kth.sePublications
Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Nanolatexes: a versatile toolbox for cellulose modification
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. (Eva Malmström)ORCID iD: 0000-0001-8317-3529
2023 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Cellulosic materials are widely used in our everyday lives, ranging from paperand packaging to biomedical applications. However, in most applications, cellulose must coexist with hydrophobic polymers which can be challenging due to its hydrophilic character. This has encouraged the exploration of chemical and physical modifications of cellulose.

The projects included in this thesis focus on the physical modification of cellulosic materials with tailor-made, highly versatile colloidal nanoparticles synthesized in water, called nanolatexes. Their synthesis is based on the combination of the reversible addition-fragmentation chain transfer (RAFT) polymerization with polymerization-induced self-assembly (PISA). The bridging of these techniques results in the formation of amphiphilic diblock copolymers which self-assemble in water forming a variety of morphologies. Spheres, worms and vesicles with pH-responsive shell polymers were prepared to investigate the parameters that tune these morphological transitions. Less investigated parameters such as the chemical composition of the RAFT agent were studied which resulted in the formation of bimodal nanolatexes with opal-like characteristics in a reproducible manner. 

A fundamental investigation of the parameters that govern the adsorption of cationically charged nanolatexes onto silica and regenerated TEMPO-oxidized cellulose model surfaces was also performed. The combination of gravimetric and a reflectometric techniques revealed the complexity of that model surface. Both the size and the charge density of the nanolatexes were found to influence their adsorption. The information gained from this study was implemented in the preparation of cellulose nanofibril (CNF)-nanocomposites with low contents of nanolatexes. It was found that when the nanolatex content was below 1 wt% the mechanical profile of the CNF-nanocomposites was improved. 

Finally, wood-based components were used to replace fossil-based monomers in nanolatexes. They were readily adsorbed onto cellulose filter papers and annealed, thus demonstrating their film formation capacity. Nanolatexes comprised of a wood-based shell polymer have a promising high-end application profile, as showcased by their interactions with Cu(II) ions, where nanolatexes prevented the formation of Cu(II) ion aggregates. 

The results summarized in this thesis add to the understanding on physical modification of cellulose and are envisaged to further promote the utilization of wood-based monomers in the production of the polymers for high-end applications.

Abstract [sv]

Cellulosamaterial används i stor utsträckning i vår vardag, i allt från papper och förpackningar till biomedicinska tillämpningar. Men i de flesta tillämpningar måste cellulosa samexistera med hydrofoba polymerer, vilket kan vara utmanande på grund av cellulosas hydrofila karaktär. Detta har lett till betydande forskning på kemiska och fysikalisk modifiering av cellulosa.

Projekten som ingår i denna avhandling fokuserar på icke-kovalent modifiering av cellulosamaterial med skräddarsydda, mycket mångsidiga kolloidala nanopartiklar syntetiserade i vatten, så kallade nanolatex-partiklar. Syntesen av dem är baserad på kombinationen av reversibel addition-fragmentation chain transfer (RAFT) polymerisation med ”polymerisationsinducerad självorganisering” (PISA). Kombinationen av dessa tekniker resulterar i bildningen av amfifila diblock-sampolymerer som självorganiseras i vatten till att bilda en mängd olika morfologier. Sfärer, worms och vesiklar med pH-känsliga skalpolymerer bereddes för att undersöka vilka reaktionsparametrar som resulterar i övergång mellan olika morfologier. Mindre undersökta parametrar som den kemiska sammansättningen av RAFT-agenten studerades vilket resulterade i bildandet av bimodala nanolatexer med opalliknande egenskaper på ett reproducerbart sätt.

En grundläggande undersökning av parametrarna som styr adsorptionen av katjoniskt laddade nanolatex-partiklar på silika och regenererade cellulosamodellytor (TEMPO-oxiderad cellulosa) genomfördes också. Kombinationen av gravimetriska och reflektometriska tekniker avslöjade komplexiteten hos modellytan. Både storleken och laddningstätheten hos nanolatexarna visade sig påverka deras adsorption. Informationen från denna studie implementerades vid framställningen av cellulosa nanofibril (CNF)-nanokompositer med låga halter av nanolatexer. Det visade sig att när nanolatexhalten var under 1 viktprocent förbättrades den mekaniska egenskapsprofilen för CNF-nanokompositerna. 

