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Keywords:

  • terpolymerization;
  • kinetics (polym.);
  • methacrylate;
  • acrylate;
  • styrene;
  • mechanistic model;
  • depropagation;
  • intramolecular transfer to polymer;
  • chain scission;
  • macromonomer reactions;
  • midchain radical

Abstract

n-Butyl methacrylate/styrene/n-butyl acrylate (BMA/ST/BA) high-temperature starved-feed solution semibatch copolymerization and terpolymerization experiments with varying monomer feed composition, final polymer content, monomer feed time, and reaction temperature were carried out. A comprehensive mechanistic terpolymerization model implemented in PREDICI includes methacrylate depropagation, acrylate backbiting, chain scission, and macromonomer propagation, as well as penultimate chain-growth and termination kinetics. The generality of the model was verified by comparison with terpolymerization data sets from two laboratories that demonstrate the impact of high-temperature secondary reactions on polymerization rate and polymer molecular weight. © 2010 American Institute of Chemical Engineers AIChE J, 2011