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Keywords = lignin-based polyurethane

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20 pages, 5622 KB  
Article
Kraft Lignin-Based Polyurethane with GVL: A Sustainable Coating Alternative for Recycled Linerboard
by Julia C. Figueiredo, Roberto C. C. Lelis, Rosane N. Castro, Fernando J. B. Gomes, Ericka F. A. Redmond and Biljana M. Bujanovic
Polymers 2026, 18(1), 118; https://doi.org/10.3390/polym18010118 - 31 Dec 2025
Abstract
Food packaging is the largest segment of the global plastics market, yet its low degradability and limited performance in preserving perishable goods highlight the need for more sustainable alternatives. This study investigates the use of industrial softwood kraft lignin, a renewable polyol, and [...] Read more.
Food packaging is the largest segment of the global plastics market, yet its low degradability and limited performance in preserving perishable goods highlight the need for more sustainable alternatives. This study investigates the use of industrial softwood kraft lignin, a renewable polyol, and γ-valerolactone (GVL), an excellent green lignin solvent, to synthesize bio-based polyurethane (PU) coatings for recycled linerboard. PU was synthesized with hexamethylene diisocyanate (HDI), GVL, and 1,4-diazabicyclo[2.2.2]octane (DABCO) as a catalyst and applied to recycled linerboard (166.6 g/m2) at three coating weights: 13.5, 16.5, and 23.5 g/m2. The coating enhanced water resistance, as shown by the reduced water vapor transmission rate (WVTR) and Cobb1800 values. Oil resistance was also significantly improved, reaching a Kit rating of 11 at the highest coating weight. Mechanical performance was maintained or enhanced, with increases in ring crush strength (RCT) and tensile index. These findings confirm the effectiveness of lignin-based PU in improving both the barrier and mechanical properties of packaging paper. Additionally, this approach presents an environmentally responsible alternative to petroleum-based coatings, adding value to lignin as a byproduct of the pulp and paper industry and supporting the transition toward more circular and sustainable packaging materials. Full article
(This article belongs to the Special Issue Lignin-Based Polymers)
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13 pages, 3362 KB  
Article
Multifunctional Bamboo Fiber/Epoxy Composites Featuring Integrated Superhydrophobicity and Enhanced Mechanical–Thermal Performance
by Yanchao Liu, Ze Yu, Rumin Li, Xiaodong Wang and Yingjie Qiao
Nanomaterials 2026, 16(1), 8; https://doi.org/10.3390/nano16010008 - 19 Dec 2025
Viewed by 210
Abstract
Developing sustainable, high-performance biomass composites is crucial for replacing non-renewable structural materials. In this study, a “bamboo steel” composite was fabricated using a multilevel modification strategy involving alkali pretreatment, toughened resin impregnation, and surface functionalization. Bamboo fibers were treated to remove hemicellulose and [...] Read more.
Developing sustainable, high-performance biomass composites is crucial for replacing non-renewable structural materials. In this study, a “bamboo steel” composite was fabricated using a multilevel modification strategy involving alkali pretreatment, toughened resin impregnation, and surface functionalization. Bamboo fibers were treated to remove hemicellulose and lignin, enhancing porosity and interfacial bonding. The bamboo scaffold was subsequently impregnated with a thermo-plastic polyurethane-modified epoxy resin to create a robust, interpenetrating network. The optimized composite (treated at 80 °C) exhibited a flexural strength of 443.97 MPa and a tensile strength of 324.14 MPa, demonstrating exceptional stiffness and toughness. Furthermore, a superhydrophobic coating incorporating silica nanoparticles was applied, achieving a water contact angle exceeding 150° and excellent self-cleaning properties. This work presents a scalable strategy for producing bio-based structural materials that balance mechanical strength with environmental durability. Full article
(This article belongs to the Section Nanocomposite Materials)
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20 pages, 4180 KB  
Article
A New Lignin-Based Polyurethane Film for Wood: Decay, Artificial Weathering, Physical and Morphological Characterization
by Swati Tamantini, Sara Bergamasco, Miha Humar, Marko Petrič and Manuela Romagnoli
Molecules 2025, 30(24), 4793; https://doi.org/10.3390/molecules30244793 - 16 Dec 2025
Viewed by 330
Abstract
Lignin-based polyurethanes represent a promising strategy for developing more sustainable wood coatings by partially replacing fossil-derived polyols with renewable aromatic biopolymers. In this study, a polyurethane formulated with organosolv lignin (LPU) was synthesized and applied on two non-durable European wood species, Fagus sylvatica [...] Read more.
