| 1. |
- Abdelaziz, Omar Y., et al.
(författare)
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Recent strides toward transforming lignin into plastics and aqueous electrolytes for flow batteries
- 2024
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Ingår i: iScience. - : Elsevier Inc.. - 2589-0042. ; 27:4
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Forskningsöversikt (refereegranskat)abstract
- Lignin is an abundant polyaromatic polymer with a wide range of potential future uses. However, the conversion of lignin into valuable products comes at a cost, and medium- to high-value applications are thus appropriate. Two examples of these are polymers (e.g., as fibers, plasticizers, or additives) and flow batteries (e.g., as redox species). Both of these areas would benefit from lignin-derived molecules with potentially low molecular weight and high (electro)chemical functionality. A promising route to obtain these molecules is oxidative lignin depolymerization, as it enables the formation of targeted compounds with multiple functionalities. An application with high potential in the production of plastics is the synthesis of new sustainable polymers. Employing organic molecules, such as quinones and heterocycles, would constitute an important step toward the sustainability of aqueous flow batteries, and lignin and its derivatives are emerging as redox species, mainly due to their low cost and renewability.
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| 2. |
- Dahlqvist, Alexander, et al.
(författare)
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Stereo- And regioselective hydroboration of 1-exo-methylene pyranoses : Discovery of aryltriazolylmethyl C-galactopyranosides as selective galectin-1 inhibitors
- 2019
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Ingår i: Beilstein Journal of Organic Chemistry. - : Beilstein Institut. - 1860-5397. ; 15, s. 1046-1060
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Tidskriftsartikel (refereegranskat)abstract
- Galectins are carbohydrate recognition proteins that bind carbohydrates containing galactose and are involved in cell signaling and cellular interactions, involving them in several diseases. We present the synthesis of (aryltriazolyl)methyl galactopyranoside galectin inhibitors using a highly diastereoselective hydroboration of C1-exo-methylene pyranosides giving inhibitors with fourfold or better selectivity for galectin-1 over galectin-3, -4C (C-terminal CRD), -4N (N-terminal CRD), -7, -8C, -8N, -9C, and -9N and dissociation constants down to 170 μM.
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| 3. |
- Guo, Zengwei, et al.
(författare)
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Development of Circularly Recyclable Low Melting Temperature Bicomponent Fibers toward a Sustainable Nonwoven Application
- 2021
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Ingår i: ACS Sustainable Chemistry and Engineering. - : American Chemical Society. - 2168-0485. ; 9:49, s. 16778-16785
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Tidskriftsartikel (refereegranskat)abstract
- Sustainable low melting temperature bicomponent polyester fibers that can be circularly recycled were developed. The potentially biobased poly(hexamethylene terephthalate) (PHT), acting as the low melting temperature sheath material in the designed bicomponent fibers, was synthesized in a pilot scale. The obtained PHT with an intrinsic viscosity of 0.47 dL/g showed suitable processability when it was processed together with a poly(butylene terephthalate) (PBT) core in a melt-spinning process of bicomponent fibers. Compared with the commercial low melting temperature terephthalate-isophthalate copolyester LMP-160, PHT showed superior mechanical properties according to DMA analysis. The low melting temperature bicomponent fibers with a ratio of the PBT core and PHT sheath at 70:30 were produced smoothly at 290 °C in a pilot melt-spinning line. Preliminary chemical recycling investigations by methanolysis revealed that PHT/PBT bicomponent fibers were completely depolymerized within 2 h at 200 °C, yielding pure terephthalate, which could be conveniently separated and recycled. This indicated the feasibility of circular recycling, which will greatly improve the sustainability of nonwovens thermally bonded by these new bicomponent fibers. © 2021 The Authors.
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| 4. |
- Ismail, Mohamed, et al.
(författare)
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Closing the loop for poly(butylene-adipate-co-terephthalate) recycling: depolymerization, monomers separation, and upcycling
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Ingår i: Green Chemistry. - 1463-9270.
