In Situ Performic Acid Epoxidation of Polyfarnesene: Evidence of Oxirane Ring Instability and Its Impact on Multifunctional Polymer Composition.
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| Title: | In Situ Performic Acid Epoxidation of Polyfarnesene: Evidence of Oxirane Ring Instability and Its Impact on Multifunctional Polymer Composition. |
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| Authors: | Porto, Geilza A.1 (AUTHOR), Paula, Luiz Guilherme A. de1,2 (AUTHOR), Batista, Luciano N.1,2 (AUTHOR), Dias, Marcos L.1,2 (AUTHOR) mldias@ima.ufrj.br |
| Source: | Polymers (20734360). Apr2026, Vol. 18 Issue 7, p844. 18p. |
| Subjects: | Epoxidation, Branched polymers, Chemical stability, Biomimetic polymers, Polymers |
| Abstract: | Polyfarnesene, a bio-based polymer, was epoxidized in situ using performic acid to investigate oxirane ring formation, stability, and the role of its bottlebrush architecture in the kinetics. The reaction reached a maximum epoxidation degree of ~20% after 6 h but underwent side reactions, producing hydroxyl and formic ester groups. FTIR and 1H NMR revealed that ring opening began within the first hour, whereas residual unsaturated bonds persisted after prolonged reaction, owing to steric shielding by the polymer's long C11–C13 side chains. Unlike smaller polydiene homologues, polyfarnesene exhibited slower ring-opening kinetics, retaining approximately 10% of oxirane groups after 20 h. GPC showed minimal molecular weight changes but an increase in polydispersity, confirming structural rearrangements without chain scission or crosslinking. DSC demonstrated that oxirane incorporation increased the Tg; however, side reactions reduced this effect by limiting chain mobility. These findings establish that the spatial constraints imposed by the bottlebrush architecture of polyfarnesene govern the reaction kinetics, restricting epoxidation efficiency and favoring esterification pathways. This interplay provides a basis for designing bio-based polymers with tunable thermal properties. Controlling the reaction environment to suppress side reactions is key to producing high-Tg epoxidized derivatives suitable for rubber technologies and sustainable materials. [ABSTRACT FROM AUTHOR] |
| Copyright of Polymers (20734360) is the property of MDPI 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 |
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| Header | DbId: egs DbLabel: Engineering Source An: 192959280 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: In Situ Performic Acid Epoxidation of Polyfarnesene: Evidence of Oxirane Ring Instability and Its Impact on Multifunctional Polymer Composition. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Porto%2C+Geilza+A%2E%22">Porto, Geilza A.</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Paula%2C+Luiz+Guilherme+A%2E+de%22">Paula, Luiz Guilherme A. de</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Batista%2C+Luciano+N%2E%22">Batista, Luciano N.</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Dias%2C+Marcos+L%2E%22">Dias, Marcos L.</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<i> mldias@ima.ufrj.br</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Polymers+%2820734360%29%22">Polymers (20734360)</searchLink>. Apr2026, Vol. 18 Issue 7, p844. 18p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Epoxidation%22">Epoxidation</searchLink><br /><searchLink fieldCode="DE" term="%22Branched+polymers%22">Branched polymers</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+stability%22">Chemical stability</searchLink><br /><searchLink fieldCode="DE" term="%22Biomimetic+polymers%22">Biomimetic polymers</searchLink><br /><searchLink fieldCode="DE" term="%22Polymers%22">Polymers</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Polyfarnesene, a bio-based polymer, was epoxidized in situ using performic acid to investigate oxirane ring formation, stability, and the role of its bottlebrush architecture in the kinetics. The reaction reached a maximum epoxidation degree of ~20% after 6 h but underwent side reactions, producing hydroxyl and formic ester groups. FTIR and 1H NMR revealed that ring opening began within the first hour, whereas residual unsaturated bonds persisted after prolonged reaction, owing to steric shielding by the polymer's long C11–C13 side chains. Unlike smaller polydiene homologues, polyfarnesene exhibited slower ring-opening kinetics, retaining approximately 10% of oxirane groups after 20 h. GPC showed minimal molecular weight changes but an increase in polydispersity, confirming structural rearrangements without chain scission or crosslinking. DSC demonstrated that oxirane incorporation increased the Tg; however, side reactions reduced this effect by limiting chain mobility. These findings establish that the spatial constraints imposed by the bottlebrush architecture of polyfarnesene govern the reaction kinetics, restricting epoxidation efficiency and favoring esterification pathways. This interplay provides a basis for designing bio-based polymers with tunable thermal properties. Controlling the reaction environment to suppress side reactions is key to producing high-Tg epoxidized derivatives suitable for rubber technologies and sustainable materials. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Polymers (20734360) is the property of MDPI 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: 10.3390/polym18070844 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 18 StartPage: 844 Subjects: – SubjectFull: Epoxidation Type: general – SubjectFull: Branched polymers Type: general – SubjectFull: Chemical stability Type: general – SubjectFull: Biomimetic polymers Type: general – SubjectFull: Polymers Type: general Titles: – TitleFull: In Situ Performic Acid Epoxidation of Polyfarnesene: Evidence of Oxirane Ring Instability and Its Impact on Multifunctional Polymer Composition. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Porto, Geilza A. – PersonEntity: Name: NameFull: Paula, Luiz Guilherme A. de – PersonEntity: Name: NameFull: Batista, Luciano N. – PersonEntity: Name: NameFull: Dias, Marcos L. IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 04 Text: Apr2026 Type: published Y: 2026 Identifiers: – Type: issn-print Value: 20734360 Numbering: – Type: volume Value: 18 – Type: issue Value: 7 Titles: – TitleFull: Polymers (20734360) Type: main |
| ResultId | 1 |
