Rigid polyurethane foams derived from cork liquefied at atmospheric pressure

The aim of this study was to evaluate the possibility of using polyols derived from liquefied cork in the production of novel bio‐based polyurethane foams (PUFs). For that purpose, different liquefaction conditions were used at atmospheric pressure and moderate temperature where poly(ethylene glycol) and glycerol were used as solvents and sulfuric acid as catalyst. The ensuing polyols were used to produce foams which were characterized using structural, morphological, thermal and mechanical analyses to demonstrate that liquefaction conditions play a crucial role in the properties of the foams. The resulting foams exhibited the typical cellular structure of PUFs with low densities (57.4–70.7 kg m^?3) and low thermal conductivities (0.038–0.040 W m^?1 K^?1). However, the mechanical properties differed significantly depending on the liquefaction conditions. The best stress–strain results were obtained for PUFs prepared using the polyol with lowest I_OH and water content (Young's modulus of 475.0 kPa, compressive stress (σ_10%) of 34.6 kPa and toughness of 7397.1 J m^?3). This PUF was thermally stable up to 200 °C and presented a glass transition temperature of around 27 °C. The results obtained demonstrate that these polyols from liquefied cork yield PUFs that are adequate materials for insulation applications. © 2014 Society of Chemical Industry     

Polyurethane foams derived from liquefied mountain pine beetle‐infested barks

In this study, lodgepole pine (Pinus contorta Dougl.) bark infested by the mountain pine beetles (Dendroctonus ponderosae hopkins) was liquefied using either polyethylene glycol (PEG) or polyethylene glycol/glycerol (PEG/G) as the solvent. It was found that the addition of glycerol to PEG reduced the residue ratio during bark liquefaction. The liquefied bark fraction obtained by using PEG/G had a slightly higher hydroxyl number than that obtained by using PEG. The residue from PEG/G liquefaction contained less lignin and more cellulose than the residue from PEG liquefaction. Various polyurethane foams containing liquefied bark fractions were made, and it was found that the weight ratios of liquefied bark to pMDI used in foam formulation and bark liquefaction solvents affected the density, gel content, thermal stability, mechanical properties, and the cell structure of the resulting foams. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Characterization of polyurethane foams prepared from liquefied sawdust by crude glycerol and polyethylene glycol

The aim of this study was to investigate polyurethane foams (PUF) properties obtained from crude glycerol (CG) and polyethylene glycol (PEG) based liquefaction of sawdust. The four types of foam were prepared by producing polyols from different weight loadings of PEG to CG as the liquefaction solvent. The produced polyurethane foams showed densities from 0.042 to 0.08 g/cm³ and compressive strengths from 200 to 311 kPa. The foams obtained from CG/PEG based liquefaction, had more uniform and regular cell structure than foams derived from liquefaction by CG. Also with the increasing percentage of PEG to CG in liquefaction, closed cell content of the synthesized foams increased and the size of cells decreased. The thermal conductivity of the produced foams was between 0.031 and 0.040 W/m K. Foams produced from liquefaction by binary solvent had lower thermal conductivity. However all foams showed approximately similar thermal degradation curves; maximum thermal decomposition temperature was seen for the foam produced from higher weight ratio of PEG to CG in liquefaction. PU foams produced from PEG/CG based liquefaction process had improved properties over from foams derived from sawdust liquefaction by CG.     

Polyurethane foams from alkaline lignin‐based polyether polyol

As a byproduct produced during biorefining, alkaline lignin (AL) possesses multiple benzene ring and phenol hydroxyl groups with high chemical reactivity, and is renewable and cheaper than petrochemical products. Here, AL was liquefied in polyethylene glycol‐400/glycerol and subsequently used to prepare polyurethane foams (PUFs). The results showed that the AL could be almost completely liquefied. The resulting lignin‐based polyether polyol (LPP) exhibited physicochemical properties similar to a commercial polyether polyol (PP). The PUFs made from LPP presented better thermal stability and higher compressive strength than those PUFs obtained from commercial PP, suggesting this could be a viable commercial application for AL. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43261.     

