Bio-based Polyurethane Research Articles

Bio-Based Polyurethane Composites with Adjustable Fluorescence and Ultraviolet Shielding for Anti-Counterfeiting and Ultraviolet Protection.

Polyurethane and its composites play an important role in innovative packing materials including anticounterfeiting and ultraviolet protection, however, they are mainly derived from petroleum resources that are not sustainable. In this study, a 100% biobased thermoplastic polyurethane (Bio-TPU) was synthesized using biobased poly(trimethylene ether) glycol, pentamethylene disocyanate, and 1,4-butanediol. Subsequently, biobased tannic acid (TA) was employed to prepare biobased composites. The structures and properties of Bio-TPU and its composites were systematically evaluated. The results showed that the Bio-TPU/TA composite films had excellent and controllable fluorescence and UV-shielding properties. The fluorescence colors of the Bio-TPU/TA composite films could be adjusted to blue, green, and yellow by varying the TA content and adding coupling agents. Moreover, the UV transmittance of the Bio-TPU/TA composites decreased from 79.25 to 5.43% below 400 nm with an increasing TA content, indicating an excellent ultraviolet-barrier performance. Consequently, biobased TPU/TA composite films can be utilized as innovative anticounterfeiting materials and UV-shielding protection films. This study is expected to facilitate sustainable development in the polyurethane industry and broaden the high-end applications of polyurethane such as fashion, electronics, food manufacturing, pharmaceuticals, and finance.

A concise strategy for enhancing the performance of bio-based polyurethane aerogels using melamine-modified sodium alginate via Aza-Michael addition reaction

Bio-based waterborne polyurethane (PU) has garnered significant attention as a sustainable alternative petroleum-derived counterpart, offering environmentally friendly alternatives. In this work, a new approach is proposed to fabricate two kinds of composite aerogels of lowly/highly melamine-modified sodium alginate (SAML/SAMH) with methacrylate-terminated PU (SAML-PU and SAMH-PU) through dynamic covalent cross-linking via Aza-Michael addition reactions. We aim to improve the poor compatibility of polysaccharide and PU associated with traditional blending methods and impart the resulting aerogels with good biodegradability, compressive strength, thermal insulation, flame-retardant, and self-healing. Comprehensive characterizations, including Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy collectively demonstrate the successful derivatization of alginate and the effective synthesis of the Aza-Michael addition copolymer involving derivate alginate and PU. Substantial improvements in compressive strength and thermal properties are realized at comparable densities. Higher compressive strength, higher decomposition temperature and lower thermal conductivity are significantly achieved for SAML-PU (0.35 MPa, 410 °C and 0.024 W/m/K at 0.13 g/cm3) and SAMH-PU (0.58 MPa, 427 °C and 0.022 W/m/K at 0.12 g/cm3) compared to pristine PU foams (0.15 MPa, 330 °C and 0.031 W/m/K at 0.15 g/cm3). Additionally, molecular simulations of the Aza-Michael addition reaction and finite element simulations of aerogel thermal-insulation properties are conducted to corroborate experimental results. Notably, the dynamic polymers of SAML-PU and SAMH-PU exhibited excellent self-healing, recycling, biodegradability, and flame-retardant attributes. The elucidated preparation methodology and the exceptional performance and versatile applications of sodium alginate-based PU aerogels suggest a promising trajectory for future research endeavors and industrial implementation.

Polyurethanes and Their Biomedical Applications.

The tunable mechanical properties of polyurethanes (PUs), due to their extensive structural diversity and biocompatibility, have made them promising materials for biomedical applications. Scientists can address PUs' issues with platelet absorption and thrombus formation owing to their modifiable surface. In recent years, PUs have been extensively utilized in biomedical applications because of their chemical stability, biocompatibility, and minimal cytotoxicity. Moreover, addressing challenges related to degradation and recycling has led to a growing focus on the development of biobased polyurethanes as a current focal point. PUs are widely implemented in cardiovascular fields and as implantable materials for internal organs due to their favorable biocompatibility and physicochemical properties. Additionally, they show great potential in bone tissue engineering as injectable grafts or implantable scaffolds. This paper reviews the synthesis methods, physicochemical properties, and degradation pathways of PUs and summarizes recent progress in applying different types of polyurethanes in various biomedical applications, from wound repair to hip replacement. Finally, we discuss the challenges and future directions for the translation of novel polyurethane materials into biomedical applications.

