Glass transition and thermal degradation of rigid polyurethane foams derived from castor oil–molasses polyols

Rigid polyurethane (PU) foams having saccharide and castor oil structures in the molecular chain were prepared by reaction between reactive alcoholic hydroxyl group and isocyanate. The apparent density of PU foams was in a range from 0.05 to 0.15 g cm^?3. Thermal properties of the above polyurethane foams were studied by differential scanning calorimetry, thermogravimetry and thermal conductivity measurement. Glass transitions were observed in two steps. The low-temperature side glass transition was observed at around 220 K, regardless of castor oil content. This transition is attributed to the molecular motion of alkyl chain groups of castor oil. The high-temperature side glass transition observed in the temperature range from 350 to 390 K depends on the amount of molasses polyol content. The high-temperature side glass transition is attributed to the molecular motion of saccharides, such as sucrose, glucose, fructose as well as isocyanate phenyl rings, which act as rigid components. Thermal decomposition was observed in two steps at 570 and 620–670 K. Thermal conductivity was observed at around 0.032 J sec^?1 m^?1 K^?1. Compression strength and modulus of PU foams were obtained by mechanical test. It was confirmed that the thermal and mechanical properties of PU foams could be controlled by changing the mixing ratio of castor oil and molasses for suitable practical applications.     

Thermal properties of lignin-and molasses-based polyurethane foams

Lignin-and molasses-based polyurethane (PU) foams with various lignin/molasses mixing ratios were prepared. The hydroxyl group in molasses and lignin is used as the reaction site and PU foams with various isocyanate (NCO)/the hydroxyl group (OH) ratios were obtained. Thermal properties of PU foams were investigated by differential scanning calorimetry (DSC), thermogravimetry (TG) and thermal conductivity measurement. Glass transition temperature (T _g) was observed depending on NCO/OH ratio in a temperature range from ca. 80 to 120°C and thermal decomposition temperature (T _d) from ca. 280 to 295°C. Mixing ratio of molasses and lignin polyol scarcely affected the T _g and T _d. Thermal conductivity of PU foams was in a range from 0.030 to 0.040 Wm⁻¹ K⁻¹ depending on mixing ratio of lignin and molasses.     

Cellulose nanofibril (CNF) reinforced starch insulating foams

In this study, biodegradable foams were produced using cellulose nanofibrils (CNFs) and starch (S). The availability of high volumes of CNFs at lower costs is rapidly progressing with advances in pilot-scale and commercial facilities. The foams were produced using a freeze-drying process with CNF/S water suspensions ranging from 1 to 7.5 wt% solids content. Microscopic evaluation showed that the foams have a microcellular structure and that the foam walls are covered with CNF’s. The CNF’s had diameters ranging from 30 to 100 nm. Pore sizes within the foam walls ranged from 20 to 100 nm. The materials’ densities ranging from 0.012 to 0.082 g/cm³ with corresponding porosities between 93.46 and 99.10 %. Thermal conductivity ranged from 0.041 to 0.054 W/m-K. The mechanical performance of the foams produced from the starch control was extremely low and the material was very friable. The addition of CNF’s to starch was required to produce foams, which exhibited structural integrity. The mechanical properties of materials were positively correlated with solids content and CNF/S ratios. The mechanical and thermal properties for the foams produced in this study appear promising for applications such as insulation and packaging.     

Glass transition temperature of polyurethane foams derived from lignin by controlled reaction rate

Sodium ligninosulfonate (LS)-based polyurethane (PU) foams were prepared using three kinds of ethylene glycols, diethylene glycol, triethylene glycol or polyethylene glycol. Two kinds of industrial NaLS, acid-based and alkaline-based NaLS, were mixed with various ratios, and foaming reactions were controlled. Mixing, cream, and rise time were used as an index of foaming reaction. Mixing time was defined as the time interval from adding isocyanate to detection of evolved heat under stirring, cream time as the time interval from termination of stirring to starting of foaming, and rise time as the time interval from starting to completion of foaming. The above reaction time increased with increasing amount of acid base NaLS content in polyols. Apparent density, compression strength and compression modulus of PU foams linearly increased with reaction time. Thermal decomposition temperature was measured by thermogravimetry and glass transition temperature by differential scanning calorimetry. Glass transition temperature can be controlled in a temperature range from 310 to 390 K by changing the mixing rate of two kinds of LS and molecular mass of ethylene glycols. It was found that mechanical and thermal properties of PU foams are controllable through the foaming reaction rate using two kinds of industrial lignin.     

