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     

Flexible polyurethane foams synthesized employing recovered polyols from glycolysis: Physical and structural properties

Polyurethane (PU) is one of the most important polymers with a global production of 17.565 million tons, which makes its recycling an urgent task. Besides, the main goal of PU recycling is to recover constituent polyol as a valuable raw material that allows to obtain new PU with suitable properties. Split‐phase glycolysis can be considered the most interesting PU recycling process since provides high‐quality recovered products in terms of polyol purity. The aim of this work was to evaluate several recovered polyols as replacement of the raw flexible polyether polyol in the synthesis of new flexible PU foams. These recovered polyols come from the split‐phase glycolysis of different types of PU foams and employing as cleavage agents diethylene glycol or crude glycerol (biodiesel byproduct). The influence of the foam waste type and of the cleavage agent on the foams properties was analyzed. The recovered polyols were evaluated by performing several foaming tests according to the method of free expansion foaming of conventional flexible foam. Synthesized flexible foams containing different proportions of recovered polyols were characterized by means of scanning electron microscopy, density and tensile properties; obtaining similar and sometimes even better values compared to the foams manufactured from commercial polyols. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45087.     

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     

Recycling waste tires: Generation of functional oligomers and description of their use in the synthesis of polyurethane foams

The accumulation of waste tires is a big environmental issue and different approaches have been proposed to eliminate or recycle this material in the end of its life. However, each approach presents drawbacks and the need for a real valorization of the tire components is still of interest. In a previous work by our group, it was demonstrated that an oxidative cleavage of the polyisoprene and polybutadiene chains contained in the tires led to the synthesis of telechelic oligomers with a ketone and an aldehyde at the chains ends. In this work, the process to obtain these carbonyl oligomers has been improved, with a particular concern for the elimination of the maximum amount of carbon black. The carbonyl oligomers can be easily reduced to hydroxyl oligomers and, in order to show the benefit of the recycling process, an application of these hydroxyl oligomers is reported: they have been used as building blocks (polyol precursors) in the preparation of polyurethane (PU) foams. The morphology of the resulting foams was observed by scanning electron microscopy technique: the images showed an almost open‐cell structure and a homogeneous distribution of cell size. Mechanical (tensile and compressive strength) and thermal properties of PU foams synthesized from “recycled” oligomers from waste tires were compared to those of PU foams synthesized from analogue oligomers derived from natural rubber. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41326.     

Processing and properties of an ethylene–vinyl acetate blend foam incorporating ethylene–vinyl acetate and polyurethane waste foams

Waste polyurethane foam (w‐PU) and waste ethylene–vinyl acetate foam (w‐EVA) were used as fillers for the production of an ethylene–vinyl acetate (EVA) blend foam. Two different foaming techniques (single‐stage and heat–chill processes) were used for this purpose. The waste foam concentration was varied up to 30 wt % of the original EVA. The physical, mechanical, and morphological properties of the filled foam were studied. The single‐stage process produced blend foams with a lower density and a greater cell size than the foams obtained by the heat–chill process. The density and compression strength of the blend foam increased as the percentage of w‐PU foam increased. However, for the w‐EVA/EVA blend foams, the addition of w‐EVA foam did not significantly affect the density or compression strength compared to the original EVA foams. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44708.     

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.     

Polyurethane Foam Wastes Recycling under Microwave Irradiation

Microwave-assisted (MW-assisted) glycolysis of waste-flexible polyurethane (PU) foams using pentaerythritol in combination with glycerin and sodium hydroxide as a PU bond degradation reagent is reported. Split phases appeared after complete foam digestion. The upper phase contained recycled polyol, and the lower phase was a brown liquid with highly functionalized oligomers, amines and unreacted degradation reagents and showed potential for application in rigid polyurethane foam formulation. Our studies showed the dependence of recovered polyol assay to the additional MW irradiation and amine-free polyol were achieved in high yields and purities.     

