Lignin

A topical collection in Polymers (ISSN 2073-4360). This collection belongs to the section "Biomacromolecules, Biobased and Biodegradable Polymers".

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Department of Applied Chemistry, Faculty of Engineering, Chiba Institute of Technology, 2-17-1 Tsudanuma, Narashino, Chiba 275-0016, Japan
Interests: biomaterial; bio-based polymer; bioplastics; biodegradable polymer; biopolymer; composite material comprising a polymer matrix
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Collection Editor
Department of Chemical Engineering and Applied Chemistry, Faculty of Applied Science & Engineering, University of Toronto, Toronto, ON, Canada
Interests: biomass; biopolymer and bio-based materials and chemicals; natural and fiber composites and nanocomposites; cellulose, lignin and extractives; polymer modification and functionalization; polymer adhesives; resins and coatings; smart and functional sensors and devices
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Topical Collection Information

Dear Colleagues,

Lignin is one of main components of ligneous biomass and is mainly obtained from forestry resources. Lignin is biologically produced, mainly from three monomers, p-coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol; however, their polymerized structure is very complicated. The content of aliphatic hydroxyl groups, phenolic hydroxy groups, methoxy groups, and carbonyl groups depends on the source plant. The whole molecular structure of lignin in its original state has not been fully determined yet, since lignin is covalently bound to cell wall polysaccharides and is insoluble in solvents because of its network structure. Therefore, the structural model of lignin has been proposed via integration of partial structures determined from chemically degraded lignin.

More practically, industrial lignin (partially degraded lignin) is obtained from the pulping process in the pulp and paper industry as low utilization value ligneous waste, and is mainly used for recovering energy by burning. Therefore, high-value utilization of industrial lignin has become a very important issue; it is not only required by the paper industry but also required to develop applications of cellulose nanofibers. Recent progress in polymer sciences and technologies has prompted several newly proposed methods of lignin utilization in material applications: (1) lignin-based thermosets, (2) lignin-based thermoplastics, (3) lignin-based additives for plastics such as plasticizers and antioxidants, and (4) lignin-based functional materials such as foams, films, and composites. However, many issues must be resolved before industrial output is possible; for example, we sometimes do not expect reproducibility of research results, because the chemical properties of lignin significantly vary, not only with the diversity of plant species but also according to the methods used to obtain it. Indeed, there are many methods to prepare lignin sources if minor modification is included. Generally, four methods are employed industrially: (1) sulfite pulping, (2) kraft pulping, (3) soda pulping and (4) organosolv pulping. The chemical properties of lignin obtained from each process varied with the quantity of functional groups such as phenolic hydroxy groups, sulfonate groups, and thiol groups. The solubility of lignin in water or organic solvents is also influenced by the extraction method. Though there exist a lot of obstacles to material applications, lignin is an attractive chemical due to its abundance and versatility. Therefore, we can expect steady development of lignin-based materials in future research.

In this collection, studies on the synthesis, physical and chemical properties, and novel functionality of lignin-based polymeric materials are welcome. Studies on the extraction, modification, and characterization of natural lignin and its applications are also welcome.

Dr. Naozumi Teramoto
Prof. Dr. Ning Yan
Collection Editors

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Keywords

  • lignin extraction and conversion
  • lignin-based chemicals and materials
  • biosynthesis of lignin
  • chemical structure and characterization of lignin
  • applications of lignin

Published Papers (3 papers)

