Search Results (76)

A series of linear isocyanate-free polyurethanes (NIPUs) were obtained via the aminolysis of erythritol dicarbonate (EDC) with polyethers (diamino-PEG, diamino-PPO, and diamino-PEG/PPO) and 1,12-diaminododecane (DADD), which acts as a chain extender to form hard segments. The obtained NIPUs contained different concentrations of DADD relative to the polyether (72.5–80 wt%). A detailed chemical structure analysis of the synthesized NIPU was performed using a combination of FTIR and ¹H NMR. FTIR spectra confirmed that the EDC/DADD segments formed a network of hydrogen bonds. This is reflected in WAXD diffractograms showing ordered crystalline domains originating in DADD. The reflections assigned to the EDC/DADD segments exhibited changes in their position and intensity with decreasing concentration, indicating an increase in interplanar spacing and a loss of higher-order order. WAXD also showed that the soft segments of PEG and PEG/PPO retain their ordered crystal structure regardless of the EDC/DADD content. At a larger length scale, SAXS revealed similar micromorphology for the different polyethers, with a broad peak indicating long-range order in the EDC/DADD-rich segments and a weak separation of the soft and hard phases. DSC analyses confirmed the complex phase behavior, where the PEG-based materials showed melting of crystalline fragments, and the amorphous PPO showed a glass transition. DMA indicated the stability of the glass transition temperature in the PPO samples and the presence of an unusual structural transition. The results emphasize the influence of the type of poly(ether) on the thermal and microphase properties of the studied non-isocyanate polyurethanes. Full article

Polyurethane asphalt (PUA) has attracted considerable attention in the field of pavement engineering. However, traditional PUA systems typically exhibit low concentrations of polyurethane (PU), leading to a continuous bitumen-dominated phase that adversely affects mechanical properties. Furthermore, the non-renewable nature of raw materials raises environmental concerns. To address these limitations, this study developed an eco-friendly and cost-efficient bio-based PUA binder (PUAB) featuring a continuous high-biomass PU matrix (over 70% biomass) and a high bitumen content (60 wt%). The effects of the isocyanate index (NCO/OH ratio) on the cure kinetics, rheological behavior (rotational viscosity over time), viscoelasticity, damping capacity, phase morphology, thermal stability, and mechanical performance were systematically investigated using Fourier-transform infrared spectroscopy, dynamic mechanical analysis, laser-scanning confocal microscopy, and tensile testing. Key findings revealed that while the rotational viscosity of PUABs increased with a higher isocyanate index, all formulations maintained a longer allowable construction time. Specifically, the time to reach 1 Pa·s for all PUABs at 120 °C exceeded 60 min. During curing, higher isocyanate indices reduced final conversions but enhanced the storage modulus and glass transition temperatures, indicating improved rigidity and thermal resistance. Phase structure analysis demonstrated that increasing NCO/OH ratios reduced bitumen domain size while improving dispersion uniformity. Notably, the PUAB with the NCO/OH ratio of 1.3 achieved a tensile strength of 1.27 MPa and an elongation at break of 238%, representing a 49% improvement in toughness compared to the counterpart with an NCO/OH ratio = 1.1. These results demonstrate the viability of bio-based PUAB as a sustainable pavement material, offering a promising solution for environmentally friendly infrastructure development. Full article

In recent decades, scientific interest has increasingly focused on sustainable and green polymers. Within this context, considerable efforts have been devoted to the synthesis and exploration of eco-friendly non-isocyanate polyurethanes (NIPUs) as alternatives to conventional polyurethanes (PUs), solving the problem of isocyanate toxicity and other environmental problems that existed. This review article highlights the synthetic pathways of NIPUs and identifies the potential hazards associated with their production and end-of-life (EoL) stages. While in the literature there are several reviews regarding the synthesis of NIPUs, the current work distinguishes itself by providing a comprehensive summary of the latest research on NIPUs, with a particular focus on their lifecycle management, recyclability, and the challenges that hinder their scalability for industrial-level production. Advances in NIPU synthesis have made them strong candidates for a diverse range of applications. This review underscores the most notable examples of these advancements, emphasizing their potential to drive sustainable polymer development. Full article

