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Swelling of cellulose stimulates etherification
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Wood Chemistry and Pulp Technology. KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Centres, Wallenberg Wood Science Center.
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Centres, Wallenberg Wood Science Center. KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Wood Chemistry and Pulp Technology.ORCID iD: 0000-0003-3858-8324
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Centres, Wallenberg Wood Science Center. KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Wood Chemistry and Pulp Technology.ORCID iD: 0000-0001-8817-2031
2025 (English)In: Holzforschung, ISSN 0018-3830, E-ISSN 1437-434X, Vol. 79, no 9, p. 445-452Article in journal (Refereed) Published
Abstract [en]

Cellulose has inherent properties that are both hydrophilic and water-insoluble, which can create challenges in certain technical applications. One solution to these challenges is derivatization, however, the crystalline structure of cellulose limits its chemical reactivity. This study explores the reactivity of highly swollen cellulose produced by dissolving and reprecipitating microcrystalline cellulose. This extreme swelling of cellulose is expected to increase the accessibility and reactivity, however, upon drying the cellulose becomes hard and inflexible a phenomenon known as hornification. Different drying methods were used to overcome the problems of hornification, including freeze-drying, acetone-drying, and drying with glycerol as a spacer. The samples were carboxymethylated and the degree of substitution (DS) was used to assess reactivity, with freeze-dried samples showing the highest DS. The findings suggest that preserving the swollen structure through appropriate drying methods enhances cellulose reactivity, offering potential improvements in industrial cellulose ether production.

Place, publisher, year, edition, pages
Walter de Gruyter GmbH , 2025. Vol. 79, no 9, p. 445-452
Keywords [en]
carboxymethyl cellulose, cellulose derivative, hornification, swelling
National Category
Paper, Pulp and Fiber Technology
Identifiers
URN: urn:nbn:se:kth:diva-366166DOI: 10.1515/hf-2025-0013ISI: 001494808000001Scopus ID: 2-s2.0-105006682645OAI: oai:DiVA.org:kth-366166DiVA, id: diva2:1981545
Note

QC 20260120

Available from: 2025-07-04 Created: 2025-07-04 Last updated: 2026-05-12Bibliographically approved
In thesis
1. Cellulose Accessibility and Reactivity after Cold-Alkali Swelling
Open this publication in new window or tab >>Cellulose Accessibility and Reactivity after Cold-Alkali Swelling
2026 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Increasing cellulose accessibility and reactivity can expand its use beyond paper products, facilitating the development of high‑performance derivatives and regenerated cellulose, as well as efficient pathways for degrading cellulose to glucose. Structurally, cellulose consists of β‑1,4‑linked D‑glucopyranoside units, each of which contains three available hydroxyl groups. However, these hydroxyl groups are not fully accessible due to cellulose’s crystalline structure. This limits reactivity, which is a key parameter not only for derivatization but also for regeneration and efficient degradation. Swelling or partial dissolution of cellulose in sodium hydroxide followed by reprecipitation has been shown to disrupt the ordered structure and increase the exposure of reactive sites. Yet the swollen material retains large amounts of water, and upon drying, it is susceptible to hornification, which reduces its ability to reswell and lowers its reactivity. This thesis explores a cold‑alkali swelling method designed to increase the reactivity across a wide range of feedstocks. A proof-of-concept with microcrystalline cellulose established strategies to mitigate hornification while preserving the swollen structure after drying. The method was then applied to paper‑grade pulps and recycled textile waste, demonstrating that these lower‑grade materials can be upcycled into more reactive cellulose suitable for derivatization, regeneration, and cellulose degradation.

Abstract [sv]

Ökad tillgänglighet och reaktivitet hos cellulosa kan bredda dess användningsområden bortom pappersprodukter och därmed främja utvecklingen av högpresterande derivat och regenererad cellulosa samt effektivisera nedbrytning till glukos. Cellulosa består av D-glukosenheter som är bundna med en β‑1,4‑glykosidbindning, där varje enhet har tre hydroxylgrupper som kan modifieras kemiskt. Tillgängligheten hos dessa grupper begränsas dock av cellulosans kristallina struktur. Detta kan begränsa reaktiviteten, som är en central parameter inte bara för derivatisering utan även för regenerering och effektiv nedbrytning. Svällning eller delvis upplösning av cellulosa i natriumhydroxid, följt av fällning, har visats leda till störningar i den ordnade strukturen och ökad exponering av reaktiva grupper. Det svällda materialet håller dock stora mängder vatten och vid torkning uppstår förhorningseffekter, vilket minskar dess förmåga att återsvälla och sänker reaktiviteten. Den här avhandlingen undersöker en kall alkalisk svällningsmetod som syftar till att öka reaktiviteten hos olika typer av cellulosabaserade råmaterial. Med mikrokristallin cellulosa som modellsystem kunde strategier identifieras för att motverka förhorning och bevara den svällda strukturen vid torkning. Svällningsmetoden tillämpades därefter på pappersmassor och återvunnet textilavfall, vilket visade att dess lägre kvaliteter kan uppgraderas till mer reaktiv cellulosa lämpad för derivatisering, regenerering eller nedbrytning.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2026. p. 83
Series
TRITA-CBH-FOU ; 2026:24
Keywords
cellulose, chemical derivatization, hornification, reactivity, swelling, cellulosa, förhorning, kemisk modifiering, reaktivitet, svällning
National Category
Paper, Pulp and Fiber Technology
Research subject
Fibre and Polymer Science
Identifiers
urn:nbn:se:kth:diva-380534 (URN)978-91-8106-630-2 (ISBN)
Public defence
2026-06-12, F3, Lindstedtsvägen 26, https://kth-se.zoom.us/j/63490364213, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Knut and Alice Wallenberg Foundation, WWSC 3.0: KAW 2021.0313
Note

QC 20260513

Available from: 2026-05-13 Created: 2026-05-12 Last updated: 2026-05-25Bibliographically approved

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von Schreeb, AntoniaEk, MonicaHenriksson, Gunnar

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