The effect of the trimerization catalyst on the thermal stability and the fire performance of the polyisocyanurate‐polyurethane foam

In this work, 3 currently used trimerization catalysts, TMR‐2 (quaternary ammonium), K‐15 (potassium octoate), and PU‐1792 (potassium acetate) were used to produce rigid polyisocyanurate (PIR) foams with certain amounts of isocyanurate contents. The results from Fourier transform infrared (FTIR) quantitative analysis showed that PU‐1792 had the highest catalytic efficiency in isocyanurate formation. Then, the effect of different amounts of PU‐1792 catalyst on isocyanurate ring output was further investigated, and the result showed that the highest amount of isocyanurate ring formation could be attained by the 5 pphp of PU‐1792 catalyst. It was also found that the increased amount of isocyanurate ring could result in reduced cell size, improved compressive strength, and lowered thermal conductivity of PIR foam. The results from thermogravimetric analysis (TGA) and cone calorimeter (CONE) test revealed that the thermal stability and fire performance of PIR foam could be improved with the increased amount of isocyanurate ring. Furthermore, the CONE test indicated that the smoke production of PIR foam decreased approximately 51.7% in comparison to the reference polyurethane (PU) foam, and the SEM image of char morphology showed that the char of PIR foam was more compact than PU foam.     

Desaminated glycolysis of water‐blown rigid polyurethane foams

Glycolysis reaction kinetics of methylene diphenyl diisocyanate‐based water‐blown polyurethane foams was examined by gel permeation chromatography. Glycolysates were reacted with butyl glycidyl ether to convert toxic aromatic amines to polyols, and their products were identified by ¹H‐NMR spectroscopy. To examine the quality of recycled polyol, polyurethane foams were reprepared using the virgin and recycled polyol mixtures with varying compositions. Cell structures and sizes of reprepared foams were similar to those of original ones when the recycled polyols were mixed up to 30 wt %. Density, thermal conductivity, and flexural strength of the reprepared foams were compared with those of the original ones, and no difference was observed below the recycled polyol concentration of 30 wt %. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2646–2656, 2000     

Surface‐modifiers of clay on mechanical properties of rigid polyurethane foams/organoclay nanocomposites

Three different surface modifiers, octadecyl trimethyl ammonium (ODTMA), octadecyl primary ammonium (ODPA), and decanediamine (DDA) were used to modify Na⁺? montmorillonite (MMT), and the resultant organoclays were coded as ODTMA‐MMT, ODPA‐MMT, DDA‐MMT, respectively. Rigid PU foams/organoclay composites were prepared by directly using organoclay as the blowing agent without the addition of water. Investigation shows that the morphology of the nanocomposites is greatly dependent on the surface modifiers of clay used in the composites. In detail, DDA‐MMT is partially exfoliated in the PU matrix with the smallest cell size, while two others are intercalated in the PU matrices with smaller cell sizes. The sequence of their cell sizes is pristine PU foams > rigid PU foams/ODTMA‐MMT > rigid PU foams/ODPA‐MMT > rigid PU foams/DDA‐MMT, and the average cell size of rigid PU foams/DDA‐MMT composites decreases evidently from 0.30 to 0.07 mm. Moreover, all rigid PU foams/organoclay composites show remarkable enhanced compressive and tensile strengths as well as dynamic properties than those of PU foams, and the enhancement degree coincides well with the relative extent of internal hydrogen bonding of materials and gallery spacing of organoclay. For example, in the case of rigid PU foams/DDA‐MMT composite, 214% increase in compressive strength and 148% increase in tensile strength compared with those of pure PU foams were observed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Processing‐structure‐property relationship in rigid polyurethane foams

