Plasticizing properties of esters of monohydric alcohols and tall oil fatty acids

Tall oil fatty acid esters prepared as intermediates in an epoxy ester plasticizer program were similarly evaluated as low-temp plasticizers in polyvinyl chloride resins. Performance characteristics as primary and secondary plasticizers in polyvinyl sheeting and extruded tapes were determined on esters from methyl to heptadecyl tallate. Results indicate that these materials impart low-temp properties which would make them of value as low-cost plasticizers in extruded and molded products where light and heat stability are not primary factors.     

Recovery of short,medium, and long chain fatty acid methyl esters using wet halogenated hydrocarbons

Fatty acid methyl esters are prepared and analyzed by gas liquid chromatography using a simple procedure that does not involve evaporation steps or drying of the final extract. The esters of fatty acids down to caproate (C₆) are recovered quantitatively. The long chain fatty acid esters, including the polyunsaturated esters, are also recovered quantitatively and are at least as stable as esters isolated by conventional procedures. Preparation of the esters in methanolic reagents is followed by partition of the mixture between a small volume of ethylene chloride and a large volume of water. The lower halogenated hydrocarbon phase contains the methyl esters ready for analysis, and the aqueous phase contains the methanol, catalysts, and other water-soluble materials.     

Loss of fatty acid esters from grape surfaces during drying

Fatty acid esters have been shown to reduce the drying time of grapes by interacting with the waxy surface of the grapes. Laboratory scale procedures were developed to determine the fate of esters during dehydration. Thompson seedless grapes were dipped in a water emulsion containing 2% fatty acid ester, 2% potassium carbonate and an emulsifier. Grapes were dried at ambient, 43 C and 71 C. Drying rates vs. fatty acid ester concentration on the grape surfaces were plotted. The fate of fatty acid esters during dehydration was determined by running the dryer exhaust through a cold trap and extracting the condensate. These studies showed that the large loss of esters during drying lowered the drying rate considerably. An additional dip during drying reduced the drying time significantly. The ester losses appeared to be caused by vapor distillation of the esters during drying.     

Tall oil fatty acid-formaldehyde derivatives and their application as vinyl plasticizers

Acid-catalyzed condensations of tall oil fatty acid and related materials with formaldehyde, in the absence of a carboxylic acid solvent, led to acidic products, lower in unsaturation, but partially polymeric due to formation of interester linkages. Hydrolysis of these linkages furnished products lower in mol wt but higher in free hydroxyl content. Some modified esters of these materials were evaluated as primary plasticizers for polyvinyl chloride by comparison with dioctyl phthalate and, when applicable, to Monsanto S409. In general, those plasticizer candidates in which free hydroxyl contents were lowered by acetylation exhibited a good overall balance of physical and permanence properties but possessed poor heat stability and borderline compatibility. A preliminary study on the acid-catalyzed reaction of ethyl tallate with anhydrous formaldehyde gave promise that an improved alternate route to fatty acid-formaldehyde esters could be developed.     

Chemistry and technology of some drying oil fatty acid esters of polyvinyl alcohol

No substitute for phenol as the mutual solvent was found. Other solvents which were tried produced deleterious side effects such as bad color and product recovery difficulties. Furthermore, the yields of ester were not as good as those in the phenol process. At the present time, the yield of ester using the standard procedure cannot be improved. The final product analyses seem to indicate polyethers are formed simultaneously with the fatty acid esters, and that polyvinyl alcohol undergoes chain cleavage with the formation of non-hydroxyl groups, or a deacylation of one of two 1舑2 hydroxyl groups which results in a ketone group. Esters of high and low mol wt polyvinyl alcohol based on 0.5/1 (fatty acid/polyol) equivalents as the optimum can be successfully prepared with and without basic catalysts. An ester as low as 0.1/1 fatty acid/LMPVA can be prepared without a gel. This ester is barely soluble in aromatic solvents. The evaluation data on several coatings indicates that improved clear varnishes and house paints are possible and that further evaluation of these esters as can coatings or industrial bakes should be considered. Linseed esters showed better properties than the soya and tall oil esters. No particular advantages were seen in the other pigmented coatings.     