2024

13 pages, 2268 KiB  
Review
Recent Progress on Conversion of Lignocellulosic Biomass by MOF-Immobilized Enzyme
by Juan Tao, Shengjie Song and Chen Qu
Polymers 2024, 16(7), 1010; https://doi.org/10.3390/polym16071010 - 08 Apr 2024
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Abstract
The enzyme catalysis conversion of lignocellulosic biomass into valuable chemicals and fuels showed a bright outlook for replacing fossil resources. However, the high cost and easy deactivation of free enzymes restrict the conversion process. Immobilization of enzymes in metal–organic frameworks (MOFs) is one [...] Read more.
The enzyme catalysis conversion of lignocellulosic biomass into valuable chemicals and fuels showed a bright outlook for replacing fossil resources. However, the high cost and easy deactivation of free enzymes restrict the conversion process. Immobilization of enzymes in metal–organic frameworks (MOFs) is one of the most promising strategies due to MOF materials’ tunable building units, multiple pore structures, and excellent biocompatibility. Also, MOFs are ideal support materials and could enhance the stability and reusability of enzymes. In this paper, recent progress on the conversion of cellulose, hemicellulose, and lignin by MOF-immobilized enzymes is extensively reviewed. This paper focuses on the immobilized enzyme performances and enzymatic mechanism. Finally, the challenges of the conversion of lignocellulosic biomass by MOF-immobilized enzyme are discussed. Full article
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12 pages, 24391 KiB  
Article
Effect of Iron Chloride Addition on Softwood Lignin Nano-Fiber Stabilization and Carbonization
by Maxime Parot, Denis Rodrigue and Tatjana Stevanovic
Polymers 2024, 16(6), 814; https://doi.org/10.3390/polym16060814 - 14 Mar 2024
Viewed by 1060
Abstract
This study presents the effect of iron chloride addition on the production of nanocarbon fibers from softwood Organosolv lignin. It was shown that adding 2% FeCl3 to the lignin solution before electrospinning to produce lignin nanofibers increased the thermal resistance of lignin [...] Read more.
This study presents the effect of iron chloride addition on the production of nanocarbon fibers from softwood Organosolv lignin. It was shown that adding 2% FeCl3 to the lignin solution before electrospinning to produce lignin nanofibers increased the thermal resistance of lignin fibers during stabilization. FTIR and XPS analyses of the lignin fibers stabilized with and without FeCl3 revealed that the temperature rate could be increased in the presence of FeCl3 from 1 to 3 °C/min. The optimal temperature to stabilize the lignin fibers was found to be 250 °C, as higher temperatures led to thermal degradation. Also, carbon fibers were successfully produced from pure softwood Organosolv lignin fibers. Carbonization tests were conducted under nitrogen and the best parameters were determined to be a ramp of 10 °C/min until 600 °C with a holding time of 2 h. Furthermore, the effect of 2% FeCl3 addition in the lignin solution was investigated during these processes. XPS analysis showed a 93% carbon content for fibers carbonized with and without FeCl3 addition, while SEM images revealed some surface roughness in fibers with FeCl3 after carbonization. These results confirm that FeCl3 addition influences the carbon nanofiber production. Full article
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34 pages, 11139 KiB  
Article
Kraft (Nano)Lignin as Reactive Additive in Epoxy Polymer Bio-Composites
by Christina P. Pappa, Simone Cailotto, Matteo Gigli, Claudia Crestini and Konstantinos S. Triantafyllidis
Polymers 2024, 16(4), 553; https://doi.org/10.3390/polym16040553 - 18 Feb 2024
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Abstract
The demand for high-performance bio-based materials towards achieving more sustainable manufacturing and circular economy models is growing significantly. Kraft lignin (KL) is an abundant and highly functional aromatic/phenolic biopolymer, being the main side product of the pulp and paper industry, as well as [...] Read more.
The demand for high-performance bio-based materials towards achieving more sustainable manufacturing and circular economy models is growing significantly. Kraft lignin (KL) is an abundant and highly functional aromatic/phenolic biopolymer, being the main side product of the pulp and paper industry, as well as of the more recent 2nd generation biorefineries. In this study, KL was incorporated into a glassy epoxy system based on the diglycidyl ether of bisphenol A (DGEBA) and an amine curing agent (Jeffamine D-230), being utilized as partial replacement of the curing agent and the DGEBA prepolymer or as a reactive additive. A D-230 replacement by pristine (unmodified) KL of up to 14 wt.% was achieved while KL–epoxy composites with up to 30 wt.% KL exhibited similar thermo-mechanical properties and substantially enhanced antioxidant properties compared to the neat epoxy polymer. Additionally, the effect of the KL particle size was investigated. Ball-milled kraft lignin (BMKL, 10 μm) and nano-lignin (NLH, 220 nm) were, respectively, obtained after ball milling and ultrasonication and were studied as additives in the same epoxy system. Significantly improved dispersion and thermo-mechanical properties were obtained, mainly with nano-lignin, which exhibited fully transparent lignin–epoxy composites with higher tensile strength, storage modulus and glass transition temperature, even at 30 wt.% loadings. Lastly, KL lignin was glycidylized (GKL) and utilized as a bio-based epoxy prepolymer, achieving up to 38 wt.% replacement of fossil-based DGEBA. The GKL composites exhibited improved thermo-mechanical properties and transparency. All lignins were extensively characterized using NMR, TGA, GPC, and DLS techniques to correlate and justify the epoxy polymer characterization results. Full article
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