Rigid polyurethane (PU) foam is used as a thermal insulating and supporting material in domestic refrigerator/freezers and it is produced by reaction injection molding (RIM) process. There is a need to improve the thermal property of rigid PU foam but this is still a challenging problem. Accordingly, this work investigates the RIM process parameters to evaluate their effects on rigid PU foam's structure and hence property. It has been found that mold temperature is a key parameter whereas curing time has negligible effect on structure of PU foam. Cell size, strut thickness, and foam density have been found very critical in controlling the thermal and mechanical properties. Upper and lower values of 30 to 32 kg/m³ density are critical to observe contribution of radiation and solid conductivity separately. Finally, PU foam with 160 µm average cell size, 16 µm strut thickness, below 10% open cell content, and 30 to 32 kg/m³ density allow obtaining better thermal insulation without significant reducing in the compressive strength. The presented work provides a better understanding of processing‐structure‐property relationship to gain knowledge on producing high‐quality rigid PU foams with improved properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44870.     

Effect of foam density on the properties of water blown rigid polyurethane foam

Density is an important parameter that influences the properties and performances of rigid polyurethane foam (PUF). Rigid PUF with different densities were prepared by varying the amount of distilled water as blowing agent. This investigation reports the mechanical, morphological, water absorption, thermal conductivity, and thermal behavior of rigid PUF varying with the density, which controls the foam architecture. The density of the PUF decreased from 116 to 42 kg/m³ with an increase in the amount of water from 0.1 to 3.0 parts per hundred polyol by weight (phr), respectively. It was found that the mechanical properties of the PUFs changed with the foam density. The results of water absorption of the PUFs showed that water absorption increased with decrease in density, due to increase in the cell size and decrease in the cell‐wall thickness. The thermal conductivity measurements showed that the thermal conductivity decreased with increase in density. It was due to the decrease in cell size. The thermal analysis of the PUFs shows that the glass transition temperature increases with the decrease in foam density, but the thermal stability decreases with the decrease in foam density. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Improvement of thermal and mechanical properties by control of formulations in rigid polyurethane foams from polyols functionalized with graphene oxide

This article addresses the optimization of water-blown rigid polyurethane (RPU) foams obtained from a polyol functionalized with graphene oxide (GO). For this purpose, a series of RPU foams are herein synthesized by varying either the isocyanate index, the contents of catalyst or the contents of surfactant, or a combination of these three components. The modifications introduced in the formulation are based on the effect of GO on the reaction kinetics. These strategies are mainly focused on the increase of both isocyanate conversion and polymerization reaction, which decrease for the foams containing GO. Density, cellular structure, thermal conductivity, and mechanical properties of the resulting foams are herein investigated. The results show how controlling PU formulation allows to improve both the thermal and the mechanical behavior in these RPU foams containing GO. The highest cell size reduction of 25% and the lowest thermal conductivity are obtained for the sample with a simultaneous increase in isocyanate index, catalyst content, and surfactant content. Moreover, the adequate combination of these components leads to a high improvement of 59% of the relative Young's modulus and of 54% of the relative collapse stress. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47474.     

Flame retardancy of different‐sized expandable graphite particles for high‐density rigid polyurethane foams

The effects of expandable graphite (EG) of different particle sizes, on the fire‐retardant properties of high‐density rigid polyurethane foam (RPUF) (0.45 g cm^?3) were studied. Samples of EG with different particle sizes were obtained by pulverization in an ultra‐high‐speed mixer for 4 and 13 min, respectively. It was shown that as received (EG0) and 4 min pulverized EG (EG4) efficiently improved the fire‐retardant properties of RPUF composites, while 13 min pulverized EG (EG13) did not. The char of the burned composites filled with EG0 and EG4 covered the whole surface of the samples and formed a complete physical barrier. This barrier material prevented combustible gases from feeding the flame and also isolated oxygen efficiently from the burning material. EG13 did not produce enough char to cover the whole surface of the burning sample, resulting in poor fire‐retardant property of the RPUF composites. Thermal degradation tests of the foams by thermogravimetric analysis indicated that EG showed negligible effects on the thermal stability of the RPUFs. Copyright © 2006 Society of Chemical Industry     

