Solvent-blown rigid urethane foams from castor-based polyols

The preparation of trichlorofluoromethane-blown rigid urethane foams using toluenediisocyanate and castor oil-derived polyols was investigated. The castor-based polyols included castor oil, hydroxylated castor oil, technical glycerol-, penta-erythritol-, and sorbitol monoricinoleates, and N,N-bis(2-hydroxyethyl) ricinoleamide. The last of these yielded the best foams when used as the sole polyol component added to the prepolymer. However better foams were obtained by using, as the polyol component, a mixture of a castor oil-derived polyol and a lower-molecular-weight polyol with a higher hydroxyl content. These polyol mixtures yielded more highly cross-linked polymers and hence foams with higher compressive strengths and less tendency to shrink after foaming. The effect of catalyst, silicone surfactant, and trichlorofluoromethane content was also investigated. An empirical relationship between density and compressive strength in a given foam system was derived. Presented at the fall meeting, American Oil Chemists' Society, New York, October 17–19, 1960. A laboratory of the Western Utilization Research and Development Division. Agricultural Research Service, U.S. Department of Agriculture.     

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     

溴化蓖麻油多元醇合成及其制备的阻燃聚氨酯硬泡性能

采用可再生的醇解蓖麻油多元醇为原料,与液溴进行加成反应制备溴化蓖麻油多元醇,通过红外光谱证实发生了溴化反应,并测定了产物粘度、羟值、酸值.通过发泡实验和氧指数、烟密度、水平燃烧等测试手段,考察了溴化蓖麻油基聚氨酯硬泡发泡参数和阻燃性质,并与工业级阻燃荆雅保RB-79制备的聚氨酯硬泡进行比较.结果表明,由溴化蓖麻油多元醇...     

Polyurethane foams from hydroxymethylated fatty diethanolamides

Satisfactory rigid polyurethane foams were prepared from diethanolamides of hydroxymethylated oleate, linseed oil, safflower oil and their methyl esters. These foams were improved when the fatty polyols were blended with a commercial, low molecular weight polyol. National Flaxseed Processors Association Fellow. ARS, USDA.     

Solvent-blown,rigid urethane foams from low cost castor oil-polyol mixtures

The preparation of solvent-blown rigid urethane foams from low cost castor oil-polyol mixtures was investigated. Solutions of triisopropanolamine, and of mixtures of triisopropanolamine and triethanolamine in castor oil, were used as the polyol component of these foams. Foams were prepared by reacting these polyol mixtures, in the presence of catalyst, surfactant, and trichlorofluoromethane, with prepolymers prepared from toluenediisocyanate and certain polyether polyols or mixtures of these polyether polyols with castor oil. The effect of polyol and prepolymer composition and blowing agent concentration on such foam properties as density and compressive strength was investigated. The properties of the castor oil-based foams were comparable to those of foams obtained from more costly polyols. Presented at the Spring Meeting of the American Oil Chemists' Society, St. Louis, Missouri, May 1–3, 1961. A laboratory of the Western Utilization Researchand Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Physical Properties of Polyurethanes Produced from Polyols from Seed Oils: II. Foams

Rigid polyurethane (PU) foams were prepared using three North American seed oil starting materials. Polyol with terminal primary hydroxyl groups synthesized from canola oil by ozonolysis and hydrogenation based technology, commercially available soybean based polyol and crude castor oil were reacted with aromatic diphenylmethane diisocyanate to prepare the foams. Their physical and thermal properties were studied and compared using dynamic mechanical analysis and thermogravimetric analysis techniques, and their cellular structures were investigated by scanning electron microscope. The chemical diversity of the starting materials allowed the evaluation of the effect of dangling chain on the properties of the foams. The reactivity of soybean oil-derived polyols and of unrefined crude castor oil were found to be lower than that of the canola based polyol as shown by their processing parameters (cream, rising and gel times) and FTIR. Canola-PU foam demonstrated better compressive properties than Soybean-PU foam but less than Castor-PU foam. The differences in performance were found to be related to the differences in the number and position of OH-groups and dangling chains in the starting materials, and to the differences in cellular structure.     