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Tidskriftsartikel (refereegranskat)abstract
- Efficient recycling and upcycling strategies to retain the material in the economy and away from the ecosystems are important to achieve a sustainable plastic system. Poly(butylene adipate-co-terephthalate) (PBAT) is a biodegradable polyester that has gained considerable interest for various applications. Here, we report a study on enzymatic depolymerization of PBAT, recovery and purification of its monomers, and feasible routes for their recycling/upcycling. PBAT films (15 g L−1) were completely hydrolysed employing a leaf-branch compost cutinase variant (LCC-WCCG, 1.4 mg per gram polymer) to its monomers at a rate of 0.49 g L−1 h−1. LCC-WCCG kinetics were superior to that of other enzymes engineered for PBAT hydrolysis; the data were supported by in silico investigations. The released monomers were separated using membrane filtration and precipitation techniques and recovered with purity exceeding 95%. To close the loop, the monomers were re-polymerized and successfully cast into PBAT films. Moreover, adipic acid was reacted with hexamethylene diamine using Novozym®435 to form a polyamide, while 1,4-butanediol was oxidized to 4-hydroxybutyrate using Gluconobacter oxydans cells. The current study exemplifies a high-impact scientific approach toward a circular plastics economy.
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| 5. |
- Mankar, Smita, et al.
(författare)
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Synthesis, life cycle assessment, and polymerization of a vanillin-based spirocyclic diol toward polyesters with increased glass transition temperature
- 2019
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Ingår i: ACS Sustainable Chemistry & Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 7:23, s. 19090-19103
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Tidskriftsartikel (refereegranskat)abstract
- Bio-based rigid diols are key building blocks in the development and preparation of high performance bioplastics with improved thermal and dimensional stability. Here, we report on the straightforward two-step synthesis of a diol with a spirocyclic acetal structure, starting from bio-based vanillin and pentaerythritol. According to a preliminary life cycle assessment (LCA), the greenhouse gas emissions of this bio-based diol are significantly lower than that of bio-based 1,3-propanediol. Copolymerization of the rigid spiro-diol with 1,6-hexanediol and dimethyl terephthalate by melt polymerization yielded a series of copolyesters, which showed improved glass transition temperature and thermal stability upon the incorporation of the spiro-acetal units. The crystallinity and melting point of copolyesters decreased with increasing content of the spirocyclic backbone structures. The copolyesters containing 10% of the new diol was semicrystalline while those with 20 and 30% spiro-diol incorporated were completely amorphous. Moreover, dynamic mechanical analysis indicated that the copolyesters showed comparable storage moduli as AkestraTM, a commercial fossil-based high-performance polyester.
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| 6. |
- Mankar, Smita V., et al.
(författare)
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Short-Loop Chemical Recycling via Telechelic Polymers for Biobased Polyesters with Spiroacetal Units
- 2023
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Ingår i: ACS Sustainable Chemistry & Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 11:13, s. 5135-5146
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Tidskriftsartikel (refereegranskat)abstract
- Spirocyclic acetal structures have recently received growing attention in polymer science due to their dual potential to raise the glass transition temperature (Tg) and enable chemical recycling of biobased polymers. In the present work, a vanillin-based diol with a spirocyclic acetal structure was incorporated in a series of rigid amorphous polyesters based on neopentyl glycol and dimethyl terephthalate (DMT). Up to 50 mol % of spirocyclic diol (with respect to DMT) could be incorporated in the copolyesters, but a reasonably high molecular weight was only achieved when ≤30 mol % of the spirocyclic diol was used. The presence of the spiroacetal units in the polyesters not only enhanced the Tg (up to 103 °C) and thermal stability (T5 ≥ 300 °C) but also the oxygen barrier of solution-cast films. We found that the acetal units in the copolyesters could be selectively hydrolyzed under acidic conditions while virtually retaining all of the ester bonds in the polymer backbone. After acidic hydrolysis, telechelic polymers exclusively terminated by two aldehyde end groups were obtained. In this work, we have demonstrated that these telechelic polyesters can be conveniently converted back into poly(acetal-ester)s via cycloacetalization reactions with pentaerythritol.
