Free Radical Entry and Secondary Nucleation in Styrene Emulsion Polymerization: A DLVO Approach.
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| Title: | Free Radical Entry and Secondary Nucleation in Styrene Emulsion Polymerization: A DLVO Approach. |
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| Authors: | Molina‐Estrada, Andrea1 (AUTHOR), Mora, Jesus Gracia1 (AUTHOR), Herrera‐Ordonez, Jorge1 (AUTHOR) jorge_ho67@fata.unam.mx |
| Source: | Macromolecular Reaction Engineering. Jun2026, Vol. 20 Issue 3, p1-17. 17p. |
| Subjects: | Emulsion polymerization, DLVO theory, Molecular interactions, Electrostatic interaction, Radicals (Chemistry), Nucleation, Surface active agents |
| Abstract: | A comprehensive model of free radical entry into particles during emulsion polymerization, recently reported in this journal, was modified to include the calculation of radical‐particle interactions based on the DLVO theory as well as the simplified calculation of secondary nucleation. Electrostatic repulsion was found to play a crucial role, causing changes in the size of the predominant entering oligomer radical, whether due to variations in ionic strength or surfactant coverage (θ). As θ increases to ∼0.1, the energy barrier for the entry of water‐soluble radicals raises sharply, causing their entry frequency (ρ) to decrease drastically and be controlled by diffusion. For θ>∼0.1, ρ becomes constant, and the predominant entering species are primary particles, whose formation is the rate‐determining step. It was also found that the onset of secondary nucleation occurs at a critical θ value rather than a critical particle concentration. Based on the results obtained and their agreement with experimental data, key mechanistic aspects of radical entry into the system under study are proposed, which contradict several postulates of one of the most accepted theories of free radical entry. These findings also suggest that nucleation mechanisms above and below the surfactant's CMC should be revisited. [ABSTRACT FROM AUTHOR] |
| Copyright of Macromolecular Reaction Engineering is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
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| Header | DbId: egs DbLabel: Engineering Source An: 194642008 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Free Radical Entry and Secondary Nucleation in Styrene Emulsion Polymerization: A DLVO Approach. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Molina‐Estrada%2C+Andrea%22">Molina‐Estrada, Andrea</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Mora%2C+Jesus+Gracia%22">Mora, Jesus Gracia</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Herrera‐Ordonez%2C+Jorge%22">Herrera‐Ordonez, Jorge</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> jorge_ho67@fata.unam.mx</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Macromolecular+Reaction+Engineering%22">Macromolecular Reaction Engineering</searchLink>. Jun2026, Vol. 20 Issue 3, p1-17. 17p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Emulsion+polymerization%22">Emulsion polymerization</searchLink><br /><searchLink fieldCode="DE" term="%22DLVO+theory%22">DLVO theory</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+interactions%22">Molecular interactions</searchLink><br /><searchLink fieldCode="DE" term="%22Electrostatic+interaction%22">Electrostatic interaction</searchLink><br /><searchLink fieldCode="DE" term="%22Radicals+%28Chemistry%29%22">Radicals (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Nucleation%22">Nucleation</searchLink><br /><searchLink fieldCode="DE" term="%22Surface+active+agents%22">Surface active agents</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: A comprehensive model of free radical entry into particles during emulsion polymerization, recently reported in this journal, was modified to include the calculation of radical‐particle interactions based on the DLVO theory as well as the simplified calculation of secondary nucleation. Electrostatic repulsion was found to play a crucial role, causing changes in the size of the predominant entering oligomer radical, whether due to variations in ionic strength or surfactant coverage (θ). As θ increases to ∼0.1, the energy barrier for the entry of water‐soluble radicals raises sharply, causing their entry frequency (ρ) to decrease drastically and be controlled by diffusion. For θ>∼0.1, ρ becomes constant, and the predominant entering species are primary particles, whose formation is the rate‐determining step. It was also found that the onset of secondary nucleation occurs at a critical θ value rather than a critical particle concentration. Based on the results obtained and their agreement with experimental data, key mechanistic aspects of radical entry into the system under study are proposed, which contradict several postulates of one of the most accepted theories of free radical entry. These findings also suggest that nucleation mechanisms above and below the surfactant's CMC should be revisited. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Macromolecular Reaction Engineering is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1002/mren.70021 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 17 StartPage: 1 Subjects: – SubjectFull: Emulsion polymerization Type: general – SubjectFull: DLVO theory Type: general – SubjectFull: Molecular interactions Type: general – SubjectFull: Electrostatic interaction Type: general – SubjectFull: Radicals (Chemistry) Type: general – SubjectFull: Nucleation Type: general – SubjectFull: Surface active agents Type: general Titles: – TitleFull: Free Radical Entry and Secondary Nucleation in Styrene Emulsion Polymerization: A DLVO Approach. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Molina‐Estrada, Andrea – PersonEntity: Name: NameFull: Mora, Jesus Gracia – PersonEntity: Name: NameFull: Herrera‐Ordonez, Jorge IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 06 Text: Jun2026 Type: published Y: 2026 Identifiers: – Type: issn-print Value: 1862832X Numbering: – Type: volume Value: 20 – Type: issue Value: 3 Titles: – TitleFull: Macromolecular Reaction Engineering Type: main |
| ResultId | 1 |
