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Publications (10 of 67) Show all publications
Bäckström, E., Odelius, K. & Hakkarainen, M. (2019). Designed from Recycled: Turning Polyethylene Waste to Covalently Attached Polylactide Plasticizers. ACS SUSTAINABLE CHEMISTRY & ENGINEERING, 7(12), 11004-11013
Open this publication in new window or tab >>Designed from Recycled: Turning Polyethylene Waste to Covalently Attached Polylactide Plasticizers
2019 (English)In: ACS SUSTAINABLE CHEMISTRY & ENGINEERING, ISSN 2168-0485, Vol. 7, no 12, p. 11004-11013Article in journal (Refereed) Published
Abstract [en]

High-density polyethylene (HDPE) waste was successfully feedstock recycled, and the obtained chemicals were utilized for synthesis of plasticizers for polylactide (PLA). First, an effective route to recycle HDPE through a microwave-assisted hydrothermal process was established. This process led to selective degradation of HDPE to a few well-defined chemicals, namely, succinic, glutaric, and adipic acid. A model plasticizer was synthesized from the same composition of dicarboxylic acids, 1,4-butanediol, and crotonic acid. The function of crotonic acid was to produce oligomers with crotonate end groups for coupling the plasticizer to PLA main chain. The plasticizer was then blended with or coupled to PLA by a reactive extrusion process. Adding the plasticizer to PLA decreased the T-g and increased the strain at break, thus reducing the brittleness of the films. The addition of 20% (w/w) grafted plasticizer increased the strain at break of PLA from 6 to 156% and decreased the T-g by 15 degrees C compared with neat PLA. Finally, to verify the concept, a plasticizer was also synthesized from the dicarboxylic acid product mixture obtained from the feedstock recycling of HDPE. The recycled grafted plasticizer increased the strain at break of PLA to 142% and reduced the T-g by 10 degrees C. A promising route for designing from recycled feedstock, turning HDPE waste to PLA plasticizers, was thus demonstrated.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2019
Keywords
HDPE, Oxidative degradation, Feedstock recycling, PLA, Plasticization
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-255190 (URN)10.1021/acssuschemeng.9b02092 (DOI)000472240900091 ()2-s2.0-85067031627 (Scopus ID)
Note

QC 20190904

Available from: 2019-09-04 Created: 2019-09-04 Last updated: 2019-09-04Bibliographically approved
Xuan, W., Hakkarainen, M. & Odelius, K. (2019). Levulinic Acid as a Versatile Building Block for Plasticizer Design. ACS Sustainable Chemistry and Engineering, 7(14), 12552-12562
Open this publication in new window or tab >>Levulinic Acid as a Versatile Building Block for Plasticizer Design
2019 (English)In: ACS Sustainable Chemistry and Engineering, ISSN 2168-0485, Vol. 7, no 14, p. 12552-12562Article in journal (Refereed) Published
Abstract [en]

The large potential of utilizing green platform chemicals such as levulinic acid, glycerol, and ethylene glycol as building blocks for the design of high-performance biobased plasticizers was demonstrated. From these green platform chemicals, esters with ketal or ketone functionalities and linear or branched structures were carefully designed and synthesized via a mild and solvent-free route and characterized by H-1 NMR, C-13 NMR, and FTIR. The effect of the structural combinations on the performance as plasticizers for polylactide (PLA), including migration resistance, was followed by a series of characterization techniques. The levulinates with ketone end-groups exhibited large capability to lower the glass transition temperature (T-g) of PLA (to 15 degrees C by 20 wt % plasticizer). Ketal end-groups provided additional thermal stability to the plasticizers, but their ability to lower T-g was not as good as that of ketone end-groups. Significantly improved flexibility reaching 546% elongation at break was achieved by the addition of 20 wt % ethylene glycol dilevulinate, as compared to 5% elongation at break for neat PLA. The structural differences for the plasticizers resulted in different degrees of hydrophobicity, which influenced the migration tendency of the plasticizers and also the hydrolysis rate of PLA. The branched ester structure with ketal end-groups maintained the processing window of PLA, but also lowered the hydrolysis rate of PLA in an accelerated migration test. In general, performance comparable to that of the reference plasticizer acetyl tributyl citrate (ATBC) was demonstrated, offering promise for a family of plasticizers derivable from green platform chemicals.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019
Keywords
Plasticizer, Levulinic acid, Polylactide, Migration, Acetyl tributyl citrate
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-255558 (URN)10.1021/acssuschemeng.9b02439 (DOI)000475838100067 ()
Note

