Unusual resin acids in tall oil

Combinations of silver nitrate column, gel permeation and gas liquid chromatography were used to isolate 8,15-pimaradien-18-oic, 8,15-isopimaradien-18-oic and the secodehydroabietic, 2α-[2′(m-isopropylphenyl)ethyl]1β,3α-dimethylcyclohexanecarboxylic acids as their methyl esters from a fraction of distilled tall oil. Presented before the Division of Cellulose, Word and Fiber Chemistry at the 155th National Meeting of the American Chemical Society, San Francisco, April 1968.     

Comparative value of fatty acids and resin acids of tall oil in soaps

Summary A study has been made of the detergency and foaming power of soaps made from a typical acid-refined American tall oil. Sodium soap of tall oil, straight tall oil fatty-acid soap, and straight tall oil resin-acid soap were evaluated. The effect of fatty acid-resin acid ratio was determined by using mixtures of those soaps. Sodium rosinate, sodium oleate, and mixtures of these soaps were used as comparison standards. Curves plotted show wash-test data and foaming values as functions of the ratio of fatty soap to resin soap. The data indicate in terms of detergency: a) tall oil soap has a higher value than sodium rosinate; b) sodium oleate is better than tall oil fatty-acid soap, but the latter is approximately equivalent to soaps from various unsaturated vegetable oils; c) both tall oil resin-acid soap and rosin soap have low detergency on cotton; d) the detergency of most mixtures of tall oil fatty-acid and resin-acid soaps at lower concentrations is greater than would be predicted from the individual soaps, indicating a synergistic effect. As a rough approximation, tall oil soap without unsaponifiables is equivalent to a corresponding mixture of sodium oleate and sodium rosinate. The presence of unsaponifiables lowers both detergency and foaming. Tall oil soap is somewhat less sensitive to hard water than sodium oleate. Significant differences between detergencies of soaps, and especially between soap mixtures, are obscured when launderometer tests are run at moderate soap concentrations. These differences are readily detected at lower concentrations. Presented at 113th meeting of the American Chemical Society, Chicago, Ill., April 14–23, 1948.     

Capillary gas chromatography-mass spectrometry of resin acids in tall oil rosin

The resin acid composition of Finnish tall oil rosin was investigated by gas chromatography and mass spectrometry employing open tubular capillary columns. On a column coated with 1,4-butanediol succinate, 16 resin acids found in tall oil rosin samples were well resolved, and mass spectra could be recorded. All resin acids were confirmed to be of the pimaric and abietic types by gas chromatographymass spectrometry. Eight of the acids were not detected in the corresponding crude tall oils and evidently had been formed during the technical distillation process. The presence of 8,15-pimaradien-18-oic and 8,15-isopimaradien-18-oic acids in the rosin, but not in the crude tall oil, indicates that the pimaric type acids also undergo extensive isomerization during tall oil distillation. Additionally, three dihydroabietic acids and two acids with identical mass spectra, tentatively stereoisomers of 7,9(11)-abietadien-18-oic acid, were formed during the distillation process.     

The fat acids of American tall oil

Summary The composition of the fat acids of six samples of American tall oil has been determined. They are all quite similar in fat acid composition. The average values were: linoleic acid 48%; oleic acid 45%; saturated acids 7%. There is present approximately 11% of conjugated linoleic acid, probably formed by the action of alkali and heat during the cooking of the pulp from which the tall oil was formed. Detailed fractional distillation of a sample of the methyl esters of the fat acids showed that the saturated acids are mostly palmitic, that there may be about 1% of palmitoleic, and that the conjugated linoleic acid present can be separated and concentrated by fractional distillation. Paper No. 65, Journal Series, Research Department, General Mills, Inc.     