Functionalization of soy fatty acid alkyl esters as bioplasticizers

The combination of various functional groups, such as epoxy, acetoxy, methoxy, thiirane, and aziridine, on the fatty acyl chain of soy fatty acid alkyl esters have been synthesized and evaluated as plasticizers in poly(vinyl chloride) (PVC) applications. Numerous synthetic procedures, such as epoxidation, methoxylation, acetylation, thiiration, and aziridination, were used for synthesizing multifunctional soy fatty acid alkyl esters. Epoxidized soybean oil fatty acid alkyl ester served as the key intermediate for functionalization. Partial or complete ring opening of the epoxide by reacting with methanol and the subsequent etherification or acetylation of the hydroxyl function produced epoxy, alkoxy, and acetoxy derivatives. The nucleophilic substitution of epoxide with sulfur by reacting with ammonium thiocyanate produced thiirane and epoxy thiiranes. Although the aziridine derivatives were synthesized by reacting unsaturated fatty acid alkyl esters with chloramine‐T, the compounds were fully characterized and their physical and analytical properties were determined. The high viscosity and darker color of aziridine and thiirane derivatives limit their usefulness, whereas the physical properties of the other derivatives were acceptable. The plasticizer evaluation of methoxy and acetoxy soy fatty acid esters (methyl and n‐butyl) demonstrated good compatibility with PVC, high efficiency (Shore hardness), and gelling properties were comparable to commercial plasticizer, di‐isoonyl phthalate. The abundant availability and cost‐effectiveness of starting materials and the readily adoptable chemical processes make the fatty acid ester derivatives viable bioplasticizers to replace the fossil fuel‐derived phthalates. J. VINYL ADDIT. TECHNOL., 23:93–105, 2017. © 2015 Society of Plastics Engineers     

Ethylene and dimethyl acetals from hydroformylated linseed,soybean, and safflower methyl esters as plasticizers for polyvinyl chloride

Dimethyl and ethylene acetals of polyformylated unsaturated fatty esters were prepared, characterized, and evaluated as polyvinyl chloride plasticizers. Dimethyl acetals were prepared with trimethyl orthoformate as a water scavenger in the acid catalyzed acetalation reaction. With ethylene acetals, water was removed azeotropically. Although the acetals prepared were mixtures, molecular distillation gave diacetal esters of 80–90% purity and triacetal esters of 80–95% purity. The samples were characterized by gas liquid chromatography and by IR and NMR spectra. Compared to di-2-ethylhexyl phthalate as a plasticizer for polyvinyl chloride, the triacetal esters (both dimethyl and ethylene acetals) gave less migration and at least equivalent volatility characteristics; the triacetals also gave equivalent compatibility and strength, but somewhat less desirable low temperature and heat stability properties. The diacetal esters also had good compatibility, equivalent strength, somewhat better low temperature, but less desirable migration and volatility properties. Presented at the AOCS Meeting, Chicago, Illinois, September 1973. ARS, USDA.     

Some fatty esters as plasticizers and fungicides for natural rubber

The prepared n-fatty alcohols from petroleum sources are esterified with a dibasic acid series (malonic, succinic, glutaric and adipic) or phthalic anhydride, giving the corresponding C₁₂ fatty esters. The prepared C₁₂ fatty esters were formulated with natural rubber. The drying time, some mechanical properties and fungitoxicity of the prepared film samples were examined. The conventional dibutyl phthalate plasticizer was used for the purpose of comparison. The data obtained indicate that the prepared fatty esters can be used as plasticizers with antifungal activity for natural rubber. ©1997 SCI     