QC 20190805

Available from: 2019-08-05 Created: 2019-08-05 Last updated: 2019-08-05Bibliographically approved
Xu, Y., Odelius, K. & Hakkarainen, M. (2019). One-Pot Synthesis of Lignin Thermosets Exhibiting Widely Tunable Mechanical Properties and Shape Memory Behavior. ACS Sustainable Chemistry and Engineering, 7(15), 13456-13463
Open this publication in new window or tab >>One-Pot Synthesis of Lignin Thermosets Exhibiting Widely Tunable Mechanical Properties and Shape Memory Behavior
2019 (English)In: ACS Sustainable Chemistry and Engineering, ISSN 2168-0485, Vol. 7, no 15, p. 13456-13463Article in journal (Refereed) Published
Abstract [en]

A series of kraft lignin based thermosets were successfully synthesized by a one-pot heat curing method composed of lignin, PEG400, and citric acid through esterification reactions with water as the only produced byproduct. The polyester thermosets were prepared by varying the ratio of lignin and PEG400 in combination with citric acid as the cross-linker. Lignin and PEG400 were chosen as the rigid and soft segments, respectively, to tailor the thermal mechanical properties of the thermosets. An increase of lignin content from 20 to 40 wt % facilitated an increase in the cross-linking density and aromatic content. This was reflected in the storage modulus at 25 degrees C, which increased from 5.7 to 2000 MPa, and the glass transition temperature, which increased from -0.3 to 102 degrees C. At the same time, the tensile strength changed from 1.2 to 34.3 MPa. The mechanical properties were, thus, tunable from flexible to rigid, demonstrating a significantly high storage modulus and tensile strength for a biobased thermoset. Furthermore, a superb thermally stimulated shape memory property was illustrated. This is promising for the use of commercial kraft lignin as a building block for versatile applications.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019
Keywords
Lignin, Polyester thermoset, One-pot synthesis, Shape memory
National Category
Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-257453 (URN)10.1021/acssuschemeng.9b02921 (DOI)000480370500088 ()2-s2.0-85070591594 (Scopus ID)
Note

QC 20190830

Available from: 2019-08-30 Created: 2019-08-30 Last updated: 2019-08-30Bibliographically approved
Hua, G., Franzén, J. & Odelius, K. (2019). Phosphazene-Catalyzed Regioselective Ring-Opening Polymerization of rac-1-Methyl Trimethylene Carbonate: Colder and Less is Better. Macromolecules, 52(7), 2681-2690
Open this publication in new window or tab >>Phosphazene-Catalyzed Regioselective Ring-Opening Polymerization of rac-1-Methyl Trimethylene Carbonate: Colder and Less is Better
2019 (English)In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 52, no 7, p. 2681-2690Article in journal (Refereed) Published
Abstract [en]

