Divinyl sulfone-eleostearate adducts as plasticizers for nitrile rubber

Four divinyl sulfone-eleostearate adducts were synthesized and compared with dibutyl sebacate as plastieizers for nitrile rubber. Three of these, the adducts of methylalpha-eleostearate, its hydrogenated derivative, and that of tung oil, were found to be satisfactory primary plastieizers. The stocks prepared from the unhydrogenated adducts were superior in plasticizing efficiency to those prepared from their hydrogenated derivatives. The divinyl sulfone-tung oil adduct yielded a rubber which met the low-temperature flexibility requirements (−40°C.) of the automotive industry. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Services, U.S. Department of Agriculture.     

Hydroperoxides formed by ferrous ion-catalyzed oxidation of methyl linolenate

An emulsion of methyl linolenate was allowed to oxidize with a catalyst of ferrous sulfate and ascorbic acid. Three oxidation products were isolated, and their hydrogenated derivatives were characterized as the isomeric mixture of methyl monohydroxyoctadecanoate (monoOH), methyl 9,16-dihydroxyoctadecanoate (diOH), and the isomeric mixture of methyl trihydroxyoctadecanoate (triOH). The monoOH isomers and diOH apparently were derived from methyl monohydroperoxyoctadecatrienoate (monoHPO) and methyl dihydroperoxyoctadecatrienoate (diHPO), respectively. Two triOH isomers (the 9,10,12- and 13,15,16-isomers) were thought to be derived from the products containing cyclic peroxide-hydroperoxide structure. 9,16-diHPO was produced by the incubation of monoHPO with ferrous sulfate and ascorbic acid. Moreover, the experiment using¹⁸O₂ demonstrated that mono-HPO yielded 9,16-diHPO by reacting with oxygen molecule. 9,10,13- and/or 9,12,13- and 12,13,16- and/or 12,15,16-triOH isomers were also detected in the hydrogenated derivatives of oxidation products from monoHPO.     

Plasticizer properties of methyl vinyl ketone-methylalpha-eleostearate adduct and derivatives

Summary The Diels-Alder adduct of methyl vinyl ketone and methylalpha-eleostearate was subjected to modification by hydrogenation and epoxidation of its unsaturated centers and by aromatization of its cyclohexene nucleus. These derivatives, as well as the original adduct, were intercompared with DOP as primary plasticizers for vinyl chloride-vinyl acetate copolymer. All of these materials were found to be highly compatible as primary plasticizers and generally more efficient than DOP. The stocks plasticized with the hydrogenated and epoxidized adducts exhibited very good thermal stability on long exposures to heat. The epoxidized adduct not only imparted excellent heat stability to the plastic but also prevented deterioration on exposure to ultraviolet irradiation. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Studies on the fatty acid composition of crayfish lipids

The fatty acid composition of carcass and exoskeleton lipids was determined for the freshwater crayfishOrconectes rusticus. Lipid fractions were isolated by column and thin-layer chromatography. Fatty acid methyl esters and alcohol acetates were then prepared and analyzed by gas-liquid chromatography. Peak identities were established from retention time data for methyl esters, hydrogenated methyl esters, and saturated, monoene, diene, and polyene methyl esters separated as acetoxy-mercuri-methoxy derivatives. Minor component acids were estimated from their relative compositions in these fractions. Presented at the symposium honoring J. B. Brown, AOCS meeting in Chicago, 1964.     

Nitrogenous derivatives of cyclic fatty acids

A number of nitrogenous derivatives of cyclized acids derived from C-18, triene-containing fatty acid sources, were prepared. Mixed amides (mp 33C), nitriles (fp −25C), and amines (fp −34C), prepared from the hydrogenated cyclic acids, have uniquely low mp for fat-derived substances of their mol wt. Compatibility with synthetic resins and solubility in organic solvents of the mixed amides are high compared to common fatty-amide mixtures. The nitriles and morpholides are compatible with polyvinyl chloride and may have potential as plasticizers for it. The hydrogenated cyclic fatty acid amines have an approximate fp of −34C. The diethanolamides, ethenoxylated amides, and quaternary amines were prepared and their surface-active properties compared with similar fat-derived substances. Presented at AOCS meeting in St. Louis, Mo., 1961. A laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U.S.D.A.     

