Search Results (23)

Bio-based polyurethane (PU) coatings offer sustainable alternatives to petrochemical coatings but often suffer from inferior mechanical performance, durability, and chemical resistance. This work addresses that challenge by integrating a trifunctional bio-based crosslinker (glycerol) and a silane-based additive (hexamethyldisilane (HMDS)) to simultaneously enhance structural robustness and hydrophobicity. Coatings were synthesized using a renewable soybean oil polyol (SOP), glycerol (5, 10, 15 and 20 wt.%), and methylene diphenyl diisocyanate (MDI), followed by the addition of HMDS (10, 20, 30, 40 and 50 wt.%). Mechanical tests identified 10 wt.% glycerol as the optimal content, yielding a maximum tensile strength of 47.18 MPa. Incorporating 10 wt.% HMDS into the optimized formulation greatly increased water contact angle (WCA, 95.76°) and chemical resistance with minimal loss of mechanical performance (38.19 MPa, tensile strength); higher HMDS loadings caused network disruption and reduced strength. Calorimetry and thermogravimetric analyses confirmed that the modified coatings retained high thermal stability. This synergistic crosslinker additive strategy produced a structurally robust, water-resistant bio-based coating, demonstrating a viable high-performance sustainable coating solution for industrial applications. Full article

To develop cosmetic film-forming agents that combine sustainability with functionality, this study synthesized a series of bio-based polyols using epoxidized soybean oil (ESO) as raw material through acid-catalyzed ring-opening reactions. These polyols partially replaced petroleum-based polyols and reacted with isophorone diisocyanate (IPDI). By incorporating β-cyclodextrin (β-CD), a water-based polyurethane (CPS-ESO) was successfully developed that combines degradability with active ingredient delivery capability. Experiments demonstrated that the resulting CPS-M film exhibits excellent water repellency (contact angle 66.7°), mechanical properties (tensile strength 14.21 MPa, elongation at break 229.42%), adhesion (Level 0), and breathability, while displaying controllable degradation behavior under both enzymatic and alkaline hydrolysis conditions. Due to the cavity structure of β-cyclodextrin, this material efficiently loaded resveratrol (RES) at a loading rate of 0.16%. Formulated into a setting spray (F1), the product demonstrated outstanding makeup longevity (lowest ΔE value after water/sweat immersion), anti-friction performance (ΔE value after friction only one-third of the control group), and antioxidant activity (DPPH scavenging rate of 86.25%), with RES remaining stable under high-temperature storage conditions. This study provides new insights for designing green multifunctional cosmetic film-forming agents. Full article

Non-isocyanate polyurethanes (NIPUs) represent a sustainable alternative to conventional isocyanate-based systems, eliminating toxic reagents while maintaining good performance. In this study, bio-based NIPU coatings were synthesized from carbonated soybean oil (CSBO) via the carbonation of epoxidized soybean oil (ESBO) using carbon dioxide (CO₂), followed by polymerization with ethylenediamine (EDA) and varying concentrations of 3-aminopropyltriethoxysilane (APTES) (0–20 wt%). The amine groups of EDA and APTES participate in the ring-opening of cyclic carbonates to form β-hydroxyurethane linkages, while the triethoxysilane moieties of APTES may undergo hydrolysis–condensation to produce Si–O–Si domains, resulting in a β-hydroxyurethane–siloxane hybrid network. The optimized formulation CEA-5 exhibited the best, including a tensile strength of 3.3 MPa, elongation at break of ~150%, glass transition temperature (T_g) of ~7 °C, and thermal stability up to ~350 °C, where major thermal degradation happens. The synthesized coating material also shows adhesion (3.6 MPa on oak for CEA-10), hydrophobic behavior (water contact angle (WCA) ~102° for CEA-5), good chemical and ultraviolet (UV) resistance, and shape memory. The synergistic effect of urethane hydrogen bonding and siloxane crosslinking imparted enhanced toughness, flexibility, and durability. These findings express a scalable, eco-friendly strategy for producing silane-modified NIPU coatings with good mechanical, thermal, and coating performance suitable for sustainable industrial coating and adhesive applications. Full article