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.     

Rigid urethane foams from hydroxymethylated linseed oil and polyol esters

Rigid urethane foams were prepared from hydroxymethylated linseed oil and its esters of glycerol, trimethylolpropane and pentaerythritol. These polyols were made by selective hydroformylation with a rhodium-triphenylphosphine catalyst followed by catalytic hydrogenation with Raney nickel. Although the hydroxymethylated linseed monoglyceride by itself yielded a satisfactory foam, better foams were made from all hydroxymethylated linseed derivatives when blended with a low-molecular weight commercial polyol. Linseed-derived foams were compared with foams from equivalent formulations of hydroxymethylated monoolein and castor oil. Hydroxymethylated products yielded polyurethane foams meeting the requirements of commercial products with respect to density, compressive strength and dimensional stability. National Flaxseed Processors Association Fellow. N. Market. Nutr. Res. Div., ARS, USDA.     

Effect of vegetable‐based polyols in unimodal glass‐transition polyurethane slabstock viscoelastic foams and some guidance for the control of their structure–property behavior. I

We investigated the synthesis and structure–property behaviors of two types of vegetable‐oil polyols (soy oil and castor oil) and their use in viscoelastic (VE) polyurethane foams (PUFs). This article is the first in a two‐part series. In this initial part, we principally address the dynamic mechanical analysis (DMA) behavior of these foams in conjunction with information on the cellular morphology, sol fraction, and rise and reaction temperature profile behavior (the latter two parameters were determined during the foaming process). Particular emphasis is placed on the DMA damping characteristics, which represent one of the most critical parameters in the application of VE PUFs. It is also shown that the damping characteristics could be modified in such foams by the variation of the isocyanate/hydroxyl (×100) index, the addition of plasticizer, and in the case of soy polyols, the soy content. The frequency dependence of the VE PUFs is also briefly addressed. In the second article in this series, which directly follows this article, we further address the details of other relevant physical properties of these same foams in view of their applied nature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of waterborne polyurethane/silica hybrid dispersions from castor oil polyols obtained by glycolysis poly(ethylene terephthalate) waste

Castor oil polyols (COLs) have been synthesized from glycolyzed oligoester polyol in order to produce waterborne polyurethane (WPU)/silica hybrid dispersions. Soft drinks poly(ethylene terephthalate) (PET) bottles were depolymerized by glycolysis with different molar ratio of poly(ethylene glycol) ( PEG 400), in the presence of zinc acetate as catalyst. The obtained glycolyzed products were reacted with castor oil (CO) to attain castor oil polyols by the process of transesterification. Five castor oil polyols were used with hydroxyl values of 255, 275, 326, 366 and 426 mg KOH g⁻¹. Several castor oil-based, polyurethane/silica hybrid dispersions having soft segment content of 39.6% to 28.2% and two concentrations of SiO₂ nanoparticles (0.5 and 1.0) have been prepared.The incorporation effect of SiO₂ nanoparticles into the PU matrix and the hydroxyl functionality of the COLs on the thermal and mechanical properties of resulting polyurethane films has been examined by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TG) and measurement of the mechanical properties. The degree of phase separation (DPS) between oxide nanoparticles and hard segment, and particle size in the polyurethane, depends to some extent on nanosilica content and the hydroxyl functionality of the polyols employed in the polyurethane preparation process.Thermal stability of obtained hybrid materials depends on the hydroxyl functionality of the COLs and nanosilica content. The T_10% and T_50% (the temperature where 10 and 50% weight loss occurred) of WPU films decreased with the rise of OH functionality of castor oil polyols, caused by the increase of hard segment content. Glass transition temperature increased with increasing OH functionality and SiO₂ content. The hardness, adhesion and gloss quality of the polyurethane films were also determined with a view to assessing the effect of mole ratios of PET to glycol in glycolyzed products, the hydroxyl functionality and the SiO₂ content.     

