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.     

Rigid urethane foams from blown castor oils

Solvent-blown rigid urethane foams prepared from a low-cost polyol mixture composed of raw castor oil and triisopropanolamine have been described. Foams with higher compressive strengths can be obtained by substituting oxidized (blown) castor oil for the raw castor oil in formulations of this type. The properties of rigid foams prepared from several commercial blown castor oils are described. The properties of these foams are correlated with the degree of oxidation of the blown oils used, as indicated by their oxygen content, density, viscosity, and refractive index. Removal of acid from blown oils having high acid values has no significant effect on the compressive strength of foams prepared from these oils. When blown castor oil is used instead of raw castor oil, less isocyanate is required to produce a urethane foam of specified density and compressive strength. Presented at the AOCS meeting in Toronto, Canada, 1962. A laboratory of the W. Utiliz. Res. & Dev. Div., ARS, U.S.D.A.     

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.     

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.     

Simulation of liquid physical blowing agents for forming rigid urethane foams

A computer‐based simulation for rigid polyurethane foam‐forming reactions was compared with experimental data for six blowing agents including methyl formate and C5‐C6 hydrocarbons. Evaporation of blowing agent was modeled as an overall mass transfer coefficient times the difference in activity of the blowing agent in the gas foam cells versus the resin walls of the cells. Successful modeling hinged upon use of a mass transfer coefficient that decreased to near zero as the foam resin approached its gel point. Modeling on density agreed with experimental measurements. The fitted parameters allowed for interpretations of the final disposition of the blowing agent, especially, if the blowing agent successfully led to larger foam cells versus being entrapped in the resin. The only component‐specific fitted parameters used in the modeling was the activity coefficient that was lower for methyl formate than the value used for hydrocarbons. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42454.     

Carbon foams prepared from polyimide using urethane foam template

Polyimide and carbon foams were successfully prepared using polyurethane foams as a template. Impregnation of polyimide precursor, poly(amide acid), followed by imidization at 200 °C gave polyurethane/polyimide (PU/PI) composite foams, which resulted in PI foams by heating above 400 °C and then carbon foams above 800 °C. Foams carbonized at 1000 °C were graphitized by the heat treatment at 3000 °C, keeping foam characteristics. Two applications of these carbon foams, i.e., an adsorbent of ambient water vapor and a substrate of photocatalyst anatase TiO₂, were experimentally confirmed. For the former application, the present foam could be characterized by prompt adsorption of ambient water vapor. Some of carbon foams prepared were floating on water, even after loading photocatalyst anatase, which might be advantageous for photodecomposition of pollutants in water in respect to the UV rays efficiency.     

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.     

Preparation of rigid,low-density,flame-retardant polyurethane foams from whey permeate

The disposal of whey and whey permeate derived from the cheese industry is a serious economic and environmental problem. Lactose in whey permeate was used to synthesise polyether polyols from which rigid, low-density polyurethane foams were prepared. Resultant foams were comparable to those made from commercially available sucrose-based polyether polyols. Brown-coloured lactose polyether polyols are characterised by low viscosity and high carbonyl content. Urea incorporated into these polyether polyols yields flame retardant (self-extinguishing) foams. Urea also reduced the amount of phosphorus and/or halogen based fire retardants needed to make the foams non-burning. A preliminary economic analysis indicates that whey-based polyether polyols can be prepared at a cost savings of up to 36% compared to the sucrose counterparts.     

Carbon foams prepared from coal tar pitch for building thermal insulation material with low cost

A new approach is provided to resolve the large-scale applications of coal tar pitch. Carbon foams with uniform pore size are prepared at the foaming pressure of normal pressure using coal tar pitch as raw materials. The physical and chemical performance of high softening point pitch(HSPP) can be regulated by vacuumizing owing to the cooperation of vacuumizing and polycondensation. Results indicate that the optimum softening point and weight ratio of quinoline insoluble are about 292℃ and 65.7%, respectively. And the optimum viscosity of HSPP during the foaming process is distributed in the range of 1000-10000 Pa·s. The resultant carbon foam exhibits excellent performance, such as uniform pore structure, high compressive strength(4.7 MPa), low thermal conductivity(0.07 W·m~(-1) ·K~(-1)), specially, it cannot be fired under the high temperature of 1200 ℃.Thus, this kind of carbon foam is a potential candidate for thermal insulation material applied in energy saving building.     

