Modeling of Network Formation in Reversible Addition-Fragmentation Transfer (RAFT) Copolymerization of Vinyl/Divinyl Monomers Using a Multifunctional Polymer Molecule Approach

A mathematical model for the kinetics of copolymerization with crosslinking of vinyl/divinyl monomers in the presence of RAFT controllers is developed. A reaction scheme considering multifunctional polymer molecules, which results in a multidimensional problem, is proposed. Molecular weight developm...

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Bibliographic Details
Published in:Macromolecular theory and simulations 2014-03, Vol.23 (3), p.147-169
Main Authors: Hernández-Ortiz, Julio César, Vivaldo-Lima, Eduardo, Dubé, Marc Arnold, Penlidis, Alexander
Format: Article
Language:English
Subjects:
Computer simulation
controlled radical polymerization
Controllers
Copolymerization
crosslinking
Free radicals
mathematical modeling
Mathematical models
Molecular weight
Monomers
Radicals
RAFT
Rafts
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Summary:A mathematical model for the kinetics of copolymerization with crosslinking of vinyl/divinyl monomers in the presence of RAFT controllers is developed. A reaction scheme considering multifunctional polymer molecules, which results in a multidimensional problem, is proposed. Molecular weight development during the pre‐gelation period was calculated using the method of moments. Flory–Stockmayer's theory is used for the post‐gelation period. The case of RAFT homopolymerization is also studied, as an example of model reduction, with identical results as those obtained with an existing model based on a simplifying premise. Good agreement between predicted profiles, our own experimental data, and data from other groups is obtained in most of the analyzed cases despite the occasional use of certain simplifying assumptions. A mathematical model for RAFT copolymerization kinetics of vinyl/divinyl monomers using a multifunctional macromolecule approach has been developed. Polymer species are allowed to hold several active, intermediate free radical, and dormant radical centers at the same time, which results in a multidimensional problem. Model performance is good and in agreement with available experimental data.
ISSN:1022-1344
1521-3919
DOI:10.1002/mats.201300144