Corrosion of alloys in tall oil distillation service

Plant corrosion tests of various metals and alloys in tall oil distillation streams present the effect of alloy composition on corrosion rate. Stream temperature, alloy composition and stream composition are correlated so as to provide a useful guide to material selection for tall oil distillation plants. Alloys exposed to corrosion test were iron or nickel base with chromium plus varying amounts of molybdenum. Molybdenum is the most important alloy addition in reducing the rate of corrosion attack, with corrosion attack at a very low rate, <.1 mil per year, at the 6% molybdenum level in the most aggressive stream tested, i.e., 85% fatty acids at 518F. The presence of chromium does not appear to be essential to obtaining good corrosion resistance to the more corrosive conditions. Corrosion rates increase with increasing temperature. The streams classed as high in fatty acids are much more corrosive than those which are classed as high in rosin acids. Vapor phase streams are more corrosive than liquid phase streams. Corrosion attack is normally from pitting. Most of the more corrosive conditions can be handled with an alloy containing 3% to 4% molybdenum (AISI Type 317), but some process conditions require higher molybdenum contents in order to obtain acceptable corrosion rates. Less corrosive streams can be handled with an alloy containing less than 3% molybdenum (AISI Type 316).     

Spectrophotometric analysis of tall oil rosin acids

Summary About half of the rosin acids in whole and distilled tall oil consist of abietic and neoabietic acids, as distinguished from hydroabietic acids, dehydroabietic acid, and the pimaric acids. In this respect the tall oil rosin acids are similar to those from gum or wood rosin. This was established by spectrophotometric analysis of the rosin acids from whole tall oil, double distilled tall oil, rosin acids crystallized from tall oil, and rosin acids separated from tall oil by fractional distillation. The rosin acids crystallized from tall oil contained the highest percentage of abietic acid, but the sum of abietic and neoabietic acids was only slightly higher. The rosin acids from acid refined tall oil contained appreciably less abietic and neoabietic acid than the others. Before spectrophotometric analysis the rosin acids were isolated from the tall oils in about 95% yield by cyclohexylamine precipitation.     

Origin of bicyclic fatty acids in tall oil

It was shown that two bicyclic fatty acids present in Finnish tall oil were formed from (5Z, 9Z, 12Z)-5, 9, 12-octadecatrienoic acid, pinolenic acid (I). Under the alkaline conditions of sulfate pulping, pinolenic acid forms conjugated isomers which undergo Diels-Alder cyclization during the heating in the tall oil distillation. The cyclization products, here called cyclopinolenic acids, are bicyclic fatty acids and stereoisomers of 4-(5-pentyl-3a, 4,5,7a-tetrahydro-4-indanyl) butanoic acid (IV and V).     

Monomer and amino resin modified tall oil fatty acid alkyds

Summary Monomer modified tall oil fatty acid trimethylolethane medium type of phthalic alkyds made by the High Polymer Alkyd Technique show improved properties in dry time, mar resistance, and flexibility as compared with monomer modified conventional prepared systems. Greater hardness, less color degradation, greater resistance to extended periods at high temperature, and alkali and detergent resistances result from the urea and melamine resin modifications of tall oil fatty acid High Polymer alkyds than is obtained with similarly modified conventional alkyds.     

蒸馏妥尔油改性酚醛树脂的合成与应用

利用造纸厂纸浆废液中分离出的蒸馏妥尔油,合成了改性酚醛树脂,并对反应机理和树脂结构进行了分析。结果表明,当苯酚与甲醛的摩尔比控制为1∶0.6~0.9,蒸馏妥尔油加入量为苯酚的40%~60%时,改性的酚醛树脂性能最佳,与聚合物和溶剂的混溶性得到提高。     

Identification of minor cyclic fatty acids in fractionated tall oil

The structure of several minor cyclic fatty acids present in Finnish tall oil fatty acids are elucidated by gas chromatography-mass spectrometry. The origin and mechanism of formation of these cyclic fatty acids are discussed. The cyclic fatty acids identified in tall oil fatty acids are: 4-(5-pentyl-3a,4,7,7a-tetrahydro-4-indanyl)butanoic acid,ω-(o-alkylphenyl)alkanoic acid, 2,6-dimethyl-9-(3-isopropylphenyl)-6-nonenoic acid, 4-(5-pentyl-4-indanyl)butanoic acid, and 4-(2-hexyl-1,2,4a,5,6,7,8,8a-octahydro-1-naphthyl)butanoic acid. In addition, three different branched or cyclic unsaturated C₁₉ fatty acids are reported to be present in tall oil.     

