A Comprehensive Kinetic Model for the Combined Chemical and Thermal Polymerization of Styrene up to High Conversions

Kotoulas, Costas; Krallis, Apostolos; Pladis, Prokopis; Kiparissides, Costas

doi:10.1002/macp.200390104

Cited by 42 publications

(56 citation statements)

References 20 publications

(39 reference statements)

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“…temperatures above 373 K. [13,51,60] In this study, the reaction mechanism proposed by Mayo [36] (Figure 3) is implemented to describe the thermal initiation of styrene. In this mechanism, 1-phenyl-1,2,3,9-tetrahydronaphthalene (D; dimer) is formed by reversible Diels-Alder dimerization (d/dr) of styrene (M).…”

Section: Chain Transfermentioning

confidence: 99%

Kinetic Modeling as a Tool to Understand and Improve the Nitroxide Mediated Polymerization of Styrene

Bentein

D’hooge

Reyniers

et al. 2011

Macro Theory & Simulations

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Kinetic modeling is used to obtain insight in the complex interplay between reaction rates and obtained polymer properties in the SG1 and the TEMPO mediated bulk polymerization of styrene at 396 K. The increase of the viscosity during NMP is accounted for. At higher targeted chain lengths, chain transfer to dimer and transfer from nitroxide to dimer are shown to cause the experimentally observed reduced control over the average polymer properties and to result in a clear fronting of the polymer chain length distribution. The potential of kinetic modeling to design tailor‐made synthesis strategies is illustrated. Simulations indicate that careful control of the polymerization conditions allows to obtain an important improvement of the polymer properties. The approach is also applicable for NMP mediated by other alkoxyamines/nitroxides and allows to expand the application range of NMP for styrene polymerization in particular to synthesize complex polymer architectures by assembly of functionalized polymers. magnified image

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Section: Chain Transfermentioning

confidence: 99%

Kinetic Modeling as a Tool to Understand and Improve the Nitroxide Mediated Polymerization of Styrene

Bentein

D’hooge

Reyniers

et al. 2011

Macro Theory & Simulations

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“…All these observations agree with the expected behavior for styrene polymerization. A comparison of model predictions and experimental data [44] of conversion versus time and molecular weight development for the polymerization of styrene at 120 8C, using DCP as initiator, is shown in Figure 6. There is good agreement in conversion versus time up to 40% monomer conversion (Figure 6a).…”

Section: S7mentioning

confidence: 99%

“…To avoid closure problems, any third moment terms [A in Equation (63)] in the previous equations are calculated using Equation (63). In the case of n branched generations, if thermal self-initiation is considered, the number of equations, n, to solve will be 7 þ [3 Â (n þ 1)] ODEs and 2 þ [3 Â (n þ 1)] algebraic equations.…”

Section: Moment Equationsmentioning

confidence: 99%

“…For the initiator effect, the polymerization of styrene at 120 8C using dicumyl peroxide (DCP) as initiator was also simulated and compared to experimental data. [44] No diffusion-controlled (DC) effects were considered in the simulations, but the thermal self-initiation of styrene was included in the model. It is observed in Figure 5a that the polymerization rate is much faster at 120 8C, very rapidly reaching 60% monomer conversion, but from there on the polymerization slows down, probably due to complete initiator consumption.…”

Section: Styrene (Sty)mentioning

confidence: 99%

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Sol MWD During Styrene, Vinyl Acetate, Methyl Methacrylate, and Butyl Acrylate Homopolymerization: A Numerical Study Using the NFT Approach

Yáñez-Martínez

Luna‐Bárcenas

Vivaldo‐Lima

2009

Macro Theory & Simulations

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Complete parameter sensitivity analyses using the numerical fractionation technique are presented for the cases of homopolymerization with chain transfer to polymer and termination by combination. Also, using reported values for the kinetic rate constants associated with the linear and non‐linear homopolymerizations of styrene, vinyl acetate, methyl methacrylate and butyl acrylate, overall molecular weight distributions and averages of the MWD were calculated using the NFT. Good agreement with the expected behavior, with MMA and STY not gelling while BA and VAc do, was obtained. It is concluded that the NFT produces coherent and reliable performance for known polymerization systems, whether linear or non‐linear.magnified image