The regioselective organocatalytic ring-opening polymerization (ROP) of a 6-membered cyclic carbonate, rac-1-methyl trimethylene carbonate, was studied using phosphazene base (t-BuP2) as the principle catalyst. The influence on the reaction kinetics caused by the reaction temperature (-74-60 degrees C), catalyst loading (0.5-2.5%), and reaction solvent (toluene and tetrahydrofuran) was systematically tuned and followed by H-1 NMR. All studied reactions reached close to or above 90% monomer conversion in 3 h, and all exhibited typical equilibrium polymerization behavior that is inherent to 6-membered cyclic carbonates. Good control over the molecular weight and distribution of the polycarbonate product was obtained in most studied conditions, with M-n ranging from similar to 4k to similar to 20k and D < 1.2. The regioregularity (X-reg) of the resulting polycarbonate was thoroughly studied using various NMR techniques, with the highest X-reg obtained being.0.90. The major influence from the reaction conditions on both the ROP kinetics and X-reg are as follows: higher reaction temperature resulted in a decrease of both; higher catalyst loading resulted in a faster ROP reaction but a slight decrease in X-reg; and toluene being a better solvent resulted in both faster reaction and higher X-reg. Throughout this study, we have demonstrated the possibility to synthesize regioregular aliphatic polycarbonate using an organic base as the ROP catalyst, contrary to the existing studies on similar systems where only metal-base catalysts were in focus and our systems showed similar high X-reg of the product.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2019
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-251201 (URN)10.1021/acs.macromol.8b02591 (DOI)000464475900007 ()2-s2.0-85064209906 (Scopus ID)
Note

QC 20190724

Available from: 2019-07-24 Created: 2019-07-24 Last updated: 2019-07-24Bibliographically approved
Feng, Z., Takahiro, D., Odelius, K., Hakkarainen, M., Tadahisa, I. & Albertsson, A.-C. (2019). Recyclable fully biobased chitosan adsorbents spray-dried in one-pot to microscopic size and enhanced adsorption capacity. International Journal of Biological Macromolecules, 20(5), 1956-1964
Open this publication in new window or tab >>Recyclable fully biobased chitosan adsorbents spray-dried in one-pot to microscopic size and enhanced adsorption capacity
Show others...
2019 (English)In: International Journal of Biological Macromolecules, ISSN 0141-8130, E-ISSN 1879-0003, Vol. 20, no 5, p. 1956-1964Article in journal (Refereed) Published
Abstract [en]

A facile one-pot spray-drying process was developed for fabrication and in-situ crosslinking of chitosan microspheres to improve the adsorption capacity by microscopic design. A fully biobased nature was achieved by utilizing genipin (GP) as a crosslinking agent and chitosan derived nano-graphene oxide (nGO) as a property tuner. The produced chitosan microspheres were further proven as powerful adsorbents for common wastewater contaminants such as anionic dyes and pharmaceutical contaminants, here modelled by methyl orange (MO) and diclofenac sodium (DCF). By regulating the amount of GP and nGO, as well as by controlling the process parameters including the spraydrying inlet temperature and post-heat treatment, the surface morphology, size, zeta potential and adsorption efficiency of the microspheres could be tuned accordingly. The adsorption efficiency for MO and DCF reached 98.9 and 100 %, respectively. The microspheres retained high DCF adsorption efficiency after six adsorption and desorption cycles and the recyclability was improved by incorporated nGO. The fabricated microspheres, thus, have great potential as reusable and eco-friendly adsorbents.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019
Keywords
In-situ crosslinking, microspheres, chitosan, spray drying, genipin, biobased, recyclable
National Category
Polymer Chemistry
Research subject
Fibre and Polymer Science
Identifiers
urn:nbn:se:kth:diva-248442 (URN)10.1021/acs.biomac.9b00186 (DOI)000468120800012 ()2-s2.0-85064830922 (Scopus ID)
Note

QC 20190410

Available from: 2019-04-09 Created: 2019-04-09 Last updated: 2019-06-11Bibliographically approved
Odelius, K. (2019). Ring-opening reactions to functional polyamides and polyurethanes. 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 >>Ring-opening reactions to functional polyamides and polyurethanes
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-257659 (URN)000478861206154 ()
Conference
257th National Meeting of the American-Chemical-Society (ACS), MAR 31-APR 04, 2019, Orlando, FL
Note