Structural analysis of hydroperoxides formed by oxidation of phosphatidylcholine with singlet oxygen

Soybean phosphatidylcholine (PC) and dilinoleoyl PC (di-18∶2 PC) were oxidized with singlet molecular oxygen using methylene blue as the photosensitizer. The oxidation products, PC monohydroperoxides (PC-MHP) and PC dihydroperoxides (PC-DHP), were isolated by reverse phase liquid chromatography, and their structures were analyzed by nuclear magnetic resonance (NMR) and gas chromatography-mass spectrometry (GC-MS). Signals for the hydroperoxy proton appeared downfield in NMR spectra of PC-MHP and PC-DHP. Soybean PC-MHP and di-18∶2 PC-MHP were converted to trimethylsilyl (TMS) derivatives of hydrogenated diglycerides when treated with phospholipase C and hydrogenated. Thetert-butyldimethylsilyl (TBDMS) derivatives of hydrogenated diglycerides were also prepared from di-18∶2 PC-MHP. Fragmentation of the TMS and TBDMS derivatives was obtained in electron impact mass spectra. The isomeric composition of hydroperoxylinoleate component in di-18∶2 PC-MHP was determined by methanolysis of the hydrogenated diglyceride and mass chromatographic analysis of the resulting isomeric hydroxy octadecanoates.     

Derivatives of jojoba oil as plasticizers for vinyl polymers and Buna-N rubber

Summary Ten maleinated jojoba oil derivatives were screened as plasticizers in a standard polyvinyl resin formulation and as softeners for Buna-N rubber. Three of these, the methyl and butyl esters and hydrogenated methyl esters of maleinated jojoba acids, were comparable to the reference standard, DOP, as primary plasticizers for the vinyl resin. Three others were satisfactory only as secondary plasticizers. Six of the derivatives were comparable to the reference softener, dibutyl sebacate, as softeners in a Buna-N formulation and yielded rubbers meeting the low temperature flexibility requirements (−40°C.) of the automotive industry. Two of the six, those made with the butyl and hydrogenated butyl esters of maleinated jojoba acids, met the still more stringent low-temperature requirements of the aircraft industry (−55°C.). In general, hydrogenation of a derivative adversely affected its compatibility in either the vinyl copolymer or the Buna-N formulations. Presented at the 51st annual meeting, American Oil Chemists’ Society, Dallas, Tex., April 4–6, 1960. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

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.     

Margarine and shortening oils by interesterification of liquid and trisaturated triglycerides

Liquid vegetable oils (VO), including cottonseed, peanut, soybean, corn, and canola, were randomly interesterified with completely hydrogenated soybean or cottonseed hardstocks (vegetable oil trisaturate; VOTS) in ratios of four parts VO and one part VOTS. Analysis of the reaction products by high-performance liquid chromatography showed that at 70°C and vigorous agitation, with 0.5% sodium methoxide catalyst, the reactions were complete after 15 min. Solid-fat index (SFI) measurements made at 50, 70, 80, 92, and 104°F, along with drop melting points, indicated that the interesterified fats possess plasticity curves in the range of commercial soft tub margarine oils prepared by blending hydrogenated stocks. Shortening basestocks were prepared by randomly interesterifying palm or soybean oil with VOTS in ratios of 1:1 or 3:1 or 4:1, respectively. Blending of the interesterified basestocks with additional liquid VO yielded products having SFI curves very similar to commercial all purpose-type shortening oils made by blending hydrogenated stocks. Other studies show that fluid-type shortening oils can be prepared through blending of interesterified basestocks with liquid VO. X-ray diffraction studies showed that the desirable β′ crystal structure is achieved through interesterification and blending. Presented at AOCS Annual Meeting & Expo, Atlanta, Georgia, May 8–12, 1994.     

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.     

Hydrogenation of methyl linolenate. I. The formation of methyl isolinoleate on the hydrogenation of methyl linolenate

Summary A highly purified sample of methyl linoleate was prepared from linolenic acid obtained by debromination of hexabromostearic acid. The methyl linolenate was hydrogenated to varying degrees of saturation, using palladium on barium sulfate as the catalyst. Ethyl acetate was used as the solvent and all hydrogenations were conducted at room temperature and atmospheric pressure. The hydrogenated samples were analyzed for their fatty acid composition (as methyl esters). The relative reactivities of the various polyunsaturated acids towards hydrogenation were calculated and may be represented by the following whole numbers: oleic (including isooleic) acid, 1; isolinoleic acid, 5; linoleic, 27; linolenic, 27. A procedure was outlined for effecting a concentration of an isolinoleic acid (methyl ester) by low temperature crystallization. The fraction isolated contained 95.8% methyl isolinoleate. Contribution No. 798 from the Department of Chemistry, University of Pittsburgh.     