Synthesis and characterization of self-healing bio-based polyurethane from microbial poly(3-hydroxybutyrate) produced in methanotrophs

Poly(3-hydroxybutyrate) (PHB) is an important class of renewable and biodegradable polymers that have recently attracted significant interest. However, the limitations of the physical properties of PHB, owing to its brittle nature, hinder its application in versatile polymers. In this study, we propose an efficient conversion of microbial PHB produced and recovered from methanotrophs to produce the oligomer PHB-diol. The PHB transesterification was conducted using different alcohols and the reaction conditions were optimized to obtain a liquid-like PHB-diol product, a low-molar-mass polyol with a molecular weight of 1000–1400 g/mol for polyurethane (PU) synthesis. A comprehensive characterization of PU samples made from PHB-derived polyol suggested that it could be a viable substitute for 50 wt% traditional petroleum-derived polyol in PU synthesis. In contrast to petroleum-based PU, the synthetic PU film made from microbiologically generated PHB-diol showed noteworthy self-healing ability with a healing efficiency of up to 91.08 % at moderate temperatures after a simple drying process. Self-healing ability is highly desirable and significant for the sustainable manufacturing of advanced materials from bioresources for a wide range of practical applications in electronic devices, coatings, biomedicine, and aerospace.

Cationic UV‐Curing of Shape Memory Biobased Polyurethanes Sensing Low Heat

ABSTRACTThe environmental problems caused by thermal reactions have prompted the search for new approaches. Photochemical curing, which uses light energy, offers a sustainable solution for polymerizing complex polymers, reducing energy consumption, and emissions. Current study involves cationic UV‐curing of biobased polyurethanes (PU) with a thermo‐responsive shape memory behavior on very low temperature almost equal to human body temperature. This product has a potential to be utilized as drug carrier or related biomedical applications, as well as self‐tightening materials against human body heat. Polymer has been designed from sesame oil, with slight modification through a facile epoxidation approach. Main objectives of this research were to prepare biobased PU recipe; to utilize a specially designed UV‐curing approach for this synthesis; and to develop shape memory properties upon sensing human body temperature. Prepared material has been analyzed through FTIR, SEM, TGA, DSC, water absorption capacity (WAC), and gel contents (GCs). Shape memory behavior has been tested in both air and water against a range of temperatures (35°C–80°C). At 35°C in 208 s, prepared sample, presented 96.60% Rr and 90.56% Rf, whereas at 80°C in 55 s Rr increased to 98.33% and Rf increased to 100%. Hydrophobic nature of sample was confirmed by 4.1% water absorption in 48 h.

Reversibly crosslinked polyurethane fibres from sugar-based 5-chloromethylfurfural: Synthesis, fibre-spinning and fibre-to-fibre recycling.

The development of recyclable crosslinked thermosetting fibres is a challenging research topic. In the present work, we have designed and synthesized polyurethane fibres from fructose-derived 5-chloromethylfurfural (CMF) and lignin-derived monomeric phenols. The greenhouse gas emissions associated with the production of CMF showed comparable results to that of 5-hydroxymethylfurfural (HMF), a high potential sugar-based platform molecule. The wet-spun biobased polyurethane fibres produced could be conveniently crosslinked using Diels-Alder chemistry to effectively enhance the glass transition temperature and mechanical properties. At a mildly elevated temperature (140 °C), the chemically crosslinked fibres could be effectively de-crosslinked, which enabled complete separation from a mixture with poly(ethylene terephthalate) (PET) and cotton fibres. These results outline a potential strategy to design and fabricate new biobased fibres with reversible crosslinking, which may enable fibre-to-fibre recycling.

Flame Retardancy and Thermal Stability of Rigid Polyurethane Foams Filled with Walnut Shells and Mineral Fillers.

