US2819318A - Alcohols derived from babassu oil - Google Patents

Description

United States Patent No Drawing. Application December 2, 1953 Serial No. 395,836 3 Claims. (Cl. 260-632) This invention pertains to a novel composition of matter and the production thereof, and in particular is concerned with the production of a novel mixture of alcohols derived from babassu oil.

Babassu kernel oil is obtained from the kernels of the seed or nut of a variety of palm. The oil is generally obtained by first decorticating the seed or nut to remove the shell from the kernel and the kernel is then subjected to either an expression or extraction operation in order to obtain the oil. Normally, the oil is not subjected to further tretament except perhaps washing, deacidification, or the like. The oils thus obtained have been used primarily in the soap and edible fat industries. As a result of my work in this field, I have found that a novel composition can be obtained from babassu oil which has many additional and diverse uses other than the uses employed for the oil itself thus far.

It is an object therefore of this invention to provide a new and novel composition of matter. A further object is to provide a mixture of alcohols derived from babassu oil. A still further object of this invention is to provide a process for preparing this mixture of alcohols. Other objects of this invention will become apparent from the discussion hereinafter.

The novel composition of this invention is a mixture of alcohols corresponding in the number of carbon atoms to the fatty acid radicals of babassu oil. The novel composition of this invention is obtained when babassu oil is reduced by an alkali metal-reducing alcohol process. The mixture of alcohols is characterized in that the unsaturation of the original babassu oil is retained when using an alkali metal-alcohol reduction process. Thus, this invention provides a novel mixture of alcohols having properties for various uses as further described here inafter.

The raw material from which the novel composition of this invention is obtained will vary somewhat in analysis. It is to be understood that the mixture of alcohols of this invention includes the mixture obtained by a reduction process when treating the raw oil and also oil which has been refined in various ways such as, for example, deacidification and the like. A typical analysis of babassu oil is as follows:

Unsaturated fatty acid constituents percent 13 Oleic-l2.2 percent Lino1eicl.l percent Saturated fatty acid constituents ..percent 87 Caproic0.3 percent Caprylic--7.l percent Capric8.3 percent Laurie-47.3 percent Myristic14.5 percent Palmitic-7.l percent Stearic-2.0 percent Arachidic0.1 percent Saponification number 254.1 Acid number 6.8 Ester number 247.3 Iodine number 19.3

Babassu oil comprises primarily triglycerides of the fatty acids. Therefore, the fatty acid constituent percentages above are percentages of the total fatty acid portion of the triglycerides. The fatty acid portion of the triglyceride comprises fatty acids containing 6 to 20 carbon atoms both saturated and unsaturated.

The novel composition of this invention is the mixture of alcohols obtained when reducing a raw mate rial such as typified above. The mixture of alcohols will vary corresponding to the variance in analysis of the starting material. However, the analysis of this new and novel composition will comprise at least a weight percent hydroxyl of 6.0, Wijs iodine number of at least 18.0, an acid number not greater than 5.0, and a saponification number not greater than 10.0. The number of carbon atoms of the individual alcohols of the mixture will correspond to the number of carbon atoms of the fatty acids of the starting material with very little, if any, change in unsaturation. Becauseof the variance in analysis of the starting material, the average molecu- "lar weight of the novel mixture of alcohols of this invention cannot be defined precisely. However, the average molecular weight ordinarily will be greater than and generally between about and 210.

As mentioned above, the novel composition of this invention is produced by treating babassu oil simultaneously with an alkali metal and a reducing alcohol. Briefly, the process involves reacting the fatty acid esters with an alkali metal and a reducing alcohol, hydrolyzing the alkali metal alcoholates thus formed, and separating the high molecular weight alcohols from the re ducing alcohol, caustic, solvent, and glycerol, when the triglycerides are reduced. In a typical process, but by no means limiting, between about the stoichiometric equivalent amount and 5 percent excess of the alkali metal is employed over that required to produce the corresponding alcoholates. Similarly, between about the stoichiometric equivalent amount and 5 percent excess of a reducing alcohol is employed over the theoretical requirement. The alcoholates formed are hydrolyzed by treating with water and the product alcohols are separated therefrom. The chemical reactions involved can be depicted as follows:

CHr-OH where R, R and R can be the same or different and are carbon chains having about 6 to 20 carbon atoms, R is an alkyl radical, and M is an alkali metal.

In carrying out the above reactions to prepare the alcohol mixture of this invention, a preferred method is to utilize the alkali metal in the form of subdivided particles. Alkali metal dispersions which are well known in the art, are well suited for this purpose. These dispersions are prepared by melting the alkali metal in an inert organic medium which generally has a boiling point above the melting point of the alkali metal. During this operation the mixture is highly agitated in order to form the dispersion. Various dispersion media are well known in the art and can be employed in preparing the alkali metal dispersions. Among such media are for example, toluene, xylene, dihydronaphthalene, petroleum fractions, heavy alkylates, and the like. Still other dispersion media can be employed, the foregoing serving merely as illustrative examples. The proportion of the alkali metal to the dispersion medium can be varied, and dispersions having metal concentrations from about trace quantities to about 60 percent by weight are common. It is preferred to utilize about a 50 percent by weight, or less, dispersion. Likewise, the particle size will vary and the solution will have particles averaging about 50 microns in size and smaller. It is preferred that the particle size average less than about 20 microns. Smaller particle sizes enhance the reaction rate and provide increased contact between the metal and the babassu oil and reducing alcohol. Although any of the alkali metals can be employed, sodium is preferred here, primarily because of its greater availability and economy.