Plasticizer properties of some acrylonitrile-eleostearate adducts and their hydrogenated derivatives

Summary The addition products obtained by the Diels-Alder reaction of acrylonitrile with the methyl, ethyl, and butyl eleostearates have been prepared in good yields and purified by means of high-vacuum distillation. It has been possible to saturate preferentially by hydrogenation both the cyclic and exocyclic double bonds of the acrylonitrile adducts without material reduction of the nitrile group. Also the acrylonitrile adduct of tung oil has been prepared. All these adducts have been intercompared with DOP and evaluated as primary plasticizers for vinyl chloride-vinyl acetate copolymer. These products, with the exception of the nonhydrogenated ethyl and butyl derivatives, were found to be satisfactory as primary plasticizers. The results obtained indicate that hydrogenation greatly improves the compatibility of the adducts without changing their other plasticizing characteristics appreciably. The outstanding characteristic of all the adducts is their high plasticizing efficiency, as reflected by their low modulus at 100% elongation. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Fatty acids,fatty alcohols,and wax esters fromLimnanthes douglassi (Meadowfoam) seed oil

Limanathes douglasii seed oil glycerides contain fatty acids which predominantly (97%) have 20 or more carbon atoms. Fatty acids were prepared by saponification; fatty alcohols, by sodium reduction of the glycerides; and liquid wax esters, byp-toluenesulfonic acid-catalyzed reaction of the fatty acids with the fatty alcohols. Solid waxes were prepared by hydrogenation of the glyceride oil and of the wax esters. Chemical and physical constants were determined forLimnanthes douglasii seed oil and its derivatives. The liquid wax esters had properties very similar to those of jojoba (Simmondsia chinensis) seed oil. The solid hydrogenated wax ester was identical in physical appearance and melting point to hydrogenated jojoba seed oil. A laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, USDA.     

Cr(CO)3-complexed,silica-bonded polyphenylsiloxane as a stereoselective catalyst for hydrogenation of sorbate and soybean methyl esters

A silica-bonded complex was prepared by reacting polyphenylsiloxane with silylated Chromosorb and then with Cr(CO)₆. This complex catalyzed stereoselective hydrogenation of sorbate tocis-3-hexenoate. Soybean methyl esters were hydrogenated at 210 C in cyclohexane to form products high incis unsaturation. The recovered catalyst could be recycled once with methyl sorbate. IR showed decreased Cr(CO)₃ in the recovered catalysts, and the hydrogenation products contained inactive Cr.     

Preparation of phosphorus esters of long-chain hydroxy fatty acids

Several procedures are evaluated for synthesis of phosphorus-containing derivatives of some long-chain hydroxy-fatty acids, including ricinoleic and lesquerolic acid and their hydrogenated products. The conventional method of preparing phosphate esters by reaction of an alcohol with a dialkyl phosphorochloridate is unsatisfactory, but introduction of the dialkyl phosphoryl group was accomplished by using dimethylformamide as catalyst. Phosphorus derivatives are obtained more conveniently by ester interchange between a long-chain hydroxy compound and a low molecular weight dialkyl phosphite. Purification of the phosphite esters was accomplished by partitoning between acetonitrile and petroleum ether and also by chromatography on a column of silicic acid. Attempts to prepare phosphorus derivatives of the allylic hydroxyl of methyl dimorphecolate resulted in extensive dehydration to the conjugated triene. Presented at the AOCS meeting in Toronto, Canada, 1962. A laboratory of the W. Utiliz. Res. & Dev. Div., ARS, U.S.D.A.     

