Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS3353966 A
Publication typeGrant
Publication dateNov 21, 1967
Filing dateMar 27, 1964
Priority dateMar 27, 1964
Publication numberUS 3353966 A, US 3353966A, US-A-3353966, US3353966 A, US3353966A
InventorsHugenberg Frederick R, Lutton Edwin S
Original AssigneeProcter & Gamble
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Salad oils and method of making them
US 3353966 A
Images(6)
Previous page
Next page
Description  (OCR text may contain errors)

United States Patent 3,353,966 SALAD OILS AND METHOD OF MAKING THEM Frederick R. Hugenberg, Deer Park, and Edwin S. Lutton, Cincinnati, Ohio, assignors to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed Mar. 27, 1964, Ser. No. 355,424 8 Claims. (Cl. 99163) ABSTRACT OF THE DISCLOSURE Salad oil containing, as an inhibitor of solids deposition, 0.001-1% carbohydrate, 50100% esterified with -85% C14"C22 hydroxy fatty acid and 15-85% (DH-C22 saturated fatty acid.

This invention relates to improved salad oils and to a method for improving salad oils. More particularly, it relates to salad oils which can be stored at relatively low temperatures for extended periods of time without clouding, and which are capable of being used in preparing mayonnaise emulsions that can be stored at low temperatures without breaking of the emulsion.

Salad oils frequently are stored in refrigerators. The prolonged cooling of such oils to temperatures normally encountered in refrigerators, such as from about 40 F. to about 50 F., generally results in the deposition of crystalline material, usually solid triglycerides, from the oil. This material may appear in the form of a cloud, or as clusters of crystals, and is considered objectionable by the consumer. In general, the tendency to form solid triglycerides in oils also adversely atfects the suitability of the oil for use in mayonnaise emulsions. Mayonnaise emulsions prepared from such oils tend to be unstable at low temperatures and are easily broken.

Frequently it is desirable to hydrogenate natural vegetable oils, such as soybean oil, which can be used as base salad oils, in order to improve their oxidative stability; however, hydrogenation tends to produce oil components of decreased solubility at ordinary refrigeration temperatures. These less soluble oil components are not completely removed by ordinary commercial winterization treatment, such as fractional crystallization.

Accordingly, the primary object of this invention is to provide an improved salad oil which will remain free from clouding or crystal formation for long periods of time at refrigeration temperatures. It is another object of this invention to provide a method for retarding the deposition of high-melting solids from salad oils.

It has now been found, according to the present invention, that the storage time at conventional refrigeration temperatures without clouding can be greatly extended for a given salad oil by dissolving therein from about 0.001% to about 1%, by weight, of a crystallization inhibitor which is a carbohydrate substance esterified with both a hydroxy higher fatty acid and a saturated higher fatty acid. The carbohydrate substance is selected from the group consisting of oligosaccharides and polysaccharides having from 2 to about 15 saccharide units per molecule and is about 50% to about 100% esterified, based on the total hydroxyl equivalency of carbohydrate substance and higher hydroxy fatty acid. About 15% to about 85% of the esterifying carboxyl equivalency is contributed by hydroxy fatty acid having from about 14 to about 22 carbon atoms and from 1 to about 8 hydroxyl groups and about 15% to about 85% of the esterifying carboxyl equivalency is contributed by saturated fatty :acid having from about 14 to about 22 carbon atoms. The balance, if any, of the esterifying carboxyl equivalency can be contributed by fatty acid selected from the group consisting of fatty acids having from 2 to about 12-carbon atoms and unsaturated fatty acids having from about 14 to about 22 carbon atoms.

The oligosaccharides and polysaccharides which can be used to form suitable esters in the practice of this invention include, by way of illustration: disaccharides such as sucrose, maltose, lactose, and melibiose; trisaccharides such as mannotriose and raffinose; tetrasaccharides such as stachyose; and dextrins and other oligosaccharides and polysaccharides having up to about 15 saccharide units per molecule.

