Ambient Temperature Transition-Metal-Free Dissociative Electron Transfer Reversible Addition–Fragmentation Chain Transfer Polymerization (DET-RAFT) of Methacrylates, Acrylates, and Styrene
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Maximiano, Pedro; Mendonça, Patrícia V.; Costa, João R. C.; Haworth, Naomi; Serra, Arménio C.; Guliashvili, Tamaz; Coote, Michelle; Coelho, Jorge F. J.
Description
Inorganic sulfites as reducing agents were successfully used in combination with typical reversible addition− fragmentation chain transfer (RAFT) agents for the controlled DET-RAFT (DET: dissociative electron transfer) of methacrylates, methyl acrylate (MA), and styrene (Sty) near room temperature (30 °C). The polymerizations were first-order with respect to monomer conversion and polymers with narrow molecular weight distributions (Đ < 1.2), and “living” features were obtained. MALDI-TOF...[Show more]
dc.contributor.author | Maximiano, Pedro | |
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dc.contributor.author | Mendonça, Patrícia V. | |
dc.contributor.author | Costa, João R. C. | |
dc.contributor.author | Haworth, Naomi | |
dc.contributor.author | Serra, Arménio C. | |
dc.contributor.author | Guliashvili, Tamaz | |
dc.contributor.author | Coote, Michelle | |
dc.contributor.author | Coelho, Jorge F. J. | |
dc.date.accessioned | 2020-09-02T01:09:04Z | |
dc.date.available | 2020-09-02T01:09:04Z | |
dc.identifier.issn | 0024-9297 | |
dc.identifier.uri | http://hdl.handle.net/1885/209209 | |
dc.description.abstract | Inorganic sulfites as reducing agents were successfully used in combination with typical reversible addition− fragmentation chain transfer (RAFT) agents for the controlled DET-RAFT (DET: dissociative electron transfer) of methacrylates, methyl acrylate (MA), and styrene (Sty) near room temperature (30 °C). The polymerizations were first-order with respect to monomer conversion and polymers with narrow molecular weight distributions (Đ < 1.2), and “living” features were obtained. MALDI-TOF experiments demonstrated the integrity of the chain-ends and clearly showed the absence of SO2 in the polymer chains. Kinetic studies revealed that an increase of either temperature or concentration of sulfites provided faster reactions, without loss of control. Ab initio quantum chemistry calculations suggested that in the presence of the reducing agent the RAFT agent undergoes one-electron reduction to a stable radical anion that can then undergo fragmentation to yield the initiating carbon-centered radical. The new metal-free DET-RAFT developed proved to be versatile and robust, as it could be also used for the polymerization of different relevant monomers, such as glycidyl methacrylate (GMA), 2-(diisopropylamino)ethyl methacrylate (DPA), and 2-(dimethylamino)ethyl methacrylate (DMAEMA). | |
dc.description.sponsorship | M.L.C. gratefully acknowledges generous allocations of supercomputing time on the National Facility of the Australian National Computational Infrastructure and financial support from the Australian Research Council Centre of Excellence for Electromaterials Science. | |
dc.format.mimetype | application/pdf | |
dc.language.iso | en_AU | |
dc.publisher | American Chemical Society | |
dc.rights | © 2016 American Chemical Society | |
dc.source | Macromolecules | |
dc.title | Ambient Temperature Transition-Metal-Free Dissociative Electron Transfer Reversible Addition–Fragmentation Chain Transfer Polymerization (DET-RAFT) of Methacrylates, Acrylates, and Styrene | |
dc.type | Journal article | |
local.identifier.citationvolume | 49 | |
dc.date.issued | 2016 | |
local.publisher.url | http://pubs.acs.org/journal/mamobx/about.html | |
local.type.status | Accepted Version | |
local.contributor.affiliation | Haworth, N., Research School of Chemistry, The Australian National University | |
local.contributor.affiliation | Coote, Michelle, Research School of Chemistry, The Australian National University | |
dc.relation | http://purl.org/au-research/grants/arc/CE140100012 | |
local.bibliographicCitation.issue | 5 | |
local.bibliographicCitation.startpage | 1597 | |
local.bibliographicCitation.lastpage | 1604 | |
local.identifier.doi | 10.1021/acs.macromol.5b02647 | |
dcterms.accessRights | Open Access | |
dc.provenance | https://v2.sherpa.ac.uk/id/publication/7790..."The Accepted Version can be archived in a non-commercial institutional repository if required by funder. 12 months embargo." from SHERPA/RoMEO site (as at 2/09/2020)." This document is the Accepted Manuscript version of a Published Work that appeared in final form in [Macromolecules], copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://dx.doi.org/10.1021/acs.macromol.5b02647 | |
Collections | ANU Research Publications |
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