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Macromolecules
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Macromolecules
Article . 2014 . Peer-reviewed
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Impact of Competitive Processes on Controlled Radical Polymerization

Authors: Ballard, N.; Rusconi, S.; Akhmatskaya, E.; Sokolovski, D.; de La Cal, J.C.; Asua, J.M.;

Impact of Competitive Processes on Controlled Radical Polymerization

Abstract

The kinetics of radical polymerization have been systematically studied for nearly a century and in general are well understood. However, in light of recent developments in controlled radical polymerization many kinetic anomalies have arisen. These unexpected results have been largely considered separate, and various, as yet inconclusive, debates as to the cause of these anomalies are ongoing. Herein we present a new theory on the cause of changes in kinetics under controlled radical polymerization conditions. We show that where the fast, intermittent deactivation of radical species takes place, changes in the relative rates of the competitive reactions that exist in radical polymerization can occur. To highlight the applicability of the model, we demonstrate that the model explains well the reduction in branching in acrylic polymers in RAFT polymerization. We further show that such a theory may explain various phenomena in controlled radical polymerization and may be exploited to design precise macromolecular architectures.

Keywords

Controlled radical polymerization

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    This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
    29
    popularity
    This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
    Top 10%
    influence
    This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
    Top 10%
    impulse
    This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
    Top 10%
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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
29
Top 10%
Top 10%
Top 10%
Green
hybrid
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