Lignin-based polyurethanes represent a promising strategy for developing more sustainable wood coatings by partially replacing fossil-derived polyols with renewable aromatic biopolymers. In this study, a polyurethane formulated with organosolv lignin (LPU) was synthesized and applied on two non-durable European wood species, Fagus sylvatica L. and Picea abies L., and compared with a commercial fossil-based polyurethane (CPU). Coated samples were evaluated for color stability, gloss evolution, wettability, adhesion, impact and scratch resistance, and biological durability. Accelerated ageing was performed under xenon-light irradiation, while decay resistance was assessed against Gloeophyllum trabeum and Trametes versicolor. Additional tests examined susceptibility to blue-stain fungi and surface morphology via SEM. LPU produced a matte film with intrinsically darker coloration but excellent chromatic stability and minimal gloss variation during ageing. Its initial hydrophobicity was higher on beech and comparable to CPU on spruce. Although CPU exhibited superior adhesion and slightly better mechanical resistance, LPU provided enhanced protection against blue-stain fungi—particularly on spruce—and a more uniform response to decay fungi across wood species. Overall, despite its darker appearance, the lignin-based formulation offered functional protection comparable to the commercial coating, confirming its potential as a viable bio-based alternative for above-ground wood applications. Full article
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17 pages, 4006 KB  
Article
A Dual Valorization Strategy of Barley Straw for the Development of High-Performance Bio-Based Polyurethane Foams
by Marina Rodríguez-Aranda, Esther Rincón, María Pinillos, Pablo E. Romero and Luis Serrano
Polymers 2025, 17(23), 3142; https://doi.org/10.3390/polym17233142 - 26 Nov 2025
Viewed by 440
Abstract
This study presents a complete and zero-waste valorization strategy for barley straw through the synthesis of bio-polyols and the concurrent utilization of its cellulose fraction as lignin-containing cellulose nanofibers (LCNF) for the development of bio-based polyurethane (PU) foams. Two types of bio-polyols were [...] Read more.
This study presents a complete and zero-waste valorization strategy for barley straw through the synthesis of bio-polyols and the concurrent utilization of its cellulose fraction as lignin-containing cellulose nanofibers (LCNF) for the development of bio-based polyurethane (PU) foams. Two types of bio-polyols were prepared: one derived from lignin isolated via biomass fractionation, named lignin bio-polyol (LBP), and another obtained directly from unfractionated barley straw, called straw bio-polyol (SBP), thereby incorporating all lignocellulosic constituents into a single reactive matrix. LCNF, produced from the same feedstock, was incorporated at different loadings to achieve full biomass utilization and reinforce the polyurethane foam structure. Foams prepared with LBP exhibited lower density and a more homogeneous structure, whereas those synthesized with SBP developed a stiffer, more crosslinked network. The incorporation of LCNF generally increased apparent density and mechanical performance, with optimal reinforcement at 3 wt.% in foams with SBP and 5 wt.% in LBP foams, corresponding to a 62.5 and 121% enhancement in compressive strength relative to their respective control foams. Moreover, the use of barley straw bio-polyol shifted some thermal degradation peaks toward higher temperatures, evidencing improved thermal resistance. Overall, this dual-route strategy provides a sustainable and versatile methodology for the comprehensive valorization of lignocellulosic biomass, enabling a systematic understanding of the role of each structural component in polyurethane foam synthesis. The resulting materials offer a renewable, low-impact pathway toward high-performance polymeric materials. Full article
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23 pages, 1771 KB  
Article
An Integrated Biorefinery Proof of Concept: The Synthesis of Fully Bio-Based, Functional Lignin Polyester Copolymers of Cyclic Anhydrides and Epoxides Towards Polyol Applications and Tunable Bio-Derived Materials
by Oliver J. Driscoll, Daniel J. van de Pas, Kirk M. Torr, Hayden P. Thomas, Richard Vendamme and Elias Feghali
Polymers 2025, 17(20), 2806; https://doi.org/10.3390/polym17202806 - 21 Oct 2025
Viewed by 1118
Abstract
A versatile, sustainable feedstock pathway to bio-based polymeric materials was developed utilizing lignin biomass and the ring-opening copolymerization (ROCOP) of cyclic anhydrides and epoxides to synthesize functional, lignin-derived, fully bio-based polyester polyols. The initial goal was to make the ROCOP reaction more applicable [...] Read more.
