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     

Rigid polyurethane foams based on soybean oil

Both HCFC‐ and pentane‐blown rigid polyurethane foams have been prepared from polyols derived from soybean oil. The effect of formulation variables on foam properties was studied by altering the types and amounts of catalyst, surfactant, water, crosslinker, blowing agent, and isocyanate, respectively. While compressive strength of the soy foams is optimal at 2 pph of surfactant B‐8404, it increases with increasing the amount of water, glycerin, and isocyanate. It also increases linearly with foam density. These foams were found to have comparable mechanical and thermoinsulating properties to foams of petrochemical origin. A comparison in the thermal and thermo‐oxidative behaviors of soy‐ and PPO‐based foams revealed that the former is more stable toward both thermal degradation and thermal oxidation. The lack of ether linkages in the soy‐based rather than in PPO‐based polyols is thought to be the origin of improved thermal and thermo‐oxidative stabilities of soy‐based foams. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 467–473, 2000     

Preparation and characterization of water‐blown polyurethane foams from liquefied cornstalk polyol

Polyurethane foams were prepared from the liquefied cornstalk polyol, which was obtained by the liquefaction of cornstalk in the presence of polyhydric alcohols using sulfuric acid as catalyst. The advisable liquefaction reaction conditions were selected by investigating their influences on the properties of liquefied cornstalk polyol, taking account of the requirement for the preparation of appropriate polyurethane foams. The influences of the contents of catalysts, water, surfactant, and isocyanate on the properties of polyurethane foams were also discussed, and feasible formulations for preparing cornstalk‐based polyurethane foams were proposed. The results indicated that the foams prepared from such liquefied cornstalk polyol exhibited excellent mechanical properties and thermal properties, and could be used as heat‐insulating materials. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Melamine amino trimethylene phosphate as a novel flame retardant for rigid polyurethane foams with improved flame retardant,mechanical and thermal properties

Melamine amino trimethylene phosphate (MATMP) as a novel nitrogen‐phosphorus flame retardant, was synthesized by the reaction of melamine with amino trimethylene phosphonic acid (ATMP) in aqueous solution. The structure of MATMP was characterized by Fourier transform infrared spectroscopy, solid state 31 P nuclear magnetic resonance, and thermogravimetric analysis. Rigid polyurethane (RPU) foams were prepared by one‐shot and free‐rise method, using MATMP as a flame retardant. The flame retardant, mechanical and thermal properties of MATMP in RPU foams were studied. It is found that the RPU foam containing 15 wt % MATMP (sample RPUMA‐15) can pass the UL‐94 V0 test with a limiting oxygen index of 25.5%. The cone calorimeter test results show that the peak heat release rate of RPUMA‐15 is reduced about 34% compared with that of untreated RPU foam. SEM results indicate that the RPU foams with MATMP can form the good and compact char during burning which provides better flame retardancy. The compressive strength of the RPU foams filled with MATMP first increases and then slightly decreases with an increase in the MATMP content comparing with that of untreated RPU foam. Moreover, thermal conductivities of the MATMP filled RPU foams are about 0.03 W/m K. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45234.     

Physical properties of water‐blown rigid polyurethane foams containing epoxidized soybean oil in different isocyanate indices

To explore the potential of isocyanate usage reduction, water‐blown rigid polyurethane foams were made by replacing 0, 20, and 50% of Voranoll® 490 in the B‐side of the foam formulation by epoxidized soybean oil (ESBO) with an isocyanate index ranging from 50 to 110. The compressive strength, density, and thermal conductivity of foams were measured. The foam surface temperature was monitored before and throughout the foaming reaction as an indirect indication of the foaming temperature. Increasing ESBO replacement and/or decreasing isocyanate index decreased the foam's compressive strength. The density of the foam decreased while decreasing the isocyanate index to 60. Further decrease in isocyanate index resulted in foam shrinkage causing a sharp increase in the foam density. The thermal conductivity of foams increased while decreasing the isocyanate index and increasing the ESBO replacement. Mathematical models for predicting rigid polyurethane foam density, compressive strength, and thermal conductivity were established and validated. Similar to compressive strength, the foaming temperature decreased while decreasing the isocyanate index and increasing the ESBO replacement. Because of the lower reactivity of ESBO with isocyanate, the rate of foaming temperature decrease with decreasing isocyanate index was in the order of 0% > 20% > 50% ESBO replacement. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

