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Modeling termination kinetics in free‐radical polymerization using a reduced number of parameters
Author(s) -
Buback Michael,
Egorov Mark,
Kaminsky Vladimir
Publication year - 1999
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/(sici)1521-3919(19990901)8:5<520::aid-mats520>3.0.co;2-o
Subject(s) - monomer , dimensionless quantity , radical polymerization , polymerization , chain (unit) , methyl methacrylate , polymer chemistry , styrene , materials science , thermodynamics , kinetics , kinetic chain length , bulk polymerization , chain termination , chemistry , copolymer , polymer , physics , composite material , classical mechanics , astronomy
An approach for modeling chain‐length dependent termination rate coefficients is presented. The method is based on the assumption that free‐radical chain length may be considered as a continuous variable. As compared to discrete numerical methods, in continuous modeling the number of independent dimensionless parameters can be significantly reduced. As a consequence, for a wide variety of monomers the conversion dependence of k t can be predicted without extensive numerical calculations. The method may also be used to determine polymerization conditions under which simpler models of k t (which neglect effects arising from the dependence of k t on chain length) may be applied. Calculations for methyl methacrylate, styrene, and butyl acrylate bulk polymerizations up to high degrees of monomer conversion show that the impact of chain length on termination varies with conversion and strongly depends on the type of monomer.