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High Temperature Free Radical Copolymerization with Depropagation and Penultimate Kinetic Effects
Author(s) -
Li Deheng,
Leiza Jose R.,
Hutchinson Robin A.
Publication year - 2005
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/mats.200500039
Subject(s) - copolymer , kinetics , chemistry , polymer chemistry , thermodynamics , styrene , limiting , methyl methacrylate , polymer , organic chemistry , physics , mechanical engineering , quantum mechanics , engineering
Summary: Methacrylate copolymers produced under higher temperature starved‐feed conditions are affected by depropagation, and some binary systems also experience a penultimate effect. In this work a generalized set of equations has been developed to describe the combined effect of depropagation and penultimate copolymerization kinetics on instantaneous copolymer composition and average copolymerization rate coefficients. Limiting cases applicable to the methacrylate/styrene system are examined. When combined with depropagation, penultimate kinetics not only decrease the effective propagation rate coefficient but also deviate from terminal model predictions of polymer composition.Copolymerization chain growth with penultimate kinetics and depropagation.