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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 ch...

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Bibliographic Details
Published in:Macromolecular rapid communications. 2016-01, Vol.37 (2), p.123-134
Main Authors: Kockler, Katrin B., Haehnel, Alexander P., Junkers, Thomas, Barner-Kowollik, Christopher
Format: Article
Language:English
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Summary: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. The pulsed laser polymerization–size exclusion chromatography (PLP–SEC) approach is the method of choice for the investigation of propagation rate coefficients and Arrhenius parameters in free radical polymerization. An overview of the state‐of‐the‐art of high‐frequency PLP and monomers studied via 500 Hz PLP is provided and observed trends and family‐type behavior are critically described, jointly with a future perspective for the field.
ISSN:1022-1336
1521-3927
DOI:10.1002/marc.201500503