Recently, the influence of the concept of environmental sustainability has increased, which includes environmentally friendly measures related to reducing the consumption of petrochemical fuels and converting post-production feedstocks into raw materials for the synthesis of polymeric materials, the addition of which would improve the performance of the final product. In this regard, the development of bio-based polyurethane foams can be carried out by, among other things, modifying polyurethane foams with vegetable or waste fillers. This paper investigates the possibility of using walnut shells (WS) and the mineral fillers vermiculite (V) and perlite (P) as a flame retardant to increase fire safety and thermal stability at higher temperatures. The effects of the fillers in amounts of 10 wt.% on selected properties of the polyurethane composites, such as rheological properties (dynamic viscosity and processing times), mechanical properties (compressive strength, flexural strength, and hardness), insulating properties (thermal conductivity), and flame retardant properties (e.g., ignition time, limiting oxygen index, and peak heat release) were investigated. It has been shown that polyurethane foams containing fillers have better performance properties compared to unmodified polyurethane foams.

A robust bio-based polyurethane employed as surgical suture with help to promote skin wound healing

Designing bio-based polyurethane materials with excellent mechanical, biocompatibility, and self-healing properties simultaneously is currently a significant challenge due to the increasing demands for high-performance materials. In this study, we propose an asymmetric backbone strategy utilizing bio-based polycarbonate as the soft segment, equimolar ratios of lysine diisocyanate and isophorone diisocyanate as asymmetric hard segments, and isophorone diamine as the chain extender. The resulting polyurethane elastomers exhibit excellent mechanical properties, including high tensile stress (46.1 MPa), toughness (213.9 MJ/m3), and fracture energy (98.47 kJ/m3). The polyurethane elastomers demonstrate good self-healing and recyclable properties under simple heat treatment. Furthermore, biological experiments confirm the degradability and bio-safety of the bio-based polyurethane elastomers, which have shown potential in accelerating wound healing in mice when used as surgical sutures. These findings highlight the promising prospects of the obtained polyurethane elastomers in various applications, including biomedicine, flexible sensing, and electronic components.

Bio-Based Polyurethane Composites from Macauba Kernel Oil: Part 1, Matrix Synthesis from Glycerol-Based Polyol

Polyurethanes are the result of a reaction between an isocyanate and a polyol. The large variety of possible reagents creates many possible polyurethanes to be made, such as soft foams, rigid foams, coatings, and adhesives. This polymer is one of the most produced and consumed polymers in the world with an ever-increasing demand. Despite its usual petrochemical nature, research on bio-based polyurethanes flourishes due to the ease in creating bio-based polyols. This work covers the synthesis of a novel macauba kernel oil polyol by the epoxidation of the oil, followed by a ring-opening reaction of the epoxide with glycerol, used for the preparation of polyurethane foams using different NCO/OH ratios. The FTIR and H1 results confirm the formation of the epoxide and polyol, and the polymers in all NCO/OH ratios were confirmed by FTIR, showing great similarities between the samples, especially PU 1.0 and PU 1.2. Despite the TGs showing close behaviors for the three samples, their DTGs showed great difference between the samples, with PU 1.0 presenting a regular PU DTG profile with three degradation peaks while the other two sample presented five degradation peaks, indicating a higher crosslinking density in them.

Mild condition lignin modification enabled high-performance anticorrosive polyurethane coating

The diverse active hydroxyl groups of lignin pose challenges in the preparation of lignin-based polyurethane coatings with exceptional long-term anticorrosive properties. Here, the dense and defect-free lignin-based polyurethane coating with a thickness of 25 ± 5 μm was successfully synthesized using a mild hydroxypropyl lignin modification approach, exhibiting outstanding barrier properties (|Z| > 109 Ω cm2) and long-term anti-corrosion performance exceeding 120 d. Under ambient conditions (i.e., 25 °C and atmospheric pressure), propylene oxide was directly blended with the alkali solution of lignin to effectively convert phenolic hydroxyl groups into more reactive aliphatic hydroxyl groups, while also minimizing the significant increase in molecular weight caused by lignin condensation. As a result, the high crosslinking density of lignin polyurethane coatings effectively prevented the penetration of corrosive media and enhanced the long-term corrosion resistance of the coatings. Overall, the results demonstrate that a mild hydroxypropyl modification process is an effective and facile strategy to prepare highly reactive lignin-based polyols, which is crucial for the development of high-performance bio-based polyurethane anticorrosive coatings.