Many of these oligosaccharides and polysaccharides are obtained from well-known commercial carbohydrate sources. For example, sugar cane contains about 15% to 20% sucrose and sugar beet about 10% to 17% sucrose; maltose is obtained in about yield by the enzymatic (diastase) degradation of starch; lactose is present in the milk of mammals and is a by-product of the cheese industry, produced from whey; and dextrins are polysaccharides produced by the incomplete hydrolysis of starch with dilute acids or by heating dry starch. Sucrose is the preferred oligosaccharide for forming the carbohydrate esters of this invention.

The hydroxy fatty acids which are used to esterify the oligosaccharides and polysaccharides are long chain, aliphatic, mono-basic hydroxy acids having from about 14 to about 22 carbon atoms and from '1 to about 8 hydroxyl groups in the molecule. They can be, for example, the mono-, di-, tri-, and tetrahydroxy derivatives of saturated or unsaturated fatty acids such as myristic, myristoleic, palmitic, pal-mitoleic, stearic, oleic, linoleic, linoienic, arachidic, elaidic, gadoleic, arachidonic, behenic, erucic, brassidic, and clupanodonic :acids.

Specific examples of the above hydroxy fatty acids are 9 hydroxystearic; 12 hydroxystearic; 9,10 dihydroxystearic; 9, 10,'12 trihydroxystearic; 9,12,13 trihydroxystearic; and 9,10,12, 13-tetrahydroxystearic acids.

All stereoisomers of the above hydroxystearic acids can be used in the practice of this invention; for example,

erythro-9,IO-dihydroxystearic acid can be substituted for three-9,10-dihydroxystearic acid with equivalent results.

Another common example of a specific suitable hydroxy fatty acid is ricinoleic acid which is 12-hydroxy-A9-octadecenoic acid. This acid is the major constituent of castor oil and is present in that oil as the glyceride in an amount of about 80% to Many of the desired hydroxy fatty acids can be prepared synthetically by oxidative hydroxylation of unsaturated fatty acids through the use of oxidizing agents such as potassium permanganate, osmium tetroxide, peracetic acid, perbenzoic acid and other peracids. For example, oleic acid can be readily dihydroxylated to form 9,10-dihydroxystearic acids and linoleic acid can be readily tetrahydroxylated to form 9,10,12,13-tetrahydroxystearic acids by methods well known to those skilled in the art. Trihydroxy fatty acidscan be readily obtained from castor oil by reaction with peracetic acid followed by saponification and splitting off of the desired acids in accordance with well-known methods of preparation.

The saturated higher fatty acids which are used to esterify the oligosaccharides and polysaccharides are long chain aliphatic monobasic acids having from about 14 to about 22 carbon atoms and include myristic, palmitic, stearic, arachidic, and behenic acids. These fatty acids can be readily obtained from hydrogenated glycerides by saponification, acidulation, and isolation procedures. The fatty acid desired determines the choice of glyceridic material used. For example, a technical grade of stearic acid can be obtained from highly hydrogenated soybean oil and a technical grade of behenic acid can be obtained from highly hydrogenated rapeseed oil.

By way of example, a suitable ester for this invention is sucrose esterified with an average of 2 hydroxy higher fatty acid groups and 4 palmitic acid groups. Other long chain saturated fatty acid groups such as myristic, stearic, arachidic, and behenic acids, and mixtures thereof, can be present in place of part or all of the palmitic acid groups. The oligosaccharides and polysaccharides should be at least about 50% esterified, based on the total hydroxyl equivalency of oligosaccharides and polysaccharides and hydroxy higher fatty acid, about 15% to about 85% of the total esterifying carboxyl equivalency being applied by hydroxy higher fatty acid and about 15% to about 85% of the total esterifying carboxyl equivalency being supplied by saturated monobasic higher fatty acid. Subject to this limitation, carboxyl equivalency can be supplied additionally from short chain fatty acids such as acetic, propionic, butyric, valeric and caproic acids, or from long chain unsaturated fatty acids such as myristoleic, palmitoleic, linoleic, linolenic, elaidic, gadoleic, arachidonic, erucic, brassidic, and/ or clupanodonic acids.