蒸馏水含量对三明治结构硬质聚氨酯泡沫性能的影响

采用异氰酸酯、聚酯多元醇、发泡剂（水）等原料通过一体发泡成型技术制备出一种新型的三明治泡沫夹心复合材料。利用热重分析、扫描电子显微镜等对不同水含量（质量分数分别为0、0.5 %和1.0 %）的硬质聚氨酯泡沫材料的泡孔直径、密度、热导率、压缩性能、三点弯曲和热力学性能等做了研究,进而确定提高硬质聚氨酯性能的最佳工艺。结果表明,随着水含量的增加,硬质聚氨酯泡沫材料泡孔直径增大,密度变小,热导率降低,保温性能提高,而压缩性能和三点弯曲却呈下降趋势;综合考虑硬质聚氨酯泡沫材料泡孔结构和良好的保温隔热及弯曲等力学性能,其最佳含水量为0.5 %。     

Effect of Evening Primrose (Oenothera biennis) Oil Cake on the Properties of Polyurethane/Polyisocyanurate Bio-Composites

Rigid polyurethane/polyisocyanurate (RPU/PIR) foam formulations were modified by evening primrose (Oenothera biennis) oil cake as a bio-filler in the amount of 5 to 50 wt.%. The obtained foams were tested in terms of processing parameters, cellular structure (SEM analysis), physico-mechanical properties (apparent density, compressive strength, brittleness, accelerated aging tests), thermal insulation properties (thermal conductivity coefficient, closed cells content, absorbability and water absorption), flammability, smoke emission, and thermal properties. The obtained results showed that the amount of bio-filler had a significant influence on the morphology of the modified foams. Thorough mixing of the polyurethane premix allowed better homogenization of the bio-filler in the polyurethane matrix, resulting in a regular cellular structure. This resulted in an improvement in the physico-mechanical and thermal insulation properties as well as a reduction in the flammability of the obtained materials. This research provided important information on the management of the waste product from the edible oil industry and the production process of fire-safe RPU/PIR foams with improved performance properties. Due to these beneficial effects, it was found that the use of evening primrose oil cake as a bio-filler for RPU/PIR foams opens a new way of waste management to obtain new “green” materials.     

Effect of Dibutyltin Dilaurate and Triethanolamine Catalysts on Structure and Properties of Polyimide Foams

A series of rigid polyimide (PI) foams were prepared by the prepolymer method with pyromellitic dianhydride and polyaryl polymethylene isocyanate as the starting materials and dibutyltin dilaurate (DBTDL), and triethanolamine (TEOA) as catalysts. The effect of the two kinds of catalysts on the structure and properties such as molecular structure, cell morphology, density, mechanical properties, thermal properties, and flame retardancy of the resulting foams were characterized in detail. The experimental results showed that the PI foams prepared in this work possessed low density, good mechanical properties, outstanding thermal stability, and excellent flame retardancy. The thermal stability and flame retardancy were improved obviously with the increase of DBTDL content. While with the increase of the content of TEOA, the mechanical strength and apparent density of PI foams increased significantly. Therefore, different structure and performance of PI foams can be prepared by adjusting the content of these two catalysts. J. VINYL ADDIT. TECHNOL., 25:385–395, 2019. © 2019 Society of Plastics Engineers     

Rigid polyurethane foams: A model of the foaming process

A model of the manufacture of rigid polyurethane foams by free rising is presented. The extent of cream and rise periods as well as the amount of blowing agent necessary to give the desired foam density are theoretically predicted. The rate of blowing agent evaporation is calculated from an experimental boiling temperature vs. composition curve. Experimental runs were carried out with a formulation consisting of a polymeric isocyanate, a polyether polyol based on sorbitol, a silicone-polyol block-copolymer as surfactant, dibutyltin dilaurate as catalyst, and trichlorofluoromethane as blowing agent. Mixing was performed in situ in the mold using a commercial foaming machine. Experimental results gave a satisfactory agreement with model predictions. A diagram containing all the relevant information may be theoretically built and used for the selection of adequate operating parameters for a given formulation.     

Grafting modification bamboo kraft lignin and its performance in rigid polyurethane foams