Nutmeg filler as a natural compound for the production of polyurethane composite foams with antibacterial and anti-aging properties

Polyurethane (PU) composite foams were successfully reinforced with different concentrations (1 wt%, 2 wt%, 5 wt%) of nutmeg filler. The effect of nutmeg filler concentration on mechanical, thermal, antimicrobial and anti-aging properties of PU composite foams was investigated. PU foams were examined by rheological behavior, processing parameters, cellular structure (Scanning Electron Microscopy analysis), mechanical properties (compression test, impact test, three-point bending test, impact strength), thermal properties (Thermogravimetric Analysis), viscoelastic behavior (Dynamic Mechanical Analysis) as well as selected application properties (thermal conductivity, flammability, apparent density, dimensional stability, surface hydrophobicity, water absorption, color characteristic). In order to Disc Diffusion Method, all PU composites were tested against selected bacteria (Escherichia coli and Staphylococcus aureus). Based on the results, it can be concluded that the addition of 1 wt% of nutmeg filler leads to PU composite foams with improved compression strength (e.g. improvement by ~19%), higher flexural strength (e.g. increase of ~11%), improved impact strength (e.g. increase of ~32%) and comparable thermal conductivity (0.023–0.034 W m⁻¹ K⁻¹). Moreover, the incorporation of nutmeg filler has a positive effect on the fire resistance of PU materials. For example, the results from the cone calorimeter test showed that the incorporation of 5 wt% of nutmeg filler significantly reduced the peak of heat release rate (pHRR) by ca. 60% compared with that of unmodified PU foam. It has been also proved that nutmeg filler may act as a natural anti-aging compound of PU foams. The incorporation of nutmeg filler in each amount successfully improved the stabilization of PU composite foams. Based on the antibacterial results, it has been shown that the addition of nutmeg filler significantly improved the antibacterial properties of PU composite foams against both Gram-positive and Gram-negative bacteria.     

Flexible polyurethane nanocomposite foam: Synthesis and properties

Flexible polyurethane (PU) nanocomposite foams were synthesized using organically modified montmorillonite clay (Cloisite 30B). The dispersion of organoclay was considered both in the isocyanate and polyol matrixes. Silicate layers of organoclay can be exfoliated in PU matrix by use of two steps mixing process. The presence of clay increased the cell density and reduced the cell size compared to the conventional PU foam. Clay dispersion was investigated by X-ray diffraction (XRD). The morphology and properties of PU nanocomposite foams were also studied. Generally, mechanical properties by addition of clay were improved. Foams in which clay was firstly dispersed in the isocyanate, showed better dispersion due to affinity of OH group on the clay surface to react with NCO groups. Better properties have been achieved with these nanofoams.     

Mechanical and thermal properties of rigid polyurethane foams derived from sodium lignosulfonate mixed with diethylene-, triethylene- and polyethylene glycols

Sodium salt of lignosulfonic acid (LS), which was obtained as by-product of cooking process in sulfite pulping, was solved in diethylene, triethylene or polyethylene glycol. Three series of polyurethane foams (LSPU) were synthesized by varying the LS content from 0 to 33 wt%. Apparent density (ρ) of LSPU foams ranged from 0.08 to 0.18 g cm⁻³ and was affected by both LS content and oxyethylene chain length. Glass transition temperatures increased with increasing amount of LS and with decreasing oxyethylene chain length. Thermal gravimetry analysis indicated that the LS component decomposes first and that the thermal stability increases with decreasing oxyethylene chain length. Compression strength and compression modulus increased linearly with increasing apparent density. It is concluded that LS is successfully utilized as a hard segment of rigid PU foams, whose thermal and mechanical properties can be tuned by changing the amount of LS and the length of soft oxyethylene chains.     

