The kinetic study of copolymer synthesis is important to understand how a material is built and how it can get some particular properties. The radical copolymerization of one, two or more monomers can be simulated with classical analytic models, but can also be simulated by a Monte Carlo model that allows a bigger flexibility and is a lot easier to compute and use. We have shown that this Monte Carlo simulation gives the same results of the kinetic study of the terpolymerization as the analytic model, and it can create easily a bank of virtual copolymers for all the compositions needed to analyze the structure of the macromolecular chains in terms of sequences of monomers occurring as a function of the global composition. The search for the sequences is very simple to compute as it consists in a simple reading of the virtual chains previously simulated. This result can thus be applied to make appear a simple correlation between the distribution of functional groups and some specific observed biological activities of biospecific copolymers.Simplified schema of the numerical virtual terpolymerization.imageSimplified schema of the numerical virtual terpolymerization.

Previous results obtained have shown that it was possible to create biospecific sites onto polymers through statistic modifications of polystyrene derivatives copolymer with given chemical groups or through synthesis of random methacrylate‐based copolymers. Such polymers show biological activities (anticoagulant, cell proliferation modulation …) dependent of the global composition and thus of the statistical distribution of the functional groups, and the number of biospecific sites is simply correlated to the observed biological activity. The study of the radical terpolymerization allows us to use a Monte Carlo based synthesis simulation and to determine the occurrence frequency of three to twenty monomers sequences as a function of the conversion rate and the global composition. The comparison of the sequences occurrence curves as a function of the global composition of the polymers with the experimental cell proliferation inhibition curve led us to extract a series of eight monomers sequences with similar structure properties representing a group of biospecific sites responsible for the observed biological activity.Radical terpolymerization of MMA, MA, and NaSS in DMSO initiated by AIBN.imageRadical terpolymerization of MMA, MA, and NaSS in DMSO initiated by AIBN.