In order to improve the efficiency of intumescent flame retardant (IFR), bamboo kraft lignin (BKL) was chemically functionalized by grafting melamine (MEL) and diethyl phosphite (DEP) and used for rigid polyurethane (RPU) foam. The BKL, MEL, and DEP in IFR system were used as char forming agent, gas, and acid source, respectively. The FTIR and XPS results indicated that the nitrogen (N) and phosphorus (P) containing BKL was successfully synthesized. The limiting oxygen index (LOI) value of N-BKL and N/P-BKL RPU foams were higher than BKL RPU foam, suggesting that N-BKL and N/P-BKL improved flame retardancy of the foams. The total heat release (THR), heat release rate (HRR), effective heat of combustion (EHC), and fire growth rate (FIGRA) values of N-BKL and N/P-BKL RPU foams were much lower than that of BKL RPU foam. The flame retardancy index value of N/P-BKL RPU foams was higher comparing to N-BKL RPU foam. These results indicated that the synergistic interaction between N containing compound of MEL and P containing compound of DEP led to the improvement flame retardant properties. Comparing to BKL RPU foam, the N/P-BKL RPU foam increased 74°C of maximum weight loss temperature and decreased 18.1 wt% of mass loss, indicating enhanced thermal stability. The morphology of char after cone calorimeter testing showed the N/P-BKL RPU foam presented more continuous and compact char residues, which could reduce heat and mass transfer, protecting underlying materials from further combustion in a fire, thus resulting in good flame retardancy and thermal stability properties. This work suggests a promising route to enhancing the flame-retardant performance of RPU foam using nontoxic and more environmentally friendly grafted bamboo lignin.     

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     

Synthesis and characterization of polyurethane foam matrices for the support of granular adsorbent materials

Polyurethane foams with different formulations were synthesized and characterized for use as supporting matrices of granular solid adsorbents. The open cell content, specific gravity, thermal stability, and hydrophobicity were determined and related to the formulation composition. The synthesized foams had open cell contents of 88.1–98.5% and specific gravity values of 120–28 kg m^?3. The thermal stability of the prepared foams was influenced mainly by the water content and the type of isocyanate used. The hydrophobicity was assessed by an analysis of the water adsorption isotherms determined on selected foams, and a correlation between these results and the formulation of the foams was attempted. Two types of activated carbons were supported in a polyurethane matrix. The adsorption characteristics evaluated before and after the supporting procedure, by nitrogen adsorption, revealed that there was only a moderate surface area reduction of 15–20%. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2045–2053, 2004     

Thermal Conductivity of Very Porous Kaolin‐Based Ceramics

A clay‐based material exhibiting high pore volume fraction and low thermal conductivity suitable for thermal insulation is described. Starting with a commercial clay containing >75% kaolinite, foams were made by mixing in water and methyl cellulose as a surfactant then beating. After drying at 70°C, the pore volume fraction >94% remains almost constant for treatments up to 1150°C. In contrast, the phases constituting the solid skeleton evolve strongly with removal of surfactant, dehydroxylation of kaolinite, and formation of mullite. The latter leads to greater mechanical strength but also an increase in thermal conductivity. Thermal treatment of the kaolin foam at 1100°C yields a suitable compromise between low thermal conductivity of 0.054 W.(m.K)^?1 at room temperature with a compressive yield stress of 0.04 MPa. The radiation component in the effective thermal conductivity is <10% at 20°C increasing to >50% at 500°C.     

Formation and characterization of polyurethane—vermiculite clay nanocomposite foams

Nanocomposites of rigid polyurethane foam with unmodified vermiculite clay are synthesized. The clay is dispersed either in polyol or isocyanate before blending. The viscosity of the polyol is found to increase slightly on the addition of clay up to 5 pphp (parts per hundred parts of polyol by weight). The gel time and rise time are significantly reduced by the addition of clay, indicating that the clay acts as a heterogeneous catalyst for the foaming and polymerization reactions. X‐ray diffraction and transmission electron microscopy of the polyurethane composite foams indicate that the clay is partially exfoliated in the polymer matrix. The clay is found to induce gas bubble nucleation resulting in smaller cells with a narrower size distribution in the cured foam. The closed cell content of the clay nanocomposite foams increases slightly with clay concentration. The mechanical properties are found to be the best at 2.3 wt% of clay when the clay is dispersed in the isocyanate; the compressive strength and modulus normalized to a density of 40 kg/m³ are 40% and 34% higher than the foam without clay, respectively. The thermal conductivity is found to be 10% lower than the foam without clay. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Effects of 4,4′‐diaminodiphenyl ether on the structures and properties of isocyanate‐based polyimide foams

A series of thermal insulation, acoustic absorption isocyanate‐based lightweight polyimide (PI) foams with 4,4′‐diaminodiphenyl ether (ODA) units were prepared from polyaryl polymethylene isocyanate (PAPI) and the esterification solution derived from pyromellitic dianhydride (PMDA) and ODA. The structures and properties of the PI foams prepared with different molar ratio of ODA/PMDA were investigated in detail. The results show that the ODA units have great influence on the foam properties. With the increase of the ODA units, the density decreases firstly and then increases. When the molar ratio of ODA/PMDA is 3/10, the foam reaches the minimum density (13.7 kg/m³). Moreover, with increasing the ODA units, the acoustic absorption properties increase firstly and then decrease owing to the variation of the average cell diameter of the PI foams. All PI foams show excellent thermal stability, and the 5% and 10% weight loss temperature are in the range of 250–270 °C and 295–310 °C, respectively. In addition, the PI foams present low thermal conductivity and thermal diffusivity. Furthermore, the mechanical property was also evaluated and the compressive strength of the PI foams is in the range of 33.0–45.7 kPa. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46029.     

