A Review of Modeling of Diffusion Controlled Polymerization Reactions

• Published in: Macromolecular theory and simulations Vol. 16; no. 4; pp. 319 - 347
• Main Author: Achilias, Dimitris S.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 25.05.2007; WILEY‐VCH Verlag; Wiley
• Subjects: Applied sciences; Diffusion-controlled reactions; Exact sciences and technology; free-radical; modeling; Organic polymers; Physicochemistry of polymers; Polycondensation; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; step-growth; Epoxy resin; Condensation polymerization; Review; Modeling; Chemical reaction kinetics; Diamine; Kinetic model; Free radical polymerization; Diffusion-controlled reactions; Curing(plastics); free-radical; step-growth; Solid state reaction
• ISSN: 1022-1344; 1521-3919
• DOI: 10.1002/mats.200700003

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.