Sol → gel transition with rings in a finite polycondensing system in solution

Abstract

We report a theoretical formulation for the mean cluster size distribution in a finite polycondensing system. Expressions for the mean number of n-mers with j bonds (m_nj) are developed. Numerical calculations show that while the non-cyclic molecules make the dominant contribution to the small clusters, the large clusters are dominated by cyclic structures. The number of particles in ringless chains, nm_n,n-1, decays monotonically with n at all extents of reaction, but nm_n becomes bimodal near the gel point. We also find that the solvent plays an important role in the cluster size distribution.