Deterministic modeling of non-adiabatic solution radical polymerization of n-butyl acrylate in light of runaway prevention

Abstract

Acrylate polymerizations with high exothermicity exhibit strongly non-isothermal characteristics. The presence of side reactions involved in the polymerization mechanisms makes process safety as well as polymer properties more sensitive to operation parameters. In this study, a deterministic moment-based modeling approach combining with the divergence criterion was developed to investigate the non-isothermality of acrylate polymerization process. In silico design of non-adiabatic processes was achieved by the modeling approach involving reaction mechanism, energy balance, and mass balance. The safe and unsafe states of the reactor under a wide range of process operating conditions were identified by a divergence criterion. From the perspective of process intensification, optimization of operating parameters was carried out. Afterwards, the pseudo-isothermal operation was mimicked by using stepwise jacket temperature profiles to investigate the effects of temperature and monomer content on molecular properties. The simulation results provide a safe operating window for the polymerization reactor under the given feed schemes and process conditions. Additionally, a pseudo-isothermal process is more suitable to tune the molecular properties of the resulting polymers during polymerization. The current work puts forward deterministic simulations in terms of both process safety and molecular properties control compared to the previous works.