Smart self-healing polymer materials are breaking open new pathways in industry, minimizing waste, and enhancing the long-term reliability of applications. Moreover, when they possess anti-corrosive properties, they effectively protect surfaces from wear and corrosion, leading to improved and more robust products. In the present work, we develop a series of new self-healing polyurethane coatings activated by temperature, through the encapsulation of vegetable oils (VO), namely olive, soybean, and castor oil, in the core of polyurea microcapsules (VO-MCs). Using a green method, water-dispersible microcapsules were embedded in water-based polyurethane matrices. Both the self-healing ability and the anti-corrosive properties of the respective films were evaluated after mechanical damage. Encapsulation allowed for the direct release of VOs into the damaged area; subsequently, the temperature increase reduced the viscosity of the oils, facilitating their flow and diffusion into the damaged area and accelerating the healing process. Soybean oil and olive oil showed remarkable performance in terms of self-healing and high anti-corrosion ability for the polyurethane coatings, while castor oil showed a limited anti-corrosion effect but quite satisfactory effectiveness in terms of self-healing. Overall, the study highlights the potential of using encapsulated oils in environmentally friendly, active coatings with dual action: corrosion protection and self-repair of damage. Full article

Flexible polyurethane foam (PUF) is a vital material across diverse applications, and its global market is projected to continue growing. Driven by regulatory and consumer demand for sustainable materials, the PUF industry is exploring alternatives to petroleum-derived raw materials, such as vegetable oil-derived bio-polyols. Although bio-based alternatives to fossil-derived foams have been developed, their environmental benefits remain to be fully assessed. Therefore, this study evaluates the environmental performance of flexible PUF production by comparing a conventional fossil-based formulation with a bio-based alternative using a cradle-to-gate Life Cycle Assessment (LCA). The bio-based PUF reduced global warming (6%), fossil resource scarcity (9%), and mineral resource scarcity (6%), but caused significant increases in freshwater eutrophication (91%) and marine eutrophication (19%), mainly due to agricultural processes associated with soybean cultivation. Regardless of the formulation, polyol and toluene diisocyanate production were identified as major environmental hotspots. These results highlight both the decarbonization potential and the trade-offs of bio-based raw materials, underlining the complexity of achieving sustainable PUF production. Overall, the findings provide quantitative insights to guide more sustainable design and sourcing strategies for flexible PUF in the transition from fossil to renewable feedstocks. Full article

Bio-based polyurethane (PU) is synthesized either via the prepolymerization or addition polymerization of bio-based polyols and isocyanates. PU synthesized from vegetable-oil-based polyols has excellent properties for various application needs. Bio-based PU coatings from renewable vegetable oil show good degradability in soil while controlling the nutrient release process. Castor oil, soybean oil, palm oil, olive oil, linseed oil, rapeseed oil, cottonseed oil, and recycled oil have been explored in the study of bio-based PU coatings for controlled nutrient release. Castor oil as a natural polyol has been widely studied. Generally, the epoxidation ring opening method is preferred to prepare bio-based polyols. Almost all of these studies used a drum coating machine to complete the coating process. To obtain better controlled release performance, a vegetable-oil-based PU (VPU) coating was modified by increasing the degrees of crosslinking and hydrophobicity and improving the coating uniformity. The nutrient release duration of the modified castor-oil-based PU-coated fertilizer reached 200 days. VPU-coated fertilizers, in contrast to traditional fertilizers, effectively reduce the detrimental impact on the environment. Although the preparation of VPU-coated fertilizers is still at the laboratory scale, application research has been carried out in field crops. Full article

UV-curable bio-based resins are widely used in the UV curing field. However, the current UV-curable bio-based resins for the application of nail polish still have the problems of too high viscosity and insufficiently excellent mechanical properties. In this study, a soybean oil-based acrylate photosensitive resin is synthesized by using epoxidized soybean oil as a raw material and reacting it with acrylic acid. The results show that the viscosity of soybean oil-based acrylate can achieve 8.31 Pa∙s, and the UV-cured film prepared by soybean oil-based acrylate and anhydride derivatives can obtain a tensile strength of 35.36 MPa and an elongation at break of 67.8%. In addition, the soybean oil-based acrylate is further reacted with isophorone diisocyanate to obtain soybean oil-based polyurethane acrylate, which can be thermally stable at 90 °C for 7 d. And then, the UV-cured film constructed by soybean oil-based polyurethane acrylate and anhydride derivatives are prepared, and the elongation at the break of the cured films can be up to 320%. This work provides a solvent-free approach by using biomass raw materials to form polyurethane acrylic resins, which have promising potential in the application of nail polish. Full article

This study aims to develop castable polyurethane suitable for applications on wet substrates or underwater construction. Polyurethanes were synthesized using various polyols with similar hydroxyl values, including poly(tetrahydrofuran) polyol, polyester polyol, castor oil-modified polyol, soybean oil-modified polyol, and cashew nut shell oil-modified polyol. The corresponding polyurethane curing products were evaluated for their underwater curing characteristics by volume expansion ratios and adhesion strength on dry and wet substrates, combined with analyses of reaction exothermic behavior, wetting properties on dry and wet substrates, interfacial tension, and microstructure characterization from the perspectives of reaction activity and water solubility. The results indicate that polyols with higher hydrophobicity and reactivity to isocyanates lead to reduced side reactions during underwater curing, making them more suitable for underwater applications. Soybean oil-based and cashew nut shell oil-based polyurethanes exhibited fast curing (gel times of 1.15 and 1.35 min, respectively), minimal volume change (within 2.5% after 7 days underwater), and strong wet adhesion (1.95 MPa and 2.38 MPa with minimal loss, respectively). The two polyols showed different mechanical properties, providing tailored options for specific underwater engineering applications. Full article

