Modeling Insights on the TEMPO Mediated Radical Polymerization of Styrene

Despite a great deal of research on nitroxide mediated radical polymerization (NMRP), its kinetic mechanism is not fully known yet. The focus of this work was to contribute further to the understanding of the kinetics of NMRP processes through refinements of a comprehensive mathematical model developed by our group for the bimolecular system. This work considered important secondary reactions that can occur during the NMRP process. It also analyzed important kinetic aspects via a sensitivity study on some key parameters of the system. It was observed that an irreversible reaction between the TEMPO controller and the chemical initiator is very important and must be considered in the NMRP mechanism, in order to be able to describe properly both conversion and average molecular weight data.

[1]  Gordon K. Hamer,et al.  Narrow molecular weight resins by a free-radical polymerization process , 1993 .

[2]  T. Fukuda,et al.  Mechanisms and kinetics of nitroxide-controlled free radical polymerization , 1996 .

[3]  D. Greszta,et al.  Mechanism of Controlled/“Living” Radical Polymerization of Styrene in the Presence of Nitroxyl Radicals. Kinetics and Simulations , 1996 .

[4]  M. Georges,et al.  The Pivotal Role of Excess Nitroxide Radical in Living Free Radical Polymerizations with Narrow Polydispersity , 1996 .

[5]  T. Fukuda,et al.  Gel permeation chromatographic determination of activation rate constants in nitroxide‐controlled free radical polymerization, 1. Direct analysis by peak resolution , 1997 .

[6]  M. Morbidelli,et al.  Kinetics of “living” free radical polymerization , 1999 .

[7]  D. Bertin,et al.  Controlled free radical polymerization of styrene in the presence of nitroxide radicals I. Thermal initiation , 1999 .

[8]  Yuliang Yang,et al.  Rate enhancement of nitroxide-mediated living free-radical polymerization by continuous addition of initiator , 2000 .

[9]  C. Floudas,et al.  Optimization of living polymerization through distributed control of a nitroxide radical , 2001 .

[10]  W. Ray,et al.  Modeling of “living” free‐radical polymerization processes. I. Batch, semibatch, and continuous tank reactors , 2002 .

[11]  E. Vivaldo‐Lima,et al.  DETAILED MODELING, SIMULATION, AND PARAMETER ESTIMATION OF NITROXIDE MEDIATED LIVING FREE RADICAL POLYMERIZATION OF STYRENE * , 2002 .

[12]  E. Vivaldo‐Lima,et al.  Effect of Regime of Addition of Initiator on TEMPO-Mediated Polymerization of Styrene , 2004 .

[13]  E. Saldívar‐Guerra,et al.  Nitroxide mediated polymerization using diphenyl azabutane N-oxides. A study of electronic effects and of the [nitroxide]/[initiator] ratio on the polymerization control , 2004 .

[14]  Antonio Flores-Tlacuahuac,et al.  Non-linear bifurcation analysis of the living nitroxide-mediated radical polymerization of styrene in a CSTR , 2006 .

[15]  L. Lona,et al.  Simulation of Styrene Polymerization by Monomolecular and Bimolecular Nitroxide‐Mediated Radical Processes over a Range of Reaction Conditions , 2007 .

[16]  L. Lona,et al.  Assessing the Importance of Diffusion‐Controlled Effects on Polymerization Rate and Molecular Weight Development in Nitroxide‐Mediated Radical Polymerization of Styrene , 2007 .

[17]  L. Lona,et al.  Nitroxide-mediated radical polymerization of styrene using mono- and di-functional initiators , 2007 .

[18]  M. Cunningham,et al.  Modeling of Nitroxide-Mediated Semibatch Radical Polymerization , 2007 .

[19]  L. Lona,et al.  Another Perspective on the Nitroxide Mediated Radical Polymerization (NMRP) of Styrene Using 2,2,6,6‐Tetramethyl‐1‐piperidinyloxy (TEMPO) and Dibenzoyl Peroxide (BPO) , 2007 .

[20]  L. Lona,et al.  Effect of the addition of inert or TEMPO-capped prepolymer on polymerization rate and molecular weight development in the nitroxide-mediated radical polymerization of styrene , 2008 .