Long‐term thermal conductivity of cyclopentane–water blown rigid polyurethane foams reinforced with different types of fillers

An understanding of the long‐term thermal conductivity of rigid polyurethane (RPU) foams presents great interest in the building field considering the conservation of energy efficiency. In this study, the effect of different types of particles (talc, diatomaceous earth and non‐porous silica) on the thermal conductivity of RPU foams blown with cyclopentane and water as blowing agents was investigated during 3 years of aging. The characterization of the cellular structure shows how the addition of particles causes a cell size reduction of the foams, and consequently an enhancement of the thermal properties just after production. However, this initial reduction is not maintained, because each foam shows a different thermal conductivity evolution with time. We have found, for the first time, a relationship between the slope of the thermal conductivity versus time at the first measurements and the internal temperature reached during the foaming process. The evolution of the RPU foams in which higher internal temperatures were reached is more pronounced than in those RPU foams where lower foaming temperatures were observed. This effect is related to the kinetics of the diffusion of the gas occluded inside the cells and imposes a new criterion for the selection of particles to reduce the thermal conductivity of RPU foams; these additives should ideally decrease the temperature reached during the foaming process. Moreover, the effect of aging on the thermal conductivity is explained by using theoretical models. © 2019 Society of Chemical Industry     

Physical properties of water‐blown rigid polyurethane foams from vegetable oil‐based polyols

Fifty vegetable oil‐based polyols were characterized in terms of their hydroxyl number and their potential of replacing up to 50% of the petroleum‐based polyol in waterborne rigid polyurethane foam applications was evaluated. Polyurethane foams were prepared by reacting isocyanates with polyols containing 50% of vegetable oil‐based polyols and 50% of petroleum‐based polyol and their thermal conductivity, density, and compressive strength were determined. The vegetable oil‐based polyols included epoxidized soybean oil reacted with acetol, commercial soybean oil polyols (soyoils), polyols derived from epoxidized soybean oil and diglycerides, etc. Most of the foams made with polyols containing 50% of vegetable oil‐based polyols were inferior to foams made from 100% petroleum‐based polyol. However, foams made with polyols containing 50% hydroxy soybean oil, epoxidized soybean oil reacted with acetol, and oxidized epoxidized diglyceride of soybean oil not only had superior thermal conductivity, but also better density and compressive strength properties than had foams made from 100% petroleum polyol. Although the epoxidized soybean oil did not have any hydroxyl functional group to react with isocyanate, when used in 50 : 50 blend with the petroleum‐based polyol the resulting polyurethane foams had density versus compressive properties similar to polyurethane foams made from 100% petroleum‐based polyol. The density and compressive strength of foams were affected by the hydroxyl number of polyols, but the thermal conductivity of foams was not. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of selected boroorganic compounds on thermal and heat properties of rigid polyurethane–polyisocyanurate foams

The effects of three selected borates {tri(hydroxypropyl), tri[(3‐chloro‐2‐hydroxy‐1‐propoxy)‐1‐methylethyl], tri[(3‐chloro‐2‐hydroxy‐1‐propoxy)propyl]} on the heat and thermal properties of rigid polyurethane–polyisocyanurate foams was studied. Increasing the amount of tri(hydroxypropyl) borate and tri[(3‐chloro‐2‐hydroxy‐1‐propoxy)propyl] borate in the foam composition from 0.1 to 0.4 chemical equivalents caused an increase in the softening point, the temperature of the first decrement of foam mass, the extrapolated temperature of the main decrement of the foam mass, and the temperature of the highest rate of the mass decrement. When tri[(3‐chloro‐2‐hydroxy‐1‐propoxy)‐1‐methylethyl] borate was added to the foam compositions, the softening point decreased but the temperatures characterizing their thermal resistance were higher in comparison with the standard foam. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 768–771, 2006     

