An Integrated Biorefinery Proof of Concept: The Synthesis of Fully Bio-Based, Functional Lignin Polyester Copolymers of Cyclic Anhydrides and Epoxides Towards Polyol Applications and Tunable Bio-Derived Materials.
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| Title: | An Integrated Biorefinery Proof of Concept: The Synthesis of Fully Bio-Based, Functional Lignin Polyester Copolymers of Cyclic Anhydrides and Epoxides Towards Polyol Applications and Tunable Bio-Derived Materials. |
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| Authors: | Driscoll, Oliver J.1,2 (AUTHOR), van de Pas, Daniel J.2 (AUTHOR), Torr, Kirk M.2,3 (AUTHOR), Thomas, Hayden P.1,2 (AUTHOR), Vendamme, Richard1,2 (AUTHOR), Feghali, Elias1,3 (AUTHOR) |
| Source: | Polymers (20734360). Oct2025, Vol. 17 Issue 20, p2806. 23p. |
| Subjects: | Lignins, Polyols, Copolymerization, Polyesters, Botanical chemistry, Thermophysical properties, Biomaterials, Biomass |
| Abstract: | A versatile, sustainable feedstock pathway to bio-based polymeric materials was developed utilizing lignin biomass and the ring-opening copolymerization (ROCOP) of cyclic anhydrides and epoxides to synthesize functional, lignin-derived, fully bio-based polyester polyols. The initial goal was to make the ROCOP reaction more applicable to bio-derived starting materials and more attractive to commercialization by conducting the polymerization under less constrained and industrially relevant conditions in air and without the extensive purification of reagents, catalysts, or solvents, typically used in the literature. A refined ROCOP system was applied as a powerful tool in lignin valorization by successfully synthesizing the lignin-derived copolyester prepolymers from lignin models and depolymerized native lignin sourced from the reductive catalytic fractionation of Pinus radiata wood biomass. After mechanistic studies based on NMR characterization, an alternative ROCOP-style mechanism was proposed. This was found to be (1) contributing to the acceleration of the observed reaction rates with added [PPNCl] organo-catalyst and (2) 'self-initiation/self-promoted' ROCOP without any added external [PPNCl] catalyst, likely due to the presence of inherent [OH] groups/ species in the lignin-derived glycidyl ether monomer promoting reactivity. As a final goal, the potential of these lignin-derived polyesters as intermediate polyols was demonstrated by applying them in the synthesis of polyurethane (PU) film materials with a high biomass content of 75–79%. A dramatic range of thermomechanical properties was observed for the resulting materials, demonstrating how the ROCOP reaction can be used to tailor the properties of the functional polyester and PU material based on the nature of the epoxide and anhydride substrates used. These findings help endeavors towards predicting the relationship between chemical structure and material thermomechanical properties and performance, relevant for industrial applications. Overall, this study demonstrated the proof of concept that PU materials can be prepared from lignocellulosic biomass utilizing industrially feasible ROCOP of bio-derived cyclic anhydrides and epoxides. [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.) | |
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| Header | DbId: egs DbLabel: Engineering Source An: 188955706 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: An Integrated Biorefinery Proof of Concept: The Synthesis of Fully Bio-Based, Functional Lignin Polyester Copolymers of Cyclic Anhydrides and Epoxides Towards Polyol Applications and Tunable Bio-Derived Materials. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Driscoll%2C+Oliver+J%2E%22">Driscoll, Oliver J.</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22van+de+Pas%2C+Daniel+J%2E%22">van de Pas, Daniel J.</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Torr%2C+Kirk+M%2E%22">Torr, Kirk M.</searchLink><relatesTo>2,3</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Thomas%2C+Hayden+P%2E%22">Thomas, Hayden P.</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Vendamme%2C+Richard%22">Vendamme, Richard</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Feghali%2C+Elias%22">Feghali, Elias</searchLink><relatesTo>1,3</relatesTo> (AUTHOR) – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Polymers+%2820734360%29%22">Polymers (20734360)</searchLink>. Oct2025, Vol. 17 Issue 20, p2806. 