fits to simulated copolymerization data. We find that all methods produce consistent predictions given the same input parameters, which implies both accuracy and precision when modeling copolymerization, fitting experimental data, and making predictions of comonomer sequence. Considering this consistency, we make a recommendation to use numerical integration of the appropriate copolymer equation to fit real copolymerization data due to its ease of implementation and single subjective parameter for implementation. We further identify the minimum number of parameters required for accurate data fitting and suggest ways to measure other information ex situ from copolymerization to expediate accurate fitting. Finally, the practical utility of the methods developed herein is demonstrated through fitting seven distinct copolymerization datasets which span a wide range of copolymerization reactivities.


reactivity ratios
reversible propagation
cleavable comonomers

Supplementary materials

Supporting Information
Methods, additional discussions and examples, equations and derivations


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