Rigid polyurethane foams made from high viscosity soy‐polyols

This study investigated the physical properties of water‐blown rigid polyurethane (PU) foams made from VORANOL®490 (petroleum‐based polyether polyol) mixed with 0–50% high viscosity (13,000–31,000 cP at 22°C) soy‐polyols. The density of these foams decreased as the soy‐polyol percentage increased. The compressive strength decreased, decreased and then increased, or remained unchanged and then increased with increasing soy‐polyol percentage depending on the viscosity of the soy‐polyol. Foams made from high viscosity (21,000–31,000 cP) soy‐polyols exhibited similar or superior density‐compressive strength properties to the control foam made from 100% VORNAOL® 490. The thermal conductivity of foams containing soy‐polyols was slightly higher than the control foam. The maximal foaming temperatures of foams slightly decreased with increasing soy‐polyol percentage. Micrographs of foams showed that they had many cells in the shape of sphere or polyhedra. With increasing soy‐polyol percentage, the cell size decreased, and the cell number increased. Based on the analysis of isocyanate content and compressive strength of foams, it was concluded that rigid PU foams could be made by replacing 50% petroleum‐based polyol with a high viscosity soy‐polyol resulting in a 30% reduction in the isocyanate content. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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     

Nanoclay filled soy‐based polyurethane foam

Polyurethane foam was fabricated from polymeric diphenylmethane diisocyanate (pMDI) and soy‐based polyol. Nanoclay Cloisite 30B was incorporated into the foam systems to improve their thermal stabilities and mechanical properties. Neat polyurethane was used as a control. Soy‐based polyurethane foams with 0.5–3 parts per hundred of polyols by weight (php) of nanoclay were prepared. The distribution of nanoclay in the composites was analyzed by X‐ray diffraction (XRD), and the morphology of the composites was analyzed through scanning electron microscopy (SEM). The thermal properties were evaluated through dynamic mechanical thermal analysis (DMTA). Compression and three‐point bending tests were conducted on the composites. The densities of nanoclay soy‐based polyurethane foams were higher than that of the neat soy‐based polyurethane foam. At a loading of 0.5 php nanoclay, the compressive, flexural strength, and modulus of the soy‐based polyurethane foam were increased by 98%, 26%, 22%, and 65%, respectively, as compared to those of the neat soy‐based polyurethane foam. The storage modulus of the soy‐based polyurethane foam was improved by the incorporation of nanoclay. The glass transition temperature of the foam was increased as the nanoclay loading was increased. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Biodegradable polyurethane foam from liquefied waste paper and its thermal stability,biodegradability, and genotoxicity

Liquefaction of waste paper (WP) was conducted in the presence of polyhydric alcohols to prepare biodegradable polyurethane foam. The liquefied‐WP‐based polyol had suitable characteristics such as apparent molecular weight, hydroxyl value, and viscosity for the preparation of rigid polyurethane foam and was successfully applied to produce polyurethane foam with the appropriate combinations of foaming agents. The obtained foams showed satisfactory densities and mechanical properties as good as those of foams obtained from liquefied wood‐ and starch‐based polyols. The foams had almost the same thermal stability at initial weight loss and seemed to be potentially biodegradable because they were degraded to some extent in leaf mold. There were no mutagens or carcinogens in the water extracts of the foams. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1482–1489, 2002     

The effect of different palm oil‐based bio‐polyols on foaming process and selected properties of porous polyurethanes