Urethane foams from animal fats. III. Oxypropylated dihydroxystearic acids in rigid foams

Liquid polyols consisting ofthreo-orerythro-9,10-dihydroxystearic acid previously reacted with 1, 2, 4, 6 and 8 moles of propylene oxide were adjusted with triisopropanolamine to equivalent weight 100. Using trichlorofluoromethane as blowing agent and triethylenediamine as catalyst, the adjusted polyols were foamed by reaction with a prepolymer made from oxypropylated sorbitol and tolylene diisocyanate. The resulting rigid foams had densities between 1.6 and 2.0 lb/ft³, the densities for thethreo series being parallel to but higher at each stage of oxypropylation than those of theerythro series. Compressive strengths in theerythro series ranged from 19 psi for the monooxypropylated compound to 38 psi for the octaoxypropylated member; in thethreo series from 27 to 39 psi. Properties improved in both series as the degree of polyol oxypropylation increased. This contrasted with foams prepared earlier from oxyethylated polyols, whose properties generally reached maxima at intermediate degrees of oxyethylation. Using the tetra-and hexaoxypropylatedthreo polyols, the proportion of blowing agent was varied to relate compressive strength to density of foams between 1.4 and 4 lb/ft³.     

Sustainable rigid polyurethane foams based on recycled polyols from chemical recycling of waste polyurethane foams

The preparation and characteristics of rigid polyurethane foams (RPUFs) based on recycled polyol obtained by glycolysis of waste RPUF scraps from end-of-life refrigerators were investigated. To deactivate the amine adducts derived from isocyanates, the recycled product obtained after depolymerization was chemically modified via addition polymerization of propylene oxide. Two kinds of recycled polyols with different hydroxyl values and viscosity were blended with conventional virgin polyether polyol to prepare the RPUFs. The effects of the recycled polyols on the physical properties of RPUFs such as cell structures, compressive strength, thermal conductivity, and limiting oxygen index were discussed. It was found that the RPUFs from recycled polyols showed superior compressive strength, thermal insulation property, and self-extinguishing property compared with conventional control foam. The results of this study reveal that the recycled polyols could be used as feedstock for RPUFs with superior performance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47916.     

Insulating rigid polyurethane foams from laurel tree pruning based polyol

The present work deals with the production of a natural polyol from laurel tree pruning waste, aiming the preparation of polyurethane foams. The obtained bio-polyol was characterized and applied into foams studying the influence of the isocyanate used and the addition of the physical blowing agent. The incorporation of the polyol allowed 40% polyol substitution for those foams in which TDI was used, and up to 60% using MDI. Apparent density, cell morphology, mechanical, and thermal properties were evaluated. Mechanical and thermal properties of the foams improve to a greater amount of polyol in the matrix. Specifically, the best thermal and mechanical properties (274.99 and 7275.91 kPa for compressive strength and Young Modulus, respectively) were obtained with 50% polyol substitution (0.63 R_NCO/OH). Foams showed small, well-defined cell morphology. Laurel derived polyol can be used for the preparation of foams using MDI, since the mechanical, and thermal properties are promising for obtaining insulation materials in the construction industry.     

Poisson's ratio for rigid plastic foams

Poisson's ratio for several low-density plastic foams has been determined in both tension and compression. For polystyrene bead foams and a polyurethane foam, Poisson's ratio is greater in tension than compression. In compression, Poisson's ratio is not linear, showing a larger value below the yield strain and a value near zero for high strains. For 0.05 and 0.10 g/cc polystyrene bead foam, Poisson's ratios are 1/3 in tension and 1/4 in compression below the yield strain; at higher strains, the value in compression is in the range 0.03–0.07.     