Water‐blown polyurethane/polyisocyanurate foams made from recycled polyethylene terephthalate and liquefied wood‐based polyester polyol

Depolymerized polyethylene terephthalate and liquefied wood polyesters can be used as a polyol for the production of polyurethane/polyisocyanurate foams. In this research, liquefied wood was synthesized by using a combination of diethylene glycol and glycerol and due to the possibility of using glycerol that is a by‐product in biodiesel production, our goal was to use as much glycerol in the liquefaction reagent as possible. We determined the properties of the polyols, properties of produced foams, and explained their correlation. Greater amount of glycerol in the liquefaction reagent resulted in higher OH number, molecular weight, functionality, and viscosity of the polyol, as well as in longer cream time and tack free time in foam preparation. Glass transition temperature, density, and water absorption of the foam increased with increasing amount of glycerol in liquefied wood. Compressive stress increased up to 30% of the glycerol in the reagent and then reduced, while thermal conductivity was not affected. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41522.     

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     

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     

Preparation of polyurethane foams using fractionated products in liquefied wood

Liquefaction of sawdust was studied using glycerol and methanol as mix solvents. A new bio‐polyol product consisting of high purity multi‐hydroxy compounds was obtained by precipitation of the hydrophobic organics from the liquefied product in an aqueous solution. As identified by GC‐MS, the dominate components in bio‐polyol were glycerol, glycerol derivatives, and multiple types of sugar derivatives. By using the mass ratio of m (sawdust) : m (glycerol) = 1 : 1, the total content of multi‐hydroxy compounds reached 90.84%. The hydroxyl number of the bio‐polyol was 1287 mgKOH/g with a rotational viscosity of 1270 cP. Preparation of polyurethane foams using bio‐polyol and isocyanate was also studied. Water was used as an environmental friendly blowing agent. The factors that influence the cell structure of foams (i.e., catalyst, dosage of blowing agent, and mass ratio of bio‐polyol to PEG‐400 were studied. The compressive strength of the synthesized foam was 150 Kpa, which met the requirement of Chinese specification for rigid foams. The synthesized foams were characterized by FTIR, SEM, and TG. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40096.     

Recent Advancement in Plant Oil Derived Polyol‐Based Polyurethane Foam for Future Perspective: A Review

Polyurethane foams (PUFs) are widely used materials because of their wide range of applications, particularly, thermal and sound insulation, mattresses, furniture, construction, cushioning, packaging, transportation of goods, etc. Recently, commercial PUF products fabricated from plant oil (PO)‐based polyols have gained increasing popularity, because of their low cost and eco‐friendly nature in comparison to petroleum‐based PUF. To date, insufficient reviews have been reported in the area of modification of plant oils for synthesizing polyol for foam synthesis. Due to abundant availability, low‐cost, and renewable nature of plant oils, they are being used as precursors for modern polyurethane industry use. There is a need for versatile and economical methods for conversion of plant oils such as castor oil (CO) and soybean oil (SO) into useful polyols for industry use. This review is an overview of the most recent advanced methods for the conversion of plant oils into polyol and further utilization of it for commercial PUF products. Since the last decade, many researchers have shown that plant‐polyol‐derived PUF can compete with conventional PUF. Practical Applications: Practical applications of the PO‐based polyurethane foams include thermal insulation, sound insulation, packaging, and waste water treatment.     

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     

Effect of auxiliary blowing agents on properties of rigid polyurethane foams based on liquefied products from peanut shell

The bio‐based rigid polyurethane (PU) foams were successfully prepared based on liquefied products from peanut shell with water as the blowing agent. The influence of reaction parameters on properties of rigid PU foams was investigated. Rigid PU foams showed excellent compressive strength and low shrinkage ratio, whereas their open‐cell ratio and water absorption were higher. Therefore, rigid PU foams were synthesized with petroleum ether, diethyl ether, and acetone as auxiliary blowing agents and their inner temperature, shrinkage performance, density, compressive strength, water absorption, and open‐cell ratio were determined. The results indicated that above rigid PU foams showed lower compressive strength than the original foam but their water absorption and close‐cell ratio were improved. Compared with the original foam, the highest inner temperature of rigid PU foams with petroleum ether, diethyl ether, and acetone as auxiliary blowing agents was reduced by 11, 19, and 23 °C, respectively. Typically, foams with petroleum ether as auxiliary blowing agent displayed better water absorption and swelling ratio in water and exhibited obvious improvement in close‐cell ratio. These foams were preferable for application in thermal insulation materials because of low thermal conductivity and better corrosion resistance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45582.     