This study explores the synthesis of photocurable non-isocyanate polyhydroxyethylurethanes (BPHUs) derived from renewable sources, designed for biomedical applications and the development towards advanced light curing processes. The following two pathways were developed: an aliphatic route using 1,4-butanediol-derived cyclic carbonates and an aromatic route with resorcinol-based carbonates. Ring-opening polymerization with dodecanediamine produced BPHU intermediates, which were methacrylated to form photoreactive derivatives (aliphatic MAs and aromatic MAs). Comprehensive characterization, including NMR, GPC, and FTIR, confirmed the successful synthesis. The UV curing of these methacrylated compounds yielded hydrogels with swelling properties. Aliphatic BPHUs achieved a gel content of 91.3% and a swelling of 1057%, demonstrating the flexibility and UV stability suitable for adaptable biomedical applications. Conversely, aromatic BPHUs displayed a gel content of 78.1% and a swelling of 3304%, indicating higher rigidity, which is advantageous for load-bearing uses. Cytotoxicity assessments adhering to the DIN EN ISO 10993-5 standard demonstrated non-cytotoxicity, with an >80% cell viability for both variants. This research underscores the potential of green chemistry in crafting biocompatible, versatile BPHUs, paving the way for eco-friendly materials in implantable medical devices. Full article

Polyurethanes (PUs) are extremely versatile materials used across different industries. Traditionally, they are synthesized by reacting polyols and isocyanates, both of which are petroleum-derived reagents. In response to the demand for more eco-friendly materials, research has increasingly focused on developing new routes for PU synthesis using renewable feedstocks. While substituting isocyanates remains a greater challenge, replacing fossil-based polyols with bio-based alternatives is now a promising strategy. This review explores the main natural sources and their transformations into bio-polyols, the incorporation of bio-fillers into PU formulations, and the production of non-isocyanate polyurethanes (NIPUs). Additionally, the study summarizes the growing body of research that has reported successful outcomes using bio-polyols in PU foams for distinct applications. Full article

The production of non-isocyanate polyurethane (NIPU) resins using recyclable biomass materials and no isocyanates as a substitute for traditional polyurethane (PU) materials has become a research focus in the polyurethane industry. The development of such NIPU resins for application as wood adhesives has also emerged as an interesting new research topic. In this study, sucrose was used to react with dimethyl carbonate, and then polymerized with an amine to prepare sucrose-based non-isocyanate polyurethane (SNIPU) adhesives and evaluate their suitability for use in plywood. Four amines, namely polyethylene amine (PEI) of molecular weight (MW) 10,000, PEI of MW 1800, diethylenetriamine, and hexanediamine were tested in the preparation of SNIPU adhesives to determine a more suitable amine showing optimal adhesion performance. The effect of the amount of the amine added on adhesive properties was further investigated. The results showed that the SNIPU adhesive prepared with PEI-10000 as amine presents a good bonding performance. The SNIPU prepared with a PEI-10000 content of 45% (w/w on sucrose) presented the highest bonding strength. The dry strength, 24 h cold water (23 °C) wet strength, and 3 h hot water (63 °C and 93 °C) wet strengths of its bonded plywood were 1.26 MPa, 0.90 MPa, 0.84 MPa, and 0.80 MPa, respectively. Furthermore, the addition of 13% (w/w on SNIPU adhesive) of ethylene glycol diglycidyl ether (EGDE) as a modifier showed a significant decrease of 20 °C of the curing temperature of the SNIPU adhesive. Full article

Inspiration from nature is a promising tool for the design of new polymeric biomaterials, especially for frontier technological areas such as tissue engineering. In tissue engineering, polyurethane-based implants have gained considerable attention, as they are materials that can be designed to meet the requirements imposed by their final applications. The choice of their building blocks (which are used in the synthesis as macrodiols, diisocyanates, and chain extenders) can be implemented to obtain biomimetic structures that can mimic native tissue in terms of mechanical, morphological, and surface properties. In recent years, due to their excellent chemical stability, biocompatibility, and low cytotoxicity, polyurethanes have been widely used in biomedical applications. Biomimetic materials, with their inherent nature of mimicking natural materials, are possible thanks to recent advances in manufacturing technology. The aim of this review is to provide a critical overview of relevant promising studies on polyurethane scaffolds, including those based on non-isocyanate polyurethanes, for the regeneration of selected soft (cardiac muscle, blood vessels, skeletal muscle) and hard (bone tissue) tissues. Full article