QC 20190903

Available from: 2019-09-03 Created: 2019-09-03 Last updated: 2019-09-03Bibliographically approved
Hua, G., Olsen, P., Franzen, J. & Odelius, K. (2018). Anionic polycondensation and equilibrium driven monomer formation of cyclic aliphatic carbonates. RSC Advances, 8(68), 39022-39028
Open this publication in new window or tab >>Anionic polycondensation and equilibrium driven monomer formation of cyclic aliphatic carbonates
2018 (English)In: RSC Advances, ISSN 2046-2069, E-ISSN 2046-2069, Vol. 8, no 68, p. 39022-39028Article in journal (Refereed) Published
Abstract [en]

The current work explores the sodium hydride mediated polycondensation of aliphatic diols with diethyl carbonate to produce both aliphatic polycarbonates and cyclic carbonate monomers. The lengths of the diol dictate the outcome of the reaction; for ethylene glycol and seven other 1,3-diols with a wide array of substitution patterns, the corresponding 5-membered and 6-membered cyclic carbonates were synthesized in excellent yield (70-90%) on a 100 gram scale. Diols with longer alkyl chains, under the same conditions, yielded polycarbonates with an M-w ranging from 5000 to 16000. In all cases, the macromolecular architecture revealed that the formed polymer consisted purely of carbonate linkages, without decarboxylation as a side reaction. The synthetic design is completely solvent-free without any additional post purification steps and without the necessity of reactive ring-closing reagents. The results presented within provide a green and scalable approach to synthesize both cyclic carbonate monomers and polycarbonates with possible applications within the entire field of polymer technology.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY, 2018
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-240041 (URN)10.1039/c8ra08219g (DOI)000451090800039 ()2-s2.0-85057293553 (Scopus ID)
Note

QC 20181210

Available from: 2018-12-10 Created: 2018-12-10 Last updated: 2018-12-10Bibliographically approved
Odelius, K. (2018). Design of renewable polymeric materials through ring-opening reactions. Paper presented at 256th National Meeting and Exposition of the American-Chemical-Society (ACS) - Nanoscience, Nanotechnology and Beyond, AUG 19-23, 2018, Boston, MA. Abstract of Papers of the American Chemical Society, 256
Open this publication in new window or tab >>Design of renewable polymeric materials through ring-opening reactions
2018 (English)In: Abstract of Papers of the American Chemical Society, ISSN 0065-7727, Vol. 256Article in journal, Meeting abstract (Other academic) Published
Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2018
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-238562 (URN)000447600002549 ()
Conference
256th National Meeting and Exposition of the American-Chemical-Society (ACS) - Nanoscience, Nanotechnology and Beyond, AUG 19-23, 2018, Boston, MA
Note

QC 20181105

Available from: 2018-11-05 Created: 2018-11-05 Last updated: 2018-11-05Bibliographically approved
Xu, Y., Hua, G., Hakkarainen, M. & Odelius, K. (2018). Isosorbide as Core Component for Tailoring Biobased Unsaturated Polyester Thermosets for a Wide Structure- Property Window. Biomacromolecules, 19(7), 3077-3085
Open this publication in new window or tab >>Isosorbide as Core Component for Tailoring Biobased Unsaturated Polyester Thermosets for a Wide Structure- Property Window
2018 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 19, no 7, p. 3077-3085Article in journal (Refereed) Published
Abstract [en]

