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.     

Rigid polyurethane foams from diethanolamides of carboxylated oils and fatty acids

New polyols of high hydroxyl content and reactivity were made from linseed and soybean oils and acids by catalytic carboxylation followed by reaction with diethanolamine. Urethane foams made with these diethanolamides were stronger than those made with castor oil at equivalent polyol wt. Because of their higher hydroxyl content, a larger amount of diethanolamides could be incorporated in foam formulations than is possible with castor oil. The rigid urethane foams prepared with the new polyols meet the requirements of commercial products with respect to density, compressive strength, and dimensional stability. National Flaxseed Processors Association Fellow, 1969–1973. Present address: Avery Products, Technical Center, 325 North Altadena Dr., Pasadena, CA 91107.     

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.     

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     

Development of karanja oil based offset printing ink in comparison with linseed oil

The conventional offset lithographic printing ink is mainly based on linseed oil. But in recent years, due to stiff competition from synthetic substitutes mainly from petroleum products, the crop production shrinks down to an unsustainable level, which increases the price of linseed oil. Though soyabean oil has replaced a major portion of linseed oil, it is also necessary to develop alternate cost effective vegetable oils for printing ink industry. The present study aims to evaluate the performance of karanja oil (Pongamia glabra) as an alternative of linseed oil in the formulation of offset printing ink because karanja oil is easily available in rural India. Physical properties of raw karanja oil are measured and compared with that of alkali refined linseed oil. Rosin modified phenolic resin based varnishes were made with linseed oil as well as with karanja oil and their properties are compared. Sheetfed offset inks of process colour yellow and cyan is chosen to evaluate the effect of karanja oil in ink properties. In conclusion, karanja oil can be accepted as an alternate vegetable oil source with its noticeable effect on print and post print properties with slower drying time on paper. However, the colour and odour of the oil will restrict its usage on offset inks.     

Emulsifiers derived from linseed oil and their potential use in coatings

In the development of a stable linseed oil emulsion paint, a series of emulsifiers were prepared from linseed, oil and its fatty acids and alcohols: (a) linseed monoglycerides, (b) mono-and dilinseed fatty sorbitan esters and a mixed ester obtained by the transesterification of linseed oil with sorbitol, (c) polyoxyethylene ether adducts formed by reacting, ethylene oxide with these sorbitan esters, and (d) linseed polyoxyethylene ether made by ethoxylation of linseed alcohols. Another series of surfactants was prepared by esterifying a polyoxyethylene ether of sorbitol with various amounts of linseed fatty acids. Conditions of preparation and pertinent physical, and chemical properties of the emulsifiers are given. Some of these emulsifiers demonstrated filmforming properties. Combinations were formulated into linseed oil emulsion paints with and without zinc oxide. Paints containing zinc oxide have been relatively stable in viscosity for about 2 yr.     

Acyl esters from oxo-derived hydroxymethylstearates as plasticizers for polyvinyl chloride

Hydroxymethylstearates were made by hydroformylation or oxo reaction of mono- and polyunsaturated fats and esters with either rhodium-triphenylphosphine or cobalt carbonyl catalysts. Rhodium-oxo products were hydrogenated with nickel catalyst, whereas, cobalt-oxo products were heated directly under hydrogen pressure. Hydroxymethyl fatty alcohols also were prepared by a two-step copper-chromite hydrogenation of hydroformylated linseed fatty esters. Of these hydroxymethyl compounds, 39 were converted to their acetates and other acyloxy derivatives and then evaluated as primary plasticizers for polyvinylchloride. For compounds with good compatibility, methyl 9(10)-acetoxymethylstearate and 9(10)-acetoxymethyloctadecyl acetate gave the lowest flex temperature (−47 C). An unusual combination of good compatibility and low flex temperature was obtained with 2-methoxyethyl 9(10)-acetoxymethylstearate. Addition of more than one acetoxymethyl group in the fatty acid molecule, made possible by rhodium hydroformylation, imparted good compatibility and outstanding permanence (low migration and volatility) but raised flex temperature. Butyl diacetoxymethylstearate, methyl triacetoxymethylstearate, and polyacetoxymethyloctadecyl acetate from linseed esters displayed good compatibility, strength, and volatility characteristics. As glycerides, acetoxymethylated safflower and linseed oils produced good compatibility and outstanding permanence, better than esters commonly used as commercial plasticizers.     

