A simulation model for long‐chain branching in vinyl acetate polymerization: 2. Continuous polymerization in a stirred tank reactor

Abstract

AbstractA new simulation model for the kinetics of long‐chain branching formed via chain transfer to polymer and terminal double bond polymerization that was proposed in Part 1 of this series is extended to a continuous stirred tank reactor. The present model is applied to the free radical polymerization of vinyl acetate in a micromixed continuous stirred tank reactor, and various information on branched structure such as the molecular weight distribution, distribution of branch points, and branching density of the largest polymer molecule are calculated. Based on the present simulation model, it was found that the method of moments used successfully to predict various average properties in a batch polymerization cannot be applied to a continuous stirred tank reactor without accounting for the outflow of polymer radicals and the existence of polyradicals. The present model has given an excellent agreement with the experimental results of Chatterjee, Park, and Graessley (1977) for a solution polymerization of vinyl acetate in a continuous stirred tank reactor. © 1994 John Wiley & Sons, Inc.