Search Results (28)

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

Polyurethane (PU) is among the most universal polymers and has been extensively applied in many fields, such as construction, machinery, furniture, clothing, textile, packaging and biomedicine. Traditionally, as the main starting materials for PU, polyols deeply depend on petroleum stock. From the perspective of recycling and environmental friendliness, advanced PU synthesis, using diversified resources as feedstocks, aims to develop versatile products with excellent properties to achieve the transformation from a fossil fuel-driven energy economy to renewable and sustainable ones. This review focuses on the recent development in the synthesis and modification of PU by extracting value-added monomers for polyols from waste polymers and natural bio-based polymers, such as the recycled waste polymers: polyethylene terephthalate (PET), PU and polycarbonate (PC); the biomaterials: vegetable oil, lignin, cashew nut shell liquid and plant straw; and biomacromolecules: polysaccharides and protein. To design these advanced polyurethane formulations, it is essential to understand the structure–property relationships of PU from recycling polyols. In a word, this bottom-up path provides a material recycling approach to PU design for printing and packaging, as well as biomedical, building and wearable electronics applications. Full article

Over the past few decades, polymer composites have received significant interest and become protagonists due to their enhanced properties and wide range of applications. Herein, we examined the impact of filler and flame retardants in hemp seed oil-based rigid polyurethane foam (RPUF) composites’ performance. Firstly, the hemp seed oil (HSO) was converted to a corresponding epoxy analog, followed by a ring-opening reaction to synthesize hemp bio-polyols. The hemp polyol was then reacted with diisocyanate in the presence of commercial polyols and other foaming components to produce RPUF in a single step. In addition, different fillers like microcrystalline cellulose, alkaline lignin, titanium dioxide, and melamine (as a flame retardant) were used in different wt.% ratios to fabricate composite foam. The mechanical characteristics, thermal degradation behavior, cellular morphology, apparent density, flammability, and closed-cell contents of the generated composite foams were examined. An initial screening of different fillers revealed that microcrystalline cellulose significantly improves the mechanical strength up to 318 kPa. The effect of melamine as a flame retardant in composite foam was also examined, which shows the highest compression strength of 447 kPa. Significantly better anti-flaming qualities than those of neat foam based on HSO have been reflected using 22.15 wt.% of melamine, with the lowest burning time of 4.1 s and weight loss of 1.88 wt.%. All the composite foams showed about 90% closed-cell content. The present work illustrates the assembly of a filler-based polyurethane foam composite with anti-flaming properties from bio-based feedstocks with high-performance applications. Full article

This study aimed to conduct a comprehensive Life Cycle Assessment (LCA) of lignin-based polyol production through organosolv fractionation of cardoon stalks and subsequent lignin liquefaction. The LCA employed a cradle-to-gate approach, en_compassing cardoon cultivation and all processing steps leading to polyol production. The research involved laboratory-scale optimization of the organosolv and liquefaction processes, followed by industrial-scale implementation. The analysis revealed that all stages of the production chain, including crop cultivation, organosolv, and liquefaction, significantly influenced overall environmental impacts. Specific materials and processes played pivotal roles, such as harvesting machinery and fertilizers in crop production, γ-Valerolactone (GVL) as the primary contributor (72–100%) to environmental impacts in the organosolv phase, and materials like polyethylene glycol 400 (PEG 400) and glycerin in the liquefaction phase, accounting for the majority (96–100%) of environmental impacts in this stage. When considering endpoint damage categories, it became evident that this production chain had a notable impact on human health, primarily due to emissions in air, water, and soil from agricultural processes. Lignin-based polyols demonstrated a moderate improvement compared to their petroleum-based counterparts, with an approximate reduction of 3–16% in environmental impact. Full article

Nowadays, climate change has become a serious concern, and more attention has been drawn to utilizing biomass sources instead of fossil sources and how petroleum chemical plastics should be reduced or replaced with bio-based materials. In this study, the optimized condition of liquefaction of driftwood was examined. There was a concern that driftwood might have some decay and chemical change. However, according to the Organic Micro Element Analyzer (CHN analyzer) test and Klason lignin and Wise methods, the results proved that lignin content (37.5%), holocellulose content (66.9%), and CHN compositions were very similar to regular wood. The lowest residue content of bio-polyols was produced using liquefaction conditions of 150 °C, reaction time of 180 min, catalyst content of 10%w/w, and 12.5%w/w driftwood loading. Polyurethane foam (PUF) derived from the liquefaction of driftwood and bio-based cyanate was prepared. The PUF prepared from the liquefaction of the driftwood exhibited slightly decreased thermal durability but was superior in terms of 3-time faster biodegradation and 2.8-time increased water adsorption rate compared to pure petroleum-based PUF. As a result, it was shown that driftwood can be identified as a biomass resource for biodegradable PUF. Full article