A versatile, sustainable feedstock pathway to bio-based polymeric materials was developed utilizing lignin biomass and the ring-opening copolymerization (ROCOP) of cyclic anhydrides and epoxides to synthesize functional, lignin-derived, fully bio-based polyester polyols. The initial goal was to make the ROCOP reaction more applicable to bio-derived starting materials and more attractive to commercialization by conducting the polymerization under less constrained and industrially relevant conditions in air and without the extensive purification of reagents, catalysts, or solvents, typically used in the literature. A refined ROCOP system was applied as a powerful tool in lignin valorization by successfully synthesizing the lignin-derived copolyester prepolymers from lignin models and depolymerized native lignin sourced from the reductive catalytic fractionation of Pinus radiata wood biomass. After mechanistic studies based on NMR characterization, an alternative ROCOP-style mechanism was proposed. This was found to be (1) contributing to the acceleration of the observed reaction rates with added [PPNCl] organo-catalyst and (2) ‘self-initiation/self-promoted’ ROCOP without any added external [PPNCl] catalyst, likely due to the presence of inherent [OH] groups/ species in the lignin-derived glycidyl ether monomer promoting reactivity. As a final goal, the potential of these lignin-derived polyesters as intermediate polyols was demonstrated by applying them in the synthesis of polyurethane (PU) film materials with a high biomass content of 75–79%. A dramatic range of thermomechanical properties was observed for the resulting materials, demonstrating how the ROCOP reaction can be used to tailor the properties of the functional polyester and PU material based on the nature of the epoxide and anhydride substrates used. These findings help endeavors towards predicting the relationship between chemical structure and material thermomechanical properties and performance, relevant for industrial applications. Overall, this study demonstrated the proof of concept that PU materials can be prepared from lignocellulosic biomass utilizing industrially feasible ROCOP of bio-derived cyclic anhydrides and epoxides. Full article
(This article belongs to the Special Issue Recent Progress on Lignocellulosic-Based Polymeric Materials)
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19 pages, 7384 KB  
Article
Lignin-Modified Petrochemical-Source Polyester Polyurethane Enhances Nutrient Release Performance of Coated Urea
by Xiaomin Hu, Baishan Liu, Siyu Chen, Qi Chen, Heping Chen, Jingjing Dong, Kexin Zhang, Junxi Wang, Min Zhang and Zhiguang Liu
Agronomy 2025, 15(9), 2030; https://doi.org/10.3390/agronomy15092030 - 25 Aug 2025
Viewed by 1193
Abstract
The development of controlled-release fertilizers (CRFs) has faced significant challenges due to high hydrophilicity and short release lifespan of bio-based materials, as well as non-renewable and high cost of polyester polyols (PPs). In this study, lignin-based polyols (LPs) and PPs were modified to [...] Read more.
