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dc.contributor.author
Soulé, Ezequiel Rodolfo  
dc.contributor.author
Borrajo Fernandez, Julio  
dc.contributor.author
Williams, Roberto Juan Jose  
dc.date.available
2020-03-05T21:57:25Z  
dc.date.issued
2004-02  
dc.identifier.citation
Soulé, Ezequiel Rodolfo; Borrajo Fernandez, Julio; Williams, Roberto Juan Jose; Presence of Two Maxima in the Isothermal Free-Radical Polymerization Rate of Isobornyl Methacrylate Retarded by Oxygen; American Chemical Society; Macromolecules; 37; 4; 2-2004; 1551-1557  
dc.identifier.issn
0024-9297  
dc.identifier.uri
http://hdl.handle.net/11336/98897  
dc.description.abstract
The kinetics of the free-radical polymerization of isobornyl methacrylate (IBoMA) at 80 °C, initiated by benzoyl peroxide (BPO), was determined by differential scanning calorimetry (DSC), using sample pans previously sealed in air or in nitrogen. The polymerization was arrested by vitrification at a final conversion close to 0.80. The kinetics in nitrogen could be fitted using initiation and propagation rate constants reported in the literature, a functionality of the termination rate constant controlled by translational diffusion based on the free-volume model, and an efficiency factor for the initiator decomposition that decreased with conversion in the medium-high conversion range. The presence of oxygen led to a significant decrease in the polymerization rate, an effect that was enhanced when decreasing the sample size (increasing the surface-to-volume ratio). The original finding was the presence of two maxima in the isothermal polymerization rate, a fact that was confirmed by replicating experiences in two different DSC devices and changing the amount of initiator in the formulation. The first maximum in the polymerization rate was explained by the decrease of the diffusion rate of macromolecular radicals to the oxygen-rich boundary, an effect that started at low conversions. The second maximum was related to the decrease in the solubility/diffusion of oxygen in the reaction medium, a phenomenon that was particularly severe at high conversions.  
dc.format
application/pdf  
dc.language.iso
eng  
dc.publisher
American Chemical Society  
dc.rights
info:eu-repo/semantics/openAccess  
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/  
dc.subject
Free-radical polymerization  
dc.subject
Autoaceleration  
dc.subject
Oxygen inhibition  
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Química Orgánica  
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Ciencias Químicas  
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CIENCIAS NATURALES Y EXACTAS  
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Otras Ingeniería de los Materiales  
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Ingeniería de los Materiales  
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INGENIERÍAS Y TECNOLOGÍAS  
dc.title
Presence of Two Maxima in the Isothermal Free-Radical Polymerization Rate of Isobornyl Methacrylate Retarded by Oxygen  
dc.type
info:eu-repo/semantics/article  
dc.type
info:ar-repo/semantics/artículo  
dc.type
info:eu-repo/semantics/publishedVersion  
dc.date.updated
2020-01-30T14:57:03Z  
dc.journal.volume
37  
dc.journal.number
4  
dc.journal.pagination
1551-1557  
dc.journal.pais
Estados Unidos  
dc.description.fil
Fil: Soulé, Ezequiel Rodolfo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina  
dc.description.fil
Fil: Borrajo Fernandez, Julio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina  
dc.description.fil
Fil: Williams, Roberto Juan Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentina  
dc.journal.title
Macromolecules  
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/ma0350314  
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info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/ma0350314  
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://arxiv.org/abs/1311.5448