Vernolic acid esters as plasticizers for polyvinyl chloride

The methyl, propyl, butyl, isobutyl, hexyl, cyclohexyl, octyl, and 2-ethylhexyl esters of vernolic (epoxyoleic) acid, a naturally-occurring epoxy acid, were prepared and evaluated as plasticizers of polyvinyl chloride. All the esters showed good compatibility. The data indicated that they are excellent low temperature plasticizers having T_f temperatures below −50C. They also have the added advantage of greatly increasing the heat stability of the polyvinyl chloride and improving the light stability. The results are compared with DOP and other epoxy-containing plasticizers now being used commercially. These esters should not only be useful as primary plasticizers but also in combination with other plasticizers as plasticizer-stabilizers. Presented at the AOCS Meeting. Cineinnati, October 1965 E. Utiliz. Res. Dev. Div., ARS, USDA.     

Catalytic hydroformylation of unsaturated fatty derivatives with cobalt carbonyl

Two cobalt-carbonyl oxo processes were developed to prepare useful products in high yield from fatty derivatives. In one process, hydroformylation in the presence of MeOH at 120 C gives dimethyl acetal esters from either methyl oleate or oleic acid. In the other, a two-step process, hydroformylation (120 C) followed by hydrogenation (180 C) gives better yields of hydroxymethyl esters from both mono- and polyunsaturated fatty substrates. Recycling the cobalt catalyst was demonstrated for the second process. The acetal and acetoxymethyl derivatives of the oxo products have utility as polyvinyl chloride plasticizers.     

The decomposition of secondary esters of castor oil with fatty acids

In this study, thermal splitting of secondary fatty acid esters of castor oil was investigated to determine the reaction kinetics under various conditions. Zinc oxide,p toluenesulfonic acid and sulfuric acid were used as catalysts. Reactions were carried out at 260, 270, and 280°C. Experimental data fitted the first-order rate equation for the catalyzed and noncatalyzed reactions. In addition to the kinetic investigation, the splitting (pyrolysis) mixture was evaluated in the preparation of a synthetic drying oil. For this purpose, the mixed fatty acids of linseed, sunflower andEcballium elaterium seed oils were used in the esterification stage of the process. Pyrolysis mixtures were converted to drying oils by combining the liberated acids with equivalent amounts of glycerol. The oils thus obtained show good drying oil properties.     

Homogeneous catalytic metathesis of unsaturated fatty esters: New synthetic method for preparation of unsaturated mono-and dicarboxylic acids

The catalytic metathesis of unsaturated fatty esters is a new, versatile method for the synthesis of a variety of fatty derivatives and alkenes. Monounsaturated esters are converted into unsaturated dicarboxylic esters which might be important technologically for the production of new polyesters and polyamides, and for the synthesis of civetone-type perfumes. Metathesis of linoleate and linolenate leads to a variety of hydrocarbons and mono- and dicarboxylates of different unsaturation. Joint reactions of unsaturated esters and alkenes are a useful means for the synthesis of homologues of oleic acid and other fatty acids. Metathesis of unsaturated fatty oils (olive, soybean, linseed, etc.) leads to the formation of high molecular dicarboxylic acid glyceryl esters with improved drying properties.     

Utilization of acid oils in making valuable fatty products by microbial lipase technology

Microbial lipase-catalyzed hydrolysis, esterification, and alcoholysis reactions were carried out on acid oils of commerce such as coconut, soybean, mustard, sunflower, and rice bran for the purpose of making fatty acids and various monohydric alcohol esters of fatty acids of the acid oils. Neutral glycerides of the acid oils were hydrolyzed byCanadida cylindracea lipase almost completely within 48 h. Acid oils were converted into fatty acid esters of short- and long-chain alcohols like C₄, C₈, C₁₀, C₁₂, C₁₆, and C₁₈ in high yields by simultaneous esterification and alcoholysis reactions withMucor miehei lipase as catalyst. Acid oils of commerce can be utilized as raw materials in making fatty acids and fatty acid esters using lipase-catalyzed methodologies.     