Synthesis of bio-polyol-functionalized nanocrystalline celluloses as reactive/reinforcing components in bio-based polyurethane foams by homogeneous environment modification

Nanocrystalline Cellulose (NCC or CNC) is widely used as a filler in polymer composites due to its high specific strength, tensile modulus, aspect ratio, and sustainability.However, CNC hydrophilicity complicates its dispersion in hydrophobic polymeric matrices giving rise to aggregate structures and thus compromising its reinforcing action. CNC functionalization in a homogeneous environment, through silanization with trichloro(butyl)silane as a coupling agent and subsequent grafting with bio-based polyols, is herein investigated aiming to enhance CNC dispersibility improving the filler-matrix interaction between the hydrophobic PU and hydrophilic CNC. The modified CNCs (m_Ci) have been studied by XRD, SEM, and TGA analyses. The TGA results show that the amount of grafted polyol is strongly influenced by both its molar mass and OH number and the maximum amount of grafted polyol reaches up to 0.32 mmol per grams of functionalized CNC, within the explored conditions. The effect of different concentrations (1–3 wt%) of m_Ci on the physical, morphological, and mechanical properties of the resulting bio-based composite polyurethane foams is evaluated. Composite PU foams present compressive modulus up to 4.81 MPa and strength up to 255 kPa more than five times higher than those reinforced with unmodified CNC or with modified CNC in heterogeneous chemical environment. The improvement of mechanical properties of the examined PU foams, as a consequence of the incorporation of bio-polyols modified CNCs where polyol's OH groups interact with polyurethane precursors, could further broaden the use of these materials in building applications.

Exploring Bio-Based Polyurethane Adhesives for Eco-Friendly Structural Applications: An Experimental and Numerical Study.

In response to heightened environmental awareness, various industries, including the civil and automotive sector, are contemplating a shift towards the utilization of more sustainable materials. For adhesive bonding, this necessitates the exploration of materials derived from renewable sources, commonly denoted as bio-adhesives. This study focuses on a bio-adhesive L-joint, which is a commonly employed configuration in the automotive sector for creating bonded structural components with significant bending stiffness. In this investigation, the behavior of joints composed of pine wood and bio-based adhesives was studied. Two distinct configurations were studied, differing solely in the fiber orientation of the wood. The research combined experimental testing and finite element modeling to analyze the strength of the joints and determine their failure mode when subjected to tensile loading conditions. The findings indicate that the configuration of the joint plays a crucial role in its overall performance, with one of the solutions demonstrating higher strength. Additionally, a good degree of agreement was observed between the experimental and numerical analyses for one of the configurations, while the consideration of the maximum principal stress failure predictor (MPSFP) proved to accurately predict the location for crack propagation in both configurations.

Dynamic covalently bio-based polyurethane-boron nitride nanosheet composites for effective self-healing and thermal management

Polymer-based composites, such as polyurethane-based composites, provide better corrosion and fatigue resistance than other materials, but their poor thermal conductivity limits their application areas. In this study, using boron nitride nanosheets (BNNSs), cardanol (CA), and 2-hydroxyethyl disulfide (HEDS) as raw materials, we have developed an innovative dynamically covalently crosslinked bio-based polyurethane thermal management composite filled with BNNSs, which takes into account the sustainability of the bio-based polyurethane and the excellent thermal conductivity of BNNSs. We further explored the effect of different BNNSs content ratios on the material properties, and we found that the thermal conductivity could improve by 156 % at 10 wt% BNNSs-doping. Meanwhile, the dynamic covalent cross-linking strategy endows the material with self-healing ability after physical damage. Incorporating disulfide bonds allows the samples to be dynamically reversible at certain temperatures to repair material damage and remodel for recycling. The development of this material offers a new approach to enhancing the performance of bio-based polymer materials. It provides a new avenue for designing and applying eco-friendly materials with high thermal conductivity.

