Modeling Kinetics and Structural Properties in High-Pressure Fluid-Phase Polymerization

Abstract

The present contribution provides an overview of actual applications in modeling free-radical polymerizations. Topics of interest are the simulation of pulsed laser polymerization experiments with subsequent analysis of the formed product by size exclusion chromatography (PLP-SEC), single pulse laser experiments, experimental techniques for determining rate coefficients of elementary reactions that control polymer properties, and technical applications. Aspects being investigated are model validation and testing predictive potential in polymerization models using well-defined experiments as well as developing and testing experimental strategies for deriving rate coefficients of elementary reactions that exist (especially when dealing with copolymerizations) within a network of complex coupled reactions. In any of these fields remarkable success in modeling can be achieved. This demonstrates the great potential that can grow from combining modern mathematical methods, computational power and detailed kinetic insights into the mechanism of polymerization. It is the wide scope of applications, e. g. ranging from modeling kinetics to the investigation of termination processes being dependent on the chain-length of the macroradical (as an example of pure fundamental research) to modeling of technical reactors, that provides attractiveness and defines challenges. Especially, the success in transforming results directly from laboratory experiments into technical applications justifies laborious efforts in determining highly precise rate coefficients and proves the concept breaking down a complex process into elementary subparts. A necessary boundary condition for this is keeping in mind the demands along the whole scope of applications and avoiding simplifications that are only applicable for part of them. Although at a first glance this may appear to hinder fast progress in one discipline, it is the essential requirement for final success.