Slutligen användes träbaserade komponenter för att ersätta fossilbaserade monomerer i nanolatexer. De adsorberades lätt på filterpapper (cellulosa) och anlöptes vid en temperatur över glasomvandlingstemperaturen, vilket demonstrerade deras filmbildningskapacitet. Nanolatexer som består av en träbaserad skalpolymer har en lovande egenskapsprofil för high-end tillämpningar vilket t ex framgår av deras interaktioner med Cu(II)-joner, där nanolatex-partiklarna förhindrade bildandet av Cu(II)-jonaggregat. 

Resultaten som sammanfattas i denna avhandling bidrar till förståelsen om icke-kovalent modifiering av cellulosa och är också avsedda att ytterligare främja användningen av träbaserade monomerer i produktionen av polymererna för avancerade applikationer.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2023. , p. 48
Series
TRITA-CBH-FOU ; 2023:5
Keywords [en]
nanolatexes, RAFT, PISA, adsorption, cellulose, modification
National Category
Polymer Chemistry
Research subject
Fibre and Polymer Science
Identifiers
URN: urn:nbn:se:kth:diva-324421ISBN: 978-91-8040-490-7 (print)OAI: oai:DiVA.org:kth-324421DiVA, id: diva2:1740459
Public defence
2023-03-24, Kollegiesalen, Brinellvägen 8, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 2023-03-02

Embargo godkänt av skolchef CBH, Amelie Eriksson Karlström, 2023-03-02, via e-mail.

Available from: 2023-03-02 Created: 2023-03-01 Last updated: 2024-03-24Bibliographically approved
List of papers
1. pH-Responsive nanolatexes stabilized by statistical copolymers obtained by RAFT-mediated PISA
Open this publication in new window or tab >>pH-Responsive nanolatexes stabilized by statistical copolymers obtained by RAFT-mediated PISA
(English)Manuscript (preprint) (Other academic)
Keywords
stimulus, responsive, PISA, latex, morphology, vesicles, worms
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-324445 (URN)
Note

QC 20230302

Available from: 2023-03-01 Created: 2023-03-01 Last updated: 2023-03-02Bibliographically approved
2. Bimodal nanolatexes prepared via polymerization-induced self-assembly: losing control in a controlled manner
Open this publication in new window or tab >>Bimodal nanolatexes prepared via polymerization-induced self-assembly: losing control in a controlled manner
(English)Manuscript (preprint) (Other academic)
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-324453 (URN)
Note

QC 20230302

Available from: 2023-03-02 Created: 2023-03-02 Last updated: 2023-03-02Bibliographically approved
3. Nanolatex architectonics: Influence of cationic charge density and size on their adsorption onto surfaces with a 2D or 3D distribution of anionic groups
Open this publication in new window or tab >>Nanolatex architectonics: Influence of cationic charge density and size on their adsorption onto surfaces with a 2D or 3D distribution of anionic groups
Show others...
2023 (English)In: Journal of Colloid and Interface Science, ISSN 0021-9797, E-ISSN 1095-7103, Vol. 634, p. 610-620Article in journal (Refereed) Published
Place, publisher, year, edition, pages
Elsevier BV, 2023
National Category
Chemical Sciences Materials Chemistry
Identifiers
urn:nbn:se:kth:diva-324121 (URN)10.1016/j.jcis.2022.12.038 (DOI)000960700700001 ()36549209 (PubMedID)2-s2.0-85144465921 (Scopus ID)
Funder
Knut and Alice Wallenberg Foundation
Note

QC 20230426

Available from: 2023-02-21 Created: 2023-02-21 Last updated: 2023-04-26Bibliographically approved
4. Modification of CNF‐Networks by the Addition of Small Amounts of Well‐Defined Rigid Cationic Nanolatexes
Open this publication in new window or tab >>Modification of CNF‐Networks by the Addition of Small Amounts of Well‐Defined Rigid Cationic Nanolatexes
Show others...
2022 (English)In: Macromolecular Chemistry and Physics, ISSN 1022-1352, E-ISSN 1521-3935, Vol. 224, no 1, p. 2200249-2200249Article in journal (Refereed) Published
Abstract [en]

Cellulose nanofibril (CNF)-networks are modified by the addition of small amounts (below 10 wt%) of well-defined cationic nanolatexes synthesized through reversible addition–fragmentation chain-transfer-mediated polymerization-induced self-assembly (PISA). Minute amounts of nanolatex inclusions lead to increased tensile and shear moduli, indicating that nanolatexes can act as bridging-points between CNFs. At higher nanolatex content, this stiffening effect is lost, likely due to interactions between nanolatexes leading to plasticization. The influence of nanolatex content and size on interparticle distance is discussed and is used as a tool to understand the effects observed in macroscopic properties. Upon annealing, the stiffening effect is lost due to the softening of the nanolatexes, indicating that the core–shell morphology is a prerequisite for this effect. These systems form a versatile platform to develop fundamental insights into complex condensed colloidal systems, to ultimately aid in the development of new sustainable material concepts.