Along with the development of technology and the increasing consumption of polymeric materials, which have become an integral part of man’s everyday life, problems related to their disposal are arising. The presented research concentrates on the studies on the enzymatic degradation of selected epoxy-polyurethane materials filled with 2 or 5 wt.% of waste unmodified or chemically modified through mercerization wood flour. Composites, subjected to the degradation process, contained up to 60% of raw materials of natural origin. The enzymatic degradation was carried out for 28 days, in three environmental conditions, differing in the type of applied buffer, pH, process temperature, the amount, and the type of applied enzyme. In this study, the influence of two lipases was tested (specifically: lipase of microbiological origin—Rhizopus Oryzae Lipase, and one of animal origin—Porcine Pancreas Lipase). There were seven compositions tested, based on the polyaddition product of epoxidized soybean oil with bisphenol A, differing in the amount of filler and the type of modification to which wood flour was subjected before the application in the polymer composite. After enzymatic degradation, the greatest progress of biodegradation was observed at T = 30 °C, in a complex phosphate buffer with pH = 6.8, in the presence of the Porcine Pancreas enzyme. Under these conditions, a slightly smaller effect was also observed in the presence of the Rhizopus Oryzae enzyme. At the same time, the compositions containing mercerized wood flour turned out to be the most susceptible to biodegradation with the above-mentioned enzymes. After conducting the process in the full 4-week cycle numerous changes were noticed within the tested sample, such as (1) 7.0 %wt. of the overall weight loss of samples, (2) reducing the value of the static contact angle (e.g., from 116.7° before degradation to 27.2° at the end of the study), and (3) morphological appearance of the sample (sample’s surface had suffered erosion noticed as smoothest roughnesses and numerous empty holes throughout its entire volume), concerning sample’s condition before enzymatic degradation. Full article

A method for obtaining non-isocyanate polyurethane (NIPU) foams from cyclic carbonate (CC) based on soybean oil was developed. For this purpose, cyclic carbonate was synthesized from epoxidized soybean oil and CO₂ using various ionic liquids (ILs) as catalysts. Among the tested ILs, the highest selectivity (100%) and CC yield (98%) were achieved for 1-ethyl-3-methylimidazolium ([emim]Br). Without any purification, the resulting cyclic carbonate was reacted directly with diethylenetriamine as a model crosslinking agent to produce NIPU foams. It was found that the soybean oil-based CC synthesized with bromide imidazolium ionic liquids exhibited significantly shorter gelling times (8 min 50 s for [emim]Br and 9 min 35 s for [bmim]Br) compared to those obtained with the conventional TBAB catalyst (26 min 15 s). A shorter gelling time is a crucial parameter for the crosslinking process in foams. The obtained foams were subjected to mechanical tests and a morphology analysis. Full article

Only 0.1% of polyurethanes available on the market are from renewable sources. With increasing concern about climate change, the substitution of monomers derived from petrochemical sources and the application of eco-friendly synthesis processes is crucial for the development of biomaterials. Therefore, polyhydroxyurethanes have been utilized, as their synthesis route allows for the carbonation of vegetable oils with carbon dioxide and the substitution of isocyanates known for their high toxicity, carcinogenicity, and petrochemical origin. In this study, polyhydroxyurethanes were obtained from carbonated soybean oil in combination with two diamines, one that is aliphatic (1,4-butadiamine (putrescine)) and another that is cycloaliphatic (1,3-cyclohexanobis(methylamine)). Four polyhydroxyurethanes were obtained, showing stability in hydrolytic and oxidative media, thermal stability above 200 °C, tensile strength between 0.9 and 1.1 MPa, an elongation at break between 81 and 222%, a water absorption rate up 102%, and contact angles between 63.70 and 101.39. New formulations of bio-based NIPHUs can be developed with the inclusion of a cycloaliphatic diamine (CHM) for the improvement of mechanical properties, which represents a more sustainable process for obtaining NIPHUs with the physicochemical, mechanical, and thermal properties required for the preparation of wound dressings. Full article

