Advanced computational strategies for modelling the evolution of full molecular weight distributions formed during multiarmed (star) polymerisations

Chaffey-Millar, H., Busch, M., Davis, T. P., Stenzel, M. H., & Barner-Kowollik, C. (2005) Advanced computational strategies for modelling the evolution of full molecular weight distributions formed during multiarmed (star) polymerisations. Macromolecular Theory and Simulations, 14(3).

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A novel computational strategy is described for the simulation of star polymerisations, allowing for the computation of full molecular weight distributions (MWDs). Whilst, the strategy is applicable to a broad range of techniques for the synthesis of star polymers, the focus of the current study is the simulation of MWDs arising from a reversible addition fragmentation chain transfer (RAFT), R-group approach star polymerisation. In this synthetic methodology, the arms of the star grow from a central, polyfunctional moiety, which is formed initially as the refragmenting R-group of a polyfunctional RAFT agent. This synthetic methodology produces polymers with complex MWDs and the current simulation strategy is able to account for the features of such complex MWDs. The strategy involves a kinetic model which describes the reactions of a single arm of a star, the kinetics of which are implemented and simulated using the PREDICI® program package. The MWDs resulting from this simulation of single arms are then processed with an algorithm we describe, to generate a full MWD of stars. The algorithm is applicable to stars with an arbitrary number of arms. The kinetic model and subsequent algorithmic processing techniques are described in detail. A simulation has been parameterised using rate coefficients and densities for a 2,2′-azoisobutyronitrile (AIBN) initiated, bulk polymerisation of styrene at 60°C. A number of kinetic parameters have been varied over large ranges. Conversion normalised simula tions were performed, leading to information regarding star arm length, polydispersity index (PDI) and the fraction of living arms. These screening processes provided a rigorous test for the kinetic model and also insight into the conditions, which lead to optimal star formation. Finally, full MWDs are simulated for several RAFT agent/initiator ratios as well as for stars with a varying number of arms. © 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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ID Code: 99101
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :36
Export Date: 5 September 2016
Correspondence Address: Barner-Kowollik, C.; Centre for Advanced Macromolecular Design (CAMD), School of Chemical Engineering and Industrial Chemistry, University of New South Wales, Sydney, NSW 2052, Australia; email:
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Keywords: Kinetics (polym.), Modelling, Reversible addition fragmentation chain transfer (RAFT), Simulations, Star polymers, Computation theory, Computer simulation, Diffusion, Free radical polymerization, Gel permeation chromatography, Living polymerization, Synthesis (chemical), Atom transfer radical polymerization (ATRP), Nitroxide-mediated polymerization (NMP), Molecular weight distribution
DOI: 10.1002/mats.200400075
ISSN: 10221344
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: 22 Sep 2016 04:50

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