Bio-based polyurethane triboelectric nanogenerator with superior low-temperature self-healing performance for unmanned surveillance

Damaged flexible triboelectric nanogenerators face difficulties in autonomous healing at low temperatures, limiting their application range. Impeded dynamic network reconstruction presents a challenge in developing materials for autonomous low-temperature healing. This study constructed a multi-dynamic network utilizing both strong and weak hydrogen and disulfide bonds to develop a biobased polyurethane elastomer (PBES-U, prepared from biobased monomers such as itaconic acid, sebacic acid, etc.), featuring a cross-linked network capable of cryogenic self-healing, superior toughness, and reprocessability. This elastomer extends to 1100 % of its original length, achieving 90 % self-healing efficiency at temperatures down to −10 °C due to the low glass transition temperature (Tg, −30 ℃) achieved by modulating the flexibility of chain segments. Consequently, a bio-based TENG (LS-TENG) was produced using this elastomer as a positive friction layer through a dynamic interfacial interlocking method. The results reveal that LS-TENG achieves a notable power density of 12.2 mW/m2, an output voltage reaching 160 V, and a 98 % output voltage recovery post-low-temperature self-healing. Furthermore, a non-contact LS-TENG-based monitoring system was developed with significant potential for applications in battlefield sensing, wildlife monitoring, and intelligent driving.

Liquefaction optimization of grape pulp using response surface methodology for biopolyol production and bio-based polyurethane foam synthesis.

Both environmental and economic disadvantages of using petroleum-based products have been forcing researchers to work on environmentally friendly, sustainable, and economical alternatives. The purpose of this study is to optimize the solvothermal liquefaction process of grape pomace using response surface methodology coupled with a central composite design. After investigating the physicochemical properties of the liquified products (biopolyol) in detail, a bio-based rigid polyurethane foam (RPUF) was synthesized and characterized. The hydroxyl and acid numbers and viscosity values of all the biopolyols were analyzed. According to variance analysis results (%95 confidence range), both the reaction temperature and catalyst loading were determined as significant parameters on the liquefaction yield (LY). The model was validated experimentally in the following reaction conditions: 4.25% catalyst loading, 50 min reaction time, and 165 °C reaction temperature, which yields an LY of 81.3%. The biopolyols produced by the validation experiment display similar characteristics (hydroxyl number: 470.5 mg KOH/g; acid number: 2.31 mg KOH/g; viscosity: 1785 cP at 25 °C) to those of commercial polyols widely preferred in the production of polyurethane foam. The physicochemical properties of bio-based foam obtained from the biopolyol were determined and the thermal conductivity, closed-cell content, apparent density, and compressive strength values of bio-based RPUF were 31.3 mW/m·K, 71.1%, 33.4 kg/m3, and 105.3 kPa, respectively.

Mechanically customizable lignin bio-elastomers based on tailorable multiscale microstructures

The development of bio-based polyurethanes (PU) elastomers with well-designed multiscale microstructures to customize their mechanical performances was desired, but remained an ongoing challenge. Herein, a novel strategy of integrating tailorable hard-soft nanophases with multiple hydrogen bond (H-bond) interactions was proposed to construct mechanically customizable PU bio-elastomers. In this strategy, highly reactive lignin with high hydroxyl contents was employed as bio-polyol monomer reacting with hexamethylene diisocyanate (HDI) to construct carbamate bonds with a function of tailoring H-bond degree via altering the feeding ratio of lignin. The rigid lignin cooperating with HDI as hard segments self-assembled to generate phase separated nanostructures. Consequently, the integration of well-defined hard-soft nanophases and multiple H-bond interactions in the synthesized lignin-based PU (LPU) achieved excellent and customizable mechanical performances ranging from highly elastic rubber to highly stiff plastic with ultrahigh strength of 72.8 MPa and unprecedented modulus of 3.5 GPa. Impressively, rubber-like LPU elastomers could recover 90 % of initial stress even after 500 stretching cycles, indicating fascinating resilience and fatigue resistance. More especially, rigid LPU plastics with fully hard domains and dense H-bond networks could be transformed into flexible and bendable paper-like elastomers once eliminating intermolecular H-bond interactions under 60 °C hot water. Thus, this work provides a feasible and promising approach to construct supramolecular PU elastomers with excellent and customizable mechanical performances to extend their on-demand applications.