Rigid Polyurethane Foam Production from Palm Oil-Based Epoxidized Diethanolamides

A new type of rigid polyurethane foam was produced by incorporating oxazolidone heterocyclic rings on to polyurethane backbones. Epoxidized diethanolamides were synthesized by reacting palm oil blends of epoxidized palm olein and refined bleached deodorized palm kernel olein with diethanolamine to produce rigid polyurethane foams. Epoxides, retained in the diethanolamides, reacted with isocyanate during foam production in the presence of AlCl₃–THF complex catalyst to form oxazolidone linkages in the polyurethane network. The carbonyl stretch of oxazolidone was identified at 1,750 cm⁻¹ through Fourier Transform Infra Red analysis. Chemical modifications of the polyurethane network also improved the thermal and mechanical properties of the foams. In addition, isocyanate index 1.4 was determined to be the most suitable in the production of foams from this newly synthesized epoxidized diethanolamides.     

The effect of resin formulation on the cellular morphology and mechanical properties of phenolic foams

In the present study, the effects of blowing agent concentration, surfactant, and resin viscosity on the cellular structure, density, and compressive strength of phenolic foams were investigated. The mechanism of foaming was studied by thermal analyses, as well. The scanning electron microscopy was performed to investigate the morphology of foams. The presence of surfactant was essential to obtain a foam structure. By increasing the amount of blowing agent in the formulation, the bubbles became larger. The variation of the resin viscosity had the sharp effect on the cell size and its distribution so that the cell size dropped from 108 to 77 μm in the sample with the highest viscosity. The mechanical properties were significantly affected by foam structure as well as the cell uniformity. By decreasing the average cell sizes, the compression strength and modulus were improved up to more than 60%. Finally, the optimum values for viscosity of resin and, blowing agent, and surfactant concentrations were obtained. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48331.     

Thermal‐Insulation,Electrical, and Mechanical Properties of Highly‐Expanded PMMA/MWCNT Nanocomposite Foams Fabricated by Supercritical CO2 Foaming

Foaming behavior of poly(methyl methacrylate) (PMMA)/multi‐walled carbon nanotubes (MWCNTs) nanocomposites and thermally‐insulating, electrical, and mechanical properties of the nanocomposite foams are investigated. PMMA/MWCNT nanocomposites containing various amounts of MWCNTs are first prepared by combining solution and melt blending methods, and then foamed using CO₂. The foaming temperature and MWCNT content are varied for regulating the structure of PMMA/MWCNT nanocomposite foams. The electrical conductivity measurement results show that MWCNTs have little effect on the electrical conductivity of foams with large expansion ratio. Thermal conductivities of both solid and foamed PMMA/MWCNT nanocomposites are measured to evaluate their thermally insulating properties. The gas conduction, solid conduction, and thermal radiation of the foams are calculated for clarifying the effects of cellular structure and MWCNT content on thermal insulation properties. The result demonstrates that MWCNTs endowed foams with enhanced thermal insulation performance by blocking thermal radiation. Moreover, the compressive testing shows that MWCNTs improve the compressive strength and rigidity of foams. This research is essential for optimizing environmentally friendly thermal insulation nanocomposite foams with enhanced thermal‐insulation and compressive mechanical properties.     

Graphene oxide-containing isocyanate-based polyimide foams: Enhanced thermal stability and flame retardancy

Isocyanate-based graphene oxide-containing polyimide foams were synthesized by a semi-prepolymer method. In this method, while the first solution containing pre-polymer was derived from pyromellitic dianhydride and excess polymethylene polyphenylene isocyanate (PM200), the second solution contains dianhydride derivatives, water, catalysts, surfactants, and graphene oxide. PIFs were prepared with 0%, 0.25%, 0.50%, 0.75%, and 1% graphene oxide by weight, respectively. PIFs exhibited a minimum side reaction and urea generation was not seen for all PIFs instead of imide bonding. The addition of graphene oxide (GO) leads to a more close-packed structure. Therefore, crosslinking density and thermal stability of graphene oxide-containing polyimide foams increased. Upon the addition of 1% GO, almost seven times higher compression strength was obtained compared to neat PIFs. Also, LOI values supported the theory that thermally stable and flame retardant PIFs can be synthesized via the isocyanate-based process with GO.     

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