Rigid polyurethane foams were successfully prepared by blending up to 70 wt% of two different palm oil‐based bio‐polyols with a petrochemical polyether polyol. The bio‐polyols were synthesized by epoxidation–oxirane ring‐opening process using water (PP102) and diethylene glycol (PP147), respectively. Due to the high viscosity of both bio‐polyols the reactive mixture was heated to start the foaming reaction at about 50 °C. Under these conditions, the gelling reactions speed up as the amount of PP147 increases but slow down to a great extent when PP102 is used. The thermal conductivity of modified foams is higher and the closed cell content lower compared to reference ones, even when the bio‐foams present a lower apparent density. However, all foams exhibit reduced water absorption, excellent dimensional stability and better thermal stability at temperatures up to 400 °C than the control foam. Conversely, their mechanical and dynamic mechanical properties become poorer as the PP147 concentration increases and even more so if PP102 is used instead. PP147 foams containing up to 50% bio‐polyol could be used as a green replacement of petroleum‐based ones in applications where excellent behaviour in compression (the most affected properties) is not fundamental, with the additional advantages of reduced density and increased content of bio‐derived components. © 2017 Society of Chemical Industry     

Characterization of flexible polyurethane foams based on soybean‐based polyols

Two series of flexible polyurethane foams were fabricated by substituting conventional petroleum‐based polyols with increasing amounts of soy‐based polyols (SBP) having different hydroxyl numbers. The mechanical properties of the foams were characterized by stress–strain analysis in the compression mode and DMA in tension mode, the cellular morphology was analyzed by SEM and the microphase‐separation of the foams was noted by SAXS. Our results showed that the cellular morphology and mechanical properties of the flexible foams were affected significantly by the foam fabrication method and SBP hydroxyl numbers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Porous polyurethane foams based on recycled poly(ethylene terephthalate) for oil sorption

In using recycled poly(ethylene terephthalate) (PET) as a petroleum sorbent we tried to achieve two important objectives simultaneously. PET waste was glycolized using trimethylolpropane (TMp) or pentaerytheritol (PEr) to produce suitable polyol oligomers for polyurethane (PU) foams. The glycolysis was carried out in the presence of manganese acetate as a catalyst under normal pressure in m‐cresol at 220 °C. Producing polyols, PEr degraded PET into lower molecular weights than TMp. So prepared oligomers were reacted with 2,4‐toluene diisocyanate providing several types of PU foam. The effect of various variables (polyol reactivity, water content, type of catalyst, isocyanate amount and surfactant) on the foam structure and properties were analyzed. Porosity of the PU foams was examined using environmental scanning electron microscopy. Foams based on glycolized TMp contain small uniform cells whereas other foams form less uniform cells with varying sizes including closed cells. Dynamic mechanical analysis gives much lower storage moduli for TMp‐based PUs that for those based on PEr, an effect of dangling ethylene chains in the former case. The glass transition temperatures T_g are higher when PEr rather than TMp is used. Our PU foams show good sorption properties and sufficient reusability. Copyright © 2012 Society of Chemical Industry     

Reinforcement of soy polyol‐based rigid polyurethane foams by cellulose microfibers and nanoclays

Water‐blown rigid polyurethane foams from soy‐based polyol were prepared and their structure–property correlations investigated. Cellulose microfibers and nanoclays were added to the formulations to investigate their effect on morphology, mechanical, and thermal properties of polyurethane foams. Physical properties of foams, including density and compressive strength, were determined. The cellular morphologies of foams were analyzed by SEM and X‐ray micro‐CT and revealed that incorporation of microfibers and nanoclays into foam altered the cellular structure of the foams. Average cell size decreased, cell size distribution narrowed and number fractions of small cells increased with the incorporation of microfibers and nanoclays into the foam, thereby altering the foam mechanical properties. The morphology and properties of nanoclay reinforced polyurethane foams were also found to be dependent on the functional groups of the organic modifiers. Results showed that the compressive strengths of rigid foams were increased by addition of cellulose microfibers or nanoclays into the foams. Thermogravimetric analysis (TGA) was used to characterize the thermal decomposition properties of the foams. The thermal decomposition behavior of all soy‐based polyurethane foams was a three‐step process and while the addition of cellulose microfibers delayed the onset of degradation, incorporation of nanoclays seemed to have no significant influence on the thermal degradation properties of the foams as compared to the foams without reinforcements. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

