Solvent effects on free-radical copolymerization of styrene and 2-hydroxyethyl methacrylate: a DFT study

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dc.authoridKarahan, Ozlem/0000-0003-4916-9715|Salman, Seyhan/0000-0002-6124-3706|Salman, Seyhan/0000-0002-6124-3706|Aviyente, Viktorya/0000-0001-9430-4096|TUGBA, OZALTIN/0000-0003-4080-8840
dc.authorwosidKarahan, Ozlem/O-3156-2019
dc.authorwosidSalman, Seyhan/F-3154-2015
dc.authorwosidSalman, Seyhan/I-1175-2012
dc.authorwosidAviyente, Viktorya/Q-2759-2015
dc.contributor.authorOzaltin, T. Furuncuoglu
dc.contributor.authorDereli, B.
dc.contributor.authorKarahan, O.
dc.contributor.authorSalman, S.
dc.contributor.authorAviyente, V.
dc.date.accessioned2024-07-18T20:56:58Z
dc.date.available2024-07-18T20:56:58Z
dc.date.issued2014
dc.departmentİstanbul Bilgi Üniversitesien_US
dc.description.abstractThe free-radical homopolymerization and copolymerization kinetics of styrene (ST) and 2-hydroxyethyl methacrylate (HEMA) in three different media (bulk, DMF, toluene) have been investigated by means of Density Functional Theory (DFT) calculations in combination with the Polarizable Continuum Model (PCM) and the Conductor-like Screening Model for Real Solvents (COSMO-RS). The conventional Transition State Theory (TST) is applied to calculate the rate parameters of polymerization. Calculated propagation rate constants are used to predict the monomer reactivity ratios, which are then used in the evaluation of the copolymer composition following the Mayo-Lewis equation. it is found that copolymerization reactions in bulk and toluene show similar transition geometries;, whereas, DMF has a tendency to form H-bonding interactions with the polar HEMA molecules, thus decreasing the reactivity of this monomer during homopolymerization and towards ST during copolymerization. Calculations of copolymer composition further show that the amount of HEMA monomer in the ST-HEMA copolymer system decreases in the polar DMF solution. The calculated spin densities of the radical species are in agreement with the rate parameters and confirm that the copolymerization propagation rate of the ST-HEMA system is in the order: k(p)(bulk) approximate to k(p)(toluene) > k(p)(DMF).en_US
dc.description.sponsorshipNational Center for High Performance Computing of Turkey (UHEM) [1002212012]; TUBITAK ULAKBIM High Performance Computing Center [DPT-2009K120520]; Bogazici University [12B05P6]en_US
dc.description.sponsorshipThe computational resources used in this work were provided by the National Center for High Performance Computing of Turkey (UHEM) under the grant number 1002212012, the TUBITAK ULAKBIM High Performance Computing Center, the project DPT-2009K120520. We gratefully acknowledge the Bogazici University research Grants under the project number 12B05P6.en_US
dc.identifier.doi10.1039/c3nj00820g
dc.identifier.endpage178en_US
dc.identifier.issn1144-0546
dc.identifier.issn1369-9261
dc.identifier.issue1en_US
dc.identifier.scopus2-s2.0-84962385180en_US
dc.identifier.scopusqualityQ2en_US
dc.identifier.startpage170en_US
dc.identifier.urihttps://doi.org/10.1039/c3nj00820g
dc.identifier.urihttps://hdl.handle.net/11411/8929
dc.identifier.volume38en_US
dc.identifier.wosWOS:000329886900023en_US
dc.identifier.wosqualityQ2en_US
dc.indekslendigikaynakWeb of Scienceen_US
dc.indekslendigikaynakScopusen_US
dc.language.isoenen_US
dc.publisherRoyal Soc Chemistryen_US
dc.relation.ispartofNew Journal of Chemistryen_US
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanıen_US
dc.rightsinfo:eu-repo/semantics/closedAccessen_US
dc.subjectPulsed-Laser Polymerizationen_US
dc.subjectPropagation Rate Coefficientsen_US
dc.subjectTransition-State Theoryen_US
dc.subjectMethyl-Methacrylateen_US
dc.subjectAqueous-Solutionen_US
dc.subjectPenultimate Uniten_US
dc.subjectAcrylic-Aciden_US
dc.subjectAb-Initioen_US
dc.subjectPlp-Secen_US
dc.subjectKineticsen_US
dc.titleSolvent effects on free-radical copolymerization of styrene and 2-hydroxyethyl methacrylate: a DFT studyen_US
dc.typeArticleen_US

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