Change search
Link to record
Permanent link

Direct link
BETA
Publications (10 of 21) Show all publications
Stamm, A., Tengdelius, M., Schmidt, B., Engström, J., Syrén, P.-O., Fogelström, L. & Malmström, E. (2019). Chemo- enzymatic pathways toward pinene- based renewable materials. Green Chemistry, 21(10), 2720-2731
Open this publication in new window or tab >>Chemo- enzymatic pathways toward pinene- based renewable materials
Show others...
2019 (English)In: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 21, no 10, p. 2720-2731Article in journal (Refereed) Published
Abstract [en]

Sobrerol methacrylate (SobMA) was synthesized and subsequently polymerized using different chemical and enzymatic routes. Sobrerol was enzymatically converted from -pinene in a small model scale by a Cytochrome P450 mutant from Bacillus megaterium. Conversion of sobrerol into SobMA was performed using both classical ester synthesis, i.e., acid chloride-reactions in organic solvents, and a more green approach, the benign lipase catalysis. Sobrerol was successfully esterified, leaving the tertiary alcohol and ene to be used for further chemistry. SobMA was polymerized into PSobMA using different radical polymerization techniques, including free radical (FR), controlled procedures (Reversible Addition Fragmentation chain-Transfer polymerization, (RAFT) and Atom Transfer Radical Polymerization (ATRP)) as well as by enzyme catalysis (horseradish peroxidase-mediated free radical polymerization). The resulting polymers showed high glass-transition temperatures (T-g) around 150 degrees C, and a thermal degradation onset above 200 degrees C. It was demonstrated that the T-g could be tailored by copolymerizing SobMa with appropriate methacrylate monomers and that the Flory-Fox equation could be used to predict the T-g. The versatility of PSobMA was further demonstrated by forming crosslinked thin films, either using the ene'-functionality for photochemically initiated thiol-ene'-chemistry, or reacting the tertiary hydroxyl-group with hexamethoxymethylmelamine, as readily used for thermally curing coatings systems.

National Category
Polymer Technologies Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-252972 (URN)10.1039/c9gc00718k (DOI)000468627800016 ()2-s2.0-85066853137 (Scopus ID)
Note

QC 20190812

Available from: 2019-08-12 Created: 2019-08-12 Last updated: 2019-08-12Bibliographically approved
Engström, J. (2019). Tailored adhesion of PISA-latexes for cellulose modification and new materials. (Doctoral dissertation). KTH Royal Institute of Technology
Open this publication in new window or tab >>Tailored adhesion of PISA-latexes for cellulose modification and new materials
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is focused on applying modification chemistry to already known cellulosic substrates from wood (i.e. cellulose nanofibrils, CNFs, and cellulose nanocrystals, CNCs). The modification is needed to overcome the drawbacks with the nanocellulosics alone, such as sensitivity to water (hydrophilicity) and the brittle material properties (however great stiffness). The first aim is to incorporate nanocellulosics into hydrophobic degradable materials of poly(ε-caprolactone) (PCL), resulting in aggregation if not modified. The challenge is to reach high fraction of nanocellulosics, whilst maintaining the flexibility of PCL and improving the properties of the resulting nanocomposite with the corresponding stiffness of the nanocellulosics. The second aim is to increase toughness and strain-at-break for nanocomposite materials of CNF-networks, to increase the plastic deformation equivalent of fossil-based polymeric materials such as polypropylene (PP). Aiming to achieve these goals, the thesis also includes new synthetic strategies of tailored-made set of block copolymers as modifying components. The modifying components, were synthesised by surfactant-free emulsion polymerisation and polymerisation induced self-assembly (PISA), so called PISA-latexes.

Two types of cationic polyelectrolytes, (poly(2-dimethylaminoethy methacrylate) (PDMAEMA) and poly(N-[3-(dimethylamino)propyl] methacrylamide (PDMAPMA)), being the corona of the latex, were synthesised. Followed by chain-extension with different hydrophobic monomers such as methyl methacrylate and butyl methacrylate, making up the core polymer of the resulting PISA-latex. The cationic PISA-latexes show narrow size distributions and the glass transition (Tg) of the core polymer can be varied between -40 °C to 150 °C. The PISA-latexes show strong adhesion to silica and cellulose surfaces as assessed by quartz crystal microbalance (QCM-D). Results also indicate that latexes with Tg below room temperature, considered soft, behave different in the wet state than latexes with Tg above room temperature, considered rigid. The softer latexes form clusters (visualised by imaging with microscopy and atomic force measurements (AFM)) and undergo film formation in the wet state. The latter, shown by colloidal probe measurements using AFM resulting in very large work of adhesion and pull-off forces.

