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Polyurethane is a versatile material that can be converted into various forms according to applications. PU foams or PUFs are the most commonly used polyurethanes. These are materials of low density and low thermal conductivity that make them highly suitable for thermal insulating applications. Most of the synthesis of PUFs is still based on the petrochemical industry. There are issues associated with the oil industry, such as environmental pollution, sustainability, and market instability. More recently, we have experienced the COVID-19 pandemic which has destroyed the global supply chain of raw materials. Such sudden disruption of the supply chain affects the global economy. To eliminate the reliance on special ingredients, it is important to find and produce alternate and domestic raw materials. Vegetable oils are organic, cost-effective, and economically viable and present in abundant amounts. The oil consists of triglycerides. It can be functionalized to provide polyol for PU foam synthesis. Herein, we review the literature on factors influencing the properties of PUFs depending on polyols from vegetable oil as well as present a glimpse of the conversion of vegetable oils into polyols for PUF synthesis.

Green manufacturing and reducing our cultural dependency on petrochemicals have been the global interest currently, especially in the polyurethane industry segments. We report the fabrication of rigid polyurethane foams (RPUFs) and their flame-retardant property from hemp seed oil as an alternative to petrochemical-based polyols. The cold-pressed hemp-seed oil (HSO) was first oxidized to epoxidized triglyceride oils with acetic acid and hydrogen peroxide, followed by a ring-opening reaction with methanol to fabricate hemp bio-polyols. The formation of polyols was characterized using FT-IR, hydroxyl, and acid values. The bio-polyol was used in different proportions with commercial polyols and other foaming ingredients to produce rigid polyurethane foams via a one-step process. Dimethyl methylphosphonate (DMMP), triethyl phosphate (TEP), and expandable graphite (EG) were added during the foam preparation to improve flame retardancy. The produced foams were analyzed for their apparent density, mechanical properties, thermal degradation behavior, closed cell content, flammability, and cellular morphology. The effect of different flame retardants had a significant influence on the cellular structures, closed-cell content, density, and compressive strength of the polyurethane. A significant improvement in anti-flaming properties was observed as the neat HSO-based foam showed a burning time of 110 s and a weight loss of 82%, whereas 10 wt% of TEP displayed a reduced burning time and weight loss of 19 s and 5%, respectively. DMMP and EG-based RPUFs exhibited similar flame retardancy and mechanical properties relative to neat HSO-based foam. The results demonstrated in this work proposed a potential combination of bio-polyols and commercial polyols as a strategy to fabricate flame-retardant polyurethane foam for high-performance applications.

Rigid polyurethane foam (RPUF) is one of the best thermal insulation materials available, but its flammability makes it a potential fire hazard. Due to its porous nature, the large specific surface area is the key factor for easy ignition and rapid fires spread when exposed to heat sources. The burning process of RPUF mainly takes place on the surface. Therefore, if a flame-retardant coating can be formed on the surface of RPUF, it can effectively reduce or stop the flame propagation on the surface of RPUF, further improving the fire safety. Compared with the bulk flame retardant of RPUF, the flame-retardant coating on its surface has a higher efficiency in improving fire safety. This paper aims to review the preparations, properties, and working mechanisms of RPUF surface flame-retardant systems. Flame-retardant coatings are divided into non-intumescent flame-retardant coatings (NIFRCs) and intumescent flame-retardant coatings (IFRCs), depending on whether the flame-retardant coating expands when heated. After discussion, the development trends for surface flame-retardant systems are considered to be high-performance, biological, biomimetic, multifunctional flame-retardant coatings.

Temperature is one of the main factors affecting the properties of polyurethane foams, and there are large differences in the mechanical properties of polyurethane foams at different temperatures. To understand the effect of temperature on the mechanical properties of polyurethane foams and to provide a theoretical basis for the application of polyurethane foams in extreme environments, this paper systematically describes the research on the effect of mold temperature, raw material temperature, and environmental temperature on the microstructure and mechanical properties of polyurethane foams in the formation and service stages of rigid polyurethane foams by domestic and foreign scholars, and summarizes the effect of temperature on the mechanical properties of polyurethane foams and the mechanism of action. A review of the literature shows that the effect of different temperatures on the mechanical properties of polyurethane foams can be summarized. The literature review shows that there are certain changes in the foaming process, pore structure, and mechanical properties of polyurethane foams at different temperatures, and the increase in temperature generally leads to the increase in pore size, decrease in density, and decrease in mechanical properties of polyurethane foams.

Polyurethane foams (PUFs) are a significant group of polymeric foam materials. Thanks to their outstanding mechanical, chemical, and physical properties, they are implemented successfully in a wide range of applications. Conventionally, PUFs are obtained in polyaddition reactions between polyols, diisoycyanate, and water to get a CO2 foaming agent. The toxicity of isocyanate has attracted considerable attention from both scientists and industry professionals to explore cleaner synthesis routes for polyurethanes excluding the use of isocyanate. The polyaddition of cyclic carbonates (CCs) and polyfunctional amines in the presence of an external blowing agent or by self-blowing appears to be the most promising route to substitute the conventional PUFs process and to produce isocyanate-free polyurethane foams (NIPUFs). Especially for polyhydroxyurethane foams (PHUFs), the use of a blowing agent is essential to regenerate the gas responsible for the creation of the cells that are the basis of the foam. In this review, we report on the use of different blowing agents, such as Poly(methylhydrogensiloxane) (PHMS) and liquid fluorohydrocarbons for the preparation of NIPUFs. Furthermore, the preparation of NIPUFs using the self-blowing technique to produce gas without external blowing agents is assessed. Finally, various biologically derived NIPUFs are presented, including self-blown NIPUFs and NIPUFs with an external blowing agent.

