Kinetics of Radical Polymerization

Abstract

This contribution expounds the principles of radical polymerization (RP) kinetics. It emphasizes the defining population‐balance equations and shows how everything springs from them. As far as possible, an equation‐ rather than modeling‐based approach is advocated, because this provides much greater understanding of kinetics. Numerous examples in support of this philosophy are presented. The treatment covers both steady‐state and nonsteady‐state polymerization and also presents some of the extra considerations involved in acrylate polymerization, copolymerization, and emulsion polymerization. Methods for measuring the values of rate coefficients are naturally elucidated in the wider context of RP kinetics in general. The strengths and limitations of equations and methods are made clear. It is argued that very little defies explanation when proper attention is given to the necessary fundamentals.

Detailed analysis of termination kinetics in radical polymerization

“…There are other variations of the methodologies above, e.g. fitting the entire molar mass distribution of the dead polymer obtained from a polymerization 29 . But such methods are in essence the same as what has already been described, because ultimately they are based on the identical population‐balance equations that give rise to Eqns () and ().…”

“…fitting the entire molar mass distribution of the dead polymer obtained from a polymerization. 29 But such methods are in essence the same as what has already been described, because ultimately they are based on the identical population-balance equations that give rise to Eqns (2) and (3). What is more pertinent is to question the validity of the assumptions underpinning these equations, and therefore these methods.…”