基于大豆蛋白的高回弹聚氨酯泡沫塑料的制备及性能研究

以大豆分离蛋白、高活性聚醚、聚合物多元醇、交联剂、发泡剂、泡沫稳定剂和混合异氰酸酯为原料,自由发泡、常温熟化制备了大豆蛋白基高回弹聚氨酯软泡。研究了大豆蛋白质(SPI)对聚氨酯泡沫物理性能、力学性能、孔结构和热性能的影响。结果表明:SPI添加量对泡沫物理和力学性能影响最大。随着SPI含量增加,泡沫的密度、尺寸稳定性提高,压陷硬度和舒适因子提高增大;回弹率下降,断裂伸长率减小,而拉伸强度先增大后减小。SPI能够提高聚氨酯的热稳定性,但最好低于150℃使用。     

Polyurethane foams from soyoil‐based polyols

The focus of this work was to synthesize bio‐based polyurethane (PU) foams from soybean oil (SO). Different polyols from SO were produced as follows: soybean oil monoglyceride (SOMG), hydroxylated soybean oil (HSO), and soybean oil methanol polyol (SOMP). The SOMG was a mixture of 90.1% of monoglyceride, 1.3% of diglyceride, and 8.6% of glycerol. The effect of various variables (polyol reactivity, water content curing temperature, type of catalyst, isocyanate, and surfactant) on the foam structure and properties were analyzed. SOMG had the highest reactivity because it was the only polyol‐containing primary hydroxyl (? OH) groups in addition to a secondary ? OH group. PU foams made with SOMG and synthetic polyol contained small uniform cells, whereas the other SO polyols produced foams with a mixture of larger and less uniform cells. The type of isocyanate also had an influence on the morphology, especially on the type of cells produced. The foam structure was found to be affected by the water and catalyst content, which controlled the foam density and the cure rate of the PU polymer. We observed that the glass transition (T_g) increased with the OH value and the type of diisocyanate. Also, we found that the degree of solvent swelling (DS) decreased as T_g increased with crosslink density. These results are consistent with the Twinkling Fractal Theory of T_g. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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.     

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     

新型聚异氰脲酸硬质泡沫材料的制备及性能研究

聚异氰脲酸硬质泡沫材料是由PM-200（异氰酸酯和二苯甲烷二异氰酸盐的混合物）、异氰脲酸苯酐聚醚酯多元醇（IPPEP）或聚环氧丙烷多元醇在异氰酸酯指数为200的情况下制备的。考察了IPPEP对泡沫材料的热稳定性和阻燃性能的影响,并讨论了n（PO）∶n（PA）对IPPEP基泡沫材料力学性能的影响。结果表明：IPPEP的使用使聚氨酯泡沫材料的玻璃化转变温度提高了45℃,热分解温度由510℃提高到540℃,氧指数提高到23.3%。随着n（PO）∶n（PA）的降低,泡沫材料的拉伸强度和压缩强度呈现先增加后降低的趋势。     

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     

Characterization of polyurethane foams from soybean oil

Modified soy‐based vegetable oil polyols were successfully incorporated as a replacement for conventional polyols to produce flexible slabstock polyurethane foams. The oil was characterized for its hydroxyl value and fatty acid composition. The modified oils had higher hydroxyl values and lower unsaturated acids than regular unmodified oils. Three different modified polyols were used to investigate the reactivity with isocyanates. The effects on the foaming reaction of two different isocyanates, namely TDI and MDI, were investigated. The reactions were also carried out with a mixture of polyols containing synthetic polyols and vegetable oil‐based polyols to delineate the effect of each component. FTIR technique was used to identify the sequence of chemical reactions during the foaming process. The effect of water levels and isocyanate content on the kinetics of the foaming reaction was investigated. Information regarding the formation of hard and soft segments with the varying compositions was obtained. As the water content increased, the amount of the hard segment and urea formation increased in both soy oil polyols and synthetic polyols. Increased synthetic polyols in the mixture increased the rate of reaction and phase mixing due to the availability of primary hydroxyl groups. Scanning electron microscopy (SEM) and small‐angle X‐ray scattering (SAXS) were used to probe the morphology. As the water content increased, the cell size increased. At lower water content a more uniform cell structure was evident and at higher water levels hard domain size increased. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3097–3107, 2002     