The reducing alcohols employed when producing the composition of this invention can be the primary, secondary, or tertiary alcohols. For example, lower molecular Weight primary, secondary, or tertiary alcohols, such as those having less than about 10 carbon atoms can be used. Likewise, the alcohols produced by the process can be employed as reducing alcohols, and these include alcohols having from about 10 to 30 carbon atoms. However, it is preferred to utilize the secondary alcohols inasmuch as it has been found that they are less reactive toward the alkali metal and are quite suitable for use in ester reduction processes. Among such secondary alcohols are for example, propanol-Z, butanol-2, pentanol-Z, pentanol-3, methylisobutylcarbinol, 2-methylbutanol-3, hexenol-Z, hexanol-3, phenylmethyl carbinol, phenylethyl carbinol, cyclopentanol, and cyclohexanol. Still other secondary alcohols can be employed, the foregoing serving merely as illustrative examples.

The solvent used in this process can be any solvent which is unreactive with the particular reactants of the process. In a preferred embodiment, the solvent which is employed is the same organic material utilized in the preparation of the alkali metal dispersion. However, other materials can be used to equal advantage. The proportion of the solvent employed can vary within wide limits. The proportion of solvent to ester can be between the limits of 0.25 and 5.0 to l, and, preferably, between 0.25 and 1.3 to 1 part by weight.

To further demonstrate the novel composition of this invention and a process for its manufacture, reference is made to the following example wherein all parts and percentages are by weight.

To a vessel equipped with external heating, a hold-up tank, and a means for agitation was added 85.8 parts of sodium and 173 parts of toluene. This mixture was then vigorously agitated and heated to a temperature of about 110 C. thereby producing a dispersion of sodium. To this dispersion was added a mixture of 200 parts babassu oil (saponification number, 254.1; acid number, 6.8; iodine number, 19.3; percent hydroxyl, 173 parts of toluene, and 198 parts of methylisobutylcarbinoi over a period of 45 minutes. The mixture was maintained at the reflux temperature during this period about 173 parts of toluene were removed therefrom by vaporization and hold-up. When the addition was completed, the mixture was permitted to reflux for an additional 15 minutes. At the end of this period, the reduction mixture was mixed with 746 parts of hot water in order to hydrolyze the alcoholates formed. During the hydrolysis, 15 parts of water and 52 parts of toluene were removed by vaporization in order to break a slight emulsion which had formed. The hydrolyzed mixture then separated into 2 layers and the water layer containing caustic and glycerine was removed therefrom. The organic layer was washed with additional water to result in a solution having a pH of about 7.0. The thus washed organic layer was then distilled under reduced pressure to remove the toluene and methylisobutylcarbinol. The mixture of product alcohols, representing a yield of 87 percent, had a saponification number of 5.8; acid number of 2.8; iodine number of 21.5; and a percent hydroxyl of 8.2.

The novel composition of this invention can be prepared by similar methods of ester reduction other than the particular mode or sequence of operations described in the preceding example. It is to be understood that the specific proportions disclosed here are merely illustrative and can be varied within wide limits. Similarly, lay-products such as glycerine and caustic can be recovered for their values. Ordinarily the solvent and reducing alcohol will be recycled for reuse in the process.

Other variations in the over-all ester reduction process can be made. It has been found that the raw babassu oil can be first transesterified, preferably with an alcohol corresponding to the reducing alcohol. A preferred method of transesterifying the glycerides is to react them with an aliphatic alcohol in the presence of an alkaline alcoholysis catalyst. In this manner, the glycerine is separated prior to the actual ester reduction operation and is replaced by the esterifying alcohol. In this instance, a secondary alcohol is again preferred, such as, for example, methylisobutylcarbinol and the like. The newly formed esters are then reduced similar to the process as indicated above. The chemical reactions are essentially the same with exception that monoesters will be reduced rather than triglycerides and the proportion of reactants will vary accordingly. A particular advantage of this technique is that glycerine yield is greater.

The novel composition of this invention can be applied to a variety of uses. When the mixture of alcohols is sulfated or sulfonated, improved alkyl sulfate and sulfonate detergents, wetting agents, emulsifiers, and the like are produced. In some instances, the sulfating or sulfonating agent may react with some of the unsaturated portions of the mixture. Likewise, various sulfation techniques can be employed which selectively sulfate only the hydroxyl radical of the alcohols of this invention. The salts of these products can be formulated with other sulfonated products, such as dodecylbenzene sulfonic acid, with amides, inorganic phosphates, and sulfates, and the like constituents of synthetic detergent compositions.

