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Self-Catalyzed Hydrolysis of Nitrile-Containing RAFT Chain-Transfer Agent and Its Impact upon Polymerization Control of Methacrylic Monomers
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Centres, Wallenberg Wood Science Center. (FibRe – Centre for Lignocellulose-based Thermoplastics)ORCID iD: 0000-0002-4639-4864
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Centres, Wallenberg Wood Science Center. (FibRe – Centre for Lignocellulose-based Thermoplastics)
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Coating Technology. KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Centres, Wallenberg Wood Science Center. (FibRe – Centre for Lignocellulose-based Thermoplastics)ORCID iD: 0000-0002-8348-2273
2024 (English)In: ACS Macro Letters, E-ISSN 2161-1653, Vol. 13, no 5, p. 565-570Article in journal (Refereed) Published
Abstract [en]

Self-catalyzed hydrolysis upon storage of the common RAFT chain-transfer agent (CTA) 4-cyano-4-[(thiothiopropyl)sulfanyl] pentanoic acid (CTPPA) is confirmed, where the nitrile group is transformed into an amide by catalysis from the adjacent carboxylic acid moiety. The amide-CTA (APP) is found to poorly control molecular weight evolution during polymerization of two methacrylates, methyl methacrylate (MMA) and N,N-(dimethylamino)ethyl methacrylate (DMAEMA), likely due to poor reinitiation speed in the pre-equilibrium. However, when attached to a macromolecule, the impact of this amide moiety becomes insignificant and chain extension proceeds as expected with CTPPA. In light of CTPPA and similarly hydrolyzable CTAs being extensively employed for aqueous polymerizations of methacrylates, these findings highlight the importance of CTA purity when performing RAFT polymerizations.

Place, publisher, year, edition, pages
American Chemical Society (ACS) , 2024. Vol. 13, no 5, p. 565-570
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-347156DOI: 10.1021/acsmacrolett.4c00112ISI: 001228810900001PubMedID: 38636106Scopus ID: 2-s2.0-85191070237OAI: oai:DiVA.org:kth-347156DiVA, id: diva2:1864829
Note

QC 20240604

Available from: 2024-06-04 Created: 2024-06-04 Last updated: 2025-05-07Bibliographically approved
In thesis
1. Assembly of Colloidal Nanoparticles and Cellulose Nanofibrils: Nanoscopic Structures Control Bulk Properties
Open this publication in new window or tab >>Assembly of Colloidal Nanoparticles and Cellulose Nanofibrils: Nanoscopic Structures Control Bulk Properties
2025 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The need for sustainable, high-performance materials is growing rapidly as society moves away from fossil-based resources. This thesis explores how materials derived from renewable sources—cellulose nanofibrils (CNFs) extracted from wood—can be combined with synthetic polymer nanoparticles to create functional, sustainable materials with tunable properties.

Polymeric nanoparticles were synthesized using polymerization-induced self-assembly (PISA), which allows precise control over particle features such as size and surface chemistry. The nanoparticles were combined with CNFs to create hybrid materials. The thesis investigates how the size, charge, and amount of nanoparticles influence the structure, mechanical behavior, and deformation mechanisms of CNF-based materials.

Advanced characterization techniques such as small- and wide-angle X-ray scattering were used to understand how nanoparticles impact material structures to gain new insights into structure-property relationships and deformation mechanisms. The results show that by carefully tuning the interactions between components, it is possible to design new bio-based materials with tailored mechanical properties.

This work contributes to the broader effort of developing environmentally friendly alternatives to conventional plastics and composites, offering insights into how nanostructure and surface chemistry can be used to control material performance. 

Abstract [sv]

Behovet av hållbara, högpresterande material växer snabbt i takt med att samhället rör sig bort ifrån fossilbaserade resurser. Denna avhandling undersöker hur material från förnybara källor - cellulosa nanofibriller (CNF) extraherade från trä - kan kombineras med syntetiska polymera nanopartiklar för att skapa funktionella, hållbara material med skräddarsydda egenskaper.

Polymera nanopartiklar syntetiserades med ’polymerization-induced self-assembly’ (PISA); en metod som möjliggör kontroll över partikelegenskaper som storlek och ytkemi. Nanopartiklarna kombinerades med CNF för att skapa hybridmaterial. Avhandlingen undersöker hur storleken, laddningen och mängden av nanopartiklar påverkar strukturen, det mekaniska beteendet och deformationsmekanismerna hos CNF-baserade material.

Avancerade tekniker som röntgenspridning användes för att förstå hur nanopartiklar påverkar materialstrukturer för att få nya insikter om struktur-egenskapsförhållanden och deformationsmekanismer. Resultaten visar att det är möjligt att, genom skräddarsydda interaktioner mellan komponenter, designa nya biobaserade material med skräddarsydda mekaniska egenskaper.

Denna avhandling bidrar till det bredare arbetet med att utveckla miljövänliga alternativ till konventionella plaster och kompositer, vilket ger insikter i hur nanostruktur och ytkemi kan användas för att styra materialprestanda.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2025. p. 99
Series
TRITA-CBH-FOU ; 2025:13
Keywords
Cellulose nanofibrils, polymeric nanoparticles, nanostructured materials, Cellulosa nanofibriller, polymera nanopartiklar, nanostrukturerade material
National Category
Polymer Technologies
Research subject
Fibre and Polymer Science
Identifiers
urn:nbn:se:kth:diva-363072 (URN)978-91-8106-276-2 (ISBN)
Public defence
2025-06-05, F3, Lindstedtvägen 26, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20250512

Embargo till 2026-06-05 godkänt av skolchef Amelie Eriksson Karlström via e-post 2025-05-09

Available from: 2025-05-12 Created: 2025-05-07 Last updated: 2026-01-28Bibliographically approved

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Jerlhagen, ÅsaWilson, Olivia R.Malmström, Eva

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