Circularity of non-isocyanate polyurethanes: Small-molecule recovery from linear and network polyhydroxyurethanes via transcarbamoylation

Circularity of non-isocyanate polyurethanes: Small-molecule recovery from linear and network polyhydroxyurethanes via transcarbamoylation | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Circularity of non-isocyanate polyurethanes: Small-molecule recovery from linear and network polyhydroxyurethanes via transcarbamoylation Yixuan Chen, Marcus LaPorte, John M. Torkelson This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4462808/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 26 Aug, 2024 Read the published version in Journal of Polymer Research → Version 1 posted 5 You are reading this latest preprint version Abstract We report the first demonstration of small-molecule recovery from polyhydroxyurethane (PHU) harnessing transcarbamoylation dynamic chemistry. We prepared linear and network PHUs by reacting a difunctional amine with a difunctional or trifunctional 5-member cyclic carbonate, respectively, with the cyclic carbonates synthesized from CO2 fixation of the corresponding epoxies. Under a mild condition using a base catalyst and methanol (MeOH), we depolymerized linear and network PHUs, recovering carbamate small molecules by leveraging the exchange reaction between urethane groups on the PHU backbone and MeOH, which is transcarbamoylation. We conducted a screening of depolymerization conditions, with a stronger base catalyst tert-butoxide, a higher temperature of 80 °C, and the use of a binary solvent system tetrahydrofuran/MeOH leading to the highest carbamate yield of 45 mol% from linear PHU. We also explored two greener solvents, water and ethanol (EtOH), as replacements for MeOH, with water leading to virtually no depolymerization and EtOH resulting in less than 5 mol% carbamate yield from linear PHU. For network PHU, the optimal condition led to a 15 mol% carbamate yield. These relatively low small-molecule yields are attributed to the abundant hydroxyl groups on the PHU backbone competing with urethane groups for binding the base catalysts, thereby reducing catalyst efficiency. Although further improvement on our small-molecule recovery method is desired, this first study highlights the potential of transcarbamoylation, an inherent dynamic chemistry of PHU, to contribute significantly to end-of-life recycling of all PHU materials. Full Text Cite Share Download PDF Status: Published Journal Publication published 26 Aug, 2024 Read the published version in Journal of Polymer Research → Version 1 posted Reviewers agreed at journal 12 Jun, 2024 Reviewers invited by journal 11 Jun, 2024 Editor invited by journal 03 Jun, 2024 Editor assigned by journal 23 May, 2024 First submitted to journal 22 May, 2024 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4462808","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":313340985,"identity":"f7dc28af-828a-4151-a2a4-113a2128aa8a","order_by":0,"name":"Yixuan Chen","email":"","orcid":"","institution":"","correspondingAuthor":false,"prefix":"","firstName":"Yixuan","middleName":"","lastName":"Chen","suffix":""},{"id":313340986,"identity":"29edc103-6d08-4b96-88ae-c373230b07d2","order_by":1,"name":"Marcus LaPorte","email":"","orcid":"","institution":"","correspondingAuthor":false,"prefix":"","firstName":"Marcus","middleName":"","lastName":"LaPorte","suffix":""},{"id":313340987,"identity":"3146b7e1-ddda-4188-8d69-c7fef6f9925d","order_by":2,"name":"John M. 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We prepared linear and network PHUs by reacting a difunctional amine with a difunctional or trifunctional 5-member cyclic carbonate, respectively, with the cyclic carbonates synthesized from CO2 fixation of the corresponding epoxies. Under a mild condition using a base catalyst and methanol (MeOH), we depolymerized linear and network PHUs, recovering carbamate small molecules by leveraging the exchange reaction between urethane groups on the PHU backbone and MeOH, which is transcarbamoylation. We conducted a screening of depolymerization conditions, with a stronger base catalyst tert-butoxide, a higher temperature of 80 °C, and the use of a binary solvent system tetrahydrofuran/MeOH leading to the highest carbamate yield of 45 mol% from linear PHU. We also explored two greener solvents, water and ethanol (EtOH), as replacements for MeOH, with water leading to virtually no depolymerization and EtOH resulting in less than 5 mol% carbamate yield from linear PHU. For network PHU, the optimal condition led to a 15 mol% carbamate yield. These relatively low small-molecule yields are attributed to the abundant hydroxyl groups on the PHU backbone competing with urethane groups for binding the base catalysts, thereby reducing catalyst efficiency. 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