Castor polyols for urethane foams

Summary A systematic investigation of some 21 castor polyols as base materials for preparing urethane foams was carried out. Prepolymers were prepared both from individual castor polyols and from mixtures of them with an anhydrous castor oil. Foams formed from these prepolymers were checked for shrinkage on cure, density, and modulus. From the wide range of results obtained it is evident that castor polyols can serve as effective urethane components. Aside from serving as major polyols for reaction with di-isocyanates, they can also be used as modifying polyols a) to speed up prepolymer preparation, b) to adjust prepolymer viscosity to any required degree, c) to minimize loss of modulus on humid aging, and as cross-linking centers with negligible loss of foam modulus. Details covering the preparation of a nonshrinking, semi-rigid, light-weight urethane foam based on an 85% anhydrous castor oil/15% epoxidized castor oil mix are outlined in the article. Presented at the Spring Meeting, American Oil Chemists' Society, Memphis, Tenn., April 20–23, 1958.     

Urethane foams from animal fats: VIII. Properties of foams from epoxidized tallow trimethylolpropane polyols

Polyols made by reacting trimethylolpropane with epoxidized tallow were converted to urethane foams by reaction with a polymethylene polyphenylisocyanate in the presence of fluorotrichloromethane. Adjusted with triisopropanolamine or an oxypropylated triamine to hydroxyl equivalent of either 100 or 120, the polyols yielded rigid foams of density 1.5–2.0 lb/ft³, open cell content 15–19%, and compressive strength 34–49 psi. These values were superior to those of similar foams from hydrated epoxidized tallow. Polyols made from epoxidized tallow-trimethylolpropane-HBr and adjusted to equivalent wt of 100 and 120 by triisopropanolamine gave foams whose small-scale flammability test samples burned less than 20% of their length. At hydroxyl equivalent 100, foams had density 1.6–1.8, open cell content 20–21%, and compressive strength 34–39 psi; in flammability tests burned <20% of length. The present foams were stronger than those made earlier from solvent-purified hydroxybrominated tallow. Formulation with half the normal amount of freon gave foams of higher compressive strength but lower flame resistance.     

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     

蓖麻油聚醚多元醇在聚氨酯软泡中的应用

利用双金属催化剂(DMC)制备了相对分子质量在2000～5600之间的聚氨酯(PU)软泡用蓖麻油聚醚多元醇,并通过发泡实验与常用软泡聚醚多元醇H-330进行了性能比较。结果表明,相对分子质量2000的蓖麻油聚醚多元醇制备的泡沫拉伸强度、伸长率和压陷硬度等均优于H-330聚醚,表明蓖麻油聚醚多元醇完全可以取代普通聚醚多元醇用于普通软泡生产。     

The preparation and properties of some urethane foams from castor oil and elaidinized castor oil

Summary The preparation and properties of two series of castor oil urethane foams, one from castor oil and the other from elaidinized castor oil, were investigated. The first series of foams was made from prepolymers containing 60% of castor oil prepared at increasing temperature levels to vary the degree of crosslinking in the final foams. These foams had lower tensile strengths than observed for a previously prepared foam of 60% castor oil and did not show significant differences in water resistance as crosslinking varied. They were increased nearly 100% in compressive strength with increased crosslinking and had very good shrinkage characteristics as values of only 1 to 2% were obtained. A second series of foams was prepared from 50, 60, 70, and 80% of elaidinized castor oil to compare with foams from a similar series from castor oil. This series of foams of 50 to 80% elaidinized castor oil contents was similar in density (1.7 to 6.7 lbs./cu. ft.), had improved shrinkage characteristics (11, 1, 3, and 4%, respectively), showed increased compressive and tensile strengths (up to 12.1 p.s.i. at 50% compression modulus and 34.7 p.s.i. ultimate tensile for the 60% foam formulation), and had better water-resistance properties (411 to 155%vs. 515 to 170% water absorption) than the analogous foams from castor oil. In general, humid aging only slightly affected the values obtained for the foams and was significant in only a few instances,e.g., decreased tensile in the elaidinized castor oil series. Thus increasing crosslinks in the foam apparently did not improve water resistance but did improve shrinkage characteristics in addition to some increased strength properties, as would be anticipated. Foams from elaidinized castor oil, while similar in density and foaming characteristics to analogous foams from castor oil, exhibited less shrinkage and improved water-resistance. Presented at the 50th Annual Meeting of the American Oil Chemists' Society, New Orleans, La., April 20–22, 1959. Ono of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

