Simulation of polymer network formation by the Monte Carlo method

A Monte Carlo method for simulation of the stepwise polyreaction generating treelike polymer structures and admitting intramolecular reactions inside the largest particle (identified with the gel) has been developed. The method is equivalent to the kinetic theory of network formation applied to finite systems. The limiting properties of an infinite system are obtained by extrapolation; among those best accessible are the critical conversion of gelation and weight fractions of sol and gel. Polymerization of a trifunctional monomer with a first-shell substitution effect was used as an example to demonstrate that, with the exception of some special cases, the results obtained by the kinetic method are virtually identical with those provided by the statistical method based on the treelike model and cascade substitution.