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This article raised the issue of studies on the use of new bio-polyol based on white mustard seed oil and 2,2’-thiodiethanol (3-thiapentane-1,5-diol) for the synthesis of rigid polyurethane/polyisocyanurate (RPU/PIR) foams. For this purpose, new formulations of polyurethane materials were prepared. Formulations contained bio-polyol content from 0 t...
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Context 1
... series of foams modified with bio-based polyol were obtained-with commercial flame retardant (ZA) and without it (BA). The formulation of polyurethane-polyisocyanurate foams is shown in Table 1. The foams were obtained on a laboratory scale using the one-step method from the two-component (A and B) system. ...Context 2
... A was obtained from mixing appropriate amounts of polyols, catalysts, surfactant, blowing agent, and, optionally, flame retardant. Component B was a technical polyisocyanate, Purocyn B. The components A and B were mixed for 10 s with a mechanical stirrer (1800 rpm) in a required mass ratio (Table 1). Next, the mixture was poured into a rectangular open mold with internal dimensions of 25 cm × 25 cm × 30 cm, where the free rising of foam took place. ...Context 3
... times were measured during the preparation of RPU/PIR foams to determine the effect of bio-polyol on foaming parameters, i.e., cream time-from the start of mixing components A and B until fine bubbles appeared; free-rise time-from the start of mixing components A and B until the foam stops expanding; string gel time-from the start of mixing components A and B until long strings of tacky material can be pulled away from foam surface when the surface is touched by a tongue depressor; tack-free time-from the start of mixing components A and B until the foam surface can be touched by a tongue depressor without sticking. All foams retained the assumed percentage of additive raw materials (Table 1) for easier interpretation of the obtained results. The results of measurements are shown in Table 2. ...Similar publications
The procedure for the liquefaction of apricot stone shells was reported in Part 1. Part 2 of this work determines the morphological, mechanical, and thermal properties of the bio-based rigid polyurethane foam composites (RPUFc). In this study, the thermal conductivity, compressive strength, compressive modulus, thermogravimetric analysis, flammabil...
Citations
... The second most advantageous solution would be to find a way to increase the flame resistance of polymer materials, thereby reducing the emission of toxic gases and carbon oxides into the atmosphere during combustion. An example of an investigation focused on bio-based reactive flame retardants is the research developed by Professor Paciorek-Sadowskaʹs research team [98][99][100]. Researchers synthesized a new type of bio-polyol based on unrefined white mustard (Sinapis alba) oil as a result of a two-step synthesis consisting of epoxidation of double bonds and subsequent opening of the created oxirane rings. ...
Polyurethanes are among the most significant types of polymers in development; these materials are used to produce construction products intended for work in various conditions. Nowadays, it is important to develop methods for fire load reduction by using new kinds of additives or monomers containing elements responsible for materials' fire resistance. Currently, additive antipyrines or reactive flame retardants can be used during polyurethane material processing. The use of additives usually leads to the migration or volatilization of the additive to the surface of the material, which causes the loss of the resistance and aesthetic values of the product. Reactive flame retardants form compounds containing special functional groups that can be chemically bonded with monomers during polymerization, which can prevent volatilization or migration to the surface of the material. In this study, reactive flame retardants are compared. Their impacts on polyurethane flame retardancy, combustion mechanism, and environment are described.
... In addition, the ban of chlorofluorocarbon (CFC) blowing agents in the 1990's and their replacement by highly flammable pentanes has caused an important increase in PIR foams flammability, which had to be counterbalanced by the incorporation of more FRs [13]. Many different FRs have been tested in PIR foams, including halogenated FRs (chlorinated, brominated) [14,15], halogen-free phosphorous-based FRs [16][17][18][19][20], intumescent expandable graphite [20][21][22][23], aluminum hydroxide [24,25], nanoclays [26,27] and synergistic combinations of various types of FRs [24][25][26][27][28][29]. ...
... The greatest weight loss was noted for PU_10SHA (about 30%), while for PU_REF, only 10% of the weight was lost after eight weeks. Borowicz et al. [38] analyzed the impact of reducing the amount of petrochemical polyol and replacing it with bio-polyol produced from white mustard seeds on the biodegradability of RPUFs. They also indicate in their article the positive impact of introducing biodegradable substances into foams on the process of their decomposition in the soil. ...
