Search Results (35)

Polyurethanes (PUs) are indispensable polymeric materials widely employed across diverse industrial sectors due to their excellent thermal stability, chemical resistance, adhesion, and mechanical durability. However, the intrinsic three-dimensional crosslinked network that underpins their performance also presents a fundamental barrier to reprocessing and recycling. Consequently, most end-of-life PU waste is currently managed through landfilling or incineration, resulting in significant resource loss and environmental impact. To address these challenges, this review presents an integrated perspective on sustainable PU systems by unifying green synthesis strategies with closed-loop recovery approaches. First, recent advances in bio-based polyols and phosgene-free isocyanate synthesis derived from renewable resources—such as plant oils, carbohydrates, and lignin—are discussed as viable means to reduce dependence on petrochemical feedstocks and mitigate toxicity concerns. Next, emerging chemical recycling methodologies, including acidolysis and aminolysis, are reviewed with a focus on the selective recovery of high-purity monomers. Finally, PU vitrimers and dynamic covalent polymer networks (DCPNs) based on urethane bond exchange reactions are examined as reprocessable architectures that combine thermoplastic-like processability with the mechanical robustness of thermosets. By integrating synthesis, recovery, and reuse within a unified framework, this review aims to outline a coherent pathway toward establishing a sustainable circular economy for PU materials. Full article

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

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

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

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

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

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

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

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

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

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

Arbutus unedo (strawberry tree) is a small Mediterranean tree capable of vigorous regrowth after disturbances like fire. Traditionally used for biomass fuel, its bark and branches hold potential for higher-value products through ecovalorization into liquid mixtures that could replace petroleum-based materials. This study aimed to explore the chemical composition of various components of Arbutus unedo and to produce a liquefied material from its internal (IB) and external bark (EB). Chemical compositions of internal and external bark were determined using TAPPI standards including ash, extractive content, lignin, and cellulose. Metal cations were analyzed by ICP. Liquefaction of bark was optimized in a PARR reactor, evaluating factors such as particle size, temperature, and time, and the best polyols were monitored by FTIR-ATR. Polyurethane foams were made with internal and external bark materials liquefied by polymerization with isocyanate, a catalyst, and water as a blowing agent. Results showed that EB has a higher extractive and lignin content, while IB contains more cellulose. Liquefaction yields were higher for IB (74%) than EB (68%), with IB yielding polyols that produced stronger and more resilient foams with higher compressive strength and modulus of elasticity. Mechanical properties of the foams were influenced by the NCO/OH ratio and catalyst levels. Overall, the internal bark demonstrated superior performance for foam production, highlighting its potential as an eco-friendly alternative to petroleum-derived materials. Full article

This article explores the important, and yet often overlooked, solid-state structures of selected bioaromatic compounds commonly found in lignin hydrogenolysis oil, a renewable bio-oil that holds great promise to substitute fossil-based aromatic molecules in a wide range of chemical and material industrial applications. At first, single-crystal X-ray diffraction (SCXRD) was applied to the lignin model compounds, dihydroconiferyl alcohol, propyl guaiacol, and eugenol dimers, in order to elucidate the fundamental molecular interactions present in such small lignin-derived polyols. Then, considering the potential use of these lignin-derived molecules as building blocks for polymer applications, structural analysis was also performed for two chemically modified model compounds, i.e., the methylene-bridging propyl-guaiacol dimer and propyl guaiacol and eugenol glycidyl ethers, which can be used as precursors in phenolic and epoxy resins, respectively, thus providing additional information on how the molecular packing is altered following chemical modifications. In addition to the expected H-bonding interactions, other interactions such as π–π stacking and C–H∙∙∙π were observed. This resulted in unexpected trends in the tendencies towards the crystallization of lignin compounds. This was further explored with the aid of DSC analysis and CLP intermolecular energy calculations, where the relationship between the major interactions observed in all the SCXRD solid-state structures and their physico-chemical properties were evaluated alongside other non-crystallizable lignin model compounds. Beyond lignin model compounds, our findings could also provide important insights into the solid-state structure and the molecular organization of more complex lignin fragments, paving the way to the more efficient design of lignin-based materials with improved properties for industrial applications or improving downstream processing of lignin oils in biorefining processes, such as in enhancing the separation and isolation of specific bioaromatic compounds). Full article

Polyurethane foam compositions derived from bioderived polyester polyols with various additives were evaluated for disintegration under composting conditions using the ISO 20200 standard and were characterized by thermogravimetric analysis, microscopy, infrared spectroscopy, and imaging to provide additional insight. Compared to polyether polyol-based polyurethanes, the bioderived polyurethanes were found to display increased disintegration with an average mass loss of 25.4 ± 3.6 weight percent when subjected to composting conditions for 45 days, suggesting that these materials are less likely to persist in the environment when compared to other types of commodity plastics. Additives such as carbon black and lignin added within the foam composition did not accelerate the disintegration. Full article

In response to the environmental impacts of conventional polyurethane adhesives derived from fossil fuels, this study introduces a sustainable alternative utilizing lignin-based polyols extracted from rice straw through a process developed at INESCOP. This research explores the partial substitution of traditional polyols with lignin-based equivalents in the synthesis of reactive hot melt polyurethane adhesives (HMPUR) for the footwear industry. The performance of these eco-friendly adhesives was rigorously assessed through Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), rheological analysis, and T-peel tests to ensure their compliance with relevant industry standards. Preliminary results demonstrate that lignin-based polyols can effectively replace a significant portion of fossil-derived polyols, maintaining essential adhesive properties and marking a significant step towards more sustainable adhesive solutions. This study not only highlights the potential of lignin in the realm of sustainable adhesive production but also emphasises the valorisation of agricultural by-products, thus aligning with the principles of green chemistry and sustainability objectives in the polymer industry. Full article