Flame‐retardant and mechanical properties of high‐density rigid polyurethane foams filled with decabrominated dipheny ethane and expandable graphite

The article reported the flame‐retardant and the mechanical properties of expandable graphite (EG), an intumescent type, and decabrominated dipheny ethane (DBDPE), a gas‐phase type of flame‐retardant‐containing high‐density rigid polyurethane foams (RPUF) with a constant density of 0.5g/cm³. The results indicated that both EG and DBDPE could effectively interdict the burning of RPUF, besides, the EG exhibited more effective flame retardancy than the DBDPE. When the flame‐retardant loadings were 20 wt %, the LOI value of DBDPE‐filled RPUF increased to 33 vol %, while, surprisingly, the EG‐filled RPUF reached 41 vol %. Unfortunately, when they were both simultaneously added into RPUF, there was not any flame‐retardant synergistic effect. Although EG had outstanding flame retardancy, the compressive strength and modulus of 20 wt % EG‐filled RPUF dropped to only 9.1MPa and 229.7MPa respectively, which were lower than those of DBDPE (12.4 MPa and 246.8 MPa). The phenomena were ascribed to the different flame‐retardant mechanisms of EG and DBDPE, which were verified by scanning electronic microscope (SEM) observation of the burned surfaces. Besides, the dynamical mechanical analysis (DMA) demonstrated that the additions of EG and DBDPE made the glass transition temperature shift to the high temperatures, and the EG‐filled RPUF had the higher storage modulus. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Properties of rigid polyurethane‐polyisocyanurate foams modified with the selected fillers

Rigid polyurethane‐polyisocyanurate foams (PUR‐PIR) containing from 2.5% to 20% w/w of fillers (talc, aluminum hydroxide, chalk, starch and borax) were the subject of our studies; a reference sample was PUR‐PIR foam with no filler added. Apparent density, compressive strength, brittleness, content of closed cells, retention (flammability) and softening point of foams were determined and the products were analyzed by thermogravimetric method. These parameters were the basis to determine effect of type and participation of the fillers studied on physicochemical, heat, and thermal properties of foams. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of the addition of wood flours on the properties of rigid polyurethane foam

The objective of this study is to investigate an appropriate process to fabricate the wood‐polyurethane hybrid composites [wood‐polyurethane foam (PUF)]. Rigid PUFs that contain up to 20% wood flours were successfully fabricated from polymeric 4,4‐diphenylmethane diisocyanate, polyols, silicone surfactant, dibutin dilaurate/dimethylethanolamine catalysts, and distilled water (chemical blowing agent). The effects of hydroxyl value of polyols, wood flour particle size, wood flour content, isocyanate index, and water amount on the compressive property of foam were investigated. The morphology of the cell was observed with a scanning electron microscope. Wood‐PUF with different densities were prepared at different water contents in the wood flours. The relationship between the compressive property and density was established following the Power law. The incorporation of wood flour improved the compressive property of PUF, whereas its tensile and flexural properties were reduced. The thermal stability of the PUF was improved with the addition of wood flour. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Comparative study of physical properties of water‐blown rigid polyurethane foams extended with commercial soy flours

The use of renewable resources (mainly carbohydrates) in rigid polyurethane foam has been known to offer several advantages, such as increased strength, improved flame resistance, and enhanced biodegradability. Less attention has been directed to inexpensive protein‐based materials, such as defatted soy flour. The objectives of this study were to develop water‐blown rigid polyurethane foams, containing defatted soy flour, that have acceptable or improved physical properties which also lower the cost of the foam formulation and to compare the properties of developed foams extended with three kinds of commercial soy flour. Water‐blown low‐density rigid polyurethane foams were prepared with poly(ether polyol)s, polymeric isocyanates, defatted soy flour, water, a catalyst mixture, and a surfactant. Soy flour and the initial water content were varied from 0 to 40% and from 4.5 to 5.5% of the poly(ether polyol) content, respectively. A standard laboratory mixing procedure was followed for making foams using a high‐speed industrial mixer. After mixing, the mixture was poured into boxes and allowed to rise at ambient conditions. Foams were removed from boxes after 1 h and cured at room temperature for 24 h before measurement of the thermal conductivity and for 1 week before other property tests. Foam properties were determined according to ASTM procedures. Measurement of the physical properties (compressive strength, modulus, thermal conductivity, and dimensional stability under thermal and humid aging) of these foams showed that the addition of 10–20% of three kinds of soy flour imparted water‐blown rigid polyurethane foams with similar or improved strength, modulus, insulation, and dimensional stability. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 10–19, 2001     