Bio-based polyurethane vitrimer with imine bonds: Excellent thermo-mechanical properties and heat recovery

Preparation of vitrimer with excellent performance from biomass feedstock can effectively reduce the waste of fossil fuels and the pollution problem to the environment. In this paper, vanillin (VAN) and 4-amino-3-methylphenol, which are biobased raw materials, were used to prepare the imine-bonded diol AMV-OH in a one-step process, which was incorporated into the main chain of vitrimer polymer, and a series of imine-bonded vitrimer materials AMV-V was obtained by using pentaerythritol tetra-3-mercaptopropionate (PETMP) as a cross-linking agent. The mechanical property analysis, solvent resistance analysis, DSC thermal analysis, DMA analysis and self-repair characterization showed that AMV-V exhibited good thermo-mechanical properties (the highest initial degradation temperature was 246 °C with a Tg value of 17 °C). The results showed that specific mechanical properties could be obtained by adjusting the contents of PETMP and AMV-OH, among which the best tensile properties were obtained at 10 mmol of AMV-OH, with a tensile strength of 8.03 MPa and an elongation at break of 316.79 %. Meanwhile, the AMV-V samples were able to achieve self-healing properties under milder conditions (100 °C, 10 MPa repair for 1 h) and had a high self-healing efficiency (H=94.80 %, R=83.72 %).

Recent Advances in the Preparation and Application of Bio-Based Polyurethanes.

Amid environmental pollution and resource depletion, developing and utilizing biomass resources as alternatives to petroleum is a prominent research focus. Driven by environmental protection and sustainable development, the shift from petroleum-based to bio-based polyurethane is a prevailing trend in polyurethane material development. Biomass sources such as vegetable oil, polysaccharides, and lignin offer extensive application prospects in bio-based polyurethane production. Functional modifications of these polyurethanes can further expand their application range. This article explores the preparation of various bio-based polyurethanes, their applications across different fields, and their anticipated future development and uses.

Improved thermal stability and flame retardancy of soybean oil-based polyol rigid polyurethane foams modified with magnesium borate hydroxide and ammonium polyphosphate

The concept of sustainable development has led to a growing research interest in bio-based flame-retardant polyurethane foams. These foams offer environmentally friendly, sustainable, and flame-retardant raw materials for the construction, automotive, and furniture industries. The 15 wt% soybean oil-based polyol rigid polyurethane foams (RPUF-S3A20B system) were modified with 20 wt% ammonium polyphosphate (APP) and homemade magnesium borate hydroxide (MgBO2(OH)). Thermogravimetric analysis, pyrolysis kinetic analysis, limiting oxygen index (LOI) test, cone calorimetry (CONE), morphological analysis, and smoke density (Ds) were employed to investigate the impact of MgBO2(OH) on the thermal stability and flame-retardant properties of the RPUF-S3A20B system. The results indicated that RPUF-S3A20B12.5 with 12.5 wt% MgBO2(OH) had better thermal stability and higher activation energy. In addition, its LOI was increased by 3.1% compared to RPUF-S3A20 without MgBO2(OH). The peak heat release rate (PHRR) and total heat release rate (THR) of RPUF-S3A20B12.5 at a radiant flux of 25 kW/m2 were reduced by 45.8% and 35.0% compared with RPUF-S3A20. RPUF-S3A20B12.5 demonstrated the lowest smoke density (17.4 and 17.5) and highest light transmission (73.9% and 73.7%) in both flameless and flame conditions, indicating superior flame-retardant and smoke-suppression properties. These findings offered valuable insights for further research on synergistic flame-retardant systems in bio-based polyurethane foams.

Post-Spinning Click Cross-Linked Biobased Polyurethane Coaxial Nanofibers

Post-Spinning Click Cross-Linked Biobased Polyurethane Coaxial Nanofibers