Domain-Specific Functionalization of Cellulose Fibers via Itaconic Anhydride-Mediated Esterification

Domain-Specific Functionalization of Cellulose Fibers via Itaconic Anhydride-Mediated Esterification | 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 Domain-Specific Functionalization of Cellulose Fibers via Itaconic Anhydride-Mediated Esterification Jelka Feldhusen, Per Tomas Larsson, Kent Malmgren, Gunnar Westman This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7258650/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 24 Mar, 2026 Read the published version in Cellulose → Version 1 posted 4 You are reading this latest preprint version Abstract Softwood kraft pulp is known to produce one of the strongest papers, with main application areas in high-quality paper, tissue, packaging, and specialty papers. These tailored applications often crave chemical modification of the fibers to optimize their inherent properties. This paper presents two scalable methodologies, gas phase reactions and kneading reactions, for the esterification of bleached kraft pulp (BKP) with itaconic anhydride (ITA). Itaconic anhydride is bioderived with a structure similar to succinic or maleic anhydride, two commonly used chemicals for modifying pulps to introduce charge groups. Although similar, itaconic derivatives also contain an exocyclic, out-of-chain unsaturation, which is useful for additional chemical modifications, such as Michael additions and polymerization reactions. The modification of BKP was performed on never-dried and water-free pulp, aiming to produce highly charged fibers while preserving the overall fiber structure and thereby their intrinsic properties. The reaction yields were investigated by varying molar ratio, temperature, and reaction time, and the modified fibers were characterized using ATR-FTIR, solid state CP/MAS 13 C-NMR, PXRD, titration techniques, and water retention values. The different modification methods showed differences in the spatial distribution of the substituents, preferably modifying the fiber surface or the fiber wall interior. In general terms, modifications facilitated through kneading showed a higher degree of modification of the fiber wall interior, whilst gas-phase mediated reactions preferentially modified the fiber surface. This allows for tailoring the location of the modification, decorating the fibers within or on the surface, and opening routes for a customizable pulp. Full Text Additional Declarations No competing interests reported. Supplementary Files SICelluloseEsterificationBKP.docx Cite Share Download PDF Status: Published Journal Publication published 24 Mar, 2026 Read the published version in Cellulose → Version 1 posted Editorial decision: Revision requested 22 Aug, 2025 Editor assigned by journal 22 Aug, 2025 Submission checks completed at journal 02 Aug, 2025 First submitted to journal 31 Jul, 2025 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-7258650","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":504398140,"identity":"45a1ed8a-a000-40a7-88a8-594973da2217","order_by":0,"name":"Jelka Feldhusen","email":"","orcid":"","institution":"Chalmers University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Jelka","middleName":"","lastName":"Feldhusen","suffix":""},{"id":504398141,"identity":"e75f7223-ba2d-4be6-aeaa-ae7f9e78e6e9","order_by":1,"name":"Per Tomas Larsson","email":"","orcid":"","institution":"KTH Royal Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Per","middleName":"Tomas","lastName":"Larsson","suffix":""},{"id":504398142,"identity":"970fcac8-d3d6-45d8-b853-32646b627fa2","order_by":2,"name":"Kent Malmgren","email":"","orcid":"","institution":"SCA","correspondingAuthor":false,"prefix":"","firstName":"Kent","middleName":"","lastName":"Malmgren","suffix":""},{"id":504398143,"identity":"29b7e2b5-d89b-48d5-89bc-acc1f920ef9c","order_by":3,"name":"Gunnar Westman","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA2UlEQVRIie2QMQrCQBBFJ42VkHZt9AobBNtcZWxMMwuCjUWKwELstA14Cb2BOBCbgG0K0ahgWkGwFLdXVu0s9hVT/cf/DIDD8ce0QYC3+jbtJeZ0jQK/Kf3ka0VuJvWpjHfRbK6rdTneh+CzXZVFEWjKLyrb5ZKpGJm6AVqVXkmepgarhUDJKkUE0ZR25VAfNT04kiK6snqgGba9fmiBQKuUUQoyLQmaZ5DVgLCgYK6mHGQlDZly7KdiYB/WmmyqG92542fR8kwxhr7Plb3mhcaPeYfD4XC84Qlj3U8By4MNEgAAAABJRU5ErkJggg==","orcid":"","institution":"Chalmers University of Technology","correspondingAuthor":true,"prefix":"","firstName":"Gunnar","middleName":"","lastName":"Westman","suffix":""}],"badges":[],"createdAt":"2025-07-31 06:23:29","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-7258650/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-7258650/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s10570-026-07011-5","type":"published","date":"2026-03-24T16:09:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":105754925,"identity":"dc9c88cf-9ff6-4228-b924-0fd5e6a60ecc","added_by":"auto","created_at":"2026-03-30 16:23:08","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1310280,"visible":true,"origin":"","legend":"","description":"","filename":"CelluloseEsterificationBKP.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7258650/v1_covered_46eb08e8-bbb6-4258-ad36-69d75d0408f8.pdf"},{"id":93656623,"identity":"e312d44d-a1ed-4243-b6c4-8f627d6204fd","added_by":"auto","created_at":"2025-10-16 07:14:28","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":1136134,"visible":true,"origin":"","legend":"","description":"","filename":"SICelluloseEsterificationBKP.docx","url":"https://assets-eu.researchsquare.com/files/rs-7258650/v1/b31b97b9686e17886484d853.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Domain-Specific Functionalization of Cellulose Fibers via Itaconic Anhydride-Mediated Esterification","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"cellulose","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"cels","sideBox":"Learn more about [Cellulose](https://www.springer.com/journal/10570)","snPcode":"10570","submissionUrl":"https://submission.nature.com/new-submission/10570/3","title":"Cellulose","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-7258650/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7258650/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eSoftwood kraft pulp is known to produce one of the strongest papers, with main application areas in high-quality paper, tissue, packaging, and specialty papers. These tailored applications often crave chemical modification of the fibers to optimize their inherent properties. This paper presents two scalable methodologies, gas phase reactions and kneading reactions, for the esterification of bleached kraft pulp (BKP) with itaconic anhydride (ITA). Itaconic anhydride is bioderived with a structure similar to succinic or maleic anhydride, two commonly used chemicals for modifying pulps to introduce charge groups. Although similar, itaconic derivatives also contain an exocyclic, out-of-chain unsaturation, which is useful for additional chemical modifications, such as Michael additions and polymerization reactions. The modification of BKP was performed on never-dried and water-free pulp, aiming to produce highly charged fibers while preserving the overall fiber structure and thereby their intrinsic properties. The reaction yields were investigated by varying molar ratio, temperature, and reaction time, and the modified fibers were characterized using ATR-FTIR, solid state CP/MAS \u003csup\u003e13\u003c/sup\u003eC-NMR, PXRD, titration techniques, and water retention values. The different modification methods showed differences in the spatial distribution of the substituents, preferably modifying the fiber surface or the fiber wall interior. In general terms, modifications facilitated through kneading showed a higher degree of modification of the fiber wall interior, whilst gas-phase mediated reactions preferentially modified the fiber surface. 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