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“…A comprehensive kinetic model was developed for the combined chemical and thermal-free radical polymerization of styrene to predict the styrene polymerization rate and molecular weight distribution of the polystyrene. 12 To determine the steady-state and dynamic behavior of a continuous process, a mathematical model for the free radical polymerization of styrene was developed. 13 Many theories have been developed to explain the polymerization autoacceleration of styrene and other vinyl monomers.…”

Section: Introductionmentioning

confidence: 99%

A new approach for the kinetic modeling of free radical bulk polymerization of styrene

Bera

Radičević

Stoiljkovic

et al. 2011

Polym J

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The kinetics of styrene-free radical bulk polymerization was studied by differential scanning calorimetry (DSC). The data obtained from DSC thermograms were used to model and predict the autoacceleration during styrene polymerization and to understand how it is influenced by temperature. The experimental data were well described by the estimated kinetic model. The model included two processes (the first-order reaction and autoacceleration), because they occur simultaneously as two parallel reactions rather than being strictly separated. It was found that the autoacceleration activation energy is approximately four times lower than the energy of the first-order reaction. In addition, the first-order reaction followed by the autoacceleration of the styrene-free radical bulk polymerization occurs simultaneously only between 41.7 and 110.5 1C. Keywords: autoacceleration; differential scanning calorimetry; polymerization kinetics; polystyrene; styrene-free radical bulk polymerization INTRODUCTION It is well known that the free radical bulk polymerization of vinyl monomers (derivates of acrylic and methacrylic acids, vinyl acetate, styrene, ethylene and so on) is characterized by the autoacceleration phenomenon. 1-3 The free radical polymerization of these monomers can be explained by classical theory up to definite conversion. After that conversion, autoacceleration of polymerization occurs. The onset of autoacceleration is the moment when the polymerization rate departs from the value anticipated by the classical theory of free radical polymerization. [3][4][5][6][7] The onset and the intensity of autoacceleration are determined by the type of monomer, initiator concentration, temperature and other reaction conditions. Ebdon and Hunt 3 used differential scanning calorimetry (DSC) to follow the course of free radical bulk polymerization of styrene and concluded that autoacceleration is less pronounced at 90 1C than at 80 1C and is absent at 100 1C and above. Autoacceleration appeared at about 2% conversion of styrene polymerized at 20 1C for 252 days in the presence of 2,2¢-azobisisobutyronitrile. 8 To explain this autoacceleration, an equation was applied to the kinetic data obtained under the condition of predominant transfer to the monomer. It was concluded that polymer molecules may move by repetition and the mobility of segments decreases with decrease of free volume. 8 Comparisons of the results obtained for styrene-free radical bulk polymerization with model predictions have quantified the dependence of the gel effect strength on the predominance of chain transfer events. 9 Cioffi et al. 10 performed a rheokinetic study of the bulk-free radical polymerization of styrene with a helical barrel rheometer. The rheokinetic measurements show that autoacceleration in the free radical polymerization of styrene can be reduced when the polymer-

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A Comprehensive Kinetic Model for the Combined Chemical and Thermal Polymerization of Styrene up to High Conversions

Cited by 42 publications

References 20 publications

Kinetic Modeling as a Tool to Understand and Improve the Nitroxide Mediated Polymerization of Styrene

Kinetic Modeling as a Tool to Understand and Improve the Nitroxide Mediated Polymerization of Styrene

Sol MWD During Styrene, Vinyl Acetate, Methyl Methacrylate, and Butyl Acrylate Homopolymerization: A Numerical Study Using the NFT Approach

A new approach for the kinetic modeling of free radical bulk polymerization of styrene

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