Role of additives in fabrication of soy-based rigid polyurethane foam for structural and thermal insulation applications

Environmental concerns continue to pose the challenge to replace petroleum-based products with renewable ones completely or at least partially while maintaining comparable properties. Herein, rigid polyurethane (PU) foams were prepared using soy-based polyol for structural and thermal insulation applications. Cell size, density, thermal resistivity, and compression force deflection (CFD) values were evaluated and compared with that of petroleum-based PU foam Baydur 683. The roles of different additives, that is, catalyst, blowing agent, surfactants, and different functionalities of polyol on the properties of fabricated foam were also investigated. For this study, dibutyltin dilaurate was employed as catalyst and water as environment friendly blowing agent. Their competitive effect on density and cell size of the PU foams were evaluated. Five different silicone-based surfactants were employed to study the effect of surface tension on cell size of foam. It was also found that 5 g of surfactant per 100 g of polyol produced a foam with minimum surface tension and highest thermal resistivity (R value: 26.11 m²·K/W). However, CFD values were compromised for higher surfactant loading. Additionally, blending of 5 g of higher functionality soy-based polyol improved the CFD values to 328.19 kPa, which was comparable to that of petroleum-based foam Baydur 683.     

Effect of the Additive Fire Retardants on the Properties of Rigid Polyurethane Foams,Obtained Using Hydroxyethyl Derivatives of Oxamide and Polymeric 4,4′-diphenylmethane Diisocyanate

The present work investigates the effect of polyol structure and physical addition of boric acid and N,N′-bis(2-hydroxyethyl)oxamide on the properties of rigid polyurethane foams. The product of hydroxyalkylation of oxamide by ethylene carbonate has been used as a polyol component. The new polyol has been foamed using polymeric 4,4′-diphenylmethane diisocyanate, water, and triethylamine. To decrease the flammability of the foams, boric acid, and N,N′-bis(2-hydroxyethyl)oxamide were used as the additive flame retardants. It has been found, that chemical modification of the foam structure by means of oxamide groups decreases their flammability only to a small extent, whereas physical addition of N,N′-bis(2-hydroxyethyl)oxamide does not influence the flammability. However, the addition of boric acid to the foam composition resulted in a distinct decrease of foam flammability, according to the amount of boric acid added. All the foams, modified and nonmodified by boron, have been categorized into flammability class HF-1, according to the applicable standard. The introduction of flame retardants had its impact on the properties of polyurethane foams obtained, as described in this work.     

Polyurethane foams from chlorinated and non‐chlorinated metathesis modified canola oil polyols

The product of 1‐butene metathesis of canola triacylglycerol (CMTAG), with shortened structures, terminal double bonds (50% of the total), and oligomers (40% dimer and trimer, and 10% higher oligomers) was used to synthesize novel polyols and polyurethane foams. A non‐chlorinated (Pol‐1) and a chlorinated polyol (Pol‐2) having OH value (170 and 190 mg KOH/g, respectively) were synthesized from CMTAG by epoxidation followed by hydroxylation, and epoxidation followed by hydrogenation, respectively. Both polyols remained liquid below ambient temperature and demonstrated physical characteristics such as viscosity which allowed for the facile preparation of polyurethane foams. The foam obtained with Pol‐1 was relatively soft (～0.32 MPa at 10% strain) and very flexible (recovery ～90%); whereas, the foam obtained with Pol‐2 was semi‐rigid (～1.1 MPa at 10% strain and recovery of 64%). The higher strength and rigidity of Pol‐2 foam compared to Pol‐1 foam is chiefly attributable to the effect of the bulky chlorines on the crosslink density. Importantly, this work highlights that one can improve and control jointly the mechanical properties and deformation recovery ability of bio‐based foams by combining primary functional groups, oligomers, and high molar volume molecules in the polyols. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46616.     

Kraft Lignin-Based Rigid Polyurethane Foam

Abstract

Kraft pine lignin was derivatized to a liquid polyol through oxypropylation. The resulting polyol was characterized by GPC, FT-IR, H¹, C¹³, and P³¹ NMR and was compared to commercial polyols in view of the mechanical property of the corresponding rigid polyurethane foams for the first time. A series of lignin-based PU was synthesized by replacing varying weight percentages of the amount of sucrose polyol and glycerol polyol, two commonly used commercial polyols employed in the control foam preparation. All foams had a low density of ～30 Kg m^?3 and showed typical linkages of PU in the FT-IR spectra. The diameter of closed-cells was ～650 μm for most of the foams as revealed by SEM images. The optimal compressive property of rigid PU foams was obtained using lignin polyol without the addition of any other commercial polyols primarily attributed to the rigidity of lignin aromatic structure and the high functionality of lignin hydroxyl groups.     

