Accessing chain length dependent termination rate coefficients of methyl methacrylate (MMA) via the reversible addition fragmentation chain transfer (RAFT) process

Johnston-Hall, Geoffrey, Theis, Alexander, Monteiro, Michael J., Davis, Thomas P., Stenzel, Martina H. and Barner-Kowollik, Christopher (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: 2047-2053.


Author Johnston-Hall, Geoffrey
Theis, Alexander
Monteiro, Michael J.
Davis, Thomas P.
Stenzel, Martina H.
Barner-Kowollik, Christopher
Title Accessing chain length dependent termination rate coefficients of methyl methacrylate (MMA) via the reversible addition fragmentation chain transfer (RAFT) process
Journal name Macromolecular Chemistry And Physics   Check publisher's open access policy
ISSN 1022-1352
Publication date 2005-10-24
Sub-type Article (original research)
DOI 10.1002/macp.200500354
Volume 206
Issue 20
Start page 2047
End page 2053
Total pages 7
Place of publication Weinheim
Publisher Wiley-V C H Verlag Gmbh
Collection year 2005
Language eng
Subject C1
250501 Synthesis of Macromolecules
680303 Polymeric materials (e.g. paints)
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 degrees C. The evolution of the chain length dependent termination rate coefficient, k(t)(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 k(t) 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, k(t) decreases with alpha (in the expression k(t)(i,i) = k(t)(0) . i(-alpha)) being close to 0.65 at 80 degrees C. At chain lengths exceeding 100, the decrease is less pronounced (affording an alpha of 0.15 at 80 degrees C). However, the data are best represented by a continuously decreasing nonlinear functionality implying a chain length dependent alpha.
Keyword Polymer Science
Kinetics
Living Polymerization
Methyl Methacrylate
Reversible Addition Fragmentation Chain Transfer Polymerization
(raft)
Termination Rate Coefficient
Free-radical Polymerization
Pulsed-laser Polymerization
Propagation Rate Coefficients
Rate-constant
Analytical Expression
Kinetics
Styrene
Bulk
25-degrees-c
Acrylate
Q-Index Code C1
Additional Notes DOI: 10.1002/macp.200500354

 
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