The PISA-latexes compatibilize CNCs and different CNFs with PCL as a matrix polymer, observed by a small increase in stiffness for the final nanocomposites, however not at a level expected by rule-of-mixtures. The promising wet feeding technique results in large increase in stiffness but maintain PCL’s flexibility, above 200% strain-at-break, which is rarely observed for CNF-reinforced nanocomposites. The, in this case, rigid latex facilitate the dispersion of CNFs in the matrix without aggregation, until finally coalescing after processing and possibly giving rise to improved adhesion between CNF and the latex in the matrix, indicated by rheology measurements. Lastly, new nanocomposite films consisting of 75wt% CNF and 25wt% of PISA-latexes were produced and evaluated. The results show that CNF and rigid 100 nm sized PISA-latex, with PMMA core, gives a very tough double network, with strain-at-break above 28%, stiffness of 3.5 GPa and a strength of 110 MPa. These are impressive properties compared to commonly used fossil-based plastic materials.

Place, publisher, year, edition, pages
KTH Royal Institute of Technology, 2019. p. 128
Series
TRITA-CBH-FOU ; 2019:7
Keywords
PISA, latex, RAFT, Cellulose Nanofibrils, Cellulose Nanocrystals, Nanocomposites
National Category
Polymer Chemistry
Research subject
Fibre and Polymer Science
Identifiers
urn:nbn:se:kth:diva-241463 (URN)978-91-7873-086-5 (ISBN)
Public defence
2019-02-22, Kollegiesalen, Brinellvägen 8, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20190123

Available from: 2019-01-23 Created: 2019-01-22 Last updated: 2019-05-20Bibliographically approved
Engström, J., Benselfelt, T., Wågberg, L., D'Agosto, F., Lansalot, M., Carlmark, A. & Malmström, E. (2019). Tailored cationic PISA-latexes for strong adhesion to anionic surfaces: Importance of purity and chain-extension as shown by adsorption. Paper presented at 257th National Meeting of the American-Chemical-Society (ACS), MAR 31-APR 04, 2019, Orlando, FL. Abstracts of Papers of the American Chemical Society, 257
Open this publication in new window or tab >>Tailored cationic PISA-latexes for strong adhesion to anionic surfaces: Importance of purity and chain-extension as shown by adsorption
Show others...
2019 (English)In: Abstracts of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 257Article in journal, Meeting abstract (Other academic) Published
Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-257662 (URN)000478861206107 ()
Conference
257th National Meeting of the American-Chemical-Society (ACS), MAR 31-APR 04, 2019, Orlando, FL
Note

QC 20190904

Available from: 2019-09-04 Created: 2019-09-04 Last updated: 2019-09-04Bibliographically approved
Engström, J., Hatton, F., Benselfelt, T., Freire, C., Vilela, C., Boujemaoui, A., . . . Malmström, E. (2019). Tailored PISA-latexes for modification of nanocellulosics: Investigating compatibilizing and plasticizing effects. Paper presented at National Meeting of the American-Chemical-Society (ACS), MAR 31-APR 04, 2019, Orlando, FL. Abstracts of Papers of the American Chemical Society, 257
Open this publication in new window or tab >>Tailored PISA-latexes for modification of nanocellulosics: Investigating compatibilizing and plasticizing effects
Show others...
2019 (English)In: Abstracts of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 257Article in journal, Meeting abstract (Other academic) Published
Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2019
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-257615 (URN)000478860503077 ()
Conference
National Meeting of the American-Chemical-Society (ACS), MAR 31-APR 04, 2019, Orlando, FL
Note

