0
TALL OIL AND TERPENE DERIVATIVES GEORGE H. EICK Arizona Chemical Company, New York, N. Y.
a natural mixture of rosin acids related to abietic acid, fatty acids related to oleic acid, and nonacidic bodies, is the product of the acidification of the skimmings from the black liquor of the alkaline paper industry. Thus, tall oil comes from the heart of the pine tree. It is a byproduct of the southern kraft pulp mills. The first plant for the recovery of the waste product probably was that designed by the Swedish around 1902. They called the product Tallolja (oil of pine). The Germans translated the word to Talloel, or "Oil of Pine" in English. In 1943, the U. S. War Production Board named it "Tall Oil" to eliminate confusion with pine oil. Today, tall oil is of increasing interest in many industries varying from cement to the washing of citrus fruit. Users of tall oil seem to be converting from use of the crude, which is crystalline and dark in color, to the more highly refined fractions, which are lighter in color, noncrystallizing, and relatively odor-free. The refined fractions are obtained either by distillation or fractionation. Examples of refined fractions are Acintol' FA-1 and Acintol FA-2 Fatty Acids, which consist roughly of an equal part of oleic and linoleic acid, and a small percentage of rosin and saturated acids, like palmitic acid. Students, researchers, department heads in chemistry, chemical engineering, and mining engineering, as well as consultants, and industrial testing laboratories all should find these tall oil derivatives of interest, as they are the most inexpensive source of organic acids available today. T A L L OIL,
However, when the tall oil derivative is heated, the abietic and neoabietic acids isomerize into levopirmaric acid, which quickly reacts with the maleic anhydride.
Abietic acid
CH-C~ kH-C)
0
No
A
Maleic anhydride
Rosin maleic anhydride adduct
Acintol D Distilled Tall Oil contains a ratio of approximately two parts of fatty acids to one of rosin acids. (These rosin acids are present in the liquid state.) There is also the pitch-like product, Acinol P Tall Oil Pitch, which is rich in P-sitosterol.
CHEMISTRY OF TALL OIL FATTY ACIDS
The formulas for the basic components are as follows: conjugated: Oleic acid: Palmitio acid:
CH3(CH2),CH=CH(CHs),COOH CH,(CH,),,COOH
The rosin acids in the distilled and fractionated tall oils are analogous to those found in natural wood and gum rosin. A higher percentage of the abietic acid isomer is present, and it is in equilibrium with neoabietic acid, another rosin isomer:
SSitosterol
PSitosterol has been used as an intermediate in the manufacture of feed supplements for cattle and sheep, and in the treatment of arteriosclerosis. USES OF THE TALL OIL FATTY ACIDS
The carboxyl group on the rosin as well as on the fatty acids is the reactive group for many of the reactions. A very important reaction is the condensation of the rosin acid portion of the mixture with maleic anhydride. 'Registered trsdemark, Arizona Chemical Company.
VOLUME 34, NO. 12, DECEMBER, 1957
In keeping in stature with its name, tall oil now ranks third only to linseed and soya bean oil in use in the protective coatings industry. The biggest uses of these tall oil fatty acids are for the preparation of alkyd resins. (An alkyd is a condensation product synthesized by reacting polyhydric alcohol such as glycerol and the glycols with dibasic organic acids such as phthalic, maleic, succinic, sebacic, and carbic.) These condensation products are almost always modified to give some property necessary to the protective coating.
The modifying agent may be a drying, a semidrying, or nondrying oil, a tall oil fatty acid, tall oil rosin, a synthetic resin of the phenol formaldehyde group, ureaformaldehyde resins, and other substances. The tall oil alkyds, for example, give better white retention (less of the yellowing type of oxidation) as compared to linseed or soya, because of the absence of linolenic acid. Another use of tall oil fatty acids is in the preparation of esters (the reaction of an acid material with a polyhydric alcohol such as pentaerythritol; or, a resinous alcohol like an epoxy to give the corresponding ester). Tall oil now fits into forty-one different industries. Some examples are as follows: Cement: As an air entraining agent. Citrus fruit washing: The purpose of washing the fruit is to get rid of dirt, bug juice, smog, and scale. Flotation: Generally speaking, the finely ground mineral 8U8pended in water is treated vith small amounts of tall oil plus a. frothing agent. The tall oil selectively reacts with those particles which are basic in nature, thereby forming a. monomoleoular film and changing the wettahility of these particular particles. The particles thus are carried into the froth and floated away; the nonreactive particles are removed from the hottam of the flotation cell. Rubber: I n the production of soaps used to emulsify and cause an emulsifier in oilfoaming in latex bponge compouids; extended rubber: in reclaiming: in the ~roductianof butvl ammonium tallate, used as an ac&ator in lubber compounding. Soaps: Cleaningcompounds; degreasingagents; disinfectants; emulsions; metallic soaps; oil well drilling compounds; sulfonation. Synthetic organic detergents: Ethylene oxide type condensates.
The U. S. Department of Agriculture has conducted some promising experiments with a-pinene. One reaction investigated is as follows: CHa
a-Pineue
Pinonic acid
COOH
NaHCIOa A
Pinic acid
The corresponding esters of these acids have shown considerable promise as jet lubricants. Another new product is pinane hydroperoxide.
I
I
I\\
I \
\ I arPinene
Pinane
IOOH I \
TERPENE DERIVATIVES
Terpene products also are derived from the sulfate process of paper pulp production. Wood chips are digested with sodium hydroxide and sodium sulfide, in order to dissolve the cementing material and reduce the wood to its basic fiber content. The steam that passes off from the digesters is condensed to yield cmde sulfate turpentine. Further refinement gives Aeintenel A a-Pinene, Acintene B p-Pinene, and Acintene P Refined Sulfate Wood Turpentine. CH2
a-Pinene is used as a solvent in paste and wax polishes and as an intermediate for a host of chemical products. It can be converted easily to terpin hydrate and subsequently to synthetic pine oil, terpineols, camphene, and synthetic camphor.
Pinane hydroperoxide
Pinane hydroperoxide is reported to he a promising catalyst for the production of GRS mbbers. 6-Pinene can be converted readily to a-pinene, but the reveme reaction is not feasible. B-Pinene offers several advantages over the alpha form, namely greater and purer yields of certain products that cannot be made from a-pinene. The beta form can be polymerized to a hydrocarbon resin of relatively high melting point. Refined sulfate wood turpentine is generally used as a solvent for paint, waxes, automobile polish, shoe polish, floor polish, and stains for wood. Even some insecticides contain turpentine because of its insectkilling abilities. As the amount of bleached and unbleached sulfate pulp is increasing each year, it has been predicted that by 1960 industry will produce about 1,440,000,M)O pounds of tall oil annually. The tall oil derivatives should, therefore, continue to be the most inexpensive source of organic acids and relatively stable in price. The future for tall oil, its distillations, and fractionations, and for its companion terpene products, appears intriguing indeed.
JOURNAL OF CHEMICAL EDUCATION