Place, publisher, year, edition, pages
Wiley, 2022
National Category
Chemical Sciences Materials Chemistry
Identifiers
urn:nbn:se:kth:diva-324128 (URN)10.1002/macp.202200249 (DOI)000896738700001 ()2-s2.0-85144135979 (Scopus ID)
Funder
Swedish Research Council, 2020‐05486
Note

QC 20230228

Available from: 2023-02-21 Created: 2023-02-21 Last updated: 2023-11-30Bibliographically approved
5. Modification of cellulose through physisorption of cationic bio-based nanolatexes - comparing emulsion polymerization and RAFT-mediated polymerization-induced self-assembly
Open this publication in new window or tab >>Modification of cellulose through physisorption of cationic bio-based nanolatexes - comparing emulsion polymerization and RAFT-mediated polymerization-induced self-assembly
Show others...
2021 (English)In: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 23, no 5, p. 2113-2122Article in journal (Refereed) Published
Abstract [en]

The polymerization of a bio-based terpene-derived monomer, sobrerol methacrylate (SobMA), was evaluated in the design of polymeric nanoparticles (nanolatexes). Their synthesis was accomplished by using emulsion polymerization, either by free-radical polymerization in the presence of a cationic surfactant or a cationic macroRAFT agent by employing RAFT-mediated polymerization-induced self-assembly (PISA). By tuning the length of the hydrophobic polymer, it was possible to control the nanoparticle size between 70 and 110 nm. The average size of the latexes in both wet and dry state were investigated by microscopy imaging and dynamic light scattering (DLS). Additionally, SobMA was successfully copolymerized with butyl methacrylate (BMA) targeting soft-core nanolatexes. The comparison of the kinetic profile of the cationically stabilized nanolatexes highlighted the differences of both processes. The SobMA-based nanolatexes yielded high T-g similar to 120 degrees C, while the copolymer sample exhibited a lower T-g similar to 50 degrees C, as assessed by Differential Scanning Calorimetry (DSC). Thereafter, the nanolatexes were adsorbed onto cellulose (filter paper), where they were annealed at elevated temperatures to result in polymeric coatings. Their morphologies were analysed by Field Emission Scanning Electron Microscopy (FE-SEM) and compared to a commercial sulfate polystyrene latex (PS latex). By microscopic investigation the film formation mechanism could be unravelled. Water contact angle (CA) measurements verified the transition from a hydrophilic to a hydrophobic surface after film formation had occured. The obtained results are promising for the toolbox of bio-based building blocks, focused on sobrerol-based monomers, to be used in emulsion polymerizations either for tailored PISA-latexes or facile conventional latex formation, in order to replace methyl methacrylate or other high T-g-monomers.

Place, publisher, year, edition, pages
Royal Society of Chemistry (RSC), 2021
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-292610 (URN)10.1039/d0gc04266h (DOI)000628913600023 ()2-s2.0-85102930298 (Scopus ID)
Note

QC 20210409

Available from: 2021-04-09 Created: 2021-04-09 Last updated: 2023-03-01Bibliographically approved
6. Bio-based nanolatexes prepared via polymerization-induced self-assembly: targeting heavy metal capturing applications
Open this publication in new window or tab >>Bio-based nanolatexes prepared via polymerization-induced self-assembly: targeting heavy metal capturing applications
(English)Manuscript (preprint) (Other academic)
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-324446 (URN)
Note

QC 20230302

Available from: 2023-03-01 Created: 2023-03-01 Last updated: 2023-03-02Bibliographically approved

Open Access in DiVA

fulltext(54548 kB)24 downloads
File information
File name FULLTEXT01.pdfFile size 54548 kBChecksum SHA-512
06ef69813cb37b306f69bf6b5418b50e589f4cc5681bdfccc4c84f032ec756369a22779ffb481369d1802928c2446e07c236b9a141afad362a77de72838f3026
Type fulltextMimetype application/pdf

Authority records

Alexakis, Alexandros Efraim

Search in DiVA

By author/editor
Alexakis, Alexandros Efraim
By organisation
Coating TechnologyWallenberg Wood Science Center
Polymer Chemistry

Search outside of DiVA

GoogleGoogle Scholar
Total: 24 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

isbn
urn-nbn

Altmetric score

isbn
urn-nbn
Total: 1090 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf