Modeling kinetics and structural properties in high-pressure fluid-phase polymerization

The present contribution provides an overview of actual applications in mod eling free-radical polymerizations. Topics of interest are the simulation o f pulsed laser polymerization experiments with subsequent analysis of the f ormed product by size exclusion chromatography (PLP-SEC), single pulse lase r experiments, experimental techniques for determining rate coefficients of elementary reactions that control polymer properties, and technical applic ations. Aspects being investigated are model validation and testing predict ive potential in polymerization models using well-defined experiments as we ll as developing and testing experimental strategies for deriving rate coef ficients of elementary reactions that exist (especially when dealing with c opolymerizations) within a network of complex coupled reactions, in any of these fields remarkable success in modeling can be achieved. This demonstra tes the great potential that can grow from combining modem mathematical met hods, computational power and detailed kinetic insights into the mechanism of polymerization It is the wide scope of applications, e.g. ranging from m odeling kinetics to the investigation of termination processes being depend ent on the chain-length of the macroradical (as an example of pure fundamen tal research) to modeling of technical reactors, that provides attractivene ss 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 prove s the concept breaking down a complex process into elementary subparts. A n ecessary boundary condition for this is keeping in mind the demands along t he whole scope of applications and avoiding simplifications that are only a pplicable for part of them. Although at a first glance this may appear to h inder fast progress in one discipline, it is the essential require ment for final success.