Energy produced from waste biomass is more environmentally friendly than that produced from fossil resources. However, the problem of managing waste from the thermal conversion of biomass arises. The overarching goal of this article was to propose a method of utilizing biomass ash (sunflower husk) as a filler that positively affects the properties of rigid polyurethane foams. The scope of the presented research is to obtain and characterize rigid polyurethane foams (RPUFs) with the addition of two types of fillers: sunflower husks (SHs) and sunflower husk ash (SHA). First, an analysis of the fillers was carried out. The carbon content of SHs (C~49%) was ten times higher in comparison to SHA’s carbon content (C~5%). The morphology of the fillers and the particle size distribution were determined, which showed that in the case of SHs, particles with a size of 500–1000 µm predominated, while in SHA, the particles were 1–20 µm. The content of inorganic compounds was also determined. Potassium and calcium compounds were the most abundant in both fillers. The second part of the research was the analysis of polyurethane materials with the addition of fillers. The obtained results indicate that filler addition had a positive effect on the dimensional stability of the foams by eliminating the risk of material shrinkage. The biodegradation process of polyurethane materials was also carried out. The reference foam weight loss after 8 weeks was ~10%, while the weight loss of the foam containing SHA was over 28%. Physical and mechanical properties, cell structure, and thermal stability tests were also carried out. The use of bio-waste fillers creates a possibility for the partial replacement of petrochemical products with environmentally friendly and recycled materials, which fits into the circular economy strategy.
... The qualities of nanopolymer compounds are comparable to those of traditional polymers, and they are ecologically benign [11]. Due to polyurethane foam's (PU) properties as an effective insulating material, polyurethane foam may be modified to improve its properties [12]. Which are commonly used in many industries, including building engineering, automotive, construction, and furniture [13,14] Polyurethane, often known as PU or PUR, is a polymer made of many organic units connected by urethane molecules. ...
In this work, the effect of adding Pb nano/microparticles in polyurethane foams to improve thermo-physical and mechanical properties were investigated. Moreover, an attempt has been made to modify the micron-sized lead metal powder into nanostructured Pb powder using a high-energy ball mill. Two types of fillers were used, the first is Pb in micro scale and the second is Pb in nano scale. A lead/polyurethane nanocomposite is made using the in-situ polymerization process. The different characterization techniques describe the state of the dispersion of fillers in foam. The effects of these additions in the foam were evaluated, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD) have all been used to analyze the morphology and dispersion of lead in polyurethane. The findings demonstrate that lead is uniformly distributed throughout the polyurethane matrix. The compression test demonstrates that the inclusion of lead weakens the compression strength of the nanocomposites in comparison to that of pure polyurethane. The TGA study shows that the enhanced thermal stability is a result of the inclusion of fillers, especially nanofillers. The shielding efficiency has been studied, MAC, LAC, HVL, MFP and Zeff were determined either experimentally or by Monte Carlo calculations. The nuclear radiation shielding properties were simulated by the FLUKA code for the photon energy range of 0.0001–100 MeV.
... The first attempts for a green and sustainable PUFs were the inclusion of polyols derived from natural sources, such as vegetable oils [13,14], agricultural wastes [15,16], and lignocellulosic biomass [17][18][19]. Different vegetable oils, such as castor oil [20,21], soybean oil [13,22], palm oil [23,24], rapeseed oil [25,26], tung oil [15,27], mustard seed oil [28,29], or canola oil [30,31], were used as precursors for the preparation of bio-polyols and the corresponding environmentally friendly bio-based PUFs [32,33]. Several studies have reported the preparation of bio-polyols or addition of post-agricultural products from corn stalks [34,35], cotton stalks [36], and wheat stalks [37][38][39] to develop PUF formulations. ...
In this study, as a product from the efficient Achmatowicz rearrangement and mild subsequent hydrogenation–reduction reactions of biorenewable C5 alcohols derived from lignocellulose, pentane-1,2,5-triol was successfully used after oxypropylation in the preparation of rigid polyurethane foams—one of the most important classes of polymeric materials. Despite the broad range of applications, the production of polyurethanes is still highly dependent on petrochemical materials considering the need of renewable raw materials and new process technologies for the production of polyol or isocyanate components as a key point for the sustainable development of polyurethane foams. The synthesized oxypropylated pentane-1,2,5-triol was analyzed using proton NMR spectroscopy, hydroxyl number, and viscosity, whereas the newly obtained foams incorporated with up to 30% biorenewable polyol were characterized using compressive stress, thermogravimetry, dynamic mechanical analysis, and scanning electron microscopy. The modified rigid polyurethanes showed better compressive strength (>400.0 kPa), a comparable thermal degradation range at 325–450 °C, and similar morphological properties to those of commercial polyurethane formulations.
