Substitution Effects in Property Relations for Stepwise Polyfunctional Polymerization

This paper extends the authors' method of calculating average properties of ideal nonlinear stepwise polymerization to systems with first-shell substitution effects. Two special cases are considered in detail: Af + B2, where the second and subsequent A groups on the A monomer can react at different rates due to the presence of other reacted groups, and Af + A2 + B2, where both Af and A2 can show substitution effects. Relations for weight-average molecular weight, the gel point, weight-fraction solubles, and cross-link density are derived.