Hydrolyzable Bio‐Based Bisphenols Enabled by the Tishchenko Reaction for Polyurethane Vitrimers with Closed‐Loop Recyclability
Abstract Polyurethane (PU) is a cornerstone of modern materials science, yet its reliance on petroleum‐based precursors and the limited recyclability of conventional formulations pose significant environmental challenges. In this study, a fully bio‐based polyurethane vitrimer system is developed ena...
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Wiley
2025-07-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202503152 |
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| author | Jiewen Wang Hongru Qiang Rong Huang Dan Zhao Zihan Tong Zhen Fan Jianzhong Du Yunqing Zhu |
| author_facet | Jiewen Wang Hongru Qiang Rong Huang Dan Zhao Zihan Tong Zhen Fan Jianzhong Du Yunqing Zhu |
| author_sort | Jiewen Wang |
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| description | Abstract Polyurethane (PU) is a cornerstone of modern materials science, yet its reliance on petroleum‐based precursors and the limited recyclability of conventional formulations pose significant environmental challenges. In this study, a fully bio‐based polyurethane vitrimer system is developed enabled by a dual‐function SmI2‐mediated strategy that integrates Tishchenko coupling and phenol deprotection in a single step, simplifying the synthesis of bio‐based bisphenols with 100% atom utilization. These bisphenols introduce hydrolyzable ester bonds, allowing for complete degradation within ≈3 d (representative model), providing an efficient and eco‐friendly end‐of‐life solution. This approach offers a sustainable alternative to conventional bisphenol A (BPA). Moreover, by leveraging the electronic effects of bio‐based bisphenols, the dissociation temperature of phenol‐carbamate bonds can be widely tuned (≈70–120 °C), endowing the resulting Covalent Adaptable Network (CAN) PUs with excellent reprocessability, closed‐loop recyclability, and reconfigurable shape memory capability. Furthermore, the aromatic and ester‐rich structure enhances thermomechanical performance, yielding tensile strengths up to 33 MPa, elongations at break exceeding 400%, and toughness reaching 30 MJ m−3, surpassing most sustainable PUs. This work pioneers a scalable and fully bio‐based PU vitrimer platform with tunable performance, recyclability, and sustainable degradability, offering a compelling alternative to traditional thermosets and thermoplastics for next‐generation green materials. |
| format | Article |
| id | doaj-art-1d3f3c481f854b7bb205b78e1ad29343 |
| institution | Kabale University |
| issn | 2198-3844 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Wiley |
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| series | Advanced Science |
| spelling | doaj-art-1d3f3c481f854b7bb205b78e1ad293432025-08-20T04:01:01ZengWileyAdvanced Science2198-38442025-07-011226n/an/a10.1002/advs.202503152Hydrolyzable Bio‐Based Bisphenols Enabled by the Tishchenko Reaction for Polyurethane Vitrimers with Closed‐Loop RecyclabilityJiewen Wang0Hongru Qiang1Rong Huang2Dan Zhao3Zihan Tong4Zhen Fan5Jianzhong Du6Yunqing Zhu7Department of Polymeric Materials School of Materials Science and Engineering Tongji University Shanghai 201804 P. R. ChinaDepartment of Polymeric Materials School of Materials Science and Engineering Tongji University Shanghai 201804 P. R. ChinaDepartment of Polymeric Materials School of Materials Science and Engineering Tongji University Shanghai 201804 P. R. ChinaDepartment of Polymeric Materials School of Materials Science and Engineering Tongji University Shanghai 201804 P. R. ChinaDepartment of Polymeric Materials School of Materials Science and Engineering Tongji University Shanghai 201804 P. R. ChinaDepartment of Polymeric Materials School of Materials Science and Engineering Tongji University Shanghai 201804 P. R. ChinaDepartment of Gynaecology and Obstetrics Shanghai Key Laboratory of Anesthesiology and Brain Functional Modulation Clinical Research Center for Anesthesiology and Perioperative Medicine Translational Research Institute of Brain and Brain‐Like Intelligence Shanghai Fourth People's Hospital School of Medicine Tongji University Shanghai 200434 P. R. ChinaDepartment of Polymeric Materials School of Materials Science and Engineering Tongji University Shanghai 201804 P. R. ChinaAbstract Polyurethane (PU) is a cornerstone of modern materials science, yet its reliance on petroleum‐based precursors and the limited recyclability of conventional formulations pose significant environmental challenges. In this study, a fully bio‐based polyurethane vitrimer system is developed enabled by a dual‐function SmI2‐mediated strategy that integrates Tishchenko coupling and phenol deprotection in a single step, simplifying the synthesis of bio‐based bisphenols with 100% atom utilization. These bisphenols introduce hydrolyzable ester bonds, allowing for complete degradation within ≈3 d (representative model), providing an efficient and eco‐friendly end‐of‐life solution. This approach offers a sustainable alternative to conventional bisphenol A (BPA). Moreover, by leveraging the electronic effects of bio‐based bisphenols, the dissociation temperature of phenol‐carbamate bonds can be widely tuned (≈70–120 °C), endowing the resulting Covalent Adaptable Network (CAN) PUs with excellent reprocessability, closed‐loop recyclability, and reconfigurable shape memory capability. Furthermore, the aromatic and ester‐rich structure enhances thermomechanical performance, yielding tensile strengths up to 33 MPa, elongations at break exceeding 400%, and toughness reaching 30 MJ m−3, surpassing most sustainable PUs. This work pioneers a scalable and fully bio‐based PU vitrimer platform with tunable performance, recyclability, and sustainable degradability, offering a compelling alternative to traditional thermosets and thermoplastics for next‐generation green materials.https://doi.org/10.1002/advs.202503152biobased bisphenolsclosed‐loop recyclabilitygreen chemistryrenewable resourcesvitrimer |
| spellingShingle | Jiewen Wang Hongru Qiang Rong Huang Dan Zhao Zihan Tong Zhen Fan Jianzhong Du Yunqing Zhu Hydrolyzable Bio‐Based Bisphenols Enabled by the Tishchenko Reaction for Polyurethane Vitrimers with Closed‐Loop Recyclability Advanced Science biobased bisphenols closed‐loop recyclability green chemistry renewable resources vitrimer |
| title | Hydrolyzable Bio‐Based Bisphenols Enabled by the Tishchenko Reaction for Polyurethane Vitrimers with Closed‐Loop Recyclability |
| title_full | Hydrolyzable Bio‐Based Bisphenols Enabled by the Tishchenko Reaction for Polyurethane Vitrimers with Closed‐Loop Recyclability |
| title_fullStr | Hydrolyzable Bio‐Based Bisphenols Enabled by the Tishchenko Reaction for Polyurethane Vitrimers with Closed‐Loop Recyclability |
| title_full_unstemmed | Hydrolyzable Bio‐Based Bisphenols Enabled by the Tishchenko Reaction for Polyurethane Vitrimers with Closed‐Loop Recyclability |
| title_short | Hydrolyzable Bio‐Based Bisphenols Enabled by the Tishchenko Reaction for Polyurethane Vitrimers with Closed‐Loop Recyclability |
| title_sort | hydrolyzable bio based bisphenols enabled by the tishchenko reaction for polyurethane vitrimers with closed loop recyclability |
| topic | biobased bisphenols closed‐loop recyclability green chemistry renewable resources vitrimer |
| url | https://doi.org/10.1002/advs.202503152 |
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