... The increased viscosity of the modified PU systems may retard the formation of bubbles. 36,37 Furthermore, PU-TCPP and PU-CR with halogenated flame retardants showed relatively long rise times. In contrast, the settling was lower when a halogenated flame retardant was added compared with that of the reference foam. ...
In this study, the mechanical and flame‐retardant properties of flexible polyurethane foams (FPUF) were analyzed as a function of the type of flame retardant. FPUF containing equal amounts of two halogenated flame retardants (tris 2‐cloropropyl phosphate [TCPP] and phosphinyl alkyl phosphate ester) and three halogen‐free flame retardants (melamine, melamine cyanurate, and expandable graphite) were considered. The foaming properties of these samples were analyzed by studying the rise time and settling rate using cup foaming. Square foaming was used to analyze the mechanical properties, including density, elongation, tensile strength, and tear strength. In addition, Fourier‐transform infrared spectroscopy was performed, and flame retardancy was evaluated using a horizontal flame test and the limited oxygen index. A cone calorimeter test was also performed to evaluate the combustion characteristics. In FPUF containing the same ratio of flame retardant (15% of the total polyol), the properties of urethane foam blended with expandable graphite were improved; the tensile strength of this blend is 20% higher than that of samples containing melamine, and its peak heat release showed a 70% reduction compared to that of samples containing TCPP. These findings provide valuable reference information for developing flame retardants for fire safety FPUF in the near future.
... The building, construction, and civil engineering industries use polymers and composites extensively in a variety of structures for a variety of purposes. One of the most significant types of polymeric materials for use in building and construction applications is polyurethane (PUR) [51,52]. Due to their rich organic nature (lignin content of 50%, cellulose content of 24%, hemicellulose content of 24%) and low ash content (3.4%), walnut shells can be used for the manufacturing of high-value bio-polyols for the creation of a new class of PUR foams [53,54]. ...
Agricultural waste is one of the wastes with a significant value in producing environmentally friendly materials that can be used in the construction sector. This review paper focuses on the potential uses of walnut shell in some building materials. Walnut shell is a type of agricultural waste that can be converted from waste into usable materials by incorporating it into the manufacture of some building materials to achieve sustainability in the construction industry. Recently, walnut waste has drawn the attention of researchers to generate building-friendly materials to boost sustainability in the construction field. In this sense, the walnut shell’s low specific gravity makes it a viable material, as a cheap agricultural waste product, for the development of building materials. According to a survey of the literature, walnut shells can be utilized in the production of structural elements and thermal insulating concrete, up to 30% and 50% as particles respectively.
... It can be seen from Figure 4 that the characteristic peaks in the regenerated polyols degraded with the cesium hydroxide catalyst and potassium hydroxide catalyst in different proportions were very similar to those of commercial polyether polyol 4110. There was a strong stretching vibration peak in the hydroxyl group at 3350 cm −1 [28] and a stretching vibration peak in the methyl group near 2900 cm −1 [29]. There was a characteristic absorption peak of the carbonyl group near 1737 cm −1 [30]. ...
In this paper, the high-efficiency degradation and alcoholysis recovery of waste polyurethane foam were realized using a combination of a high-efficiency alkali metal catalyst (CsOH) and two-component mixed alcoholysis agents (glycerol and butanediol) in different proportions, using recycled polyether polyol and one-step foaming to prepare regenerated thermosetting polyurethane hard foam. The foaming agent and catalyst were adjusted experimentally to prepare regenerated polyurethane foam, and a series of tests were conducted on the viscosity, GPC, hydroxyl value, infrared spectrum, foaming time, apparent density, compressive strength, and other properties of the degradation products of the regenerated thermosetting polyurethane rigid foam. The resulting data were analyzed, and the following conclusions were drawn: The optimal conditions of alcoholysis were obtained when the mass ratio of glycerol to butanediol was 3:2, the amount of cesium hydroxide was 0.08%, the reaction temperature was 170 °C, and the reaction time was 2.5 h. Regenerated polyurethane foam with an apparent density of 34.1 kg/m3 and a compressive strength of 0.301 MPa was prepared under these conditions. It had good thermal stability, complete sample pores, and a strong skeleton. At this time, these are the best reaction conditions for the alcoholysis of waste polyurethane foam, and the regenerated polyurethane foam meets various national standards.
