The Use of Simulation Techniques in Developing Kinetic Models for Polymerization

The demands on simulations of polymerization reactions grow continuously, as do their capabilities. Using two examples it will be demonstrated how the use of detailed kinetic models in such simulations can contribute to the development of experimental strategies for determining rate coefficients, assist in mechanistic analysis and enable feasibility studies about operational strategies. Using the high‐temperature butyl acrylate polymerization as an example, it will be illustrated, based on detailed analytical information, how the kinetic scheme of the butyl acrylate polymerization expands to a complex network of elementary reactions. Based on this model an experimental strategy will be developed for the selective determination of the individual rate coefficients. A comparison of the results from these simulations with experimental data shows that a realization of the developed concept appears to be within reach. The second example is based on a kinetic scheme of the, high‐temperature high‐pressure, polymerization of ethene. In addition, using this kinetic scheme, the capability of nitroxyl species in establishing a controlled radical polymerization mechanism in polymerizations that show high polymerization rates and significant quantities of intra‐ and inter‐molecular branching reactions will be tested. This feasibility study will examine the potential effect a nitroxyl species has on the kinetic mechanism with respect to its stability and the structural characteristics of a polymer that results from such a polymerization.