LAPSE:2018.0229
Published Article
LAPSE:2018.0229
Aqueous Free-Radical Polymerization of Non-Ionized and Fully Ionized Methacrylic Acid
Eric Jean Fischer, Giuseppe Storti, Danilo Cuccato
July 31, 2018
Water-soluble, carboxylic acid monomers are known to exhibit peculiar kinetics when polymerized in aqueous solution. Namely, their free-radical polymerization rate is affected by several parameters such as monomer concentration, ionic strength, and pH. Focusing on methacrylic acid (MAA), even though this monomer has been largely addressed, a systematic investigation of the effects of the above-mentioned parameters on its polymerization rate is missing, in particular in the fully ionized case. In this work, the kinetics of non-ionized and fully ionized MAA are characterized by in-situ nuclear magnetic resonance (NMR). Such accurate monitoring of the reaction rate enables the identification of relevant but substantially different effects of the monomer and electrolyte concentration on polymerization rate in the two ionization cases. For non-ionized MAA, the development of a kinetic model based on literature rate coefficients allows us to nicely simulate the experimental data of conversion versus time at a high monomer concentration. For fully ionized MAA, a novel propagation rate law accounting for the electrostatic interactions is proposed: the corresponding model is capable of predicting reasonably well the electrolyte concentration effect on polymerization rate. Nevertheless, further kinetic information in a wider range of monomer concentrations would be welcome to increase the reliability of the model predictions.
Keywords
electrostatic interactions, electrostatic screening, free radical polymerization, kinetics, methacrylic acid, Modelling, NMR, propagation, termination
Subject
Suggested Citation
Fischer EJ, Storti G, Cuccato D. Aqueous Free-Radical Polymerization of Non-Ionized and Fully Ionized Methacrylic Acid. (2018). LAPSE:2018.0229
Author Affiliations
Fischer EJ: Institute for Chemical and Bioengineering, ETH Zurich, Vladimir-Prelog-Weg 1, 8093 Zurich, Switzerland [ORCID]
Storti G: Institute for Chemical and Bioengineering, ETH Zurich, Vladimir-Prelog-Weg 1, 8093 Zurich, Switzerland
Cuccato D: Institute for Chemical and Bioengineering, ETH Zurich, Vladimir-Prelog-Weg 1, 8093 Zurich, Switzerland
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Journal Name
Processes
Volume
5
Issue
2
Article Number
E23
Year
2017
Publication Date
2017-04-27
Published Version
ISSN
2227-9717
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PII: pr5020023, Publication Type: Journal Article
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LAPSE:2018.0229
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doi:10.3390/pr5020023
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Jul 31, 2018
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