The development of controlled-release fertilizers (CRFs) has faced significant challenges due to high hydrophilicity and short release lifespan of bio-based materials, as well as non-renewable and high cost of polyester polyols (PPs). In this study, lignin-based polyols (LPs) and PPs were modified to form a cross-linked polymer film on the surface of urea through an in situ reaction. This approach effectively balanced the slow-release ability and environmental protection of controlled-release fertilizer films. A two-factor, five-level orthogonal test was designed for the mass ratio of lignin/polyester polyol and polyol/polyaryl polymethylene isocyanate (PAPI), comprising a total of 25 treatments. The results indicated that the appropriateness of lignin polyols increased the hydrogen bond content of polyurethane membrane, improved the mechanical strength of the fertilizer membrane shell, and effectively reduced friction losses during storage and transportation. Moreover, optimizing the polyol-to-PAPI ratio minimized coating porosity, produced a smoother and denser surface, and prolonged the nitrogen release period. When the lignin polyol dosage was 25% and the polyol to PAPI ratio was 1:2, the nitrogen release time of the prepared coated urea extended to 32 days, which was 3.5 times longer than that of lignin polyurethane coated urea (7 days). The incorporation of lignin and the optimal ratio of coating materials significantly improved the controlled-release efficiency of coated fertilizer, providing theoretical support for the sustainable agricultural application of biomass. Full article
(This article belongs to the Special Issue Advances Towards Innovative Fertilizers for Sustainable Agriculture)
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45 pages, 4647 KB  
Systematic Review
A Systematic Review of Biopolymer Phase Change Materials for Thermal Energy Storage: Challenges, Opportunities, and Future Direction
by Nadia Parwaty Wijanarko, Sindu Daniarta and Piotr Kolasiński
Energies 2025, 18(16), 4262; https://doi.org/10.3390/en18164262 - 11 Aug 2025
Cited by 1 | Viewed by 2681
Abstract
This article systematically reviews biopolymer phase change materials (PCMs) for TES applications. The review was conducted based on Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) guidelines using databases from Scopus, Web of Science, and Google Scholar. The biopolymer PCMs are categorized [...] Read more.
This article systematically reviews biopolymer phase change materials (PCMs) for TES applications. The review was conducted based on Preferred Reporting Items for Systematic Reviews and Meta-Analyses (PRISMA) guidelines using databases from Scopus, Web of Science, and Google Scholar. The biopolymer PCMs are categorized as natural, synthetic, and hybrid (a combination of natural and synthetic). A total of 82 articles were included in the analysis. Several thermal properties, mechanical properties, advancements, and challenges are discussed. This article aims to review biopolymer PCMs and identify research gaps for future development. Natural biopolymer PCMs include lipid, lignin, polysaccharides, proteins, etc. Synthetic biopolymer PCMs include supramolecular, polyethylene glycol, polyurethane, polyrotaxane, polylactic acid, etc. Hybrid biopolymer PCMs combine natural and synthetic polymers with conductive fillers, balancing high latent heat with improved thermal stability and durability, although issues, like leakage and low conductivity, persist. It is found that biopolymers can be used as the core and supporting matrix of PCMs. Several cases and configurations of core, supporting matrix, and fillers in the development of PCM from biopolymers are discussed. This article also demonstrates that several natural, synthetic, and hybrid biopolymer PCMs hold promise for demanding TES applications due to their tunable properties and reliability. Biopolymer PCMs offer a sustainable alternative to petroleum-derived substances by minimizing environmental harm, cutting carbon emissions, and promoting a circular economy. This review also highlights several challenges, such as feedstock selection, purification and encapsulation, system compatibility, and standardization, that future research might address to enable scalable, safe, and cost-effective biopolymer PCM solutions. Full article
(This article belongs to the Section D: Energy Storage and Application)
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23 pages, 6941 KB  
Article
Isolation and Characterization of Lignin from Sapele (Entandrophragma cylindricum): Application in Flexible Polyurethane Foam Production
by Hubert Justin Nnanga Guissele, Arnaud Maxime Cheumani Yona, Armel Edwige Mewoli, Désiré Chimeni-Yomeni, Lucioni Fabien Tsague, Tatiane Marina Abo, Jean-Bosco Saha-Tchinda, Maurice Kor Ndikontar and Antonio Pizzi
Polymers 2025, 17(15), 2156; https://doi.org/10.3390/polym17152156 - 6 Aug 2025
Viewed by 840
Abstract
Lignin used in this work was isolated from sapele (Entandrophragma cylindricum) wood through a hybrid pulping process using soda/ethanol as pulping liquor and denoted soda-oxyethylated lignin (SOL). SOL was mixed with a polyethylene glycol (PEG)–glycerol mixture (80/20 v/v) [...] Read more.