A study of rigid polyurethane foams: The effect of synthesized polyols and nanoporous graphene

Rigid polyurethane foams (RPUF) with nanoporous graphene (NPG) were synthesized and their properties, including density, mechanical, morphological, and thermal‐resistant properties were studied. In the current work, polyols of the RPUF formulation were synthesized and NPG content was varied from 0.1 to 0.5 wt %. Scanning electron microscopy (SEM) observation was used to observe the dispersion of NPG and cell size in the RPUF nanocomposites. Only 0.25 wt % of NPG improved compressive strength and modulus respectively by 10.7% and 66.5%. The TGA analysis confirmed that an increase in NPG loading slightly increase the degradation temperature of the samples. These results additionally indicated that NPG enhances the mechanical properties of the RPUF nanocomposites more effectively compared to other nanoparticles (clay, silica etc.). The superiority of NPG over other nanoparticles can be attributed to unique two‐dimensional geometrical morphology and a higher specific surface area. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45001.     

Thermal degradation studies on rigid polyurethane foams blown with pentane

The effect of sodium dihydrogenphosphate, trisodium pyrophosphate, and sodium aluminocarbonate on the thermal decomposition of rigid polyurethane (PUR) foams, based on diphenylmethane‐4,4‐diisocyanate, diphenyl‐2,2‐propane‐4,4‐dioxyoligo(ethylene oxide), and oxyalkylenated toluene‐2,6‐diamine, blown with pentane, was studied. Thermogravimetric (TG) data have shown that there is a stabilization effect of additives in the initial stage of degradation, both in nitrogen and air atmosphere, and the decomposition proceeded in two steps up to 600°C. Results of the kinetic analysis by the isoconversional methods of Ozawa–Flynn–Wall and Friedman yielded values of (apparent) activation energy (E_a) and preexponential factor (A). For phosphate‐stabilized PUR samples, E_a remained stable over a broad area of the degree of conversion, while for carbonate‐containing sample two regions of E_a were observed. Further advanced kinetic analysis by a nonlinear regression method revealed the form of kinetic function that was the best approximation for experimental data—for a two‐stage consecutive reaction the first step was the Avrami–Erofeev nucleation‐dependent model, and the second step was a chemical reaction (1st or nth order) model. The integrated thermogravimetric (TG)/Fourier transform infrared (FTIR) technique probed the thermal degradation of modified PURs by analyzing the evolved gases. The solid residue remaining at different temperatures was identified by diffuse reflection FTIR (Kubelka–Munk format). The complex thermal behavior was discussed on the basis of the obtained results—it can be shown that the global stabilization effect is a multistage process whose initial conditions are of critical importance in governing the nature of the entire process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2319–2330, 2003     

Electrical conductivity and major mechanical and thermal properties of carbon nanotube‐filled polyurethane foams

