Toward a General Methodology for Modeling Diffusive-Controlled Reactions in Free Radical Polymerization

Victoria‐Valenzuela, David; Herrera‐Ordóñez, Jorge; Luna-Bárcenas, Gabriel

doi:10.1002/mats.201500025

Cited by 18 publications

(58 citation statements)

References 37 publications

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“…As far as the authors know, there is no another mathematical model reported in the literature that can predict such minimum. This latter has also been observed in the bulk free‐radical polymerizations of MMA and VAc, as it was reported in references …”

Section: Resultssupporting

confidence: 82%

“…The aim of this work is to study the kinetics of bulk‐FRP of the butyl methacrylate isomers on the base of R p measurements obtained by DSC and to discuss the results with the aid of simulations using a mathematical model previously reported by two of the authors . In this context, differences and similarities with work reported by Buback and Junkers regarding kinetic aspects of the FRP of the monomers under studied, are discussed.…”

Section: Introductionmentioning

confidence: 89%

“…〈 k td 〉 was estimated with the following Equation

(⟨⟩, k_{normaltd}) = (\frac{1}{⟨t_{td}⟩}) (N_{A} v_{r} γ_{normalkt} p)

where 〈 t td 〉 and γ kt are, respectively, the average time and the collision probability for a short radical to collide with the reactive terminal unit of any of the long radicals that surround it. N A is Avogadro's number, v r is the volume associated with the reaction, and p is probability that the molecules are correctly oriented to form the CC bond.…”

Section: Mathematical Modelmentioning

confidence: 99%

“…Usually the theoretical results are compared to conversion versus time experimental data, which behavior is, for the naked eye, almost linear. Therefore, a more rigorous validation of kinetic models should include the derivative of such data, this is, the R p ; however, works in which this kind of validation is employed, are scarce …”

Section: Introductionmentioning

confidence: 99%

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Kinetics of Bulk Free‐Radical Polymerization of Butyl Methacrylate Isomers Studied by Reaction Calorimetry

Victoria‐Valenzuela¹,

Herrera‐Ordóñez²,

Arcos-Casarrubias

et al. 2017

Macro Reaction Engineering

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The kinetics of bulk free‐radical polymerizations of n‐butyl methacrylate (n‐BMA), iso‐butyl methacrylate (i‐BMA), and tert‐butyl methacrylate (t‐BMA) are studied by differential scanning calorimetry and with the aid of a mathematical model previously reported by the authors. In all the cases, the rate of polymerization (Rp) evolution curve exhibits a minimum at low conversions and the characteristic maximum of the autoacceleration effect. It is found that the monomer conversion xmin at which the minimum is observed, follows the order n‐BMA > i‐BMA > t‐BMA and that for monomer conversions (x) smaller than xmin, the termination rate coefficient (kt) shows a plateau. According to the model results it is obtained that for x > xmin, the termination reaction is chemically controlled whereas for x > xmin, it is diffusion‐controlled and that the xmin values are related to the value of the termination rate coefficient of the chemical step (kt0) of every isomer, which is highly influenced by the steric hindrance of the alkyl substituent group.

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Section: Resultssupporting

confidence: 82%

Section: Introductionmentioning

confidence: 89%

“…〈 k td 〉 was estimated with the following Equation

(⟨⟩, k_{normaltd}) = (\frac{1}{⟨t_{td}⟩}) (N_{A} v_{r} γ_{normalkt} p)

Section: Mathematical Modelmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Kinetics of Bulk Free‐Radical Polymerization of Butyl Methacrylate Isomers Studied by Reaction Calorimetry

Victoria‐Valenzuela¹,

Herrera‐Ordóñez²,

Arcos-Casarrubias

et al. 2017

Macro Reaction Engineering

Self Cite

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“…In the present work, an alternative explanation for the effect of a CTA on the autoacceleration effect is proposed. This hypothesis is based on simulations of the bulk free‐radical polymerization using a modified version of a mathematical model recently reported by the authors and validated with experimental data reported in the literature in which the effect of the CTA concentration on the kinetics was studied using 2,2′‐azobisisobutyronitrile (AIBN) as initiator.…”

Section: Introductionmentioning

confidence: 71%

Autoacceleration in Bulk Free‐Radical Polymerization: Effect of Chain Transfer

Victoria‐Valenzuela¹,

Herrera‐Ordóñez²,

Ricardo³

et al. 2017

Macro Chemistry & Physics

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The model and methodology for estimating diffusion‐controlled rate coefficients for the methyl methacrylate polymerization system reported in Parts I and II of this series is extended to include the chain transfer reaction to an agent (CTA). Theoretical and experimental results exhibit minima in the rate of polymerization curves at low conversions as it is observed in the absence of CTA. Such minima are proposed to be the onset of the autoacceleration effect where the termination reaction undergoes a transition from chemically controlled to diffusion controlled where the segmental mobility of the chain ends plays a key role. As the CTA concentration increases, the conversion at which the minimum is presented is higher and the autoacceleration is less pronounced. This behavior is explained in terms of the effect of polymer chain entanglements and segmental mobility of the chain ends on the termination rate coefficient k t.

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Infusible acrylic thermoplastic resins: Tailoring of chemorheological properties

Cousins

Howell

Suzuki

et al. 2019

J of Applied Polymer Sci

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Infusible liquid resins that polymerize into a thermoplastic are desirable for many applications. Similar to unsaturated and vinylester thermosetting systems, they consist of polymers dissolved in reactive monomer. This work presents a method to decrease cycle time by tuning the molecular weight and concentration of the predissolved polymer in the resin. Variation of these properties allows precise control of the viscosity which in turn controls the time at which peak exotherm is reached, the maximum temperature for a given part thickness, and cure time. Predictive models for the viscosity dependence on molecular weight, polymer concentration, shear rate, and temperature are developed. Two fiberglass panels are fabricated and tested; one with a lower molecular weight (Mw~30 kg mol−1) poly(methyl methacrylate) dissolved in methyl methacrylate and the second with higher molecular weight (Mw~500 kg mol−1) predissolved polymer in the resin. Mechanical properties are indistinguishable but the lower molecular weight panel cures up to three times faster. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 48006.

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Toward a General Methodology for Modeling Diffusive-Controlled Reactions in Free Radical Polymerization

Cited by 18 publications

References 37 publications

Kinetics of Bulk Free‐Radical Polymerization of Butyl Methacrylate Isomers Studied by Reaction Calorimetry

Kinetics of Bulk Free‐Radical Polymerization of Butyl Methacrylate Isomers Studied by Reaction Calorimetry

Autoacceleration in Bulk Free‐Radical Polymerization: Effect of Chain Transfer

Infusible acrylic thermoplastic resins: Tailoring of chemorheological properties

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