23p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Lignins%22">Lignins</searchLink><br /><searchLink fieldCode="DE" term="%22Polyols%22">Polyols</searchLink><br /><searchLink fieldCode="DE" term="%22Copolymerization%22">Copolymerization</searchLink><br /><searchLink fieldCode="DE" term="%22Polyesters%22">Polyesters</searchLink><br /><searchLink fieldCode="DE" term="%22Botanical+chemistry%22">Botanical chemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Thermophysical+properties%22">Thermophysical properties</searchLink><br /><searchLink fieldCode="DE" term="%22Biomaterials%22">Biomaterials</searchLink><br /><searchLink fieldCode="DE" term="%22Biomass%22">Biomass</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: A versatile, sustainable feedstock pathway to bio-based polymeric materials was developed utilizing lignin biomass and the ring-opening copolymerization (ROCOP) of cyclic anhydrides and epoxides to synthesize functional, lignin-derived, fully bio-based polyester polyols. The initial goal was to make the ROCOP reaction more applicable to bio-derived starting materials and more attractive to commercialization by conducting the polymerization under less constrained and industrially relevant conditions in air and without the extensive purification of reagents, catalysts, or solvents, typically used in the literature. A refined ROCOP system was applied as a powerful tool in lignin valorization by successfully synthesizing the lignin-derived copolyester prepolymers from lignin models and depolymerized native lignin sourced from the reductive catalytic fractionation of Pinus radiata wood biomass. After mechanistic studies based on NMR characterization, an alternative ROCOP-style mechanism was proposed. This was found to be (1) contributing to the acceleration of the observed reaction rates with added [PPNCl] organo-catalyst and (2) 'self-initiation/self-promoted' ROCOP without any added external [PPNCl] catalyst, likely due to the presence of inherent [OH] groups/ species in the lignin-derived glycidyl ether monomer promoting reactivity. As a final goal, the potential of these lignin-derived polyesters as intermediate polyols was demonstrated by applying them in the synthesis of polyurethane (PU) film materials with a high biomass content of 75–79%. A dramatic range of thermomechanical properties was observed for the resulting materials, demonstrating how the ROCOP reaction can be used to tailor the properties of the functional polyester and PU material based on the nature of the epoxide and anhydride substrates used. These findings help endeavors towards predicting the relationship between chemical structure and material thermomechanical properties and performance, relevant for industrial applications. Overall, this study demonstrated the proof of concept that PU materials can be prepared from lignocellulosic biomass utilizing industrially feasible ROCOP of bio-derived cyclic anhydrides and epoxides. [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.) |
| PLink | https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=egs&AN=188955706 |
| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.3390/polym17202806 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 23 StartPage: 2806 Subjects: – SubjectFull: Lignins Type: general – SubjectFull: Polyols Type: general – SubjectFull: Copolymerization Type: general – SubjectFull: Polyesters Type: general – SubjectFull: Botanical chemistry Type: general – SubjectFull: Thermophysical properties Type: general – SubjectFull: Biomaterials Type: general – SubjectFull: Biomass Type: general Titles: – TitleFull: An Integrated Biorefinery Proof of Concept: The Synthesis of Fully Bio-Based, Functional Lignin Polyester Copolymers of Cyclic Anhydrides and Epoxides Towards Polyol Applications and Tunable Bio-Derived Materials. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Driscoll, Oliver J. – PersonEntity: Name: NameFull: van de Pas, Daniel J. – PersonEntity: Name: NameFull: Torr, Kirk M. – PersonEntity: Name: NameFull: Thomas, Hayden P. – PersonEntity: Name: NameFull: Vendamme, Richard – PersonEntity: Name: NameFull: Feghali, Elias IsPartOfRelationships: – BibEntity: Dates: – D: 15 M: 10 Text: Oct2025 Type: published Y: 2025 Identifiers: – Type: issn-print Value: 20734360 Numbering: – Type: volume Value: 17 – Type: issue Value: 20 Titles: – TitleFull: Polymers (20734360) Type: main |
| ResultId | 1 |
