Accessing chain length dependent termination rate coefficients of Methyl Methacrylate (MMA) via the Reversible Addition Fragmentation Chain Transfer (RAFT) process

Johnston-Hall, G., Theis, A., Monteiro, M. J., Davis, T. P., Stenzel, M. H., & Barner-Kowollik, C. (2005) Accessing chain length dependent termination rate coefficients of Methyl Methacrylate (MMA) via the Reversible Addition Fragmentation Chain Transfer (RAFT) process. Macromolecular Chemistry and Physics, 206(20).

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Abstract

The RAFT-CLD-T methodology is demonstrated to be not only applicable to 1-substituted monomers such as styrene and acrylates, but also to 1,1 -disubstituted monomers such as MMA. The chain length of the terminating macromolecules is controlled by CPDB in MMA bulk free radical polymerization at 80°C. The evolution of the chain length dependent termination rate coefficient, kt i,i, was constructed in a step-wise fashion, since the MMA/CPDB system displays hybrid behavior (between conventional and living free radical polymerization) resulting in initial high molecular weight polymers formed at low RAFT agent concentrations. The obtained CLD of kt in MMA polymerizations is compatible with the composite model for chain length dependent termination. For the initial chain-length regime, up to a degree of polymerization of 100, kt decreases with a (in the expression kt i,i = kt 0·-α) being close to 0.65 at 80°C. At chain lengths exceeding 100, the decrease is less pronounced (affording an α of 0.15 at 80°C). However, the data are best represented by a continuously decreasing nonlinear functionality implying a chain length dependent aα. © 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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ID Code: 99107
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :62
Export Date: 5 September 2016
CODEN: MCHPE
Correspondence Address: Barner-Kowollik, C.; Centre for Advanced Macromolecular Design, School of Chemical Engineering and Industrial Chemistry, University of New South Wales, Sydney, NSW 2052, Australia; email: barner-kowollik@unsw.edu.au
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Keywords: Kinetics, Living polymerization, Methyl methacrylate, Reversible addition fragmentation chain transfer polymerization (RAFT), Termination rate coefficient, Concentration (process), Free radical polymerization, Macromolecules, Molecular weight, Reaction kinetics, Substitution reactions, RAFT agents, Reversible addition fragmentation chain transfer polymerization, Monomers
DOI: 10.1002/macp.200500354
ISSN: 10221352
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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