The oligosaccharide and polysaccharide esters of this invention can be prepared by various well-known methods for preparing esters. For example, the oligosaccharides and polysaccharides can be reacted with acid anhydrides of suitable hydroxy fatty acids and saturated fatty acids or of (hydroxy-esterified) hydroxy fatty acids.

It is preferred to obtain the oligosaccharide and polysaccharide esters by means of alcoholysis with the methyl esters of the hydroxy higher fatty acids and saturated higher fatty acids in the presence of suitable catalysts. In these interesterification reactions, it is preferable to react the oligosaccharides and polysaccharides with a methyl ester of the hydroxy higher fatty acid followed by reaction with a methyl ester of the saturated higher fatty acid, although the reverse order of interesterification can be used if desired. Mutual solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, dioxane, pyridine, xylene and toluene are of good value in these interesterification reactions. Catalysts of greatest value are such compounds as sodium methoxide, benzyl trimethyl ammonium methoxide, and others described by Eckey, US. Patent 2,442,532, at col. 24, line 18 et seq., granted June 1, 1948.

Since the hydroxyl groups on the hydroxy fatty acid are esterifiable as well as those on the oligosaccharides and polysaccharides, it should be understood that branching of the acid chain can occur during the above esteri fication or interesterification reactions. This chain-branching, of course, would tend to occur more extensively when the polyhydroxy acids are used. In actual practice, partial removal of branched methyl esters and acids from the reaction products was facilitated by a combination of distillation and alcohol washing or extraction, but it should be understood that the esterified oligosaccharide crystallization inhibitor of this invention can include ester mixtures which contain the branched acid chains.

Although various methods of preparation of the crystallization inhibitors of this invention are described herein, it is to be understood that the invention is not to be limited to any specific method of preparation of these compounds.

A wide variety of oils can be used as base oils which can be made resistant to deposition of high-melting solids at low temperatures in accordance with this invention. Included among suitable oils are the so-called natural salad oils such as olive oil, sunflower seed oil, safliower oil and sesame seed oil. Oils such as cottonseed oil and corn oil preferably are given a preliminary Winterizing, dewaxing, or similar other treatment to remove the highermelting solids to form a good base salad oil. Other oils, such as soybean oil, may require hydrogenation to improve resistance to oxidative deterioration with prolonged storage, and the higher-melting glycerides formed during this hydrogenation treatment preferably are removed by winterization. Base salad oils can be formed also by directed, low-temperature interesterification of animal or vegetable fatty material, followed by removal of highermelting glycerides formed du g U16 r a tio 5 for example, U.S. Patent 2,442,532, granted to E. W. Eckey, June 1, 1948. Another group of oils includes those in which one or more short chain or lower fatty acids having from 2 to about 6 carbon atoms, such as acetic and propionic acids, replace, in part, the longer chain or higher fatty acids present in natural triglyceride oils. Other base salad oils will suggest themselves to those skilled in the art, provided they have a suitable chill test as hereinafter defined. The base salad oils can be used individually or as mixtures of oils. As used herein, the term base salad oil is intended to include any salad oil which will not immediately form solids when cooled to 30 F.

The procedure for measuring the resistance of salad oils to clouding and the crystal inhibiting activity of the esters as used hereinafter involves preheating the oil or oil with inhibitor to a temperature of about 140 F., then aircooling a 100 gram sample at about 30 F. until solids form in the oil. As used herein, the term chill test is intended to define the total length of time at 30 F. (unless some other temperature is specified), until such solids form.

The ester and the base salad oil can be mixed together in any convenient manner. For example, ester in liquid form can be mixed with the oil. If the ester is in solid form, it can be dissolved in the oil, although it may be desirable to heat the oil or the mixture of the oil and ester to facilitate solution. It is to be kept in mind, however, that in all cases the resulting product is merely a physical mixture and there is no chemical reaction between the ester and the oil.