Column types for the chromatographic analysis of oleochemicals

Chromatography has developed into one of the principle methods of analysis of oleochemicals. Gas chromatography has been used extensively for the analysis of long-chain fatty acids as well as for the analysis of triglycerides and plant sterols. In recent years, high pressure liquid chromatography (HPLC) has been used for the analysis of triglycerides as well as for other related materials. Specialized gas chromatography columns have been developed for the separation of long-chain fatty acids such as the methyl esters. These columns have generally used high polarity stationary phases which separate fatty acids by degree of unsaturation. A specialized use of these high polarity stationary phases is separation ofcis-trans isomers as well ascis-cis andtrans-trans isomers. In this paper, packed and capillary columns are compared for the separation of thecis-trans isomers of fatty acid methyl esters prepared from a hydrogenated vegetable oil. For HPLC separations, the presence of a double bond is approximately equivalent chromatographically to shortening the alkyl chain by two carbons. The long-chain polyenic acids or ethyl esters thus elute near but are resolved from the short-chain saturated fatty acids or esters. HPLC is the method of choice for relatively complex, high molecular weight, or labile esters, such as those of retinyl or cholesterol. Glyceryl esters are particularly well resolved by HPLC in terms of both total chain length and degree of unsaturation. This technique is also useful for lipid class separations and for the analysis of modified fatty acid products, such as prostaglandins and related materials. In general, these analyses are conducted with octadecyl bonded phase column packings.     

Reactions of conjugated fatty acids. V. Preparation and properties of diels-alder adducts and their esters fromtrans,trans-conjugated fatty acids derived from soybean oil

Summary Soybean fatty acids were conjugated with alkali, and the contained, conjugated dienoic acids were isomerized with iodine to thetrans,trans configuration. Adducts were prepared from thesetrans,trans-conjugated acids by condensation with maleic anhydride and acrylic acid. The adducts were isolated, purified, and converted to esters by using a variety of alcohols, including methyl, ethyl,n-propyl,n-butyl, and allyl alcohols. Esters made from saturated alcohols were converted into the corresponding epoxy derivatives. All of the esters (except allyl) and all of the epoxy esters were compatible with an equal weight of polyvinyl chloride and appeared to be primary plasticizers for this plastic. The epoxy esters were effective in inhibiting heat deterioration of polyvinyl chloride. Presented at fall meeting. American Oil Chemists' Society, September 23–26, 1956, Chicago, Ill.     

Analysis of epoxidized soybean oil by gas chromatography

A fast and cost-effective procedure to quantitate epoxidized soybean oil by means of an external standard method is reported. This procedure is applicable to commercial epoxidized oils, polymer additive packages and polymers—polyvinyl chloride (PVC)—containing epoxidized oils. The epoxidized soybean oil is converted into fatty acid methyl esters with tetramethylammonium hydroxide, and analyzed by capillary gas chromatography with flame-ionization detection. In PVC samples, the epoxidized soybean oil was extracted with toluene and followed by derivatization prior to analysis. The methyl esters of monoepoxyoctadecanoic, diepoxyoctadecanoic and triepoxyoctadecanoic acid were separated with a short capillary column.     

The lipids of human pancreas with special reference to the presence of fatty acid methyl esters

Total lipids were extracted from human pancreas with chloroform-methanol, chloroform-methanol following acidification, and benzene. A similar proportional amount of total lipid was obtained by each procedure. Regardless of the method of extraction (i.e., whether or not methanol was present), a small proportion (about 1%) of the total lipid was found to consist of fatty acid methyl esters. Triglycerides constituted the major fraction (about 80%) of the pancreatic lipids; in addition to methyl esters, the remaining lipids comprised free fatty acids, phospholipids, cholesterol esters, and traces of free cholesterol. In general, each class of lipid had a similar over-all fatty acid composition with palmitic and oleic acids as predominant components. The methyl esters had a relatively high content of linolenic acid, and the free fatty acids contained a notably high proportion of palmitic acid, in each case accompanied by a corresponding decrease in the proportion of oleic acid present.     

