The Measurement and Meaning of Radical Reactivity Ratios

Johan P.A. Heuts, Michelle L. Coote, Thomas P. Davis, Lloyd P.M. Johnston

Research output: Chapter in Book/Report/Conference proceedingChapterpeer-review

21 Citations (Scopus)


Problems in the current experimental determination of radical reactivity ratios (i.e., 's values') in free-radical copolymerization and the resulting limited physical meaning of these reactivity ratios are highlighted in the present work. It is exemplified that the radical reactivity ratios obtained via fitting of average propagation rate coefficients are very sensitive to small uncertainties in monomer reactivity ratios and homopropagation rate coefficients. Furthermore, the failure to select an appropriate modelling method, and to design experiments so as to satisfy its assumptions, may lead to incorrect parameter estimates. These problems result in large uncertainties in the measured values of the radical reactivity ratios, which in turn lead to large uncertainties in calculated ratios of propagating radical concentrations. This suggests that experimental determinations of the relative radical concentrations may lead to complimentary means for obtaining information on radical reactivity ratios, andd possible ways of obtaining this information through catalytic chain transfer experiments are discussed.

Original languageEnglish
Title of host publicationControlled Radical Polymerization
EditorsKrzysztof Matyjaszewski
Place of PublicationUSA
PublisherAmerican Chemical Society (ACS)
Number of pages25
ISBN (Print)0-8412-3545-7
Publication statusPublished - 8 Jan 1998
Externally publishedYes

Publication series

NameACS Symposium Series
ISSN (Print)0097-6156


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