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| 7. |
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| 8. |
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| 9. |
- Sayed, Mahmoud, et al.
(författare)
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5-Hydroxymethylfurfural from fructose : An efficient continuous process in a water-dimethyl carbonate biphasic system with high yield product recovery
- 2020
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Ingår i: Green Chemistry. - : Royal Society of Chemistry (RSC). - 1463-9262 .- 1463-9270. ; 22:16, s. 5402-5413
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Tidskriftsartikel (refereegranskat)abstract
- Bio-based 5-hydroxymethylfurfural (5-HMF) and its derivatives have attracted enormous attention due to their valuable market potential. Production of pure 5-HMF is challenging owing to the high reactivity of its functional groups and formation of by-products. In this study, an efficient continuous process for 5-HMF production in a biphasic system and its recovery at high yield and selectivity was developed. After an initial screening of different solvents, a water/dimethyl carbonate (DMC) system was selected for acid catalyzed fructose dehydration in a continuous mode using 0.23 M HCl as a catalyst. Effects of various reaction parameters on substrate conversion, product yield and selectivity, were determined. The process using 30% (w/v) fructose in water with three times the volume of DMC at 1 min residence time in a tube reactor at 200 °C provided 96.5% fructose conversion and 87.2% 5-HMF yield with a selectivity of 85.5% and 95.8% in aqueous and organic phases, respectively. Increasing the fructose concentration in the water phase to 52% gave 96.4% conversion and 74% 5-HMF yield. Using a fructose-glucose mixture as substrate had no effect on fructose conversion but affected slightly the selectivity of 5-HMF in the aqueous phase. Recovery of 5-HMF with ≥93% purity from DMC was achieved by solvent evaporation under vacuum, and improved by prior treatment with activated carbon, especially together with Na2CO3. Evaluation of the purified 5-HMF in a reaction with pentaerythritol showed comparable performance to the commercial 5-HMF in the production of a spirocyclic diol, a monomer for the production of polyesters and polyurethane.
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| 10. |
- Valsange, Nitin, et al.
(författare)
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Biobased aliphatic polyesters from a spirocyclic dicarboxylate monomer derived from levulinic acid
- 2021
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Ingår i: Green Chemistry. - 1463-9270. ; 23:15, s. 5706-5723
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Tidskriftsartikel (refereegranskat)abstract
- Levulinic acid derived from lignocellulose is an important biobased building block chemical. Here, we report on the synthesis and polymerization of a rigid spirocyclic diester monomer to produce polyesters and copolyesters. The monomer was prepared via a one-step acid catalyzed ketalization involving ethyl levulinate and pentaerythritol by employing a straightforward, solvent-free, and readily scalable method which required no chromatographic purification. Still, careful removal of traces of water from the spirodiester prior to the polycondensations proved crucial to avoid side reactions. A preliminary life cycle assessment (LCA) in terms of greenhouse gas (GHG) emissions indicated that the corresponding spirodiacid tended to be environmentally favourable, producing less CO2 emission than e.g., biobased succinic acid and adipic acid. A series of aliphatic polyesters with reasonably high molecular weights was subsequently prepared in melt and modified melt polycondensations of the spiro-diester with 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 1,4-cyclohexanedimethanol, respectively. The resulting fully amorphous polyesters showed glass transition temperatures (Tgs) in the range 12-49 °C and thermalstability up to 300 °C. Hot-pressed films of the polyesters based on neopentyl glycol and 1,4-cyclohexanedimethanol were transparent and mechanically strong, and dynamic melt rheology showed stable shear moduli over time to indicate good processability. In addition, the spiro-diester monomer was employed in copolycondensations with diethyl adipate and 1,4-butanediol and demonstrated good reactivity and stability. Hence, the results of the present study indicate that the spiro-diester based on levulinic acid is an effective monomer for the preparation of aliphatic polyesters and other condensation polymers.
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