Free radical polymerization of ethyl methacrylate and ethyl α-hydroxy methacrylate: A computational approach to the propagation kinetics

Berna Dogan, Saron Catak, Veronique Van Speybroeck, Michel Waroquier, Viktorya Aviyente*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

18 Citations (Scopus)

Abstract

The propagation kinetics of ethyl methacrylate (EMA) and ethyl α-hydroxy methacrylate (EHMA) has been subject to a computational study to understand their free radical polymerization (FRP) behavior in bulk and in solution using Density Functional Theory (DFT). The propagation of EHMA is studied in ethanol and toluene to assess the effect of hydrogen-bonding solvents on FRP of monomers with α-hydroxy functionality. Although EMA and EHMA resemble each other in structure, EHMA propagates faster in bulk due to the presence of intermolecular hydrogen-bonds, which tend to facilitate the approach of the propagating species. This falls in contrast with the experimentally observed lower propagation rates of EHMA in ethanol compared to toluene. Calculations show that the 2.28 rate acceleration in toluene is governed by the ratio of the pre-exponential factors, which reflect the entropies of activation, in both media. The polar protic solvent ethanol has a disruptive effect via hydrogen-bonding on the 6-membered ring shape of EHMA monomers thus decreasing the entropy of activation of the reaction. In the case of toluene, there are no special interactions with the hydrophobic solvent, the entropy of activation is higher than in ethanol.

Original languageEnglish
Pages (from-to)3211-3219
Number of pages9
JournalPolymer
Volume53
Issue number15
DOIs
Publication statusPublished - 6 Jul 2012
Externally publishedYes

Funding

Computing resources used in this work were provided by the National Center for High Performance Computing of Turkey (UYBHM) under grant number 1001322011 . The UGent authors thank the FWO (Fonds voor Wetenschappelijk Onderzoek - Vlaanderen, Fund for Scientific Research – Flanders), the research board of Ghent University for the bilateral project Ghent – Istanbul and the IAP-BELSPO project in the frame of IAP 6/27 for financial support of this research. B.D. would like to thank Dr. Isa Degirmenci for his suggestions and comments.

FundersFunder number
Fonds voor Wetenschappelijk Onderzoek - Vlaanderen
IAP-BELSPO
National Center for High Performance Computing of Turkey
UYBHM1001322011
Universiteit Gent

    Keywords

    • Free radical polymerization
    • Modeling
    • Solvent effect

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