Amide plasticizers from safflower and tall oil derived fatty acids

Fatty acids derived from a high oleic strain of safflower seeds are eminently suited for the preparation of compatible and efficient N,N-disubstituted fatty acid amide polyvinyl chloride plasticizers with low temperature properties in the adipate-azelate range. N,N-disubstituted amides of tall oil-derived acids, Westvaco Type 1480, give comparable plasticizing performance. Polyvinyl chloride compositions plasticized with the hexachlorocyclopentadiene adduct of N,N-dibutyloleamide show no soapy water extraction loss. So. Market. Nutr. Res. Div., ARS, USDA.     

Improved method for rosin and fatty acids in tall oil

Journal of the American Oil Chemists' Society - An analytical procedure is presented for determination of the rosin and fatty acid contents of tall oil products. Rosin acids are determined by...     

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.     

Characterization of products from clay catalyzed polymerization of tall oil fatty acids

Products obtained by acid clay catalyzed dimerization of oleic, elaidic, and tall oil fatty acids were characterized. The monomeric products (35% of total) consisted of stearic, octadecenoic (66%trans-), and mid chain monomethyl branched acids, both saturated and unsaturated. The polymeric products (65% of total) consisted of linear, alicyclic, aromatic, and polycyclic dimers. The tall oil fatty acid based dimer closely resembled oleic dimer in polycyclic character and linoleic dimer in aromatic and linear structures. Oleic dimers contained the highest linear structural content, while linoleic dimer contained the largest polycyclic content. Alicyclic structures were the principal components of all three products. The monocyclic dimer structures present consisted of six membered ring systems with linoleic and tall oil fatty acid dimers containing the highest aromatic contents. Presented at the National American Chemical Society Meeting, New York, August 1972.     

Diterpene resin acids: Major active principles in tall oil against Variegated cutworm,Peridroma saucia (Lepidoptera: Noctuidae)

Tall oil, a by-product of the kraft process for pulping softwood, has been shown to have insecticidal properties. In the present study, the active principles in tall oil against the variegated cutworm,Peridroma saucia Hübner, were investigated. GC-MS analysis showed that abietic, dehydroabietic, and isopimaric acids were major resin acid components of crude tall oil and depitched tall oil. When crude tall oil samples of differing resin acid composition were incorporated into artificial diet at a concentration of 2.0% fresh weight, they suppressed larval growth by 45–60% compared to controls. This suppression was significantly (P0.05) correlated with the equivalent contents of abietic, dehydroabietic, isopimaric, and total resin acids. These results were also evident from a diet choice test, showing that the second-instar larvae obviously selected diets with low levels of resin acids when different diets were randomly arranged in a Petri dish. Bioassays with pure resin acids (abietic, dehydroabietic, and isopimaric acids) demonstrated that all individual chemicals have similar bioactivity against this insect. Comparison of the bioactivities of depitched tall oil and an equivalent mixture of pure resin acids in thePeridroma chronic growth bioassay indicated that pure resin acids and depitched tall oil share a common mode of action to this insect. This study confirms that resin acids are major active principles in tall oil against the variegated cutworm, but other chemicals likely also contribute to the bioactivity of tall oil.     

HPLC determination of long chain saturated fatty acids in tall oil rosin

A method was developed for the analysis of long chain saturated fatty acids or their esters from tall oil or tall oil rosin. The method is specific for 18 through 28 even carbon number acids with a detection limit for each at 0.05% based on rosin. Ultraviolet detection is achieved through phenacyl derivatization. Omission of the saponification step allows selective determination of the free fatty acids.