Polymer Reaction Engineering, Vol.7, No.3, 379-400, 1999
The use of continuous system modeling programming to simulate polymer modification reactions - irreversible, reversible and epimerization reactions
Continuous System Modeling of polymer analogous reactions is shown to provide a simple, convenient method for calculating structural features of polymer reaction products. Eased on approximate differentials for triads discussed earlier by Plate et al. (1995), simple CSMP, ACSL and DESIRE programs were written to calculate triad distributions for the products of irreversible polymer analogous reactions. The results obtained using this program were identical with those obtained using the predictor-corrector method of Bauer (1979). They were also identical with the results of Monte-Carlo and exact calculations. Using the AA- and B-approximations described by Plate et al. (1995), differential equations for triad concentrations were written for reversible polymer analogous reactions and CSMP, ACSL and DESIRE programs were written to integrate these equations numerically. The outputs of these programs provided triad concentrations as a function of time and at equilibrium that were in excellent agreement with the results of Monte-Carlo simulations. Modified versions of these programs were used to model the epimerization of stereoregular polymers and again there was excellent agreement with Monte-Carlo simulation results. Analysis of the set of differentials derived for modeling polymer epimerization reactions, indicates that the completely equilibrated (time similar to infinity) polymers have Bemoullian stereosequence distributions if a single kinetic parameter, sigma 1/(1 + root k(o)/k(o)'), is used to characterize the epimerization system.