Rigid polyurethane foams (RPUF) are the most consumed cellular polymer in the world. Bio-based polyols are sometimes used as raw material for RPUF but with a detrimental effect on mechanical properties. In this paper, micro fibrillated cellulose (MFC) was used as a reinforcement to enhance the mechanical, thermal and dynamic mechanical properties of bio-based RPUF. A bleached Eucalyptus sp. pulp was dispersed in glycerine and then subjected to mechanical defibrillation to extract the MFC, a route that does not require dispersants or drying, which is advantageous for the MCF incorporation. The RPUF were manufactured in a closed mould in a way to obtain overpacking. The higher the overpacking degree, the higher the apparent density and stiffness of the RPUF. Also, expansion under confinement yielded more rounded polymer cells with decreased anisotropy. The MFC and overpacking acted synergistically, improving strength, stiffness, thermal stability and dynamic mechanical properties of the RPUF. Thermal conductivity of the RPUF, on the other hand, was unaffected by those factors.Graphic abstract

•This study shows the levels of COHb, cyanide and MetHb in 38 RPUF fire victims.•Victims were classified into two groups to scrutinize the toxic gas poisoning.•Group 1 relatively showed the high levels of COHb and cyanide compared to group 2.•Group 2 may have a possibility of NO2 inhalation in company with CO and HCN. [Display omitted] Rigid polyurethane foam (RPUF) is widely used for thermal and sound insulation owing to their low thermal conductivity and light weight. However, they have serious disadvantages, including flammability and toxic gas generation, which can cause chemical asphyxia during a fire. Carbon monoxide (CO) and hydrogen cyanide (HCN) are representative toxic gases formed by incomplete combustion and HCN, in particular, is closely related to polyurethane product fires. In this study, the risk of inhalation of toxic gases such as CO, HCN and NO2 during RPUF fires was demonstrated convincingly through the analysis of carboxyhemoglobin (COHb), cyanide (CN-) and methemoglobin (MetHb) in the postmortem blood samples of 38 victims of RPUF fires. To better understand the toxic gas poisoning and chemical asphyxia, we classified all cases into two groups based on the extent of injuries and location where the victim was found. Mean concentrations of COHb and cyanide in group 1 without injuries were approximately two times higher than in group 2 with severe injuries, while concentrations of free MetHb showing possibility of NO2 inhalation were approximately six times lower than in group 2. Furthermore, we presumed concentrations of cyanide at the time of death and five cases showed the possibility of cyanide poisoning.

This work intends to provide a preliminary approach concerning the preparation of 3D printed products derived from recycled raw-materials. In that sense, recycled polyurethane foam (PUF) particles were added (up to 10% wt/wt) to thermoplastic polyurethane (TPU) to prepare 3D printed products. From the results, it was observed that the presence of PUF particles reduces the density of filaments. Moreover, even though filler and matrix are polyurethane (PU) polymers, the fact that PUF scraps consists of crosslinked PU, it affects inter-layer adhesion, reducing the mechanical performance of the 3D printed specimens, especially when high PUF particles contents were used. Nonetheless, despite of the limitations identified, the addition of PUF particles did not affect the thermal stability of the composites, meaning that these composites can be processed at high temperatures. Therefore, PUF scraps were successfully reused which proved to be a low cost additive for the production 3D printed composites (when using low content), with the advantage of being an alternative to the disposal of PUF.

Flexible polyurethane foam (FPUF) has a widespread application across aerospace, furniture and vehicles, while its flammability always arouses severe safety concerns. Herein, a novel, bio-based flame retardant, i.e. polyol (PADEA) that contains phosphorus and nitrogen elements, was successfully synthesized by using phytic acid (a bio-organic acid) and diethanolamine as crude materials. Then, PADEA partially substituted the commercial polyether polyols in the foaming process, during which PADEA reacted in situ with isocyanate to construct an inherently flame-retardant FPUF. Due to the purposive designed P-N synergistic molecular structure, PADEA can serve as a highly efficient intumescent flame-retardant (IFR) system. When 40 php (ca. 21.51wt%) PADEA was added into the system, the limiting oxygen index (LOI) of the obtained FPUF reached up to 24.1%, achieving a 22.0% increase compared to that of primitive FPUF without PADEA. Moreover, the addition of PADEA can considerably reduce the total number of melt drips in the UL-94 HB rating test. And the cone calorimeter (CC) results demonstrated a 47.08% reduction in total heat release (THR) was achieved as 40 php PADEA was added. At the end, various characterization methods were carried out, revealing the flame-retardant mechanism of PADEA both in condense and gaseous phase. This work highlights a facile and green strategy for designing functional polyol to address the flame-retardant issues of high-performance FPUF.

High-quality rigid polyurethane (PU) foam thermal insulation material has been developed solely using bio-polyols synthesized from second-generation bio-based feedstock. High functionality bio-polyols were synthesized from cellulose production side stream—tall oil fatty acids by oxirane ring-opening as well as esterification reactions with different polyfunctional alcohols, such as diethylene glycol, trimethylolpropane, triethanolamine, and diethanolamine. Four different high functionality bio-polyols were combined with bio-polyol obtained from tall oil esterification with triethanolamine to develop rigid PU foam formulations applicable as thermal insulation material. The developed formulations were optimized using response surface modeling to find optimal bio-polyol and physical blowing agent: c-pentane content. The optimized bio-based rigid PU foam formulations delivered comparable thermal insulation properties to the petro-chemical alternative.