This study presents the synthesis and characterization of non-isocyanate polyurethanes (NIPU) derived from the copolymerization of cyclic-carbonated soybean oil (CSBO) and cyclic carbonate (CC)-terminated poly(ether carbonate) (RCC). Using a double-metal cyanide catalyst, poly(ether carbonate) polyol was first synthesized through the copolymerization of carbon dioxide and propylene oxide. The terminal hydroxyl group was then subjected to a substitution reaction with a five-membered CC group using glycerol-1,2-carbonate and oxalyl chloride, yielding RCC. Attempts to prepare NIPU solely using RCC and diamine were unsuccessful, possibly due to the low CC functionality and the aminolysis of RCC’s linear carbonate repeating units. However, when combined with CSBO, solid NIPUs were successfully obtained, exhibiting good thermal stability along with enhanced mechanical properties compared to conventional CSBO-based NIPU formulations. Overall, this study underscores the potential of leveraging renewable resources and carbon capture technologies to develop sustainable NIPUs with tailored properties, thereby expanding their range of applications. Full article

The use of alternative raw material sources in polyurethane chemistry is necessary given the limited supply of fossil fuels, their rising prices and the concern for sustainability. The production of biopolyols from edible vegetable oils such as rapeseed oil, soybean oil or sunflower oil is often proposed. In order to avoid conflict with the global food economy, non-edible or waste oils are hoped to find application in chemical synthesis. The possibility of using oils from selected fruit seeds to obtain biopolyols is analyzed in this manuscript. Five biopolyols were obtained from watermelon, cherry, black currant, grape and pomegranate fruit seeds using the transesterification reaction of the oils with triethanolamine. Thermal insulating polyurethane foams were then obtained by replacing 75% of petrochemical polyol with the biopolyols in polyurethane systems. Based on an analysis of the foaming process, it was found that the incorporation of triethanolamine molecules into the biopolyols causes a catalytic effect. The use of such biopolyols allows eliminating the catalyst from a polyurethane foam formulation. The polyurethane biofoams obtained with the pomegranate-seed-based biopolyol were characterized by the highest content of closed cells (45 vol.%). The lowest content was found for the foams containing the currant-seed-based biopolyol (9%). The foams were characterized by thermal conductivity coefficients between 32 and 35 kW/m·K and densities of approximately 40 kg/m³. Good dimensional stability and compressive strength between 100 and 250 kPa make them suitable for use in construction. Full article

Bio-polyols (BPOs), characterized by a hydroxyl number up to around 90 mg KOH/g, narrow polydispersity index and relatively low molecular mass up to 2000 g/mol, were synthetized from partially and completely epoxidized soybean and linseed oils and caprylic acid or 3-phenyl butyric acid. These BPOs were used in the presence of toluene diisocyanate to produce polyurethane (PU) foams by using a quasi-prepolymer method involving a two-step reaction. A detailed structural investigation of the prepolymers from toluene diisocyanate and both BPOs and polypropylene glycol was conducted by SEC and solution NMR. The apparent density of the foams was in the range of 40–90 kg/m³, with higher values for foams from the aromatic acid. All the foams showed an open-cell structure with uniform and regular shape and uniform size. The specific Young’s moduli and compression deflection values suggest superior mechanical properties than the reference foams. The novel synthesized polyurethanes are excellent candidates to partially replace petroleum-based materials. Full article

Thermoplastic polyurethanes (TPUs) are remarkably versatile polymers due to the wide range of raw materials available for their synthesis, resulting in physicochemical characteristics that can be tailored according to the specific requirements of their final applications. In this study, a renewable bio-based polyol obtained from soybean oil is used for the synthesis of TPU via reactive extrusion, and the influence of the bio-based polyol on the multi-phase structure and properties of the TPU is studied. As raw materials, 4,4′-diphenylmethane (MDI), 1,4-butanediol, a fossil-based polyester polyol, and a bio-based polyol are used. The fossil-based to soybean-based polyol ratios studied are 100/0, 99/1, 95/5, 90/10, 80/20, and 50/50% by weight, respectively. The TPUs were characterized by size exclusion chromatography (SEC), gel content analysis, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), dynamic mechanical analysis (DMA), and contact angle measurements. The results reveal that incorporating the renewable polyol enhances the compatibility between the rigid and flexible segments of the TPU. However, due to its high functionality, the addition of soybean-based polyol can promote cross-linking. This phenomenon reduces the density of hydrogen bonds within the material, also reducing polarity and restricting macromolecular mobility, as corroborated by higher glass transition temperature (T_g) values. Remarkably, the addition of small amounts of the bio-based polyol (up to 5 wt.% of the total polyol content) results in high-molecular-weight TPUs with lower polarity, combined with suitable processability and mechanical properties, thus broadening the range of applications and improving their sustainability. Full article