Predictive model of polymer reaction kinetics and coagulation behavior in seeded emulsion co- and ter-polymerizations

TL;DR

This paper develops a mathematical model based on classical equations to predict the kinetics and coagulation behavior in seeded emulsion co- and ter-polymerizations, validated with experimental data and used for process control.

Contribution

The paper introduces a calibrated predictive model for emulsion polymerization kinetics of co- and ter-polymers, incorporating gel-effect coefficients and applied to complex ter-polymer systems.

Findings

Model accurately predicts particle size and conversion over time.

Quantifies surfactant coverage and counterion concentration during polymerization.

Provides insights for controlling coagulation behavior.

Abstract

A mathematical model to describe the emulsion polymerization kinetics of co- and ter-polymerizations is developed. The model is based on the classical Smith-Ewart (SE) equations, within the pseudo-homopolymerization approach, with state-of-the-art models for radical entry and desorption. For co- and ter-polymerizations there are unknown parameters in the model which are related to monomer-specific gel-effect coefficients, that are needed to compute the bimolecular termination reaction rates. The unknown parameters are determined through extensive calibration of the model on literature data for homo- and co-polymerizations of \textit{n}-butyl acrylate (n-BA) and methyl methacrylate (MMA). The so-obtained predictive model is then applied to the modelling of the ter-polymerization of n-BA and MMA with 2-hydroxyethyl methacrylate (2-HEMA) with sodium persulphate (SPR) as initiator: predictions for the time-evolution of particle size and conversion are in excellent agreement with experimental measurements using Dynamic Light Scattering (DLS) and Gas Chromatography (GC), upon tuning the gel-effect coefficient related to 2-HEMA. The developed model is used to quantify the surfactant surface coverage of the particles as well as the total concentration of counterions in the system throughout the entire polymerization process. This key information provides a way to rationalize and control the coagulation behavior during the whole polymerization process.