Lignin as a Partial Polyol Replacement in Polyurethane Flexible Foam

This study was focused on evaluating the suitability of a wide range of lignins, a natural polymer isolated from different plant sources and chemical extractions, in replacing 20 wt.% of petroleum-based polyol in the formulation of PU flexible foams. The main goal was to investigate the effect of unmodified lignin incorporation on the foam’s structural, mechanical, and thermal properties. The hydroxyl contents of the commercial lignins were measured using phosphorus nuclear magnetic resonance (³¹P NMR) spectroscopy, molar mass distributions with gel permeation chromatography (GPC), and thermal properties with differential scanning calorimetry (DSC) techniques. The results showed that incorporating 20 wt.% lignin increased tensile, compression, tear propagation strengths, thermal stability, and the support factor of the developed PU flexible foams. Additionally, statistical analysis of the results showed that foam properties such as density and compression force deflection were positively correlated with lignin’s total hydroxyl content. Studying correlations between lignin properties and the performance of the developed lignin-based PU foams showed that lignins with low hydroxyl content, high flexibility (low T_g), and high solubility in the co-polyol are better candidates for partially substituting petroleum-based polyols in the formulation of flexible PU foams intended for the automotive applications.     

Preparation and properties of 3-aminopropyltriethoxysilane functionalized graphene/polyurethane nanocomposite coatings

Silicone-modified graphene was successfully synthesized by treating graphene oxide with 3-aminopropyltriethoxysilane (AMEO) and then reduced by hydrazine hydrate. Subsequently, the AMEO-functionalized graphene was incorporated into polyurethane (PU) matrix to prepare AMEO-functionalized graphene/PU nanocomposite coatings. The functionalized graphene could disperse homogenously by means of a covalent connection with PU. AMEO-functionalized graphene (AFG)-reinforced PU nanocomposite coatings showed more excellent mechanical and thermal properties than those of pure PU. A 227 % increase in tensile strength and a 71.7 % improvement of elongation at break were obtained by addition 0.2 wt% of AFG. Meanwhile, thermogravimetric analysis reveals that thermal degradation temperature was enhanced almost 50 °C higher than that of neat PU, and differential scanning calorimetry analysis demonstrates that glass transition temperature decreased by around 9 °C. The thermal conductivity of AFG/PU nanocomposite coatings also increased by 40 % at low AFG loadings of 0.2 wt%.     

Preparation of magnetic polyurethane rigid foam nanocomposites

Super paramagnetic Fe₃O₄@SiO₂ nanoparticle was incorporated into polyurethane rigid foams in order to prepare new corresponded magnetic nanocomposite foams via one-shot method. The core–shell-structured nanoparticles were prepared by sol–gel method and characterized by transmission electron microscopy, X-ray diffraction, as well as Fourier transform infrared spectroscopy techniques. Magnetic nanoparticles were used up to 3 % in the foam formulations and the samples prepared successfully. Thermal, mechanical, and magnetic properties of nanocomposites were studied and the results showed superior properties in comparison with pristine foams.     

On the role of TiO<Subscript>2</Subscript> nanoparticles on thermal behavior of flexible polyurethane foam sandwich panels

A series of flexible polyurethane foam (FPUF) and monolithic polyurethane (PU) sandwich panels reinforced with different contents of TiO₂ nanoparticles (0, 0.5 and 1 mass%) have been successfully prepared by compression molding process at room temperature. The influence of TiO₂ nanoparticles on the thermal properties of PU matrix has been investigated by thermogravimetric and dynamic mechanical thermal analysis (DMTA). The morphology of porous structure of FPUF sandwich panels has been characterized by scanning electron microscopy. The presence of TiO₂ nanoparticles as reinforcement has improved the thermal properties of the FPUF and PU sandwich panel samples. It has been observed that FPUF and PU sandwich panel reinforced with 1 mass% of TiO₂ nanoparticles possessed the highest enhancement in thermal properties in all accomplished thermal tests. The DMTA results for the FPUF and PU sandwich panel reinforced with 1 mass% of TiO₂ nanoparticles indicated that the storage modulus and loss modulus have increased about 1.22 and 1.25 times, 1.5 and 1.55 times, respectively, compared to pure samples. Furthermore, the glass transition (T _g) obtained from the damping factor (tanδ) curves has increased 2 and 1 °C for FPUF and PU sandwich panels, respectively.     

Thermogravimetry on wood powder-filled polyurethane composites derived from lignin

Novel polyurethane (PU) composites whose matrix is derived from lignin, molasses polyol and filler from wood powder were successfully prepared. Two kinds of polyol were mixed 0/100 to 100/0 in seven steps, and filler content was varied from 50 to 100 mass % to polyol content. Decomposition behaviour of PU composites was investigated by thermogravimetry. Apparent density and mechanical properties of the above composites were also measured. Surface texture was observed by scanning electron microscopy. Thermal decomposition of PU composites was found to occur in two stages. The first decomposition observed at 570–580 K (DT _d1, peak temperature of derivative curve) is attributed to the matrix of composites. The second stage decomposition depending on filler content, observed in a temperature range from 590 to 630 K (DT _d2), is attributable to filler homogenously associated with PU matrix. Marked differences were not found, when the kinds of lignin and molasses polyol composition were varied. The above PU composites were found to be thermally stabilised by the introduction of filler.     