New polyol for production of rigid polyurethane‐polyisocyanurate foams,Part 2: Preparation of rigid polyurethane‐polyisocyanurate foams with the new polyol

The method of preparation, determination of foaming parameters, and methods for the determination of physicochemical properties of polyurethane‐polyisocyanurate (PUR‐PIR) foams prepared with the use of N,N′‐di(methyleneoxy‐2‐hydroxyethyl)urea and boric acid derivatives are presented in this paper. It was found that application of the borate as a polyol component and simultaneously as a flame retardant in the recipe for production of PUR‐PIR foams was very favorable. The foams prepared were characterized by reduced brittleness, higher compressive strength and content of closed cells, as well as considerably lower flammability in comparison with standard foam. The results show that the new polyol prepared on the basis of N,N′‐di(methyleneoxy‐2‐hydroxyethyl)urea and boric acid can be applied for production of rigid PUR‐PIR foams, and it improves their physicochemical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Recycling of off‐grade pet via partial alcoholysis to synthesize functionalized pet oligomer nanocomposites

Off‐grade poly(ethylene terephthalate) (PET) of industrial manufacturers was partially depolymerized using excess ethylene glycol in the presence of manganese acetate as a transesterification catalyst to synthesize PET oligomers. Influences of reaction time, Ethylene Glycol (EG)/PET molar ratio, catalyst concentrations, and particle size of off‐grade PET on yield of partial glycolysis reaction were investigated based on Box–Behnken's design of experiment. Thermal analyses of glycolyzed products are examined by differential scanning calorimetry. The optimum samples were also well‐characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy (¹H‐NMR and ¹³C‐NMR). The optimal conditions to synthesize PET oligomer (melting point of about 180°C) for a 120‐min glycolysis reaction time were EG/PET molar ratio of 2 with no catalyst using granule‐shaped PET. The same results were obtained for a 60‐min glycolysis reaction time, including EG/PET molar ratio of 1 with the weight ratio (catalyst to PET) of 0.5% using average particle size of PET. Then, maleated PET as a compatibilizer for preparing PET nanocomposites was produced via reaction between maleic anhydride/phthalic anhydride composition and optimized PET oligomers based on central composite design of experiment. The combination of reaction time of 106 min and PhA/MA molar ratio of 0.85 gave the best results based on d‐spacing and peak shift of nanocomposite samples. Hence, melt mixing of maleated PET with organoclay produced a good intercalation of layered silicate and good dispersion of clay in maleated PET matrix. Analysis of variance (ANOVA) was studied for both glycolyzed products and functionalized PET oligomers. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Rapeseed oil‐based polyurethane foams modified with glycerol and cellulose micro/nanocrystals

A rapeseed oil‐based polyol (ROPO) was synthesized using chemical modification of the rapeseed oil (RO) by epoxidation reaction followed by oxirane ring‐opening with diethylene glycol. The ROPO was used in the formulation of low‐density green polyurethane (PU) foams. The use of glycerol as hydroxyl component, water as a reactive blowing agent and micro/nanocellulose (MNC) as a reinforcement increases the content of natural components in the formulations with important effects on the final foam properties. The ROPO and their intermediate products are characterized by analytical techniques and FTIR spectroscopy, while the final PU foams are characterized by morphological and mechanical analysis. The results show that the addition of glycerol increases the modulus and yield stress. The incorporation of MNC in small amounts is enough to increase the modulus at low temperatures. Both modifiers cause an increase in water absorption and the fragility of the cell walls, reflected in the micrographs of the foams. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41602.     

