Copolymer Composition Deviations from Mayo-Lewis Conventional Free Radical Behavior in Nitroxide Mediated Copolymerization

The validity of the Mayo‐Lewis (ML) terminal model for copolymer composition in nitroxide mediated copolymerization is systematically tested by simulation. Significant deviations in copolymer composition from ML behavior occur under various parameter combinations before the nitroxide quasi‐equilibri...

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Bibliographic Details
Published in:Macromolecular theory and simulations 2014-05, Vol.23 (4), p.245-265
Main Authors: Zapata-González, Iván, Hutchinson, Robin A., Matyjaszewski, Krzysztof, Saldívar-Guerra, Enrique, Ortiz-Cisneros, José
Format: Article
Language:English
Subjects:
Computer simulation
controlled radical polymerization
Conversion
Copolymerization
copolymerization terminal model
Copolymers
Deviation
Free radicals
mathematical modeling
Mathematical models
nitroxide mediated polymerization
Radicals
Terminals
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Summary:The validity of the Mayo‐Lewis (ML) terminal model for copolymer composition in nitroxide mediated copolymerization is systematically tested by simulation. Significant deviations in copolymer composition from ML behavior occur under various parameter combinations before the nitroxide quasi‐equilibrium condition (QEC) is reached. Maximum deviations are usually below 5 pp, and absent at conversions higher than 3%, but after 10% in some cases. High reactivity ratios lead to larger deviations; low reactivity ratios (faster cross‐propagation) produce near ML behavior. An additional continuous radical source leads to faster attainment of the QEC and reduces the deviations from ML behavior. An issue of practical and theoretical interest in controlled radical copolymerization is whether or not the reactivity ratios measured in conventional free radical copolymerization, based on the terminal model, can be applied in the controlled case as well. This paper tries to answer this question for nitroxide‐mediated copolymerization.
ISSN:1022-1344
1521-3919
DOI:10.1002/mats.201300137