Quantum chemical mapping of initialization processes in RAFT polymerization

Coote, M. L., Izgorodina, E. I., Krenske, E. H., Busch, M., & Barner-Kowollik, C. (2006) Quantum chemical mapping of initialization processes in RAFT polymerization. Macromolecular Rapid Communications, 27(13).

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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. © 2006 WILEY-VCH Verlag GmbH & Co. KGaA.

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54 citations in Web of Science®
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ID Code: 99126
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :58
Export Date: 5 September 2016
CODEN: MRCOE
Correspondence Address: Coote, M.L.; ARC Centre of Excellence in Free Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia; email: mcoote@rsc.anu.edu.au
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Keywords: Ab initio calculations, Chain initialization, Polymerization mechanism and kinetics, Reversible addition fragmentation chain transfer (RAFT), Computer simulation, Concentration (process), Data reduction, Homopolymerization, Mapping, Molecular orientation, Styrene, Equilibrium constants, Molecular orbital theory, Quantum chemical mapping, Quantum theory
DOI: 10.1002/marc.200600170
ISSN: 10221336
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 30 Sep 2016 01:57

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