QC 20190918

Available from: 2019-09-18 Created: 2019-09-18 Last updated: 2019-11-06Bibliographically approved
Engström, J., Benselfelt, T., Wågberg, L., D'Agosto, F., Lansalot, M., Carlmark, A. & Malmström, E. (2019). Tailoring adhesion of anionic surfaces using cationic PISA-latexes – towards tough nanocellulose materials in the wet state. Nanoscale, 11, 4287-4302
Open this publication in new window or tab >>Tailoring adhesion of anionic surfaces using cationic PISA-latexes – towards tough nanocellulose materials in the wet state
Show others...
2019 (English)In: Nanoscale, ISSN 2040-3364, E-ISSN 2040-3372, Vol. 11, p. 4287-4302Article in journal (Refereed) Published
Abstract [en]

Cationic latexes with Tgs ranging between −40 °C and 120 °C were synthesised using n-butyl acrylate (BA) and/or methyl methacrylate (MMA) as the core polymers. Reversible addition–fragmentation chain transfer (RAFT) combined with polymerisation-induced self-assembly (PISA) allowed for in situ chain-extension of a cationic macromolecular RAFT agent (macroRAFT) of poly(N-[3-(dimethylamino)propyl] methacrylamide) (PDMAPMA), used as stabiliser in so-called surfactant-free emulsion polymerisation. The resulting narrowly distributed nanosized latexes adsorbed readily onto silica surfaces and to model surfaces of cellulose nanofibrils, as demonstrated by quartz crystal microbalance with dissipation monitoring (QCM-D) measurements. Adsorption to anionic surfaces increased when increasing ionic strength to 10 mM, indicating the influence of the polyelectrolyte effect exerted by the corona. The polyelectrolyte corona affected the interactions in the wet state, the stability of the latex and re-dispersibility after drying. The QCM-D measurements showed that a lower Tg of the core results in a more strongly interacting adsorbed layer at the solid–liquid interface, despite a comparable adsorbed mass, indicating structural differences of the investigated latexes in the wet state. The two latexes with Tg below room temperature (i.e. PBATg-40 and P(BA-co-MMA)Tg3) exhibited film formation in the wet state, as shown by AFM colloidal probe measurements. It was observed that P(BA-co-MMA)Tg3 latex resulted in the largest pull-off force, above 200 m Nm−1 after 120 s in contact. The strongest wet adhesion was achieved with PDMAPMA-stabilized latexes soft enough to allow for interparticle diffusion of polymer chains, and stiff enough to create a strong adhesive joint. Fundamental understanding of interfacial properties of latexes and cellulose enables controlled and predictive strategies to produce strong and tough materials with high nanocellulose content, both in the wet and dry state.

National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-241447 (URN)10.1039/C8NR08057G (DOI)000465410200012 ()2-s2.0-85062644682 (Scopus ID)
Note

QC 20190123

Available from: 2019-01-22 Created: 2019-01-22 Last updated: 2019-05-29Bibliographically approved
Gicquel, E., Martin, C., Gauthier, Q., Engström, J., Abbattista, C., Carlmark, A., . . . Bras, J. (2019). Tailoring Rheological Properties of Thermoresponsive Hydrogels through Block Copolymer Adsorption to Cellulose Nanocrystals. Biomacromolecules, 20(7), 2545-2556
Open this publication in new window or tab >>Tailoring Rheological Properties of Thermoresponsive Hydrogels through Block Copolymer Adsorption to Cellulose Nanocrystals
Show others...
2019 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 20, no 7, p. 2545-2556Article in journal (Refereed) Published
Abstract [en]

This study investigates the adsorption of a block copolymer composed of a poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) cationic polyelectrolyte and a poly(di(ethylene glycol) methyl ethermethacrylate) (PDEGMA) on oxidized cellulose nanocrystals (TO-CNCs) to produce hydrogels. PDMEAMA-b-PDEGMA was synthesized by atom-transfer radical polymerization. The extent and dynamics of the adsorption of PDMAEMA-b-PDEGMA on TO-CNCs were determined by electromechanical microbalance and optical techniques. Electrostatic adsorption was identified on TO-CNCs with the quaternized block copolymer. Small-angle neutron scattering experiments were performed to investigate the polymer behavior on the TO-CNC surfaces. Depending on the temperature, block copolymer induces the aggregation of nanocrystals after adsorption by connecting CNCs bundles with block copolymer chains. A reversible liquid-to-gel transition, triggered by temperature, was clearly detected by rheological measurements for the copolymer-CNC mixtures. At the optimal copolymer to CNC ratio the viscosity increased by 4 orders of magnitude at low shear rates. These stimuli-responsive CNC-based materials could be used as injectable biomedical systems.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:kth:diva-255395 (URN)10.1021/acs.biomac.9b00327 (DOI)000474812200009 ()31244017 (PubMedID)2-s2.0-85068116503 (Scopus ID)
Note