Lignin used in this work was isolated from sapele (Entandrophragma cylindricum) wood through a hybrid pulping process using soda/ethanol as pulping liquor and denoted soda-oxyethylated lignin (SOL). SOL was mixed with a polyethylene glycol (PEG)–glycerol mixture (80/20 v/v) as liquefying solvent with 98% wt. sulfur acid as catalyst, and the mixture was taken to boil at 140 °C for 2, 2.5, and 3 h. Three bio-polyols LBP1, LBP2, and LBP3 were obtained, and each of them exhibited a high proportion of -OH groups. Lignin-based polyurethane foams (LBPUFs) were prepared using the bio-polyols obtained with a toluene diisocyanate (TDI) prepolymer by the one-shot method. Gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), and carbon-13 nuclear magnetic resonance spectroscopy (13C NMR) were used characterize lignin in order to determine viscosity, yield, and composition and to characterize their structure. The PEG-400–glycerol mixture was found to react with the lignin bio-polyols’ phenolic -OHs. The bio-polyols’ viscosity was found to increase as the liquefaction temperature increased, while simultaneously their molecular weights decreased. All the NCO groups were eliminated from the samples, which had high thermal stability as the liquefaction temperature increased, leading to a decrease in cell size, density, and crystallinity and an improvement in mechanical performance. Based on these properties, especially the presence of some aromatic rings in the bio-polyols, the foams produced can be useful in automotive applications and for floor carpets. Full article
(This article belongs to the Section Circular and Green Sustainable Polymer Science)
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75 pages, 15988 KB  
Review
Tailoring Polymer Properties Through Lignin Addition: A Recent Perspective on Lignin-Derived Polymer Modifications
by Nawoda L. Kapuge Dona and Rhett C. Smith
Molecules 2025, 30(11), 2455; https://doi.org/10.3390/molecules30112455 - 3 Jun 2025
Cited by 6 | Viewed by 3839
Abstract
Lignin, an abundant and renewable biopolymer, has gained significant attention as a sustainable modifier and building block in polymeric materials. Recent advancements highlight its potential to tailor mechanical, thermal, and barrier properties of polymers while offering a greener alternative to petroleum-based additives. This [...] Read more.
Lignin, an abundant and renewable biopolymer, has gained significant attention as a sustainable modifier and building block in polymeric materials. Recent advancements highlight its potential to tailor mechanical, thermal, and barrier properties of polymers while offering a greener alternative to petroleum-based additives. This review provides an updated perspective on the incorporation of lignin into various polymer matrices, focusing on lignin modification techniques, structure–property relationships, and emerging applications. Special emphasis is given to recent innovations in lignin functionalization and its role in developing high-performance, biodegradable, and recyclable materials such as polyurethanes, epoxy resins, phenol-formaldehyde resins, lignin-modified composites, and lignin-based films, coatings, elastomers, and adhesives. These lignin-based materials are gaining attention for potential applications in construction, automated industries, packaging, textiles, wastewater treatment, footwear, supporting goods, automobiles, printing rollers, sealants, and binders. Full article
(This article belongs to the Special Issue Advances in Polymer Materials Based on Lignocellulosic Biomass)
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34 pages, 763 KB  
Review
Bio-Based Polyurethane Materials: Technical, Environmental, and Economic Insights
by Piumi Jayalath, Kalyani Ananthakrishnan, Soyeon Jeong, Reshma Panackal Shibu, Mairui Zhang, Deepak Kumar, Chang Geun Yoo, Julia L. Shamshina and Obste Therasme
Processes 2025, 13(5), 1591; https://doi.org/10.3390/pr13051591 - 20 May 2025
Cited by 12 | Viewed by 6958
Abstract
Polyurethane (PU) is widely used due to its attractive properties, but the shift to a low-carbon economy necessitates alternative, renewable feedstocks for its production. This review examines the synthesis, properties, and sustainability of bio-based PU materials, focusing on renewable resources such as lignin, [...] Read more.