A still further use for the novel composition of this invention comprises additives and additive intermediates for lubricants. Thus, for example, when the mixture of alcohols of this invention or their derivatives such as, for example, esters, metal salts, and the like, is added to mineral lubricating oils, it will enhance their lubricant properties. Likewise, when the sulfated and sulfonated derivatives, as mentioned above, of the mixture of alcohols are employed in the lubricating oils, improved lubricants are obtained.

The novel mixture of alcohols of this invention is also admirably suited as an intermediate for the production of other useful organic chemicals or mixtures thereof. For example, the double bonds of the unsaturated constituents can be subjected to any of the known reactions of double bonds to produce compounds such as epoxides, halogenation derivatives, and the like. Further, the alcohols can be reacted with various acids to produce the corresponding esters. Likewise, they may be oxidized to produce the corresponding aldehydes and acids. A still further use of the novel composition of this invention is that it, and its ester and ether derivatives can be employed as a plasticizer composition. Additionally, when the novel mixture of alcohols of this invention is fractionated, as for example, into a fraction containing lower molecular weight alcohols and a fraction containing the higher alcohols, these fractions can be employed in the foregoing uses and others. These and many other uses will be apparent to those skilled in the art.

Having thus described the novel composition of this invention and a process for its manufacture, it is not intended that it be limited except as noted and prescribed in the following claims.

I claim:

1. As a new composition of matter, a mixture essentially of higher molecular alcohols derived from babassu oil corresponding in the number of carbon atoms, degree of unsaturation, and in substantially the same percentages to the fatty acid radicals of said oil, said mixture being characterized by having an average molecular weight greater than 160, a percent hydroxyl of at least 6.0, and an iodine number of at least 8.0.

2. As a new composition of matter a mixture essentially of higher molecular alcohols derived from babassu oil, said alcohols corresponding in the number of carbon atoms and degree of unsaturation to, and in substantially the same percentages as, the fatty acid radicals of babassu oil, said mixture having a saponification number of about 5.8, an acid number of about 2.8, an iodine number of about 21.5, and percent hydroxyl of about 8.2.

3. A process for the manufacture of a mixture of alcohols derived from babassu oil comprising reacting said oil with between about the stoichiometric equivalent amount and 5 percent in excess of that amount of sodium, and between about the stoichiometric equivalent amount and 5 percent in excess of reducing alcohol in the presence of between 0.25 to 5 parts by weight of an inert organic solvent based upon the weight of said oil, hydrolyzing the resulting mixture, and separating the product alcohols from the reducing alcohol and solvent thereby recovering a mixture of higher molecular alcohols corresponding in the number of carbon atoms to the fatty acid radicals contained in babassu oil with essentially the same degree of unsaturation and in substantially the same percentages as the fatty acid radical of said oil.

References Cited in the file of this patent UNITED STATES PATENTS 1,968,797 Bertsch July 31, 1934 2,104,803 Henke et al. Jan. 11, 1938 2,563,044 Kamlet Aug. 7, 1951 2,579,257 Hansley et al. Dec. 18, 1951 2,607,806 Bigot Aug. 19, 1952 2,647,932 Blinka et al. Aug. 4, 1953 2,748,175 Wilson May 29, 1956 OTHER REFERENCES Kastens: Ind. and Eng. Chem., vol. 41 (1949), pages 438-46.

Miner et al.: Glycerol, Reinhold, N. Y., 1953; pp. 71-76.

Levitt: Oil, Fat and Soap, Chemical Publ. Co., N. Y., 1951, pp. 14-18.

Lange: Handbook of Chemistry (8th edit), Handbook Publishers Inc., Sandusky, Ohio, pp. 738-45.

Jamieson: Vegetable Fats and Oils, pages 140-142, second edition, 1943.

Romanus: Inst. Biol. e Tecnol., Inst. Biol. e Pesquisas tecnoL, vol. 8, pp. 813-47 (1953), Chem. Abs., vol. 49, 15723.

Barrett et al.: Industrial and Engineering Chem., vol. 45, pp. 1114-16 (May 1953); Chem. Abs., vol. 48, 2566C.

Hansley: Industrial and Engineering Chem., vol. 39, pp. -62 (1947).

Hilditch: Industrial Fats and Waxes, 3d edit., Balliere, Tindall and Cox, London, 1949; pp. 117-24, 169-72.

Fieser et al.: Organic Chemistry (2d edit), Heath and Co., Boston, 1950; pages 408-17.

Claims (1)

1. AS A NEW COMPOSITION OF MATTER, A MIXTURE ESSENTIALLY OF HIGHER MOLECULAR ALCOHOLS DERIVED FROM BABASSU OIL CORRESPONDING IN THE NUMBER OF CARBON ATOMS, DEGREE OF UNSATURATIOON, AND IN SUBSTANTIALLY THE SAME PERCENTAGES TO THE FATTY ACID RADICALS OF SAID OIL, SAID MIXTURE BEING CHARACTERIZED BY HAVING AN AVERAGE MOLECULAR WEIGHT GREATER THAN 160, A PERCENT HYDROXYL OF AT LEAST 6.0, AND AN IODINE NUMBER OF AT LEAST 8.0.