Quantum Chemical Mapping of Initialization Processes in RAFT Polymerization
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Coote, Michelle; Izgorodina, Ekaterina; Krenske, Elizabeth; Busch, Markus; Barner-Kowollik, Christopher
Description
We present the first ab initio simulation of a reversible addition fragmentation chain transfer (RAFT) polymerization. Using ab initio molecular orbital theory, we calculate the equilibrium constants for the first eight addition-fragmentation steps in the cyanoisopropyl dithiobenzoate-mediated polymerization of styrene. We then simulate the concentration profiles for the RAFT agent, and its unimeric and dimeric adducts, assuming standard experimental parameters for styrene homopolymerization...[Show more]
dc.contributor.author | Coote, Michelle | |
---|---|---|
dc.contributor.author | Izgorodina, Ekaterina | |
dc.contributor.author | Krenske, Elizabeth | |
dc.contributor.author | Busch, Markus | |
dc.contributor.author | Barner-Kowollik, Christopher | |
dc.date.accessioned | 2015-12-13T23:02:33Z | |
dc.identifier.issn | 1022-1336 | |
dc.identifier.uri | http://hdl.handle.net/1885/84945 | |
dc.description.abstract | We present the first ab initio simulation of a reversible addition fragmentation chain transfer (RAFT) polymerization. Using ab initio molecular orbital theory, we calculate the equilibrium constants for the first eight addition-fragmentation steps in the cyanoisopropyl dithiobenzoate-mediated polymerization of styrene. We then simulate the concentration profiles for the RAFT agent, and its unimeric and dimeric adducts, assuming standard experimental parameters for styrene homopolymerization and the addition of the styryl radical to the RAFT agent. The simulated data show excellent agreement with published experimental data, high-lighting the accuracy of quantum chemistry. In contrast, the currently used chain-length independent models fail to describe even the qualitative trends in the data, regardless of whether the fragmentation reaction is assumed to be fast or slow. The calculated chain-length dependent equilibrium constants are large, in agreement with the earlier proposed slow fragmentation model. | |
dc.publisher | Wiley-VCH Verlag GMBH | |
dc.source | Macromolecular Rapid Communications | |
dc.subject | Keywords: Computer simulation; Concentration (process); Data reduction; Homopolymerization; Mapping; Molecular orientation; Styrene; Equilibrium constants; Molecular orbital theory; Quantum chemical mapping; Reversible addition fragmentation chain transfer (RAFT); Ab initio calculations; Chain initialization; Polymerization mechanism and kinetics; Reversible addition fragmentation chain transfer (RAFT) | |
dc.title | Quantum Chemical Mapping of Initialization Processes in RAFT Polymerization | |
dc.type | Journal article | |
local.description.notes | Imported from ARIES | |
local.description.refereed | Yes | |
local.identifier.citationvolume | 27 | |
dc.date.issued | 2006 | |
local.identifier.absfor | 030305 - Polymerisation Mechanisms | |
local.identifier.absfor | 030799 - Theoretical and Computational Chemistry not elsewhere classified | |
local.identifier.ariespublication | MigratedxPub13164 | |
local.type.status | Published Version | |
local.contributor.affiliation | Coote, Michelle, College of Physical and Mathematical Sciences, ANU | |
local.contributor.affiliation | Izgorodina, Ekaterina, College of Physical and Mathematical Sciences, ANU | |
local.contributor.affiliation | Krenske, Elizabeth, College of Physical and Mathematical Sciences, ANU | |
local.contributor.affiliation | Busch, Markus, Darmstadt University of Technology | |
local.contributor.affiliation | Barner-Kowollik, Christopher, University of New South Wales | |
local.description.embargo | 2037-12-31 | |
local.bibliographicCitation.issue | 13 | |
local.bibliographicCitation.startpage | 1015 | |
local.bibliographicCitation.lastpage | 1022 | |
local.identifier.doi | 10.1002/marc.200600170 | |
dc.date.updated | 2015-12-12T07:47:59Z | |
local.identifier.scopusID | 2-s2.0-33746041072 | |
Collections | ANU Research Publications |
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