Polyurethane (PU) is widely used due to its attractive properties, but the shift to a low-carbon economy necessitates alternative, renewable feedstocks for its production. This review examines the synthesis, properties, and sustainability of bio-based PU materials, focusing on renewable resources such as lignin, vegetable oils, and polysaccharides. It discusses recent advances in bio-based polyols, their incorporation into PU formulations, and the use of bio-fillers like chitin and nanocellulose to improve mechanical, thermal, and biocompatibility properties. Despite promising material performance, challenges related to large-scale production, economic feasibility, and recycling technologies are highlighted. The paper also reviews life cycle assessment (LCA) studies, revealing the complex and context-dependent environmental benefits of bio-based PU materials. These studies indicate that while bio-based PU materials generally reduce greenhouse gas emissions and non-renewable energy use, their environmental performance varies depending on feedstock and formulation. The paper identifies key areas for future research, including improving biorefinery processes, optimizing crosslinker performance, and advancing recycling methods to unlock the full environmental and economic potential of bio-based PU in commercial applications. Full article
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25 pages, 5095 KB  
Article
Adverse Outcome Pathways (AOPs) Oriented Approach to Assess In Vitro Hazard of Silica and Lignin Nanomaterials Derived from Biomass Residues
by Rossella Daniela Bengalli, Maurizio Gualtieri, Mariana Ornelas, Tzanko Tzanov and Paride Mantecca
Nanomaterials 2025, 15(7), 549; https://doi.org/10.3390/nano15070549 - 4 Apr 2025
Cited by 3 | Viewed by 1117
Abstract
Bio-based nanomaterials (B-NMs), such as silica oxide (SiO2)- and lignin (Lig)- based nanoparticles (NPs) derived from biomass waste, have gained attention in the last few years in the view of promoting the sustainability principles in several applications. However, scarce data are [...] Read more.
Bio-based nanomaterials (B-NMs), such as silica oxide (SiO2)- and lignin (Lig)- based nanoparticles (NPs) derived from biomass waste, have gained attention in the last few years in the view of promoting the sustainability principles in several applications. However, scarce data are available about their safety. Thus, a hazard-testing strategy was designed considering as a reference the safe-and-sustainable-by-design (SSbD) framework for chemicals and materials, prioritizing the use of new approach methodologies (NAMs), such as in vitro and adverse outcome pathways (AOPs) approaches, for generating data about the potential hazard of B-NMs. Literature research was performed to identify the adverse outcomes (AOs) related to the selected B-NMs. All the AOPs investigated shared at least oxidative stress, inflammation and cytotoxicity as key events (KEs) that were investigated in lung and immune cells. The tested B-NMs resulted either non-toxic or moderately toxic towards human cells, validating their biocompatibility when compared to reference NMs of similar composition, but not of bio-origin. However, attention should be given to possible AOs deriving after specific functionalization of the B-NMs. Considering the lack of knowledge in this field, the studies performed represent a step forward in the state of the art of the safety assessment of B-NMs. Full article
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17 pages, 3884 KB  
Article
Preparation of Wood Fiber–Polyurethane Plastic Composite with Water Resistance and High Strength
by Xi Yuan, Shiyu Fu and Hao Liu
Materials 2025, 18(6), 1314; https://doi.org/10.3390/ma18061314 - 17 Mar 2025
Cited by 2 | Viewed by 1407
Abstract
The current widespread use of plastics is a significant source of environmental pollution and increases the carbon load in the atmosphere, which has precipitated an urgent drive to replace plastics with biomass-based materials. In this paper, we prepared a lignocellulose-based, high-strength, water-resistant composite [...] Read more.