The carbon nanotubes (CNTs)/rigid polyurethane (PU) foam composites with a low percolation threshold of ～ 1.2 wt % were prepared by constructing effective conductive paths with homogeneous dispersion of the CNTs in both the cell walls and struts of the PU foam. The conductive foam presented excellent electrical stability under various temperature fields, highlighting the potential applications for a long‐term use over a wide temperature range from 20 to 180°C. Compression measurements and dynamical mechanical analysis indicated 31% improvement in compression properties and 50% increase in storage modulus at room temperature in the presence of CNTs (2.0 wt %). Additionally, the incorporation of only 0.5 wt % CNTs induced remarkable thermal stabilization of the matrix, with the degradation temperature increasing from 450 to 499°C at the 50% weight loss. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Morphology,mechanical properties,and thermal stability of polyurethane–epoxide resin interpenetrating polymer network rigid foams

A series of rigid interpenetrating network foams (IPNFs) based on a rosin‐based polyurethane (PU) and a crosslinked epoxide resin (ER) were prepared by a simultaneous polymerization technique. The morphology, mechanical properties, thermal stability, and changes in the chemical structure during the thermal degradation process of the rigid IPNFs were investigated by scanning electron microscopy (SEM), compressive testing, thermogravimetric analysis (TGA), and Fourier‐transform infrared spectroscopy (FTIR). The SEM micrographs showed that the cell structure of the rigid IPNFs became less homogeneous with increasing ER content. The brittleness of the cell walls increased as the ER content and the cure time of the rigid IPNFs increased. The compressive strength of the rigid PU/ER IPNFs increased to a maximum value and then decreased with further increase in the ER content. Similar behavior was observed for the elastic modulus. This behavior was related to the nonhomogeneous cells and more brittle cell walls for the rigid IPNFs with high ER content. The TGA data showed that the thermal stability of the rigid PU foam increased with the addition of increasing levels of ER, due to the better thermal stability of the ER compared to that of the PU. With the exception of the ER alone, a two‐stage weight‐loss process was observed for all these rigid IPNFs and for the PU foam alone. The FTIR analysis suggested that the first stage of weight loss was due to the degradation of the polyol–derived blocks of the PU, and the second weight loss stage was governed by both the degradation of the ER component and that of the isocyanate‐derived blocks of the PU. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 406–416, 2000     

Preparation and characterization of rigid polyurethane foams with carbamide and borate groups

The results of research on the application of hydroxyethyl urea derivatives modified with boron as polyol components to produce foamed polyurethane materials are presented. The obtained rigid polyurethane foams are characterized by good heat‐insulating parameters and decreased flammability. The decrease in flammability of the foams follows from the presence of boron and increased nitrogen content, resulting from the use of polyol with urea groups. The incorporation of boron into the foam structure also results in a substantial increase in the compression strength, compared to classic foams and to non‐boron‐modified ones. The self‐extinguishing foams of high mechanical strength can find application as heat‐insulating construction elements for the building industry. © 2016 Society of Chemical Industry     

Properties of rigid polyurethane foams blown by HCFC 141B and distilled water

Rigid polyurethane foams (PUFs) were prepared from polymeric 4,4′‐diphenylmethane diisocyanate, polyester polyol, 1,4‐butane diol, silicone surfactant, hydrochlorofluorocarbon (HCFC) 141B, and distilled water. The properties and structure of the PUFs were investigated with differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and a universal testing machine. The density of the PUF blown by distilled water and/or HCFC 141B decreased from 175.7 to 28.2 kg/m³ with an increase of blowing agents. From the SEM results, the average cell size of the PUF blown by distilled water increased from 150 to 290 μm with the distilled water content. From the DSC results, the glass‐transition temperature (T_g) of the PUF blown by distilled water increased from 85.7 to 101.7°C with increasing distilled water content, whereas the T_g of the PUF blown by HCFC 141B remained unchanged with HCFC 141B content. The compressive strength and modulus of the PUF blown by a mixture of distilled water and HCFC 141B was increased from 0.13 to 0.25 MPa and from 3.00 to 7.23 MPa, respectively, with the distilled water content at the sample density of about 44.0 kg/m³. The increase of the compressive strength and modulus of the PUF at the same density was related to the increase of the T_g from 86.0 to 100.9°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 486–493, 2001