Mathematical Modeling of Atom-Transfer Radical Polymerization Using Bifunctional Initiators

• Published in: Macromolecular theory and simulations Vol. 15; no. 3; pp. 198 - 214
• Main Authors: Al-Harthi, Mamdouh, Soares, João B. P., Simon, Leonardo C.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 12.04.2006; WILEY‐VCH Verlag; Wiley
• Subjects: Applied sciences; atom-transfer radical polymerization (ATRP); bifunctional initiators; Exact sciences and technology; living polymerization; molecular weight distribution/molar mass distribution; Organic polymers; Physicochemistry of polymers; polymer reaction engineering; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; Kinetic model; molecular weight distribution/molar mass distribution; bifunctional initiators; Molecular weight distribution; Atom transfer polymerization; Living polymer; living polymerization; Theoretical study; atom-transfer radical polymerization (ATRP); Modeling; polymer reaction engineering
• ISSN: 1022-1344; 1521-3919
• DOI: 10.1002/mats.200500078

Bifunctional initiators can produce polymers with higher molecular weight at higher initiator concentrations than monofunctional initiators. In this study, we developed a mathematical model for ATRP with bifunctional initiators. The most important reactions in ATRP were included in the model. The method of moments was used to predict monomer conversion, average molecular weights and polydispersity index as a function of polymerization time in batch reactors. The model was used to understand the mechanism of ATRP and to quantify how polymerization conditions affect monomer conversion and polymer properties by examining the effect of several rate constants (activation, deactivation, propagation and chain termination) and of catalyst and initiator concentration on polymerization kinetics and polymer properties. When compared to monofunctional initiators, bifunctional initiators not only produce polymers with higher molecular weight averages at higher polymerization rates, but also control their molecular weight distributions more effectively. Effect of initial catalyst concentration on polydispersity index as a function of time.