Theoretical Analysis of Nitroxide‐Mediated Copolymerization of Styrene and α‐Methyl‐Styrene under Different Operating Policies and Reactor Designs

Abstract

The polymerization that IUPAC terms reversible‐deactivation radical polymerization is a controlled radical polymerization technique (CRP) that allows producing polymers with tailored properties without the stringent conditions typical in ionic polymerization. A theoretical analysis is presented of the influence of operating and design conditions on the product properties for the nitroxide‐mediated copolymerization (NMP) of styrene and α‐methyl styrene. Several reactor configurations are analyzed, with different feeding policies and temperature profiles. To this end a mathematical model is developed to predict copolymer average properties and the complete bivariate MWD. The results help establishing design parameters and optimal operating policies to obtain desired copolymer microstructures.

Deterministic Approaches for Simulation of Nitroxide-Mediated Radical Polymerization

“…These authors later extended this work to analyze polymerizations in tubular reactors [66]. Fortunatti et al [67] used the double-index moment method to predict average molecular weights and copolymer composition in the nitroxide-mediated copolymerization of styrene and α-methyl styrene.…”

“…Deterministic models of the SLD are usually set up by formulating a parallel kinetic mechanism that considers the sequences of monomers as the reacting species [68]. For instance, Table 1 shows an extract of a conventional NMP kinetic mechanism, and Table 2 shows the corresponding parallel kinetic mechanism for modelling the SLD [67].…”

“…The model was used to describe the conventional and NMP of styrene and 4-methylstyrene. Fortunatti et al [67] used the same methodology to compute the averages of the copolymer SLD in the nitroxide-mediated copolymerization of styrene and α-methyl styrene. Table 1: Kinetic steps of a nitroxide-mediated copolymerization in terms of the reacting polymer chains.…”

How penultimate monomer unit effects and initiator influence ICAR ATRP of n‐butyl acrylate and methyl methacrylate

“…To reduce the complexity and taking into account the limited knowledge on penultimate rate coefficients most CRP kinetic modeling studies resort to the use of the simplified terminal model to calculate the intrinsic reactivities . In case a PMU model is used, it only relates to the propagation reactivity—thus not to the CRP (de)activation reactivity—and this almost exclusively in an implicit way .…”

Mathematical Tools and Approaches for Polymerization Reaction Engineering

“…The papers published here discuss the use of modeling and numerical tools in polymerization processes for different purposes and based on distinct techniques. The paper by Fortunatti et al [8] concerns the use of mathematical models for design of operation policies in a tubular reaction process. The use of mathematical models for design and optimization of polymerization processes constitutes a classical and important illustration of how useful numerical tools can be in this field.…”