Determining Free‐Radical Propagation Rate Coefficients with High‐Frequency Lasers: Current Status and Future Perspectives

Detailed knowledge of the polymerization mechanisms and kinetics of academically and industrially relevant monomers is mandatory for the precision synthesis of tailor-made polymers. The IUPAC-recommended pulsed-laser polymerization-size exclusion chromatography (PLP-SEC) approach is the method of choice for the determination of propagation rate coefficients and the associated Arrhenius parameters for free radical polymerization processes. With regard to specific monomer classes-such as acrylate-type monomers, which are very important from a materials point of view-high laser frequencies of up to 500 Hz are mandatory to prevent the formation of mid-chain radicals and the occurrence of chain-breaking events by chain transfer, if industrially relevant temperatures are to be reached and wide temperature ranges are to be explored (up to 70 °C). Herein the progress and state-of-the-art of high-frequency PLP-SEC with pulse repetition rates of 500 Hz is reported, with a critical collection of to-date investigated 500 Hz data as well as future perspectives for the field.