Optimizing the lignin based synthesis of flexible polyurethane foams employing reactive liquefying agents

The present work is focused on the optimization of a green process based on the employment of by‐products obtained from wood treatments as raw materials for producing flexible polyurethane foams. More specifically, lignin was employed in flexible polyurethane foams in order to partially replace the usual fossil polyols; therefore glycerol (GLY) and glycerin polyglycidyl ether (EJ 300) were used as the polyol fraction for lignin liquefaction. Polypropylene glycol triol was used as a chain extender in different ratios with liquefaction solvents, and polymeric diphenylmethane diisocyanate as an isocyanate fraction. Liquefaction of lignin was performed by microwave irradiation, thus reducing the processing time and energy required compared to present industrial production processes. All the foams were produced in controlled expansion through the adoption of a ‘one‐shot’ approach, using water as a blowing agent and with an isocyanate index (NCO/OH) of less than 100 to improve the flexibility of the foam. This approach allowed for the substitution of up to 12% of common petro derived polyol with commercial soda lignin. Finally, the foams were characterized, presenting properties that could be modulated as a function of lignin content, GLY/EJ 300 ratio and isocyanate index. The qualities of the foams were compatible with existing materials used for furniture and for the interiors of car seats and couches. © 2015 Society of Chemical Industry     

Structures and physical properties of rigid polyurethane foam prepared with rosin‐based polyol

Rosin‐based polyester polyols were synthesized from a rosin–maleic anhydride adduct, diethylene glycol, and ethylene glycol with and without adding adipic acid and phthelic anhydride, in the presence of catalyst. Rigid polyurethane (PU) foams were prepared with these rosin‐based polyols and compared with foam made with an industrial polyester Daltolac? P744. The experimental results show that the foaming behavior for the foams prepared from such rosin‐based polyols is similar to that of industrial products, but their 10% compression strength, both parallel and vertical to foaming rise direction, is higher and the dimensional stability at 100 and ?30°C is similar or somewhat better than that of a comparable system. Furthermore, the rosin‐modified PU foams exhibit even lower thermal conductivity and much higher activation energies during the pyrolysis process. All these unique physical properties of the rosin‐modified rigid PU foams were correlated to the structures of these PU foams. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 598–604, 2002; DOI 10.1002/app.10312     

Rigid polyurethane foams based on activated soybean meal

Soybean meal (SM), an abundant biomass resource, was used as the surrogate to partially replace polyols in rigid polyurethane foam synthesis. Compared with polyurethanes based on other soybean‐based resources, such as soybean protein isolate (SPI), polyurethane foams based on activated SM showed better thermal and mechanical properties. The amount of SM in the final polyurethane foams can be as high as 30 wt % (base on the total weight of foam), which dramatically decreases the cost of the foams. The results also showed that SM played a vital role in improving the foam properties, which could be attributed to the participation of the functional groups in SM in the polyurethane foam synthesis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Soybean oil based polyisocyanurate cast resins

Two series of polyisocyanurates were prepared from polymeric 4,4′‐diphenylmethane diisocyanate (MDI) and soy‐based or polypropylene oxide polyols by varying isocyanate indexes from 105 to 350. Increasing isocyanate index gave polyisocyanurates with increased thermal stability, flame resistance, tensile strength, modulus, and glass transition. Impact was lower. Soy‐based polyisocyanurates displayed better thermal stability, higher rigidity (modulus), and higher strength than those based on the propylene oxide polyols of the same molecular weight and functionality. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3333–3337, 2003