可再生聚酯多元醇的合成及其在聚氨酯材料中的应用

采用油酸为主要原料合成了羟值为236mgKOH／g、酸值为2．8mgKOH／g的可再生聚酯多元醇,并以此聚酯多元醇为原料制备了聚氨酯硬质泡沫。研究了该聚酯多元醇用量对泡沫发泡和力学性能的影响。结果表明,随着聚酯多元醇加入量的增加,形成聚氨酯硬质泡沫的反应速度增加;与纯聚醚多元醇制备的聚氨酯硬质泡沫相比,加入20％～30％的该聚酯多元醇制备的聚氨酯泡沫的尺寸稳定性和压缩强度增加。     

Synthesis of polymeric dyes based on self-colored network of castor oil-based waterborne polyurethane

The development of vegetable oil-based polymers was particularly suitable for the era of increasingly scarce petroleum. Self-colored castor oil-based waterborne polyurethanes (PUs) were successfully synthesized based on castor oil and 1-amino-4-hydroxy-2-(6-hydroxyhexyl) anthraquinone (DR) as polyols. The UV–Vis spectrum showed that the addition of carboxylic acid groups make the spectrum of the PU produce the hyperchromic effect under alkaline conditions. Castor oil-based waterborne colored PUs possessed excellent stability under weak alkaline conditions. The connection of castor oil caused the PU to constitute soft polymer networks. PU coatings on cotton fabrics possessed excellent color properties. The urethane groups in the PUs formed hydrogen bonds with the hydroxyl groups on the cotton fibers and the polymer network structure formed by the PU coating itself made the color fastness of the cotton coatings reached grade 5. With the increase of castor oil content, the degradation rate of castor oil-based waterborne colored PU increased from 3.45% to 3.65%. This work provides a way to impart excellent color properties and fastness to PU coatings by inserting dye molecules and vegetable oils into the PU macromolecular chain.     

Rigid urethane foams from hydroxymethylated castor oil,safflower oil,oleic safflower oil,and polyol esters of castor acids

Castor, safflower, and oleic safflower oil derivatives with enhanced reactivity and hydroxyl group content were prepared by hydroformylation with a rhodium-triphenylphosphine catalyst, followed by hydrogenation. Rigid urethane foams prepared from these hydroxymethylated derivatives had excellent compressive strengths, closed cell contents, and dimensional stability. Best properties were obtained from hydroxymethylated polyol esters of castor acids.     

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.     

Solvent‐free synthesis of polyols from 1‐butene metathesized palm oil for use in polyurethane foams

Green Polyols were synthesized from a 1‐butene cross metathesized palm oil (PMTAG) using a green, solvent free epoxidation and hydroxylation pathway. The synthetic strategy was adapted to control the degree of double bond epoxidation and ultimately the hydroxyl value of the polyols. The polyols comprised diol and tetrol monomers with terminal hydroxyl groups content as high as ～18 mol %, and achieved hydroxyl values between 83 and 119 mg KOH g^?1. Functional Rigid and highly flexible foams were prepared from two designer Green Polyols. The foams presented a high thermal stability (T_on of degradation of ～270 °C), suitable glass transition temperatures (～?12 °C and ～50 °C) and compressive strength (0.21 MPa at 10% strain and ～1 MPa at 10% strain for the flexible and rigid foams, respectively) which are superior to existing lipid‐based counterparts. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43509.