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Modification of cellulose through physisorption of cationic bio-based nanolatexes - comparing emulsion polymerization and RAFT-mediated polymerization-induced self-assembly
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.ORCID iD: 0000-0001-8317-3529
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.ORCID iD: 0000-0002-9572-6888
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Coating Technology.ORCID iD: 0000-0001-8727-2102
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Centres, Wallenberg Wood Science Center. Wallenberg Wood Sci Ctr WWSC, Tekn Ringen 56-58, SE-10044 Stockholm, Sweden..ORCID iD: 0000-0002-5661-0874
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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. Vol. 23, no 5, p. 2113-2122
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-292610DOI: 10.1039/d0gc04266hISI: 000628913600023Scopus ID: 2-s2.0-85102930298OAI: oai:DiVA.org:kth-292610DiVA, id: diva2:1542999
Note

QC 20210409

Available from: 2021-04-09 Created: 2021-04-09 Last updated: 2023-03-01Bibliographically approved
In thesis
1. Exploring the Use of Terpenes as Renewable Polymer Feedstock
Open this publication in new window or tab >>Exploring the Use of Terpenes as Renewable Polymer Feedstock
2021 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Rising environmental awareness and responsibility has increased the demand for novel,  bio-based  sustainable  materials.  Therefore,  there  is  an  extensive  need  to research  and  develop  closed-loop  materials  from  novel  feedstocks  that  can  be generated  using  benign,  environmentally  friendly  synthetic  routes.  The  work presented in this thesis was focused on the development of polymeric materials from  biomass  waste-feedstocks.  Especially  the  use  of  turpentine,  a  classical underutilized side-stream of the forest industry, and its main component α-pinene was the key objective of this work. To showcase the inherent potential of terpenes as a source material for novel biopolymers, α-pinene was transformed into different monomers and subsequently polymerized.  The  synthesis  and  polymerization  of  the  pinene  derived  sobreryl  methacrylate (SobMA) was studied using different radical polymerization techniques, including free radical polymerizations and controlled procedures. Post-modifications were further demonstrated by synthesizing crosslinked thin films, utilizing the tertiary alcohol and the unsaturation present in each monomer unit. The same methacrylic monomer  was  further  utilized  for  the  polymerization  of  amphiphilic  block copolymers to form cationic polymer latexes.  Pinene derived polyesters were further developed via two different pathways. In the first  pathway,  α-pinene  was  oxidized  into  the  bicyclic  verbanone  based  lactone (VaL)  and  subsequently  polymerized  resulting  in  a  biobased  semicrystalline polyester.  In  the  second  pathway,  polyesters  were  synthesized  via polycondensation,  utilizing  the  diol  (1-(1'-hydroxyethyl)-3-(2'-hydroxyethyl)-2,2-dimethylcyclobutane (HHDC)) obtained from the oxidative cleavage of the double bond  of  α-pinene  together  with  unsaturated  biobased  diacids.  The  resulting terpene based unsaturated polyester resins were  afterwards crosslinked via UV-irradiation to yield polyester networks with adjustable properties.  The use of enzymatic catalysis in key synthetic steps was elaborated to showcase the potential of replacing harsh chemical conditions with mild reaction conditions in aqueous environment. 

Abstract [sv]

Ökande  miljömedvetenhet  och  ansvar  har  ökat  efterfrågan  på  nya,  biobaserade hållbara material. Därför finns det ett stort behov av forskning och utveckling av hållbara  material  från  förnyelsebara  råvaror  som  kan  syntetiseras  med  hjälp  av ofarliga  och  miljövänliga  metoder.  Arbetet  som  presenteras  i  denna  avhandling fokuserar  på  utvecklingen  av  polymera  material  från  råvaror  härrörande  från biomassa och dess sidoströmmar. Särskilt användningen av terpentin, en klassisk underutnyttjad sidoström från skogsindustrin, och dess huvudkomponent α-pinen var huvudmålet för detta arbete. För att visa upp den inneboende potentialen hos terpener som ett källmaterial för nya biopolymerer omvandlades α-pinen till olika monomerer vilka därefter polymeriserades.  Syntes och polymerisation av den pinen-baserade monomeren sobrerylmetakrylat (SobMA) studerades, varvid olika radikal polymerisationstekniker, inklusive fria radikal  polymerisationer  användes  och  kontrollerade  polymerisationsmetoder. Eftermodifieringar  demonstrerades  vidare  genom  framställning  av  tvärbundna tunna filmer genom användning av den tertiära alkoholen och den omättnad som finns  i  varje  monomerenhet.  Samma  metakrylmonomer  användes  vidare  för polymerisation  av  amfifila  segmentsampolymerer  för  att  bilda  katjoniska polymerlatexer. Pinen-härledda polyestrar utvecklades vidare via två olika vägar. I den första vägen oxiderades α-pinen till den bicykliska verbanonbaserade laktonen (VaL)  som  därefter  polymeriserades,  vilket  resulterade  i  en  biobaserad semikristallin  polyester.  I  den  andra  vägen  syntetiserades  polyestrar  via polykondensering  med  användning  av  diolen  (1-(1'-hydroxyethyl)-3-(2'-hydroxyethyl)-2,2-dimethylcyclobutane (HHDC)) erhållen från oxidativ klyvning av dubbelbindningen i α-pinen  tillsammans med omättade biobaserade syror. De resulterande  terpenbaserade  omättade  polyesterhartserna  tvärbands  därefter genom UV-bestrålning för att ge polyesternätverk med kontrollerbara egenskaper. Användningen av enzymatisk katalys i viktiga syntessteg utforskades ytterligare för att  visa  upp  potentialen  i  att  ersätta  hårda  kemiska  förhållanden  med  milda, vattenbaserade reaktionsförhållanden. 

Place, publisher, year, edition, pages
Stockholm 2021: KTH Royal Institute of Technology, 2021. p. 69
Series
TRITA-CBH-FOU ; 2021:15
Keywords
Bio-based polymers, terpenes, α-pinene, sobrerol methacrylate (SobMA), verbanone lactone (VaL), 1-(1'-hydroxyethyl)-3-(2''-hydroxyethyl)-2, 2- dimethylcyclobutane (HHDC).
National Category
Polymer Technologies
Research subject
Chemistry
Identifiers
urn:nbn:se:kth:diva-294245 (URN)978-91-7873-855-7 (ISBN)
Public defence
2021-06-11, https://kth-se.zoom.us/j/67582093844, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 2021-05-12

Available from: 2021-05-12 Created: 2021-05-12 Last updated: 2022-06-25Bibliographically approved
2. Nanolatexes: a versatile toolbox for cellulose modification
Open this publication in new window or tab >>Nanolatexes: a versatile toolbox for cellulose modification
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
nanolatexes, RAFT, PISA, adsorption, cellulose, modification
National Category
Polymer Chemistry
Research subject
Fibre and Polymer Science
Identifiers
urn:nbn:se:kth:diva-324421 (URN)978-91-8040-490-7 (ISBN)
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

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Alexakis, Alexandros EfraimEngström, JoakimStamm, ArneRiazanova, AnastasiaBrett, CalvinRoth, Stephan V.Syrén, Per-OlofFogelström, LindaReid, Michael S.Malmström, Eva

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