A Review of Modeling of Diffusion Controlled Polymerization Reactions

Abstract

A plethora of models have been developed quantifying the effect of diffusion‐controlled phenomena on polymerization reactions. The most prominent approaches are reviewed here, including innovative ones that have emerged over the last decade. Free‐radical and step‐growth polymerizations are considered in a way to show that similar models have been used in both mechanisms. In free‐radical polymerization the models proposed are subdivided according to their theoretical background into four categories: (i) based on a Fickian description of reactant diffusion; (ii) free‐volume theory based; (iii) chain‐length dependent; and, (iv) empirical. The reversible addition‐fragmentation technique is discussed, together with two industrially important case‐studies, solid state polycondensation and epoxy‐amine curing.magnified image

Brownian cluster dynamics with short range patchy interactions: Its application to polymers and step-growth polymerization

“…polyesters, polyamides, polyurethanes, etc [54], it is clear that the physics involved in these process is of great practical use. Most of the existing theoretical studies rely on population balance models [55,56] which keep track of the concentration of every chain length from the knowledge of the starting populations and the effective constant rates [57][58][59]. In practice, some difficulties appear when assigning values to the effective step-growth chemical rates, as it is still not fully understood how they are influenced by chain-length, diffusion effects and ring formation.…”

MMA bulk polymerization and its influence on in situ resin viscosity comparing several chemorheological models

“…Recent reviews have treated dynamic conversion in bulk radical polymerization, [1][2][3] and specific models have been developed for polypropylene, 4 polyphenylene oxide, 5 polymethyl methacrylate (PMMA), [6][7][8] other acrylates, 9 polyamides, 10 epoxies, 11 norbornenes, 12,13 and low density polyethylene, 14,15 with the focus on plant efficiency and safety. 16,17 Similar rheological assessments during chemical reaction have also been performed with reactive extrusion.…”

Structure and rheology of branched polyamide 6 polymers from their reaction recipe

“…With such systems, one should therefore consider different reaction kinetics, as a function of the chain status. 33,34 V.1.2 Viscoelastic properties. The viscoelastic properties of the linear PA6 samples have been predicted by using the TMA tube model and based on their experimental MWD.…”