亚麻籽油在化妆品中的应用

简要介绍了亚麻籽油的来源、特性与传统应用,着重介绍了亚麻籽油在化妆品中的应用.亚麻籽油作为一种特殊天然功能油脂,在各种保湿护肤护发化妆品中用作营养和保湿剂.作为Omega -3系必需脂肪酸补充剂,不仅应用于具有特殊疗效的肤用化妆品中缓解或治疗皮肤问题,还应用于发用化妆品中发挥促进生发的功效.最后对亚麻籽油如何更好地应用于我国化妆品行业进行了展望.     

Polymerization of linseed oil in an electric discharge

Summary The treatment of linseed oil by the action of electric discharges (voltolization) in a hydrogen atmosphere (80 mm. Hg, 70°C.) is described. It has been known for a long time that voltolization of linseed oil brings about a polymerization of the oil. Now it has been proven that the nature of the polymerization product thus obtained is absolutely different from that of thermally or catalytically polymerized linseed oils. In contrast to the latter, voltolized linseed oils contain only small amounts of cyclic compounds. Their viscosity is relatively low, even at a high polymerization degree, and considerably less than that of thermally polymerized oils of a corresponding degree of polymerization. Atomic hydrogen seems to play an important part in the voltolization process. Coupling of fatty acid chains is made possible by combining radicals, formed primarily by the action of hydrogen atoms. Coupling reaction occurs almost exclusively intermolecularly. The possibility of transforming linseed oil and other drying oils into polymerization products of a completely different chemical structure, depending on the applied polymerization process, opens new possibilities for their manufacture. Compare T. Hoekstra, Thesis, Delft 1958 (in Dutch).     

Nucleophilic and radical addition of H2S to methyl linolenate and linseed oil

Hydrogen sulfide was added to methyl linolenate and linseed oil to yield mercapto, thio, and thiolan derivatives. Nucleophilic conditions at low temperatures gave faster and more complete reactions than did free radical conditions. Major reaction products were identified by gas liquid chromatography, mass spectrometry, and nuclear magnetic resonance. Nucleophilic addition of hydrogen sulfide to the methyl esters of hydrogenated nonconjugatable linseed oil was made at −70 C in the presence of boron trifluoride, and thiolan derivatives appeared to form in preference to thiane derivatives. Presented at the AOCS meeting, Cincinnati, September 1975.     

亚麻油改性特-辛基酚醛树脂的合成及性能研究

利用亚麻油与松香对辛基酚醛树脂进行改性合成改性辛基酚醛树脂。对改性产品进行了GPC、FT-IR的表征分析及其软化点、脂肪烃溶解性和溶剂溶解性能等的研究。实验表明,亚麻油与松香质量比在20%~40%之间时,所得产品分子量(Mn)6 000~10 000,分子量分布范围(PD I)小于4,庚烷容纳度在10~20 mL/2 g,软化点大于110℃,是平版印刷油墨用的一种新型高分子聚合物。     

Chemical reactions involved in the deep-fat frying of foods1

Deep-fat frying is one of the most commonly used procedures for the preparation and manufacture of foods in the world. During deep-fat frying, oxidative and thermal decompositions may take place with the formation of volatile and nonvolatile decomposition products, some of which in excessive amounts are harmful to human health. A limited survey of frying fats used in commercial operations indicated that some were maintained at good quality and others were overused or abused. The volatile decomposition products produced by corn oil, hydrogenated cotton-seed oil, trilinolein, and triolein, under simulated commercial frying conditions, were collected, fractionated, and identified. A total of 211 compounds were identified. The nonvolatile decomposition products produced by trilinolein, triolein, and tristearin under simulated commercial frying conditions were collected and characterized. After being treated under deep-fat frying conditions at 185 C for 74 hr, trilinolein yielded 26.3% non-urea-adduct-forming esters, triolein yielded 10.8%, and tristearin also yielded 4.2%.     