Epoxidized esters of fatty acids as internal and external plasticizers for polyvinyl acetate

Summary Fatty acid esters modified with epoxy or acetoxy groups were found to be compatible with polyvinyl acetate. These esters are good plasticizers for polyvinyl acetate compositions and may be used for plasticizing polyvinyl acetate in latex form. The use of a good swelling agent, such as toluene, was found desirable for permitting plasticization of these emulsions. The epoxidized oils may also assist in reducing container corrosion and in stabilizing the emulsions by reacting with the acetic acid formed by the hydrolysis of residual vinyl acetate. Emulsions of copolymers of vinyl acetate and vinyl epoxystearate were prepared, yielding clear, hard films which were internally plasticized. The epoxy group in these interpolymers is a potential source for cross-linking vinyl acetate polymer films. The epoxy group of the co-polymers (internal-phase stabilization) and the epoxidized oils (external-phase stabilization) were found to be virtually equivalent for removal of acetic acid from polyvinyl acetate emulsions. Presented at the Fall Meeting, American Oil Chemists' Society, Philadelphia, Pa., October 11, 1955. A laboratory of the Eastern Utilization Research Branch, Agricultural Research Service, U. S. Department of Agriculture.     

Die katalytische Metathese von ungesättigten Fettsäureestern

Catalytic Metathesis of Esters of Unsaturated Fatty Acids Several active and selective catalysts have been developed for the metathesis of unsaturated hydrocarbons in homogeneous medium. These are based on WCl₆ and MoCl₅ with Sn(CH₃)₄, Sn(C₆H₅)₄ and Pb(C₆H₆)₄ as the most important co-catalysts. These catalyst systems also permit the metathesis of compounds having functional groups, such as esters of fatty acids and halogenated hydrocarbons. The metathesis of esters of fatty acids enables the synthesis of numerous compounds, which so far were either unknown or difficult to synthesize. Such compounds are, for instance, certain long chain unsaturated dicarboxylic acids which are derived from monoenoic fatty acids, such as oleic acid and erucic acid. From technological viewpoint the unsaturated dicarboxylic acids might be significant as raw material for the preparation of unsaturated polyesters and polyamides, as well as for the synthesis of certain flavoring agents. The metathesis of fatty oils (glycerides) leads to the formation of high molecular weight compounds. The metathesis of semi-drying and drying oils offers the possibility to prepare stand oils having good drying properties.     

Analysis of hydroxylated fatty acids from plant oils

A novel process has been described recently for the preparation of hydroxylated fatty acids (HOFA) and HOFA methyl esters from plant oils. HOFA methyl esters prepared from conventional and alternative plant oils were characterized by various chromatographic methods (thin-layer chromatography, high-performance liquid chromatography, and gas chromatography) and gas chromatography-mass spectrometry as well as¹H and¹³C nuclear magnetic resonance spectroscopy. HOFA methyl esters obtained fromEuphorbia lathyris seed oil, low-erucic acid rapeseed oil, and sunflower oil contain as major constituents methylthreo-9,10-dihydroxy octadecanoate (derived from oleic acid) and methyl dihydroxy tetrahydrofuran octadecanoates, e.g., methyl 9,12-dihydroxy-10,13-epoxy octadecanoates and methyl 10,13-dihydroxy-9,12-epoxy octadecanoates (derived from linoleic acid). Other constituents detected in the products include methyl esters of saturated fatty acids (not epoxidized/derivatized) and traces of methyl esters of epoxy fatty acids (not hydrolyzed). The products that contain high levels of monomeric HOFA may find wide application in a variety of technical products.