Skip navigation
Skip navigation

Modeling the solvent effect on the tacticity in the free radical polymerisation of methyl methacrylate

Degirmenci, Isa; Eren, Sukru; Aviyente, Viktorya; De Sterck, Bart; Hemelsoet, Karen; van Speybroeck, Veronique; Waroquier, Michel

Description

The control of stereochemistry in the free radical polymerization of methyl methacrylate (MMA) is important because the physical properties of PMMA are often significantly affected by the main-chain tacticity. In this study, the role of the solvent on the tacticity of MMA polymerization has been investigated by considering the propagation rate constants for the syndiotactic and isotactic free radical polymerization of MMA in vacuum, in methanol (CH3OH), and in...[Show more]

dc.contributor.authorDegirmenci, Isa
dc.contributor.authorEren, Sukru
dc.contributor.authorAviyente, Viktorya
dc.contributor.authorDe Sterck, Bart
dc.contributor.authorHemelsoet, Karen
dc.contributor.authorvan Speybroeck, Veronique
dc.contributor.authorWaroquier, Michel
dc.date.accessioned2015-12-10T23:03:19Z
dc.identifier.issn0024-9297
dc.identifier.urihttp://hdl.handle.net/1885/62121
dc.description.abstractThe control of stereochemistry in the free radical polymerization of methyl methacrylate (MMA) is important because the physical properties of PMMA are often significantly affected by the main-chain tacticity. In this study, the role of the solvent on the tacticity of MMA polymerization has been investigated by considering the propagation rate constants for the syndiotactic and isotactic free radical polymerization of MMA in vacuum, in methanol (CH3OH), and in 1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-ol ((CF3)3COH). All geometry optimizations have been carried out with the B3LYP/6-31+G(d) methodology. The kinetics of the propagating dimer have been evaluated with the B3LYP/6-31+G(d), B3LYP/6-311 +G(3df,2p), MPWB1K/6-311+G(3df,2p), and B2PLYP/6-31+G(d) methodologies. The role of the solvent has been investigated by using explicit solvent molecules and also by introducing a polarizable continuum model (IEF-PCM) with a dielectric constant specific to the solvent. Experimentally, the free radical polymerization of MMA in (CF3)3COH is found to be highly syndiotactic (rr = 75% at 20 °C): the stereoeffects of fluoroalcohols are claimed to be due to the hydrogenbonding interaction of the alcohols with the monomers and growing species. This modeling study has revealed the fact that the solvents CH3OH and (CF3)3COH, which are H-bonded with the carbonyl oxygens located on the same side of the backbone hinder the formation of the isotactic PMMA to some extent. Methanol is less effective in reducing the isotacticity because of its small size and also because of the relatively loose hydrogen bonds (∼1.9 Å) with the carbonyl oxygens. The methodologies used in this study reproduce the solvent effect on the free radical polymerization kinetics of MMA in a satisfactory way.
dc.publisherAmerican Chemical Society
dc.sourceMacromolecules
dc.subjectKeywords: Carbonyl oxygen; Dielectric constants; Explicit solvents; Geometry optimization; H-bonded; Hydrogen bonding interactions; In-vacuum; Isotacticities; Isotactics; MMA polymerization; Modeling studies; Polarizable continuum model; Propagation rate constant;
dc.titleModeling the solvent effect on the tacticity in the free radical polymerisation of methyl methacrylate
dc.typeJournal article
local.description.notesImported from ARIES
local.identifier.citationvolume43
dc.date.issued2010
local.identifier.absfor030701 - Quantum Chemistry
local.identifier.ariespublicationU4217927xPUB670
local.type.statusPublished Version
local.contributor.affiliationDegirmenci, Isa, College of Physical and Mathematical Sciences, ANU
local.contributor.affiliationEren, Sukru, Bogazici University
local.contributor.affiliationAviyente, Viktorya, Bogazici University
local.contributor.affiliationDe Sterck, Bart, Ghent University
local.contributor.affiliationHemelsoet, Karen, Ghent University
local.contributor.affiliationvan Speybroeck, Veronique, Ghent University
local.contributor.affiliationWaroquier, Michel, Ghent University
local.description.embargo2037-12-31
local.bibliographicCitation.issue13
local.bibliographicCitation.startpage5602
local.bibliographicCitation.lastpage5610
local.identifier.doi10.1021/ma100608g
dc.date.updated2016-02-24T10:44:39Z
local.identifier.scopusID2-s2.0-77955891275
CollectionsANU Research Publications

Download

File Description SizeFormat Image
01_Degirmenci_Modeling_the_solvent_effect_on_2010.pdf3.09 MBAdobe PDF    Request a copy


Items in Open Research are protected by copyright, with all rights reserved, unless otherwise indicated.

Updated:  19 May 2020/ Responsible Officer:  University Librarian/ Page Contact:  Library Systems & Web Coordinator