The current widespread use of plastics is a significant source of environmental pollution and increases the carbon load in the atmosphere, which has precipitated an urgent drive to replace plastics with biomass-based materials. In this paper, we prepared a lignocellulose-based, high-strength, water-resistant composite based on eucalyptus waste sawdust combined with a polyurethane prepolymer. The preparation process included pretreating sawdust with deep eutectic solvents (DESs) to remove some of the lignin and hemicellulose. A prepolymer preparation involving isocyanate groups using the prepolymerization of polyethylene glycol (PEG) with hexamethylene diisocyanate (HDI) grafted the prepolymers to the hydroxyl of the pretreated wood fibers, which were subsequently blended with acetylated pretreated sawdust to create the composite. The composite contained 67% wood fibers, possessed good tensile strength, and exhibited Young’s moduli of 18 MPa and 484 MPa. It was water-resistant with a contact angle of 92° and had a low water absorption of 32%, and it maintained a wet tensile strength of 5.71 MPa. The composite offers several advantages, including UV protection and thermal stability. This high-performance wood waste composite provides an alternative green production option for producing plastic materials. Full article
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16 pages, 3137 KB  
Article
Functionalization of Phenolic Aldehydes for the Preparation of Sustainable Polyesters and Polyurethanes
by Rachele N. Carafa, Brigida V. Fernandes, Clara Repiquet, Sidrah Rana, Daniel A. Foucher and Guerino G. Sacripante
Polymers 2025, 17(5), 643; https://doi.org/10.3390/polym17050643 - 27 Feb 2025
Cited by 1 | Viewed by 2093
Abstract
Biobased organic diols derived from the phenolic aldehyde by-products in the depolymerization of lignin (4-hydroxybenzaldehyde, vanillin, and syringaldehyde) for the synthesis of polyesters and polyurethanes is described. Methods to prepare lignin-based diols involved a two-step synthetic route using either a hydroxy alkylation and [...] Read more.
Biobased organic diols derived from the phenolic aldehyde by-products in the depolymerization of lignin (4-hydroxybenzaldehyde, vanillin, and syringaldehyde) for the synthesis of polyesters and polyurethanes is described. Methods to prepare lignin-based diols involved a two-step synthetic route using either a hydroxy alkylation and aldehyde reduction or an aldehyde reduction and Williamson–Ether substitution. The preparation of five polyesters (PEs) and ten polyurethanes (PUs) from lignin-based diols was also performed and their physical and thermal properties were analyzed. DSC analysis confirmed the amorphous nature of all synthesized polymers, and GPC analysis revealed broad dispersities and high molecular weights. Two PE polyols were also derived from a vanillin-based diol at concentrations of 10 and 25 wt% for their usage in sustainable PU foams. PU foams were prepared from these polyols, where it was found that only the foam containing the 10 wt% formulation was suitable for mechanical testing. The PU foam samples were found to have good hardness and tensile strengths compared to both control foams, showing potential for the incorporation of biobased polyols for PU foam formation. Full article
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18 pages, 6206 KB  
Article
Exploring the Effect of the Polyol Structure and the Incorporation of Lignin on the Properties of Bio-Based Polyurethane
by Bomin Kim, Jihoon Lee, Sunjin Jang, Jaehyeon Park, Jinsil Choi, Seungyeol Lee, Joonhoo Jung and Jaehyung Park
Polymers 2025, 17(5), 604; https://doi.org/10.3390/polym17050604 - 24 Feb 2025
Cited by 6 | Viewed by 2634
Abstract
This study developed bio-based waterborne polyurethane (BWPU) dispersions containing lignin as a sustainable filler with castor oil (CO), polycaprolactone diol (PCL), or poly(trimethylene ether) glycol (PO3G). The effects of the polyol structure and the presence of lignin on the mechanical performance, thermal stability, [...] Read more.