Urethane foams from animal fats: X. urethane polyols from epoxidized tallow,trimethylolpropane, and propylene oxide1

A convenient three-stage reaction has been devel-oped for the preparation of polyols from epoxidized tallow (ET), trimethylolpropane (TMP), and propyl-ene oxide (PO), without the previously required water washing step. ET is first heated with excess TMP under catalysis by BF₃, causing rapid ring open-ing of the oxirane function. In the second stage, KOH catalyzes ester interchange of TMP with the triglyc-eride. Finally, PO is caused to react with free TMP and with other available hydroxylic components, to produce a homogeneous mixture of polyols. The polyols, all liquid at room temperature, were adjusted to equivalent weights of 100 and 120 with added triisopropanolamine and reacted with a polymeric isocyanate in the presence of a blowing agent to give low-density rigid foams. Densities ranged from 1.6 to 1.8 lb/ft³ and compressive strengths from 21 to 30psi. Presented at AOCS Meeting, New Orleans, April 1976.     

Hierarchically porous lanthanum zirconate foams with low thermal conductivity from particle-stabilized foams

Lanthanum zirconate (LZO) ceramic foams with hierarchical pore structure were fabricated by particle-stabilized foaming method for the first time, and the as-prepared ceramics have high porosity of 90.7%-94.9%, low thermal conductivity, and relatively high compressive strength. The LZO powder was synthesized by solid-state method. The porosity of the ceramic foams was tailored by suspensions with different solid loadings (20-40 wt%). The sample with porosity of 94.9% has thermal conductivity of 0.073 W/(m·K) and compressive strength of 1.19 MPa, which exhibits outstanding property of thermal insulation and mechanical performance, indicating that LZO ceramic foam is a promising thermal insulation material in high temperature applications.     

Foam stability and polymer phase morphology of flexible polyurethane foams synthesized from castor oil

Foam stability and segmented polymeric phase morphology of polyurethane foams synthesized partially and completely from castor oil are investigated. Preliminary analysis of the impact of alterations in the polymeric phase on macroscopic stress dissipation in foams is also carried out. The stability and morphology show unique trends depending on the concentration of castor oil used in foam synthesis. While low and intermediate concentrations of castor oil does not significantly affect the foaming process; at high concentrations, the volumetrically expanding liquid matrix remains in a nonequilibrium state during the entire foaming period, resulting in significant foam decay from top. This increases the final foam cell density and decreases the plateau border thickness at bottom. In the polymeric phase of castor oil based foams, the fraction of monodentate urea increases at the cost of non‐hydrogen bonded urea. These monodentate urea domains undergo flocculation in foams synthesized completely from castor oil, thus prominently modifying the segmented morphology. The glass transition temperature of soft segments of partially substituted foams shows moderate increase, with indications of phase mixing between the polyether and castor oil generated urethane domains. Foams synthesized entirely from castor oil have significant sol fraction due to unreacted oligomers. The microscopic alterations in polymeric phase reduce the elastic recovery of partially substituted castor oil foams compared to its viscous dissipation under an applied stress. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40668.     

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.     

Predicting the compressive properties of rigid urethane foam

The classic equation¹ in use throughout the urethane industry to predict the compressive properties of rigid foams is ((1)) The value of K and a need to be determined experimentally for each foam system at a given temperature. By evaluating the compressive properties of 14 different rigid urethane foams, a was defined as 1.75 for all materials at all test temperatures. General equations for predicting the foam's compressive properties over a temperature range of ?65° to 325°F (?54° to 204°C) were then developed. These general equations appear to be reasonably accurate in predicting the compressive properties of any rigid urethane at any temperature up to the foam's softening point. The equations are of the form shown above with K being a function of temperature only. Finally, the K term was defined as a function of temperature. The equations developed for predicting the compressive strength and modulus of the rigid urethane foams are: ((2)) for T equal to or greater than 77°F (25°C), and ((3)) for T equal to or greater than ?65°F (?54°C), where the compressive strength and modulus are in pounds per square inch and density is pounds per cubic foot. These equations are valid up to the softening point of the foam.