Open Access
ARTICLE
Modeling Degradative Chain Transfer in d-Limonene/n-Butyl Methacrylate Free-Radical Copolymerization
Yujie Zhang1, Marc A. Dubé1,*, Eduardo Vivaldo-Lima2
1 Department of Chemical and Biological Engineering, Centre for Catalysis Research and Innovation, University of Ottawa, 161 Louis
Pasteur Pvt., Ottawa, Ontario, Canada K1N 6N5
2 Faculty of Chemistry, Department of Chemical Engineering, National Autonomous University of Mexico, 04510, Mexico D.F., Mexico
* Corresponding Author:
Journal of Renewable Materials 2015, 3(4), 318-326. https://doi.org/10.7569/JRM.2015.634115
Received 27 May 2015; Accepted 06 August 2015;
Abstract
Renewable monomers containing allylic C-H bonds in their structure are prone to degradative chain
transfer in free-radical polymerization, which will dramatically decrease the polymerization rate. In order
to understand this mechanism, a kinetic model incorporating a degradative chain transfer mechanism for
the free-radical copolymerization of
d-limonene (LIM) and
n-butyl methacrylate (BMA) was developed
using PREDICI. Model predictions offered insight on how degradative chain transfer reactions affect
conversion, copolymer composition and molecular weight in the polymerization. Experimental data from
copolymerizations at monomer feed compositions (LIM/BMA, mol/mol) of 10/90, 20/80 and 30/70 were
compared to the model’s predictions. Moreover, it was discovered that degradative chain transfer results
in elevated concentrations of growing polymer chains ending in allylic limonene radicals, which inevitably
influences termination reactions and molecular weight development.
Keywords
Cite This Article
Zhang, Y., Dubé, M. A., Vivaldo-Lima, E. (2015). Modeling Degradative Chain Transfer in
d-Limonene/
n-Butyl Methacrylate Free-Radical Copolymerization.
Journal of Renewable Materials, 3(4), 318–326.