Dietary modulation of phospholipid fatty acid composition and lipoxygenase products in mouse lung homogenates

This study investigated the potential of dietary fats to modulate the arachidonic acid content of mouse lung phospholipids and the formation of lipoxygenase products from arachidonic and eicosapentaenoic acids. Prior to breeding, female mice were fed for five months diets with 10 wt% of either olive oil, safflower oil, fish oil, or linseed oil. The same diets were fed to the females during gestation and to the pups from day 18 to day 42 postpartum. On day 42, the phospholipids were extracted from fresh lung tissue and separated into classes [phosphatidylethanolamine (PE), phosphatidylserine (PS), phosphatidylcholine (PC), and phosphatidylinositol (Pl)] by thin-layer chromatography. Methyl esters of phospholipid fatty acids and unesterified fatty acids were analyzed by gas chromatography. At comparable dietary n-3/n-6 ratios, arachidonic acid was reduced 85 and 75% in lungs from mice fed linseed oil and fish oil, respectively, compared to lungs of safflower oil-fed mice. Dietary fats affected the proportion of arachidonic acid in phospholipids in the order: PE>PS>PS>Pl. Following incubation of homogenized lung tissue, the total amount of 12-lipoxygenase products was lowest in lungs from mice fed olive oil, and 12-hydroxyeicosatetraenoic acid was lowest in incubated lungs from mice fed linseed oil. Comparison of the amounts of lipoxygenase substrate fatty acids in the individual phospholipids with the lipoxygenase products suggested that the major substrate pool for the 12-lipoxygenase pathway in mouse lung homogenates was PC.     

Polyurethane foams based on crude glycerol-derived biopolyols: One-pot preparation of biopolyols with branched fatty acid ester chains and its effects on foam formation and properties

Environmentally friendly biopolyols have been produced with crude glycerol as the sole feedstock using a one-pot thermochemical conversion process without the addition of extra catalysts and reagents. Structural features of these biopolyols were characterized by rheology analysis. Rigid polyurethane (PU) foams were obtained from these crude glycerol-based biopolyols and the foaming mechanism was explored. Investigations revealed that partial carbonyl groups hydrogen-bonded with N–H were replaced by aromatic rings after the introduction of branched fatty acid ester chains in the “urea rich” phase, and that distinct microphases had formed in the foams. Studies showed that branched fatty acid ester chains in the biopolyols played an important role in reducing the degree of microphase separation and stabilizing bubbles during foaming processes. PU foams with thermal conductivity comparable to commercial products made from petroleum-based polyols were obtained. These studies show the potential for development of PU foams based on crude glycerol, a renewable resource.     

Preparation and film properties of oils conjugated by dimsyl salts

A study was made of the conjugation of soybean and linseed oils with dimsylsodium and dimsylpotassium as catalysts. Dimsylpotassium had markedly greater catalytic activity than dimsylsodium. The most effective cosolvent used with dimethyl sulfoxide for the conjugation at room temperature was tetrahydrofuran. Bis(2-ethoxyethyl) ether was less effective as a cosolvent than tetrahydrofuran at room temperature but was nearly as effective at 50 C. An adduct with maleic anhydride was prepared from the conjugated linseed oil under mild conditions. Drying characteristics of the conjugated linseed oil also were investigated. Baked conjugated linseed oil films were comparable to baked dehydrated castor oil films. Presented in part at AOCS Meeting, New Orleans, April 1973. ARS, USDA.     

Polyphenolic fractions improve the oxidative stability of microencapsulated linseed oil

The main objective of this study was to evaluate the effect of incorporating polyphenolic‐enriched fractions from murta leaves on the oxidative stability of linseed oil microencapsulated by spray drying. For this purpose, polyphenol‐enriched fractions from murta leaves were separated by gel permeation chromatography and chemically characterized. The oxidative stability of microencapsulated linseed oil (MLO) with antioxidants was evaluated in storage conditions at 25°C for 40 days. The antioxidant effects of the polyphenolic fractions and commercial antioxidants (BHT and trolox) on microencapsulated oil were evaluated by the value of conjugated dienes, peroxide, and p‐anisidine. In the initiation step of the oxidation, no significant oxidation delay (p>0.05) in MLO containing fractions F₆, F₈, or BHT and trolox was observed. However, in the termination step of the oxidation, the addition of fractions F₆, F₈, and BHT and trolox decreases significantly (p ≤ 0.05) the rancidity in MLO. Furthermore, the results of this study demonstrated the importance of the addition of natural antioxidants such as fractions of murta leaf extract in microencapsulated linseed oil to increase its resistance to oxidation. Practical applications: For incorporating linseed oil, a source of omega‐3 fatty acids, in the diet it is necessary to protect it against oxidative rancidity, the main cause of deterioration that affects food with a high unsaturated fat content. Microencapsulation is effective in retarding or suppressing the oxidation of unsaturated fatty acids and natural plants extracts are effective in inhibiting the lipid oxidation of microencapsulated oil. The use of process technology and a natural additive is expected to increase storage stability and enable its use in dry foods such as instant products. Linseed oil can be used in human nutrition as well as in animal feed as a replacement for fish oil.     