... In recent years, there have been many different scientific studies on the introduction of various elements from this group. The most common chemically incorporated flame-retardant elements include boron, sulfur, phosphorus, nitrogen, silicon, etc. [27,[32][33][34][35]. The system of heteroatoms presented in this article (boron and sulfur) incorporated into the structure of bio-polyols based on white mustard oil is one of the very effective combustion inhibitors. ...
... This article is a development of the technology of synthesis of bio-polyols based on mustard oil, which was presented in the authors' earlier publications [6,33]. The main aim of the research was a comparison of the properties of bio-polyols based on MO containing boron and sulfur heteroatoms in their structure. ...
... According to ISO 3582:2002/A1:2008, these materials can be classified as self-extinguishing [57]. The reason for this was the decomposition of bio-polyols containing sulfur and boron atoms with the simultaneous formation of a glassy layer (from boron atoms) on their surface and the emission of volatile products with sulfur atoms that inhibit chemical reactions in a flame [33,55]. ...
The article compares the properties of bio-polyols obtained from white mustard (Sinapis alba) seed oil, which contain boron and sulfur atoms. Each of the bio-polyols was prepared by a different method of testing the efficiency of the incorporation of boron and sulfur atoms. All synthesis methods were based on the epoxidation of unsaturated bonds followed by the opening of epoxy rings by compounds containing heteroatoms. Two of the bio-polyols were subjected to additional esterification reactions of hydroxyl groups with boric acid or its ester. Three new bio-polyols were obtained as a result of the performed syntheses. The synthesized compounds were subjected to detailed physicochemical (physical state, color, smell, density, viscosity and pH), analytical (hydroxyl number, acid number, water content, content of C, H, N, S, O, B elements and GPC analysis), spectroscopic (FTIR, 1H NMR and 13C NMR) and thermal (DSC) tests. The obtained results allowed for a detailed characterization of the synthesized bio-polyol raw materials. Their suitability for obtaining polyurethane materials was also determined. The synthesized compounds have been found to be an interesting alternative to petrochemical polyols. The influence of the synthesized compounds on the flammability of polyurethane materials was tested experimentally. On the basis of this testing, a number of rigid polyurethane/polyisocyanurate foams were obtained, which were then subjected to flammability tests with the methods of horizontal and vertical burning, limiting oxygen index (LOI) and using the cone calorimeter. Based on this research, it was found that the presence of sulfur and boron heteroatoms reduced the flammability of polyurethane materials based on synthesized bio-polyols.
... Polyols based on renewable natural resources are easily available, comparatively not expensive, and biodegradable. The constant increase of foam products on one hand and environmental requirements on the other hand imposes on the searchfor biodegradable polyols from plant oils [4,5] or carbohydrates such asstarch and cellulose [6][7][8][9][10][11]. Chitosan also belongs to the latter group of compounds and was not used untilnow to obtain polyols. ...
At present, majority of polyols used in the synthesis of polyurethane foams are of petrochemical origin. The decreasing availability of crude oil imposes the necessity to convert other naturally existing resources, such as plant oils, carbohydrates, starch, or cellulose, as substrates for polyols. Within these natural resources, chitosan is a promising candidate. In this paper, we have attempted to use biopolymeric chitosan to obtain polyols and rigid polyurethane foams. Four methods of polyol synthesis from water-soluble chitosan functionalized by reactions of hydroxyalkylation with glycidol and ethylene carbonate with variable environment were elaborated. The chitosan-derived polyols can be obtained in water in the presence of glycerol or in no-solvent conditions. The products were characterized by IR, 1H-NMR, and MALDI-TOF methods. Their properties, such as density, viscosity, surface tension, and hydroxyl numbers, were determined. Polyurethane foams were obtained from hydroxyalkylated chitosan. The foaming of hydroxyalkylated chitosan with 4,4′-diphenylmethane diisocyanate, water, and triethylamine as catalysts was optimized. The four types of foams obtained were characterized by physical parameters such as apparent density, water uptake, dimension stability, thermal conductivity coefficient, compressive strength, and heat resistance at 150 and 175 °C. It has been found that the obtained materials had most of the properties similar to those of classic rigid polyurethane foams, except for an increased thermal resistance up to 175 °C. The chitosan-based polyols and polyurethane foams obtained from them are biodegradable: the polyol is completely biodegraded, while the PUF obtained thereof is 52% biodegradable within 28 days in the soil biodegradation oxygen demand test.
