Journal
MACROMOLECULAR THEORY AND SIMULATIONS
Volume 12, Issue 4, Pages 276-286Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/mats.200390028
Keywords
copolymerization; frontal polymerization; free-radical polymerization; modeling
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Frontal copolymerization is a process in which a spatially localized reaction zone propagates into a mixture of two monomers, converting them into a copolymer. In the simplest case of free-radical copolymerization a mixture of monomers and initiator is placed into a test tube. Reaction is initiated at one end of the tube, and a self-sustained thermal wave, in which chemical conversion occurs, develops and propagates through the tube. We develop a mathematical model of the frontal copolymerization process and analytically determine the structure of the polymerization wave, the propagation velocity, maximum temperature, and degree of conversion of the monomers. Specifically, we examine their dependence on reactivity ratios as well as other kinetic parameters, monomer feed composition, and exothermicity of the reactions. Our analytic results are in good quantitative agreement with both direct numerical simulations of the model and experimental data, which are also presented in the paper.
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