This study developed bio-based waterborne polyurethane (BWPU) dispersions containing lignin as a sustainable filler with castor oil (CO), polycaprolactone diol (PCL), or poly(trimethylene ether) glycol (PO3G). The effects of the polyol structure and the presence of lignin on the mechanical performance, thermal stability, water absorption, ethanol resistance, and UV-blocking capabilities of the resulting BWPU samples were evaluated. The results revealed that lignin affects the molecular packing and interchain interactions of CO-based BWPU, thus improving its tensile strength and thermal stability while reducing its water absorption and ethanol permeability. In the PCL-based BWPU, lignin had a minimal impact on water absorption and ethanol resistance but led to greater UV-blocking ability due to interactions between the semi-crystalline matrix of PCL and the aromatic structure of the lignin. In the PO3G-based BWPU, lignin disrupted the polymer network, increasing its water absorption and reducing its ethanol resistance but significantly improving its elongation and UV-shielding behavior. These results highlight the dual role of lignin as a sustainable reinforcing agent and functional additive in enhancing the properties of BWPU. By tailoring the polyol structure and optimizing lignin use, this study demonstrates a framework for the development of eco-friendly PU composites suitable for use as coatings, barriers, UV-shielding films, and packaging Full article
(This article belongs to the Section Biobased and Biodegradable Polymers)
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21 pages, 4102 KB  
Article
Investigation on Dynamic and Static Modulus and Creep of Bio-Based Polyurethane-Modified Asphalt Mixture
by Biao Han, Yongming Xing and Chao Li
Polymers 2025, 17(3), 359; https://doi.org/10.3390/polym17030359 - 28 Jan 2025
Cited by 1 | Viewed by 1276
Abstract
The superior mechanical qualities of polyurethane have garnered increasing attention for its application in modifying asphalt mixtures. However, polyurethane needs to use polyols to cure, and polyols need to be produced by petroleum refining. As we all know, petroleum is a non-renewable energy [...] Read more.
The superior mechanical qualities of polyurethane have garnered increasing attention for its application in modifying asphalt mixtures. However, polyurethane needs to use polyols to cure, and polyols need to be produced by petroleum refining. As we all know, petroleum is a non-renewable energy source. In order to reduce oil consumption and conform to the trend of a green economy, lignin and chitin were used instead of polyols as curing agents. In this paper, a biological polyurethane-modified asphalt mixture (BPA-16) was designed and compared with a polyurethane-modified asphalt mixture (PA-16) and a matrix asphalt mixture (MA-16). The viscoelastic characteristics of the three asphalt mixtures were evaluated using dynamic modulus, static modulus, and creep tests. The interplay between dynamic and static modulus and frequency is examined, along with the variations in the correlation between dynamic and static modulus. The creep behavior of the mixture was ultimately examined by a uniaxial static load creep test. The findings indicate that the dynamic modulus of BPA-16 exceeds those of PA-16 and MA-16 by 8.7% and 30.4% at 25 Hz and −20 °C, respectively. At 25 Hz and 50 °C, the phase angle of BPA-16 decreases by 26.3% relative to that of MA-16. Lignin and chitin, when utilized as curing agents in place of polyol, can enhance the mechanical stability of asphalt mixtures at low temperatures and diminish their temperature sensitivity. A bio-based polyurethane-modified asphalt mixture can also maintain better elastic properties in a wider temperature range. At −20–20 °C, the dynamic and static moduli of BPA-16, PA-16 and MA-16 are linear, and they can be converted by formula at different frequencies. The failure stages of BPA-16, PA-16, and MA-16 are not observed during the 3600 s creep duration, with BPA-16 exhibiting the least creep strain, indicating that lignin and chitin enhance the resistance to permanent deformation in PU-modified asphalt mixes. Full article
(This article belongs to the Section Polymer Applications)
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