Polyhydroxyurethanes (PHUs) synthesized from cyclic carbonates are promising alternatives to conventional polyurethanes due to their advantageous isocyanate-free synthesis and reprocessability characteristics. While many studies focus on PHUs derived from five-membered cyclic carbonates (5CCs) for more sustainable synthesis routes, PHUs from six-membered cyclic carbonates (6CCs) exhibit enhanced reactivity towards amines. Their reprocessability is facilitated by the presence of hydroxyl groups along the polymer chain, enabling transcarbamoylation reactions. However, since non-catalyzed transcarbamoylation is typically a sluggish reaction, catalysts are often required to enhance network reprocessability. This study presents a life cycle assessment (LCA) of PHU-5CC and PHU-6CC syntheses, with catalysts, for recycling applications targeting end-of-life scenarios. Environmental impact categories, including climate change, particulate matter, fossil resource depletion, mineral and metal resource use and freshwater eutrophication, were evaluated. Sensitivity analyses were also conducted to assess key variables. Our results indicate that PHUs from 6CCs show a higher environmental footprint due to their solvent-intensive synthesis process. Despite the increased reactivity and shorter reaction times associated with the 6CC monomer, these benefits do not fully offset the environmental impacts of the synthesis process. In conclusion, this study highlights potential improvements for future PHU synthesis, such as solvent-free processes, metal-free catalysts and optimized reaction monitoring. Full article

The increasing quest for greener and more sustainable polymeric materials has gained interest in the past few decades. Non-isocyanate polyurethanes (NIPUs) have attracted attention considering that they are produced through less toxic methods compared to the conventional polyurethanes (PUs) obtained from petroleum resources and toxic isocyanates. In this context, adipic acid, glycerol carbonate, 1,2-ethylenediamine, and 1,6-hexamethylenediamine, were used to synthesize NIPU_ethyl and NIPU_hexa, respectively. The obtained NIPUs were characterized using nuclear magnetic resonance spectroscopy (H-NMR spectra) and Fourier-transform infrared spectroscopy (FTIR) analysis, which verified the structures of the intermediate and final products. Calorimetric and dielectric studies provided direct and indirect support for the facilitated thermal stability of NIPU_ethyl and NIPU_hexa. Compared to the intermediate product, the NIPUs exhibit elevated glass transition temperatures, suggesting the formation of more rigid structures. The NIPUs were also tested in terms of swelling properties, and the results indicated that NIPU_hexa absorbs and withholds increased amounts of water for longer time periods compared to NIPU_ethyl, and their hydrolysis and enzymatic hydrolysis confirmed that NIPU_hexa is more stable in aqueous environments than NIPU_ethyl. Therefore, the successful production of adipic-acid-based NIPUs through a novel perspective of the polyaddition path is reported and complemented by the characterization of the obtained materials with several techniques. Full article

Glycerol is a biogenic waste that is generated in both the biodiesel and oleo-chemical industries. The value addition of surplus glycerol is of utmost importance for making these industries economically profitable. In line with this, glycerol is converted into glycerol carbonate, a potential candidate for the industrial production of polymers and biobased non-isocyanate polyurethanes. In addition, glycerol can also be converted into solketal, which is the protected form of glycerol with a primary hydroxyl functional group. In this contribution, we developed a microwave-assisted solvent and catalyst-free method for converting solketal into solketal carbonate. Under conventional heating conditions, the reaction of solketal with dimethyl carbonate resulted in 70% solketal carbonate in 48 h. However, under microwave heating, 90% solketal carbonate was obtained in just 30 min. From the perspective of sustainability and green chemistry, biomass-derived heterogeneous catalysts are gaining importance. Therefore, in this project, several green catalysts, such as molecular sieves (MS, 4Å), Hβ-Zeolite, Montmorillonite K-10 clay, activated carbon from groundnut shell (Arachis hypogaea), biochar prepared from the pyrolysis of sawdust, and silica gel, were successfully used for the carbonyl transfer reaction. The obtained solketal carbonate was thoroughly characterized by ¹H NMR, ¹³C NMR, IR, and MS. The method presented here is facile, clean, and environmentally benign, as it eliminates the use of complicated procedures, toxic solvents, and toxic catalysts. Full article