Polyurethane foams made from liquefied bark‐based polyols

Liquefaction is known to be an effective method for converting biomass into a polyol. However, the relationships between bark liquefaction conditions and properties of the resulting foams are unclear. In this study, polyurethane foams (PUF) were made using bark‐based polyols obtained through liquefaction reactions of bark at two different temperatures (90 and 130°C). Through systematic characterization of the PUFs the influence of the liquefied bark and liquefaction conditions on foam properties could be observed. The bark‐based foams had similar foaming kinetics, thermal stability, and glass transition temperatures compared with the PEG‐based control foam. The bark‐based PUF from the polyol obtained at the higher liquefaction temperature showed comparable specific compressive strength to the PEG‐based control foam. Lastly, both bark foams exhibited a high amount of open‐cell content, with the foam made from the lower temperature liquefied polyol having poor cell morphology. This deviation from the controls in the open‐cell content may explain the lower modulus values observed in the bark PUFs due to the lack of cell membrane elastic stretching as a strengthening mechanism. These results demonstrated the influence of the bark liquefaction conditions on foam properties, thereby providing a better fundamental understanding for the practical application of bark‐based PUFs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40599.     

Fabrication,characterization and low‐velocity impact testing of hybrid sandwich composites with polyurethane/layered silicate foam cores

A series of nanophased hybrid sandwich composites based on polyurethane/montmorillonite (PU/MMT) has been fabricated and characterized. Polyaddition reaction of the polyol premix with 4,4′‐diphenylmethane diisocyanate was applied to obtain nanophased PU foams, which were then used for fabrication of sandwich panels. It has been found that the incorporation of MMT resulted in higher number of PU cells with smaller dimensions and higher anisotropy index (cross sections RI and RII). The obtained materials exhibited improved parameters in terms of thermal insulation properties. The results also show that nanophased sandwich structures are capable of withstanding higher peak loads than those made of neat PU foam cores when subject to low‐velocity impact despite their lower density than that of neat PU foams. This is especially significant for multi‐impact recurrences within the threshold loads and energies studied. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

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.     

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     

Highly flame‐retardant polyurethane foam based on reactive phosphorus polyol and limonene‐based polyol

Polyurethane foams are in general flammable and their flammability can be controlled by adding flame‐retardant (FR) materials. Reactive FR have the advantage of making strong bond within the polyurethane chains to provide excellent FR over time without compromising physico‐mechanical properties. Here, phenyl phosphonic acid and propylene oxide‐based reactive FR polyol was synthesized and used along with limonene based polyol for preparation of FR polyurethanes. All the obtained foams showed higher closed cell content (above 96%). By the addition of FR–polyol, the compressive strength of the foams showed 160% increment which could be due to reactive nature of FR–polyol. Moreover, 1.5 wt % of phosphorus (P) content reduced the self‐extinguishing time of the foam from 81 (28% weight loss) to 11.2 s (weight loss of 9.8%). Cone test showed 68.6% reduction in peak heat release rate along with 23.4% reduction in thermal heat release. The change in char structure of carbon after burning was analyzed using Raman spectra which, suggests increment in the graphitic phase of the carbon over increased concentration of phosphorus. It can be concluded from this study that phosphorous based polyol could be blended with bio‐based polyols to prepare highly FR and superior physico‐mechanical rigid polyurethane foams. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46224.     

Highly flame‐retardant bio‐based polyurethanes using novel reactive polyols

Poor flame retardancy of polyurethanes (PU) is a global issue as it limits their applications particularly in construction, automobile, and household appliances industries. The global challenge of high flammability of PU can be addressed by incorporating flame‐retardant materials. However, additive flame‐retardants are non‐compatible and depreciate the properties of PU. Hence, reactive flame‐retardants (RFR) based on aliphatic (Ali‐1 and Ali‐2) and aromatic (Ar‐1 and Ar‐2) structured bromine compounds were synthesized and used to prepare bio‐based PU using limonene dimercaptan. The aromatic bromine containing foams showed higher close cell content (average 97 and 100%) and compressive strength (230 and 325 kPa) to that of aliphatic bromine containing foams. Similar behavior was observed for a horizontal burning test where with a low concentration of bromine (5 wt %) in the foams for Ar‐1 and Ar‐2 displayed a burning time of 12.5 and 11.8 s while, Ali‐1 and Ali‐2 displayed burning time of 25.7 and 37 s, respectively. Neat foam showed a burning time of 74 s. The percentage weight loss for neat PU foam was 26.5%, while foams containing 5 wt % bromine in Ali‐1, Ali‐2, Ar‐1, and Ar‐2 foams displayed weight loss of 11.3, 14, 7.9, and 14%, respectively. Our results suggest that flame retardant PU foams could be prepared effectively by using RFR materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46027.