Effect of walnut shells and silanized walnut shells on the mechanical and thermal properties of rigid polyurethane foams

In the study walnut shells (WS) and silanized walnut shells (S_WS) were used as cellulosic fillers for novel polyurethane (PU) composite foams. The impact of 1, 2 and 5 wt% of WS and S_WS on the foaming parameters, mechanical and thermo-mechanical properties of obtained materials were evaluated. The results have shown that compared to untreated WS filler, the application of S_WS leads to PU foams with more regular structure and improved physico-mechanical behavior of PU materials. For example, compared to controlled WS_0 foam, PU foams enhanced with 1 wt% of the S_WS exhibited better mechanical properties, such as higher compressive strength (~15% of improvement), better impact strength (~6% of improvement), and improved tensile strength (~9% of improvement). The addition of S_WS improved the thermomechanical stability of PU foams. This work provides a better understanding of a relationship between the surface modification of the walnut shell filler and the mechanical, insulating and thermal properties of the PU composites. Due to these positive and beneficial effects, it can be stated that the use of WS and S_WS as natural fillers in PU composite foams can promote a new application path in converting agricultural waste into useful resources for creating a new class of green materials.     

Poly(ether–imide)/polyurethane foams reinforced with graphene nanoplatelet: Microstructure,thermal stability,and flame resistance

Novel poly(ether–imide)/polyurethane (PEI/PU)-based nanocomposite and foamed systems reinforced with graphene nanoplatelet (GNP) were developed. Field emission scanning electron microscopy revealed hexagonal nanocelluar morphology due to fine interaction between PEI/PU and functional GNP. Compression strength and modulus values were raised up to 72.3 MPa and 27.3 GPa, respectively, for PEI/PU/GNP Foam 1, thus revealing a defensive role of GNP layer against damage. T_max of PEI/PU/GNP Foam 0.1–1 was measured as 479–565°C. The UL 94 showed V-0 rating for nanocomposite, while foams attained V-1 rating. Water absorption capacity was improved steadily with time and was at maximum after 96 h for PEI/PU/GNP Foam 1 (12.3%).     

Synthesis of NIPU by the carbonation of canola oil using highly efficient 5,10,15‐tris(pentafluorophenyl)corrolato‐manganese(III) complex as novel catalyst

For the green synthesis of polyurethane (PU), non‐isocyanate routes are worthy alternatives. In the present work, we have explored 5,10,15‐tris(pentafluorophenyl)corrolato‐manganese(III) complex as novel catalyst for coupling reaction between epoxidized canola oil and CO₂ (gaseous) to introduce cyclic carbonate moieties in the oil and further used it to obtain non‐isocyanate PU, generally abbreviated as NIPU, by curing with different diamines. The results obtained indicated a 1/4th of the reduction in reaction time with the use of 5,10,15‐tris(pentafluorophenyl)corrolato‐manganese(III) complex as catalyst as compared to the previously reported literature data. As per the reported studies, the corrole metal complex has not been used for this reaction earlier. The structure of products and intermediates were confirmed by using different characterization techniques like ¹H NMR and FTIR spectroscopies. The thermal and mechanical behavior of final product was analyzed by TGA and universal testing machine, respectively. The non‐isocyanate PU obtained showed a good thermal stability up to 200°C and a tensile strength of up to 8 MPa. The effect of structure of diamines on the properties of non‐isocyanate PU was also extensively studied.     

Preparation and properties of negative ion/polyurethane flexible foam composites

Abstract

In this study, negative ionpowder was modified with a silane coupling agent and then added to the polyurethane flexible foam to prepare NI/PU flexible foam composites by the one-step foaming method. The effects of the amount of negative ion powder on the mechanical properties, thermal properties and release of negative ions were investigated using scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and negative ion detectors. The SEM results showed that modified negative ion powder could be more uniformly distributed around the cell walls of the polyurethane flexible foam. The thermal stability, tensile strength and resilience of the NI/PU flexible foam composite were improved with the increase of the amount of modified negative ion powder. Increasing the amount of modified negative ion powder could also result in an increase in the release of negative ions, and it reached 5500/cm³ or higher at a negative ion content of 3%.     

