An adaptive calorimetric method, coupled with state estimators for emulsion
copolymerization, is shown to provide accurate, on-line information on the
evolution of the composition and kinetics of an emulsion copolymerization.
This method was evaluated for the emulsion copolymerization of methyl meth
acrylate-vinyl acetate (MMA-VAc) under nonisothermal conditions. In additio
n to providing on-line estimates of the number of moles of each polymerizin
g species in the reactor, the state estimator provides a value for a lumped
kinetic parameter proportional to the product of (n) over bar N-p. This in
formation can be combined with off-line measurements to study the evolution
of polymerization kinetics and to explain the trends observed for the mole
cular weight distribution and glass transition temperatures. Values of (n)
over bar were found to vary from 0.5 to 30 for the homopolymerization of MM
A. However, the presence of VAc in the copolymerizing system drastically re
duces (n) over bar. This can lead to a dramatic increase in the average mol
ecular weight of the copolymer since it alters the ratio of propagation to
termination in the polymerizing particles. (C) 2000 John Wiley & Sons, Inc.