1,2-Cycloaddition of Haloalkenes to Conjugated Fatty Esters

We have studied the reaction of 1,1-dichloro-2,2-difluoro-, chlorotrifluoro-, and tetrafluoro-ethylenes and also hexafluoropropylene withcis,trans andtrans,trans isomers of conjugated methyl octadecadienoate. Reactions gave 50-82% yields of cycloaddition products. The pre-ponderance of products with a cyclobutane struc-ture and a double bonda,β to the cyclobutane ring was shown by IR and NMR spectra. Reactions were carried out in diluent with hy-droquinone inhibitor at autogenous pressure and a temperature of 200C for 5 hr. The distilled adducts are colorless liquids with viscosities rang-ing from 11 to 19 centistokes at 100F. These products and their hydrogenated derivatives ex-hibit low pour points (down to -76F) and may be useful as low-temperature plasticizers or lubricant additives. Presented at AOCS Meeting, Cincinnati, October 1965. N. Utiliz. Ees. and Dev. Div., ARS, USDA.     

Modification of vegetable oils. XIV. Properties of aceto-oleins

Summary Pure 1,2-diaceto-3-olein was prepared by acetylating mono-olein. A mixture of aceto-oleins was prepared by acetylating a mixture of mono-, di-, and trioleins derived from commercial oleic acid. Several natural oils were acetylated either by ester-ester interchange with triacetin or by glycerolysis followed by acetylation. The various products were examined for cloud and solid points, point of complete melting, and consistency. The 1,2-diaceto-3-olein, which contains 19.5% of acetyl group on a weight basis, has a melting point of −18.3°C. while the mixture of aceto-oleins, which contained 14.3% of acetyl on a weight basis, melted at −24°C. Acetylation of the natural oils raises in most instances their cloud and solid points and point of complete melting, but it also greatly increases their plasticity at lower temperatures. Aceto-compounds were used to plasticize highly hydrogenated cottonseed oil. These mixtures were prepared so that they possessed the consistency of margarine oil at room temperature. These mixtures, when compared with partially hydrogenated oil, butterfat, or a mixture of cottonseed oil and hydrogenated cottonseed oil, were softer below room temperature and firmer above room temperature. A margarine-like product containing 79% of aceto-olein and 18.5% of highly hydrogenated cottonseed oil had a practically constant consistency over the temperature range of −15° to 49°C. (5° to 120°F.). Presented at the 26th Fall Meeting of the American Oil Chemists' Society, Cincinnati, O., Oct. 20–22, 1952. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, U. S. Department of Agriculture.     

Formulation of products from soybean oil

High quality shortenings and margarines may be produced using soybean oil as the only fat source or using soybean oil as the primary fat source with the addition of a small amount of hydrogenated cottonseed or palm oil to provide crystal stability. These shortenings and margarines are manufactured by direct hydrogenation or by blending hydrogenated and/or unhydrogenated base stocks. The properties of soybean oil preclude the need for processes other than hydrogenation and blending to produce most margarine and shortening products. It is possible to design an integrated base stock program in which a limited number of base stocks may be used jointly in margarine and shortening formulations. This type of base stock program results in fewer hydrogenation department heels and simplifies scheduling of the hydrogenation department as well as scheduling of overall operations. Solid fat index (SFI) is the analysis used for final product consistency control. While base stocks are blended to meet a final SFI requirement, this analysis is too time-consuming to be used in hydrogenation control and individual hydrogenation batches are controlled using refractometer number and congeal points. Finished product characteristics are a result of decisions that must be made regarding characteristics such as plastic range and AOM stability, which are incompatible.     

Production of branched-chain fatty acids from sterculia oil

Methyl sterculate was rearranged by use of 0.5% of rhodium catalyst to isomeric conjugated diene fatty acid methyl esters containing both methylene-and methyl-branched isomers. The rearanged products were hydrogenated directly to saturated, methyl-substituted, branched-chain fatty acid methyl esters with the methyl substituent at one of the positions formerly occupied by the cyclopropenoid ring. The crude branched-chain fatty acids from these esters were purified by recrystallization from a mixed solvent of ethanol and water (80:20, v/v) and flash distillation; the product contained about 90% of branched-chain fatty acids (C₁₉:80%, C₁₈:10%). Esters of the branched-chain fatty acid were prepared with 2-ethylhexyl alcohol or trimethylolpropane, and the characteristic properties of these esters were investigated. The branched-chain fatty esters appear to have potential utility in lubricants; other uses may be possible. Presented at the AOCS meeting in New Orleans, May 1981.