Carbon nanofibers reinforced soy polyol-based polyurethane nanocomposites

Vapor-grown carbon nanofiber (CNF)-modified soy polyol-based polyurethane (PU) nanocomposites with different hydroxyl value of polyols (OH) were synthesized. The glass transition, thermal stability, mechanical properties, and morphology of the PU nanocomposites were characterized through differential scanning calorimetry, thermogravimetry, universal test machine, and scanning electron microscopy. The addition of CNFs increased the glass transition temperature as well as significantly improved tensile strength and Young’s modulus of PU nanocomposites. Meanwhile, thermal and mechanical properties of PU composites were influenced by the different hydroxyl value of polyols due to those different structures. In particular, in the case of 2 mass% CNF addition in PU derived from soy polyol with the OH number of 164 mg KOH g^?1, 20.8 °C improvement in the glass transition temperature, 115 % increment in tensile strength, and nearly eightfold increase in Young’s modulus were obtained.     

Preparation and properties of poly(urethane-imide)s derived from amine-blocked-polyurethane prepolymer and pyromellitic dianhydride

Poly(urethane-imide)s were prepared using amine-blocked-polyurethane (PU) prepolymer and pyromellitic dianhydride. The PU prepolymers were prepared by the reaction of different diols (polypropyleneoxy glycol, polytetramethyleneoxy glycol, polycaprolactonediol and hydroxyl terminated polybutadiene) and different diisocyanates (2,4-tolylene diisocyanate, 1,4-phenelene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate and 4,4^′-methylenebis(cyclohexyl)isocyanate) and end capped with N-methylaniline. The polymerization was faster with aromatic isocyanates than with aliphatic isocyanates. The effect of imide content on the thermal and mechanical properties was studied. The poly(urethane-imide)s were characterized by FTIR, GPC, TGA and for dynamic and static mechanical properties. Weight average molecular weight (M_w) of the polymers did not vary significantly with change in -NCO/-OH ratio where as number average molecular weight (M_n) increased with increasing -NCO/-OH ratio, correspondingly, the dispersity (PD) decreased. Polymers with higher hard segment content exhibited higher glass transition temperature. The thermal stability of the PU was found to increase significantly by the introduction of imide component.     

Lanthanum phenylphosphonate–based multilayered coating for reducing flammability and smoke production of flexible polyurethane foam

In the present work, lanthanum phenylphosphonate (LaPP)–based multilayered film was fabricated on the surface of flexible polyurethane (PU) foam by layer‐by‐layer self‐assembled method. The successful deposition of the coating was confirmed by scanning electron microscopy (SEM) and energy‐dispersive X‐ray (EDX). Subsequently, the thermal decomposition and burning behavior of untreated and treated PU foams were investigated by thermogravimetric analysis (TGA) and cone calorimeter, respectively. The TGA results indicated that T_max2 of treated PU foams were increased by approximately 15°C to 20°C as compared with untreated PU foam. The peak heat release rate (PHRR) and total heat release (THR) of PU‐6 (with 19.5 wt% weight gain) were 188 kW/m² and 20.3 MJ/m², with reductions of 70% and 15% as compared with those of untreated PU foam, respectively. Meanwhile, the smoke production of treated PU foam was suppressed after the construction of LaPP‐based coating.     

Chemo‐ and Regioselective Additions of Nucleophiles to Cyclic Carbonates for the Preparation of Self‐Blowing Non‐Isocyanate Polyurethane Foams

Polyurethane (PU) foams are indisputably daily essential materials found in many applications, notably for comfort (for example, matrasses) or energy saving (for example, thermal insulation). Today, greener routes for their production are intensively searched for to avoid the use of toxic isocyanates. An easily scalable process for the simple construction of self‐blown isocyanate‐free PU foams by exploiting the organocatalyzed chemo‐ and regioselective additions of amines and thiols to easily accessible cyclic carbonates is described. These reactions are first validated on model compounds and rationalized by DFT calculations. Various foams are then prepared and characterized in terms of morphology and mechanical properties, and the scope of the process is illustrated by modulating the composition of the reactive formulation. With impressive diversity and accessibility of the main components of the formulations, this new robust and solvent‐free process could open avenues for construction of more sustainable PU foams, and offers the first realistic alternative to the traditional isocyanate route.