QC 20190729

Available from: 2019-07-29 Created: 2019-07-29 Last updated: 2019-10-04Bibliographically approved
Vilela, C., Engström, J., Valente, B. F. A., Jawerth, M., Carlmark, A. & Freire, C. S. R. (2018). Exploiting poly(ɛ-caprolactone) and cellulose nanofibrils modified with latex nanoparticles for the development of biodegradable nanocomposites. Polymer Composites
Open this publication in new window or tab >>Exploiting poly(ɛ-caprolactone) and cellulose nanofibrils modified with latex nanoparticles for the development of biodegradable nanocomposites
Show others...
2018 (English)In: Polymer Composites, ISSN 0272-8397, E-ISSN 1548-0569Article in journal (Refereed) Published
Abstract [en]

This study reports the development of nanocomposites based on poly(?-caprolactone) (PCL) and cellulose nanofibrils (CNF) modified with cationic latex nanoparticles. The physical adsorption of these water-based latexes on the surface of CNF was studied as an environment-friendly strategy to enhance the compatibility of CNF with a hydrophobic polymeric matrix. The latexes are composed of amphiphilic block copolymers based on cationic poly(N,N-dimethylaminoethyl methacrylate-co-methacrylic acid) as the hydrophilic block, and either poly(methyl methacrylate) or poly(n-butyl methacrylate) as the hydrophobic block. The simple and practical melt-mixing of PCL- and latex-modified CNF yielded white homogeneous nanocomposites with complete embedment of the nanofibrils in the thermoplastic matrix. All nanocomposites are semicrystalline materials with good mechanical properties (Young's modulus?=?43.6?52.3 MPa) and thermal stability up to 335?340°C. Degradation tests clearly showed that the nanocomposites slowly degrade in the presence of lipase-type enzyme. These PCL/CNF-latex nanocomposite materials show great promise as future environmentally friendly packaging materials. POLYM. COMPOS., 2018. ? 2018 Society of Plastics Engineers

Place, publisher, year, edition, pages
John Wiley & Sons, Ltd, 2018
National Category
Materials Chemistry
Identifiers
urn:nbn:se:kth:diva-241451 (URN)10.1002/pc.24865 (DOI)000463102200009 ()2-s2.0-85045412566 (Scopus ID)
Note

QC 20190123

Available from: 2019-01-22 Created: 2019-01-22 Last updated: 2019-04-29Bibliographically approved
Lo Re, G., Engström, J., Wu, Q., Malmström, E., Gedde, U. W., Olsson, R. & Berglund, L. (2018). Improved Cellulose Nanofibril Dispersion in Melt-Processed Polycaprolactone Nanocomposites by a Latex-Mediated Interphase and Wet Feeding as LDPE Alternative. ACS Applied Nano Materials, 1(6), 2669-2677
Open this publication in new window or tab >>Improved Cellulose Nanofibril Dispersion in Melt-Processed Polycaprolactone Nanocomposites by a Latex-Mediated Interphase and Wet Feeding as LDPE Alternative
Show others...
2018 (English)In: ACS Applied Nano Materials, ISSN 2574-0970, Vol. 1, no 6, p. 2669-2677Article in journal (Refereed) Published
Abstract [en]

