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Title: Assessment of copolymerization models via stochastic integrodifferential estimation
Author: Lopez-Serrano, F.
Puig, J.E.
Alvarez, J.
Issue Date: 2007
Abstract: The model assessment and discrimination problems for copolymerization systems with measurements of polymer composition and average propagation rate constant versus feed composition are addressed via an integrodifferential stochastic estimation approach with error propagation analysis. The methodology is applied to perform the ultimate versus penultimate model discrimination problem for two previously studied representative systems with experimental data: styrene/methyl methacrylate (STY/MMA) and para-chlorostyrene/para- chloromethoxystyrene (PCS/PMOS). It was found that, in each case, (i) the model discrimination task can be performed with more precision than with the integral method alone in the light of the experimental data uncertainty, (ii) nearly constant reactivity ratios (ri) are exhibited, (iii) a complex radical reactivity ratios (si) functionality, not reported before, was found in the STY/MMA system, (iv) approximately constant radical reactivity ratios are presented in the PCS/PMOS system, a feature that is typical of the (implicit or) penultimate model statement, and (v) the radical stabilization mechanism differs from the one proposed in previous reports (s1s 2/r1r2 ? 1). Zapotitlán 2007 American Chemical Society.
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