Chain length dependent termination rate coefficients of methyl methacrylate (MMA) in the gel regime: Accessing kti,i using reversible addition-fragmentation chain transfer (RAFT) polymerization

Johnston-Hall, G., Stenzel, M. H., Davis, T. P., Barner-Kowollik, C., & Monteiro, M. J. (2007) Chain length dependent termination rate coefficients of methyl methacrylate (MMA) in the gel regime: Accessing kti,i using reversible addition-fragmentation chain transfer (RAFT) polymerization. Macromolecules, 40(8).

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Abstract

The termination rate coefficient, kti,i, for propagating chains of near equal length, i, was evaluated using the RAFT-CLD-T method over a wide range of chain lengths and up to a conversion of 70% for MMA polymerizations carried out in the presence of the RAFT agent, CPDB, at 80°C. We found that the conversion for the gel onset corresponded to the conversion at which polymer chains begin to overlap (i.e., c), and was found to range from 15 to 30% conversion depending on the Mn. It was further shown that c also corresponded with the gel onset conversions for vinyl acetate and methyl acrylate. The chain length dependence of kt in the gel regime scaled as agel(x) = 1.8x + 0.056, suggesting that reptation alone does not play a role in our system. A composite model was then derived to accurately describe kti,i for chain lengths up'to 3200 and conversions up to 70%. The kti,i, profiles for well-known termination models were tested and most gave unsatisfactory agreement with our experiments. Our model can be readily applied to any monomer provided accurate kti,i(x) data can be determined. © 2007 American Chemical Society.

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ID Code: 99149
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :36
Export Date: 5 September 2016
CODEN: MAMOB
Correspondence Address: Monteiro, M.J.; Australian Institute of Bioengineering and Nanotechnology, School of Molecular and Microbial Sciences, University of Queensland, Brisbane, QLD 4072, Australia; email: m.monteiro@uq.edu.au
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Keywords: Acrylic monomers, Gels, Polymerization, Rate constants, Vinyl resins, Polymer chains, Reversible addition-fragmentation chain transfer (RAFT), Vinyl acetate, Aromatic compounds
DOI: 10.1021/ma062405v
ISSN: 00249297
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: 06 Oct 2016 23:55

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