Effect of Scandium Triflate on the RAFT Copolymerization of Methyl Acrylate and Vinyl Acetate Controlled by an Acid/Base “Switchable” Chain Transfer Agent

2.50
Hdl Handle:
http://hdl.handle.net/2436/621110
Title:
Effect of Scandium Triflate on the RAFT Copolymerization of Methyl Acrylate and Vinyl Acetate Controlled by an Acid/Base “Switchable” Chain Transfer Agent
Authors:
Tselepy, Ashton; Schiller, Tara L. ( 0000-0002-3973-1308 ) ; Harrisson, Simon ( 0000-0001-6267-2599 ) ; Guerrero-Sanchez, Carlos; Moad, Graeme ( 0000-0002-4375-5580 ) ; Keddie, Daniel J. ( 0000-0003-3422-2034 )
Abstract:
Modulation of the activity of an acid/base switchable dithiocarbamate RAFT agent, cyanomethyl (4-fluorophenyl)(pyridin-4-yl)carbamodithioate, with the Lewis acid scandium triflate (Sc(OTf)3) was investigated to examine the ability to deliver improved control over RAFT copolymerizations involving both more-activated and less-activated monomers—specifically the copolymerization of methyl acrylate (MA) and vinyl acetate (VAc). The introduction of either 0.5 or 1 mol equiv of Sc(OTf)3, with respect to RAFT agent, into a RAFT copolymerization of MA and VAc provides substantially improved control resulting in significantly reduced molar mass dispersities (Đ) (∼1.1–1.3) than achieved in its absence (Đ ∼ 1.3–1.4). Furthermore, similar introduction of Sc(OTf)3 into MA homopolymerization mediated by the same RAFT agent also delivered polymers of very low Đ (∼1.15). Sc(OTf)3 was also found to lower the rate of polymerization and alter the copolymerization reactivity ratios for MA and VAc. Increasing the Lewis acid concentration provides enhanced incorporation of the less active monomer, VAc, into the copolymers ([Sc(OTf)3]/[RAFT] = 0, rMA = 4.04, rVAc = 0.032; [Sc(OTf)3]/[RAFT] = 0.5, rMA = 3.08, rVAc = 0.17; [Sc(OTf)3]/[RAFT] = 1, rMA = 2.68, rVAc = 0.62). Carbon nuclear magnetic resonance (13C NMR) and differential scanning calorimetry (DSC) analysis of preparative samples confirm the enhanced VAc incorporation with increased levels of Sc(OTf)3. Importantly the inclusion of Sc(OTf)3 does not deleteriously affect the thiocarbonylthio end-groups of the RAFT polymers, with high end-group fidelity being observed in all copolymerizations.
Citation:
Effect of Scandium Triflate on the RAFT Copolymerization of Methyl Acrylate and Vinyl Acetate Controlled by an Acid/Base “Switchable” Chain Transfer Agent 2018, 51 (2):410 Macromolecules
Publisher:
American Chemical Society Publications
Journal:
Macromolecules
Issue Date:
5-Jan-2018
URI:
http://hdl.handle.net/2436/621110
DOI:
10.1021/acs.macromol.7b02104
Additional Links:
http://pubs.acs.org/doi/10.1021/acs.macromol.7b02104
Type:
Article
Language:
en
ISSN:
1520-5835
Appears in Collections:
FSE