The depletion of natural resources and increasing environmental apprehension regarding the reduction of harmful isocyanates employed in manufacturing polyurethanes (PUs) have generated significant attention from both industrial and academic sectors. This attention is focused on advancing bio-based non-isocyanate polyurethane (NIPU) resins as viable and sustainable substitutes, possessing satisfactory properties. This review presents a comprehensive analysis of the progress made in developing bio-based NIPU polymers for wood adhesive applications. The main aim of this paper is to conduct a comprehensive analysis of the latest advancements in the production of high-performance bio-based NIPU resins derived from lignin and tannin for wood composites. A comprehensive evaluation was conducted on scholarly publications retrieved from the Scopus database, encompassing the period from January 2010 to April 2023. In NIPU adhesive manufacturing, the exploration of substitute materials for isocyanates is imperative, due to their inherent toxicity, high cost, and limited availability. The process of demethylation and carbonation of lignin and tannin has the potential to produce polyphenolic compounds that possess hydroxyl and carbonyl functional groups. Bio-based NIPUs can be synthesized through the reaction involving diamine molecules. Previous studies have provided evidence indicating that NIPUs derived from lignin and tannin exhibit enhanced mechanical properties, decreased curing temperatures and shortened pressing durations, and are devoid of isocyanates. The characterization of NIPU adhesives based on lignin and tannin was conducted using various analytical techniques, including Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), matrix-assisted laser desorption/ionization with time-of-flight (MALDI-TOF) mass spectrometry, and gel permeation chromatography (GPC). The adhesive performance of tannin-based NIPU resins was shown to be superior to that of lignin-based NIPUs. This paper elucidates the potential of lignin and tannin as alternate sources for polyols in the manufacturing of NIPUs, specifically for their application as wood adhesives. Full article

Rigid polyurethane foams (RPUFs) were synthesized using exclusively lignin-based polyol (LBP) obtained via the oxyalkylation of kraft lignin with propylene carbonate (PC). Using the design of experiments methodology combined with statistical analysis, the formulations were optimized to obtain a bio-based RPUF with low thermal conductivity and low apparent density to be used as a lightweight insulating material. The thermo-mechanical properties of the ensuing foams were compared with those of a commercial RPUF and a RPUF (RPUF-conv) produced using a conventional polyol. The bio-based RPUF obtained using the optimized formulation exhibited low thermal conductivity (0.0289 W/m·K), low density (33.2 kg/m³), and reasonable cell morphology. Although the bio-based RPUF has slightly lower thermo-oxidative stability and mechanical properties than RPUF-conv, it is still suitable for thermal insulation applications. In addition, the fire resistance of this bio-based foam has been improved, with its average heat release rate (HRR) reduced by 18.5% and its burn time extended by 25% compared to RPUF-conv. Overall, this bio-based RPUF has shown potential to replace petroleum-based RPUF as an insulating material. This is the first report regarding the use of 100% unpurified LBP obtained via the oxyalkylation of LignoBoost kraft lignin in the production of RPUFs. Full article

This study aimed to develop new rigid polyurethane foams (RPUFs) for thermal insulation based on kraft lignin, the main by-product of the pulp and paper industry. Crude lignin-based polyol (LBP) was obtained via the oxyalkylation of kraft lignin using propylene carbonate (PC). A design of experiments (DoE) was used to evaluate the effect of the isocyanate (NCO)-to-hydroxyl (OH)-group’s ratio, the content of crude LBP, the blowing agent (BA), and catalyst on the thermal conductivity and density of RPUFs. Statistical analysis revealed that the increase in crude LBP and BA content in the formulation decreases the thermal conductivity and density of the foams. In addition, the fact that LBP is a viscous polyol containing PC-oligomers appears to affect the cellular structure of RPUFs, and consequently reduces their mechanical and thermal properties. The main novelty of this study consisted in the careful optimization of the formulation, namely, with regard to the type of blowing agent and with the high content of crude LBP obtained from the oxyalkylation of LignoBoost kraft lignin without purification to obtain good quality RPUF that meets market requirements for insulation materials. Full article