Preparation and physico‐mechanical,thermal and acoustic properties of flexible polyurethane foams based on hydroxytelechelic natural rubber

Novel flexible polyurethane foams were successfully prepared from a renewable source, hydroxytelechelic natural rubber (HTNR) having different molecular weights (1000–3400 g mol^?1) and variation of epoxide contents (EHTNR, 0–35% epoxidation) by a one‐shot technique. The chemical and cell structures as well as physico‐mechanical, thermal, and acoustic properties were characterized and compared with commercial polyol analogs. The obtained HTNR based foams are open cell structures with cell dimensions between 0.38 and 0.47 mm. The HTNR1000 based foam exhibits better mechanical properties but lower elongation at break than those of commercial polyol analog. However, the HTNR3400 based foam shows the best elastic properties. In a series of EHTNR based foams, the tensile and compressive strengths show a tendency to increase with increasing epoxide content and amount of 1,4‐butanediol (BD). The HTNR based foams demonstrate better low temperature flexibility than that of the foam based on commercial polyol. Moreover, the HTNR based polyurethane foams was found to be an excellent absorber of acoustics. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

软段分子链结构对PUF性能的影响

通过将聚乙二醇(PEG)、聚己内酯(PCL)、聚乳酸(PLA)和聚四氢呋喃醚(PTMG)等不同特性的聚合物链段引入聚氨酯(PU)基体,制备了具有不同软段结构的聚氨酯泡沫塑料(PUF)。考察了不同软段分子链结构对PUF力学性能、热性能及在土壤中降解性能的影响。结果表明,随着软段中PEG或PLA含量的增加,PUF的拉伸强度下降;不同软段结构PUF的玻璃化转变温度顺序为:PTMG1000相似文献   

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。     

Biobased flexible polyurethane foams manufactured from lactide-based polyester-ether polyols for automotive applications

In this study, biobased polyester-ether polyols derived from meso-lactide and dimer acids were evaluated for flexible polyurethane foams (PUF) applications. Initially, the catalyst concentration was optimized for the biobased PUF containing 30% of biobased polyol (70% petroleum-based polyol). Then, the same formulation was used for biobased PUF synthesis containing 10%–40% of biobased polyols. The performance of biobased PUF was compared with the performance of the control foam made with 100% petroleum-based polyol. The characteristic times (cream, top of the cup, string gel, rise, tack-free) of biobased PUF were determined. The biobased PUF were evaluated for the mechanical (tensile and compressive) and morphological properties. As the wet compression set is important for automotive applications, it was measured for all biobased PUF. The thermal degradation behavior of biobased PUF was also evaluated and compared with the control foam. The effect of different hydroxyl and acid values of polyols on the mechanical properties of biobased PUF is also discussed. The miscibility of all components of PUF formulations is crucial in order to produce a foam with uniform properties. Thus, the miscibility of biobased polyols with commercial petroleum-based polyol was studied.     

Polyisobutylene-based urethane foams. II. Synthesis and properties of novel polyisobutylene-based flexible polyurethane foams

Novel polyisobutylene-based flexible polyurethane foams (PIB–PUF) have been prepared manually by the prepolymer method using three-arm star hydroxyl-terminated polyisobutylenes (PIB–triols) and toluene diisocyanate (TDI). Solvent extraction and IR spectroscopy of PIB–PUFs indicated essentially complete crosslinking. Conventional polyether-based polyrethane foams (PE–PUFs) and polybutadiene-based polyurethane foams (PBD–PUFs) have also been prepared by the same method and select physical-mechanical properties of all these urethane foams, such as tensile strength, elongation, resilience, water permeability, hot air stability, and hydrolytic stability, have been examined and compared. Although the density of PIB–PUF is lower than that of PE–PUF, its tensile strength is superior to the latter. Elongation of PIB–PUF is almost the same as those of the other foams. The PIB–PUF exhibits low resilience which indicates good damping properties. Due to the hydrophobicity of the soft segment, PIB–PUF exhibits very low water permeability. The hydrolytic and hot air stability of PIB–PUFs are outstanding. Attempts have been made to determine gas permeabilities; however, due to the open-cell nature of the foams, these studies could not be completed. The new PIB-based urethane foams combine excellent thermal, environmental, barrier, and mechanical properties, unmatched by conventional PUFs.     