Full metadata record

DC FieldValue Language
dc.contributor.authorTselepy, Ashtonen
dc.contributor.authorSchiller, Tara L.en
dc.contributor.authorHarrisson, Simonen
dc.contributor.authorGuerrero-Sanchez, Carlosen
dc.contributor.authorMoad, Graemeen
dc.contributor.authorKeddie, Daniel J.en
dc.date.accessioned2018-02-15T12:18:23Z-
dc.date.available2018-02-15T12:18:23Z-
dc.date.issued2018-01-05-
dc.identifier.citationEffect of Scandium Triflate on the RAFT Copolymerization of Methyl Acrylate and Vinyl Acetate Controlled by an Acid/Base “Switchable” Chain Transfer Agent 2018, 51 (2):410 Macromoleculesen
dc.identifier.issn1520-5835en
dc.identifier.doi10.1021/acs.macromol.7b02104-
dc.identifier.urihttp://hdl.handle.net/2436/621110-
dc.description.abstractModulation of the activity of an acid/base switchable dithiocarbamate RAFT agent, cyanomethyl (4-fluorophenyl)(pyridin-4-yl)carbamodithioate, with the Lewis acid scandium triflate (Sc(OTf)3) was investigated to examine the ability to deliver improved control over RAFT copolymerizations involving both more-activated and less-activated monomers—specifically the copolymerization of methyl acrylate (MA) and vinyl acetate (VAc). The introduction of either 0.5 or 1 mol equiv of Sc(OTf)3, with respect to RAFT agent, into a RAFT copolymerization of MA and VAc provides substantially improved control resulting in significantly reduced molar mass dispersities (Đ) (∼1.1–1.3) than achieved in its absence (Đ ∼ 1.3–1.4). Furthermore, similar introduction of Sc(OTf)3 into MA homopolymerization mediated by the same RAFT agent also delivered polymers of very low Đ (∼1.15). Sc(OTf)3 was also found to lower the rate of polymerization and alter the copolymerization reactivity ratios for MA and VAc. Increasing the Lewis acid concentration provides enhanced incorporation of the less active monomer, VAc, into the copolymers ([Sc(OTf)3]/[RAFT] = 0, rMA = 4.04, rVAc = 0.032; [Sc(OTf)3]/[RAFT] = 0.5, rMA = 3.08, rVAc = 0.17; [Sc(OTf)3]/[RAFT] = 1, rMA = 2.68, rVAc = 0.62). Carbon nuclear magnetic resonance (13C NMR) and differential scanning calorimetry (DSC) analysis of preparative samples confirm the enhanced VAc incorporation with increased levels of Sc(OTf)3. Importantly the inclusion of Sc(OTf)3 does not deleteriously affect the thiocarbonylthio end-groups of the RAFT polymers, with high end-group fidelity being observed in all copolymerizations.en
dc.language.isoenen
dc.publisherAmerican Chemical Society Publicationsen
dc.relation.urlhttp://pubs.acs.org/doi/10.1021/acs.macromol.7b02104en
dc.rightsArchived with thanks to Macromoleculesen
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/*
dc.subjectRAFTen
dc.subjectpolymerizationen
dc.subjectLewis aciden
dc.subjectcopolymerizationen
dc.subjectmethyl acrylateen
dc.subjectvinyl acetateen
dc.titleEffect of Scandium Triflate on the RAFT Copolymerization of Methyl Acrylate and Vinyl Acetate Controlled by an Acid/Base “Switchable” Chain Transfer Agenten
dc.typeArticleen
dc.identifier.journalMacromoleculesen
dc.contributor.institutionChemistry, School of Science and Technology, University of New England, Armidale, NSW 2351, Australia-
dc.contributor.institutionInternational Institute of Nanocomposites Manufacturing, WMG, University of Warwick, Coventry CV4 7AL, United Kingdom-
dc.contributor.institutionIMRCP, UMR CNRS 5623, Université de Toulouse, 118 route de Narbonne, Cedex 9 31062 Toulouse, France-
dc.contributor.institutionCSIRO Manufacturing Flagship, Bag 10, Clayton South, VIC 3169, Australia-
dc.contributor.institutionCSIRO Manufacturing Flagship, Bag 10, Clayton South, VIC 3169, Australia-
dc.contributor.institutionChemistry, School of Science and Technology, University of New England, Armidale, NSW 2351, Australia-
dc.date.accepted2017-12-
rioxxterms.funderCSIRO Manufacturing and the School of Science and Technology at UNEen
rioxxterms.identifier.projectUoW150218DKen
rioxxterms.versionAMen
rioxxterms.licenseref.urihttps://creativecommons.org/CC BY-NC-ND 4.0en
rioxxterms.licenseref.startdate2019-01-05en
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