Evidence for cyclic monomers in heated linseed oil

Summary The monomeric, non-urea-adduct-forming material from the ethanolysis of heated linseed oil exhibits an infrared absorption band at 660 cm.⁻¹ (15.2 μ). This absorption is not present in the spectrum of the esters of unheated linseed oil acids or in that of the adduct-forming esters prepared from heated linseed oil. The monomeric, non-urea-adduct-forming material, on aromatization and oxidation, yielded about 1% of phthalic anhydride, thus providing chemical evidence for the existence in this material of a compound containing an unsaturated six-membered ring. Issued as N.R.C. No. 4001.     

Safflower oil

Summary A brief account is given of experiments with safflower oil in Australia. Under practical conditions, the drying power of safflower oil equals that of linseed oil. The non-yellowing properties of the former render it superior to the latter as a vehicle in coatings for interior decoration and in stoving enamels. In the heat polymerization of safflower oil, temperatures 10° to 15°C. higher than those normally employed for linseed oil are recommended. During three years of outdoor exposure trials, paints based on safflower oil have performed at least as well as similar paints from linseed oil. The commercial production of the oil by solvent extraction presents no difficulty. Decortication prior to extraction is not necessary. The resulting oil has a very good colour and is free from “foots.” On alkali refining, losses are very small. Notwithstanding the high hull content of the meal, it has proved valuable as a stock fodder.     

Production of structured lipids containing essential fatty acids by immobilizedRhizopus delemar lipase

An attempt was made to produce structured lipids containing essential fatty acid by acidolysis with 1,3-positional specificRhizopus delemar lipase. The lipase was immobilized on a ceramic carrier by coprecipitation with acetone and then was activated by shaking for 2 d at 30°C in a mixture of 5 g safflower or linseed oil, 10 g caprylic acid, 0.3 g water and 0.6 g of the immobilized enzyme. The activated enzyme was transferred into the same amount of oil/caprylic acid mixture without water, and the mixture was shaken under the same conditions as for the activation. By this reaction, 45–50 mol% of the fatty acids in oils were exchanged for caprylic acid, and the immobilized enzyme could be reused 45 and 55 times for safflower and linseed oils, respectively, without any significant loss of activity. The triglycerides were extracted withn-hexane after the acidolysis and then were allowed to react again with caprylic acid under the same conditions as mentioned above. When acidolysis was repeated three times with safflower oil as a starting material, the only products obtained were 1,3-capryloyl-2-linoleoylglycerol and 1,3-capryloyl-2-oleoyl-glycerol, with a ratio of 86∶14 (w/w). Equally, the products from linseed oil were 1,3-capryloyl-2-α-linolenoyl-glycerol, 1,3-caprylol-2-linoleoyl-glycerol, and 1,3-capryloyl-2-oleoly-glycerol (60∶22∶18, w/w/w). All fatty acids at the 1,3-positions in the original oils were exchanged for caprylic acid by the repeated acidolyses, and the positional specificity ofRhizopus lipase was also confirmed to be strict.     

Synthetic oils from residual dimerized fat acids

Summary Synthetic oils have been prepared from residual dimerized fat acids with soybean and linseed fat acids by esterification with polyalcohols, and with or without maleic anhydride or phthalic anhydride. Preliminary evaluation indicates that these oils give films which dry faster and are more resistant to water and alkali than linseed oil films. This enhancement of water and alkali resistance may result from an increase in C-C bonds present in the films. Ester gum varnishes made from these oils were not markedly superior to similar varnishes made from linseed oil. The Northern Regional Research Laboratory is one of four Regional Laboratories authorized by Congress in the Agricultural Research Act of 1938 for the purpose of conducting research to develop new uses and outlets for agricultural commodities. These Laboratories are administered and operated by the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.