Though polyurethanes (PUs) are widely used in people’s daily lives, traditional PUs are generally fabricated from toxic (poly)isocyanates. Furthermore, (poly)isocyanates are commonly industrially prepared from a seriously toxic and injurious chemical compound named phosgene, which is a dangerous gas that can cause lung irritation and eventually death. As is known to all, the consumption of carbon dioxide (CO₂)-based raw materials in chemical reactions and productions will be conducive to reducing the greenhouse effect. In this paper, non-isocyanate polyurethane (NIPU) diol was fabricated through a polyaddition reaction from ethylenediamine and CO₂-based ethylene carbonate, and then NIPU-based silicone-containing thiol hyperbranched polymers (NIPU-SiHPs) were synthesized from the NIPU diol. Finally, UV-curable optical-silicone-modified CO₂-based coatings (UV-NIPUs) were fabricated from NIPU-SiHPs and pentaerythritol triacrylate by a UV-initiated thiol-ene click reaction without a UV initiator. The UV-NIPUs demonstrated high transparency over 90% (400–800 nm), good mechanical performance with tensile strength reaching 3.49 MPa, superior thermal stability with an initial decomposition temperature (T_d5) in the range of 239.7–265.6 °C, moderate hydrophilicity with a water contact angle in the range of 42.6–62.1°, a high pencil hardness in the range of 5–9H, and good adhesive performance of grade 0. The results indicate that it is a promising green chemical strategy to fabricate CO₂-based high-performance materials. Full article

This minireview presents some unusual but encouraging examples of lignocellulosic-based adhesives and coatings used for metals, glass, and some other difficult-to-adhere materials. The reactions and applications presented are as follows. (i) The reactions of tannins and wood lignin with phosphate salts, in particular triethylphosphate, to adhere and join steel and aluminum to Teflon, in particular for non-stick frying pans. These adhesive coatings have been shown to sustain the relevant factory industrial test of 410 °C for 11 min and, moreover, to present a 50% material loss even at 900 °C for 5 min. (ii) Non-isocyanate polyurethanes (NIPU) based on glucose and sucrose as coatings of steel and glass. These were obtained by the carbonation of carbohydrates through reaction with the inexpensive dimethyl carbonate followed by reaction with a diamine; all materials used were bio-sourced. Lastly, (iii) the use of citric acid-based adhesive coupled with any hydroxyl groups carrying material for coating metals is also described. These three approaches give a clear indication of the possibilities and capabilities of biomaterials in this field. All these are presented and discussed. Full article

This work discusses the synthesis and properties of nonisocyanate polyurethanes (NIPUs) as an environmentally friendly alternative to traditional polyurethanes. NIPUs are made without the use of toxic isocyanates, reducing the environmental impact and safety concerns associated with their production. However, their synthesis reactions often require longer time and more energy to be completed. The sustainability of NIPUs is considered from various angles; the main methods for the synthesis of NIPUs, including rearrangement reactions, transurethanization, and ring-opening polymerization of cyclic carbonates with amines, are examined. Another part focuses on renewable sources, such as vegetable oils, terpenes, tannins, lignins, sugars, and others. The synthesis of waterborne and solvent-free NIPUs is also discussed, as it further reduces the environmental impact by minimizing volatile organic compounds (VOCs) and avoiding the use of harmful solvents. The challenges faced by NIPUs, such as lower molecular weight and higher dispersity compared to traditional polyurethanes, which can affect mechanical properties, were also addressed. Improving the performance of NIPUs to make them more competitive compared to conventional polyurethanes remains a key task in future research. Full article

The preparation and application of non-isocyanate polyurethane (NIPU) from biomass raw materials as a substitute for traditional polyurethane (PU) has recently become a research hot topic as it avoids the toxicity and moisture sensitivity of isocyanate-based PU. In the work presented here, self-blowing GNIPU non-isocyanate polyurethane (NIPU) rigid foams were prepared at room temperature, based on glucose, with acids as catalysts and glutaraldehyde as a cross-linker. The effects of different acids and glutaraldehyde addition on foam morphology and properties were investigated. The water absorption, compressive resistance, fire resistance, and limiting oxygen index (LOI) were tested to evaluate the relevant properties of the foams, and scanning electron microscopy (SEM) was used to observe the foams’ cell structure. The results show that all these foams have a similar apparent density, while their 24 h water absorption is different. The foam prepared with phosphoric acid as a catalyst presented a better compressive strength compared to the other types prepared with different catalysts when above 65% compression. It also presents the best fire resistance with an LOI value of 24.3% (great than 22%), indicating that it possesses a good level of flame retardancy. Thermogravimetric analysis also showed that phosphoric acid catalysis slightly improved the GNIPU foams’ thermal stability. This is mainly due to the flame-retardant effect of the phosphate ion. In addition, scanning electron microscopy (SEM) results showed that all the GNIPU foams exhibited similar open-cell morphologies with the cell pore sizes mainly distributed in the 200–250 μm range. Full article