Modification of tung oil–based polyurethane foam by anhydrides and inorganic content through esterification process

In this study, we have reported the synthesis of modified polyol from tung oil. The synthesis involves three steps: first, conversion of tung oil to hydroxylated tung oil by hydroxylation; second, alcoholysis with triethanolamine; and finally, the esterification of polyester polyol when reacted with phthalic anhydride (PA) or maleic anhydride (MA). Boric acid is also introduced into the polyol by chemical modification, which enhances the thermal properties of polyurethane foam (PUF). PUF is formulated by the reaction between polyol and isocyanate. A systematic comparison of flame retardancy and mechanical and thermal properties of modified PUF has been examined. The structural properties of modified polyol were characterized by Fourier transform infrared spectroscopy, proton NMR spectroscopy, and gel permeation chromatography, while the thermal and mechanical properties of the formulated PUF were studied by scanning electron microscopy, limiting oxygen index, differential scanning calorimetry, Izod impact, and flexural and compression strength. Thus PUF prepared from modified polyol with a proper distribution of soft and hard segments possesses better mechanical and thermal properties. The PA‐modified foams show better properties compared to unmodified and MA‐modified foams due to the aromaticity and crosslinking behavior of PA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45786.     

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     

Preparation and Characterization of Sustainable Polyurethane Foams from Soybean Oils

Polyol derived from soybean oil was made from crude soybean oil by epoxidization and hydroxylation. Soy-based polyurethane (PU) foams were prepared by the in-situ reaction of methylene diphenyl diisocyanate (MDI) polyurea prepolymer and soy-based polyol. A free-rise method was developed to prepare the sustainable PU foams for use in automotive and bedding cushions. In this study, three petroleum-based PU foams were compared with two soy-based PU foams in terms of their foam characterizations and properties. Soy-based PU foams were made with soy-based polyols with different hydroxyl values. Soy-based PU foams had higher T _g (glass transition temperature) and worse cryogenic properties than petroleum-based PU foams. Bio-foams had lower thermal degradation temperatures in the urethane degradation due to natural molecular chains with lower thermal stability than petroleum skeletons. However, these foams had good thermal degradation at a high temperature stage because of MDI polyurea prepolymer, which had superior thermal stability than toluene diisocyanate adducts in petroleum-based PU foams. In addition, soy-based polyol, with high hydroxyl value, contributed PU foam with superior tensile and higher elongation, but lower compressive strength and modulus. Nonetheless, bio-foam made with high hydroxyl valued soy-based polyol had smaller and better distributed cell size than that using low hydroxyl soy-based polyol. Soy-based polyol with high hydroxyl value also contributed the bio-foam with thinner cell walls compared to that with low hydroxyl value, whereas, petroleum-based PU foams had no variations in cell thickness and cell distributions.     

Influences of copolymer polyol on structural and viscoelastic properties in molded flexible polyurethane foams

In this study, the viscoelastic and morphological properties of molded foams were investigated to determine the influence of the presence or absence of reinforcing particulate copolymer polyols (CPP). The molded foams were based on toluene diisocyanate (TDI) and glycerol‐initiated ethylene‐oxide endcapped polypropylene oxide and, in most samples, some amount of copolymer polyol. Two series of foams were studied. In Series 1, as CPP is added to the formulation, the amount of TDI fed is kept constant. This results in a constant amount of hard‐segment content as the filler in the system displaces, by weight, the polyether polyol in the foam, and it increases the hard segment to soft segment ratio (HS/SS). In Series 2, the amount of hard‐segment material is proportionally decreased as CPP is added, resulting in a constant HS/SS ratio. Structural investigations of the foams displayed rather similar textures. The cellular structures of a CPP‐containing foam was very similar to a foam lacking the copolymer polyols. Transmission electron microscopy revealed that the CPP particles were well dispersed and that they possessed significant rigidity even at high temperature and under high compression. Although all of the foams were microphase‐separated, they varied slightly in that the copolymer polyol containing foams exhibited higher weight fractions of extractables in both Series 1 and Series 2. This suggests that not all of the CPP material is covalently bonded into the polyol matrix. It was found that temperatures above ambient as well as humidity plasticized the viscoelastic behavior of all the molded foams evaluated. It was also found that the copolymer polyol particles, as added to the molded foams of Series 1, increased load‐bearing capabilities but had a negative effect on the stress relaxation, creep, and compression set properties. In particular, the viscoelastic properties of the CPP‐containing foam were distinctly more time‐dependent than those of the foam lacking these particles. However, the Series 2 foams show that most of these effects are a result of the increased HS/SS ratio and not a result of the CPP particulate. It was shown that adding CPP while maintaining a constant HS/SS ratio improves percent load loss and load bearing under high‐humidity conditions, two important properties in flexible polyurethane foams. Finally, it was shown that at high temperatures (ca. 100°C), an additional relaxation mechanism occurs which cannot be attributed to changes in the HS/SS ratio, but must be a result of the CPP components themselves. This additional mechanism results in higher rates of load relaxation and creep in foams containing CPP at high temperatures for foams of both series. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 766–786, 2000