Biobased unsaturated polyester thermosets as potential replacements for petroleum-based thermosets were designed. The target of incorporating rigid units, to yield thermosets with high thermal and mechanical performance, both in the biobased unsaturated polyester (UP) and reactive diluent (RD) while retaining miscibility was successfully achieved. The biobased unsaturated polyester thermosets were prepared by varying the content of isosorbide, 1,4-butanediol, maleic anhydride, and succinic anhydride in combination with the reactive diluent isosorbide-methacrylate (IM). Isosorbide was chosen as the main component in both the UP and the RD to enhance the rigidity of the formed thermosets, to overcome solubility issues commonly associated with biobased UPs and RDs and volatility and toxicity associated with styrene as RD. All UPs had good solubility in the RD and the viscosity of the mixtures was primarily tuned by the feed ratio of isosorbide but also by the amount of maleic anhydride. The flexural modulus and storage modulus were tailorable by altering the monomer composition The fabricated thermosets had superior thermal and mechanical properties compared to most biobased UP thermosets with thermal stability up to about 250 degrees C and a storage modulus at 25 degrees C varying between 0.5 and 3.0 GPa. These values are close to commercial petroleum-based UP thermosets. The designed tailorable biobased thermosets are, thus, promising candidates to replace their petroleum analogs.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2018
National Category
Biochemistry and Molecular Biology
Identifiers
urn:nbn:se:kth:diva-232790 (URN)10.1021/acs.biomac.8b00661 (DOI)000438470800071 ()29897737 (PubMedID)2-s2.0-85048725262 (Scopus ID)
Note

QC 20180803

Available from: 2018-08-03 Created: 2018-08-03 Last updated: 2018-11-29Bibliographically approved
Feng, Z., Odelius, K., Rajarao, G. K. & Hakkarainen, M. (2018). Microwave carbonized cellulose for trace pharmaceutical adsorption. Chemical Engineering Journal, 346, 557-566
Open this publication in new window or tab >>Microwave carbonized cellulose for trace pharmaceutical adsorption
2018 (English)In: Chemical Engineering Journal, ISSN 1385-8947, E-ISSN 1873-3212, Vol. 346, p. 557-566Article in journal (Refereed) Published
Abstract [en]

A promising sustainable strategy to valorize cellulose to high-value adsorbents for trace pharmaceuticals, like diclofenac sodium (DCF), in the water is demonstrated. Carbon nanospheres (CN) as the DCF adsorbent were derived from cellulose through a one-pot microwave-assisted hydrothermal carbonization method. CN exhibited efficient DCF removal (100% removal of 0.001 mg/mL DCF in 30 s and 59% removal of 0.01 mg/mL DCF in 1 h). The adsorption kinetics and isotherm data were well-fitted with the pseudo-second-order kinetic model and Langmuir model, respectively. The adsorption process was endothermic and spontaneous as confirmed by the thermodynamic parameters. Multiple characterization techniques including SEM/EDS, FTIR, FTIR-imaging and zeta potential were applied to qualitatively investigate the adsorption process. π-π stacking and hydrogen bonding were proposed as the dominant adsorption interactions. CN also demonstrated effective adsorption capacity towards three other commonly-detected contaminants in the wastewater including ketoprofen (KP), benzophenone (BZP), and diphenylamine (DPA), each bearing partial structural similarity with DCF. The affinity of the contaminants towards CN followed the order DPA > BZP > DCF > KP, which could be explained by the different configurations and chemical units. It was speculated that for DCF and KP, the steric hindrance and electrostatic repulsion produced by dissociated carboxyl groups can impede the adsorption process as compared to DPA and BZP. This methodology could offer further insights into the drug adsorption on the cellulose-derived carbon adsorbents and the use of bioderived carbons for treatment of wastewaters contaminated with pharmaceuticals.

Place, publisher, year, edition, pages
Elsevier, 2018
Keywords
Adsorption, Carbon nanosphere, Carbonization, Cellulose, Diclofenac, Microwave
National Category
Chemical Sciences Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-227509 (URN)10.1016/j.cej.2018.04.014 (DOI)000432878400057 ()2-s2.0-85045434362 (Scopus ID)
Note

QC 20180518

Available from: 2018-05-18 Created: 2018-05-18 Last updated: 2019-04-10Bibliographically approved
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0002-5850-8873

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