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.     

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.     

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.     

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.     

Development of rigid toughened photocurable epoxy foams

This study present a fast and efficient method for preparing photocurable rigid epoxy foams. A system based on the anionic photopolymerization of diglycidyl ether of bisphenol A (DGEBA) combined with a thiol-ene photopolymerization, was used. A tertiary diamine curing agent functionalized with four allyl groups was used in conjunction with a multifunctional thiol. The presence of several basic species, like tertiary amines, thiolates, polythioethers and alkoxide groups induced the anionic ring opening polymerization of the epoxy groups. At the same time the double bonds of the curing agent reacted with the multifunctional thiol generating polythioethers. The flexibility of the polythioethers modified the properties of the epoxy polymers, improving their toughness. Benzenesulfonyl hydrazide as foaming agent and zinc oxide as activator were added to DGEBA to produce the epoxy foams. The photopolymerization kinetics showed that conversion of the epoxide groups reached 80% in 600 s. Thermal curing studies performed by DSC showed that the main curing exotherm were determined at 84–89 °C, which match the temperature at which the photocuring was carried out in the UV light chamber (85 °C). It was found that the viscosity of the formulations plays a key role in the pore size of the foamed polymer, the higher the viscosity the larger the pore sizes. It was also determined that the impact resistance of the produced foams increased with increasing concentration of the thiol-ene system, as a consequence of a greater amount of polythioethers present in the co-network.     

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.     

Synthesis of rigid polyurethane foams from oligoester alcohols obtained from dimethyl terephthalate production wastes

A study was conducted to synthesize oligoester alcohols from dimethyl terephthalate production wastes via transesterification with diethylene glycol and trimethylol propane. The oligoester alcohols obtained are suitable for preparing rigid polyurethane foams. The oligoester alcohols from trimethylol propane possess good physical and mechanical properties. The oxygen indices indicate that the polyurethane foams exhibit improved resistance to combustion due to the increased content of aromatic nuclei in the oligoester alcohols.     

Application of waste products from agricultural-food industry for production of rigid polyurethane-polyisocyanurate foams

Solid parts of the wheat slops (90% w/w of dry mass and 10% w/w of water) were applied as a filler (5–30% w/w in relation to the sum of polyisocyanate and polyol masses) in PUR-PIR composition. Six foams containing different amounts of slops were prepared by this method and then, their physical–mechanical properties i.e. apparent density, compressive strength, brittleness, after-combustion residue, stability of linear dimensions, change of volume, loss in mass (48 h, temp 120 °C), softening point, content of the closed cells and absorbability of water were determined. Moreover, the foams were subjected to thermogravimetric and infrared analyses.     

Preparation and properties of rigid polyurethane foams containing modified cornstarches

Rigid polyurethane foams were prepared containing 20% (based on weight of polyol) unmodfied or modified cornstarches. The cornstarches had been modified by breeding or conversion methods and included waxy, acid-modified waxy, malto-dextrin, and canary dextrin. Due to its more favorable role as an extender, canary dextrin was added to additional foam formulations at 10–40%. Foams containing dextrins responded to compressive stress as control foams with yield points before 10% deformation. Foams filled with the unmodified or waxy cornstarches did not give clearly defined yield points and were measured at 10% deformation. After 14 days under 70°C and ambient conditions, volume increases for the filled foams were 4.0–7.1% vs. 4.6% for the control. The foams filled with canary dextrin increased in volume 4.3%. With the addition of 40% canary dextrin, the volume increases for the foams were 4.4% under thermal conditions and 4.5% under humid conditions (38°C and 98% relative humidity). Under humid conditions for 14 days, the foams containing canary dextrin increased in weight as dextrin content increased (1.5, 3.2, 3.4, and 7.6% with 10, 20, 30, and 40% dextrin, respectively). with 40% canary dextrin in the foams, thermal conductivity was 0.0235 vs. 0.0242 W/mK (0.163 vs. 0.168 Btu in/ft²h°F) for the control.     

聚氨酯硬泡氯氟烃发泡剂替代技术的新进展

对聚氨酯硬泡工业CFC发泡剂的4种替代路线和最新进展作了简单综述。