This work reports the development of a sustainable and green one-step wet-feeding method to prepare tougher and stronger nanocomposites from biodegradable cellulose nanofibrils (CNF)/polycaprolactone (PCL) constituents, compatibilized with reversible addition fragmentation chain transfer-mediated surfactant-free poly(methyl methacrylate) (PMMA) latex nanoparticles. When a PMMA latex is used, a favorable electrostatic interaction between CNF and the latex is obtained, which facilitates mixing of the constituents and hinders CNF agglomeration. The improved dispersion is manifested in significant improvement of mechanical properties compared with the reference material. The tensile tests show much higher modulus (620 MPa) and strength (23 MPa) at 10 wt % CNF content (compared to the neat PCL reference modulus of 240 and 16 MPa strength), while maintaining high level of work to fracture the matrix (7 times higher than the reference nanocomposite without the latex compatibilizer). Rheological analysis showed a strongly increased viscosity as the PMMA latex was added, that is, from a well-dispersed and strongly interacting CNF network in the PCL.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2018
National Category
Materials Chemistry
Identifiers
urn:nbn:se:kth:diva-241449 (URN)10.1021/acsanm.8b00376 (DOI)000461400700029 ()
Note

QC 20190123

Available from: 2019-01-22 Created: 2019-01-22 Last updated: 2019-04-23Bibliographically approved
Benselfelt, T., Engström, J. & Wågberg, L. (2018). Supramolecular double networks of cellulose nanofibrils and algal polysaccharides with excellent wet mechanical properties. Green Chemistry, 20(11), 2558-2570
Open this publication in new window or tab >>Supramolecular double networks of cellulose nanofibrils and algal polysaccharides with excellent wet mechanical properties
2018 (English)In: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 20, no 11, p. 2558-2570Article in journal (Refereed) Published
Abstract [en]

Supramolecular double network films, consisting of cellulose nanofibrils (CNF) entangled with the algal polysaccharides alginate or carrageenan, were prepared using a rapid vacuum filtration process to achieve water-resistant CNF nanopapers with excellent mechanical properties in both the wet and dry states following the locking of the structures using Ca2+. The rigid network of calcium alginate was more efficient than the more flexible network of calcium carrageenan and 10% by weight of alginate was sufficient to form a network that suppressed the swelling of the CNF film by over 95%. The resulting material could be compared to a stiff rubber with a Young's modulus of 135 MPa, a tensile strength of 17 MPa, a strain-at-break above 55%, and a work of fracture close to 5 MJ m(-3) in the wet state, which was both significantly stronger and more ductile than the calcium-treated CNF reference nanopaper. It was shown that the state in which Ca2+ was introduced is crucial, and it is also hypothesized that the alginate works as a sacrificial network that prevents the CNF from aligning during loading and that this leads to the increased toughness. The material maintained its barrier properties at elevated relative humidities and the extensibility and ductility made possible hygroplastic forming into three-dimensional shapes. It is suggested that the attractive force in the CNF part of the double network in the presence of multivalent ions is due to the ion-ion correlation forces generated by the fluctuating counter-ion cloud, since no significant ion coordination was observed using FTIR.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY, 2018
National Category
Paper, Pulp and Fiber Technology
Identifiers
urn:nbn:se:kth:diva-231187 (URN)10.1039/c8gc00590g (DOI)000434313100018 ()2-s2.0-85048040852 (Scopus ID)
Funder
Knut and Alice Wallenberg Foundation
Note

QC 20180718

Available from: 2018-07-18 Created: 2018-07-18 Last updated: 2019-04-08Bibliographically approved
Engström, J., Hatton, F., Boujemaoui, A., Sanchez, C. C., Wågberg, L., D'Agosto, F., . . . Carlmark, A. (2018). Tailored nano-latexes for modification of nanocelluloses: Compatibilizing and plasticizing effects. Paper presented at 255th National Meeting and Exposition of the American-Chemical-Society (ACS) - Nexus of Food, Energy, and Water, MAR 18-22, 2018, New Orleans, LA. Abstract of Papers of the American Chemical Society, 255
Open this publication in new window or tab >>Tailored nano-latexes for modification of nanocelluloses: Compatibilizing and plasticizing effects
Show others...
2018 (English)In: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 255Article in journal, Meeting abstract (Other academic) Published
Place, publisher, year, edition, pages
American Chemical Society (ACS), 2018
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-240157 (URN)000435537702783 ()
Conference
255th National Meeting and Exposition of the American-Chemical-Society (ACS) - Nexus of Food, Energy, and Water, MAR 18-22, 2018, New Orleans, LA
Note

QC 20190111

Available from: 2019-01-11 Created: 2019-01-11 Last updated: 2019-01-11Bibliographically approved
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0002-9572-6888

Search in DiVA

Show all publications