The following examples which come within the scope of the claims will serve to further illustrate the invention; however, it should be understood that the invention is not limited to these illustrative examples since the skilled artisan will be able to devise many more examples after reading the specification and appended claims. In each of the esterified carbohydrate substances used as crystallization inhibitors in these examples, the carbohydrate substance is from about 50% to about 100% esterified, based on the total hydroxyl equivalency of carbohydrate substance and esterifying hydroxy fatty acid, from about 15 to about of the esterifying carboxyl equivalency being contributed by material selected from the group con sisting of saturated and unsaturated hydroxy fatty acids having from about 14 to about 22 carbon atoms and from 1 to about 8 hydroxyl groups, from about 15 to about 85% of the esterifying carboxyl equivalency being contributed by saturated fatty acids having from about 14 to about 22 carbon atoms, and any balance of the esterifying carboxyl equivalency being contributed by material selected from the group consisting of fatty acids having from 2 to about 12 carbon atoms and unsaturated fatty acids having from about 14 to about 22 carbon atoms.

Example 1 Methyl ester of hydrogenated castor oil was prepared by refluxing hydrogenated castor oil with methanol in the presence of alkaline catalyst as follows:

One kilogram of hydrogenated castor oil (iodine value 3.51; acid value 2.58; saponification value 178.5; and hydroxyl value 157.0) was warmed in 400 grams methanol. Three grams KOH dissolved in grams methanol was added and the mixture was refluxed for 2 hours on a steam bath. One liter of hexane was added to the mixture, and it was allowed to stand at room temperature for about 12 hours. Then 250 grams of water was added and the product was thoroughly washed and recovered. Flash distillation yielded 819 grams of methyl ester product having the following analysis:

Iodine value 2.35 Acid value 2.41 Saponificat'ion value 182.2 Hydroxyl value 145.7

Mixed sucrose ester of hydrogenated castor oil and palmitic acid was prepared by catalytic alcoholysis of sucrose and the above methyl ester followed by acylation with palmitoyl chloride as follows:

Sucrose (11.4 grams) was reacted with methyl ester of hydrogenated castor oil (100 grams) in the presence of dimethylformam-ide (100 cubic centimeters) and Triton B40% benzyl trimethylammonium hydroxide catalyst in methanol(10 cubic centimeters) at 60 to 70 C. The methyl alcohol formed by the reaction was driven off by heating with 100 cubic centimeters cyclohexane at 120 to 135 C. over a 3-hour period. The solvents, dimethylformamide and cyclohexane, were stripped off and the reaction product was held under high vacuum for 2 hours at 140 to 145 C. The product (97 grams) was water-washed and recovered from hexane. Analysis:

Twenty grams of the above product was treated with twenty grams palmitoyl chloride in 10 cubic centimeters pyridine and 100 cubic centimeters toluene. The ester was first dissolved in the solvents and then the fatty acid chloride was slowly added with cooling in a water bath. After standing for 2 hours, the reaction mixture was heated to reflux temperature and then allowed to stand at room temperature for 2 days. The solvents were stripped off and the product (30 grams) was washed with water, then washed with .5 K CO solution and was then recovered from hexane. Analysis:

Acid value 10.9 Saponification value 196.7 Hydroxyl value Total fatty acid percent 98.8

When the above mixed sucrose ester of hydrogenated castor oil acids and palmitic acid was dissolved in salad oil consisting of 90% winterized cottonseed oil (refined and bleached liquid oil) and 10% cottonseed oil (refined and bleached liquid oil) and held at 30 F., the chill test was extended beyond the 12 hours for the original salad oil without inhibitor as follows:

Percent added ester: Chill test, hours 0.0 12

Example I] Sucrose (6.85 grams) was dissolved in dimethylformamide (100 cubic centimeters) at 80 C. Then 58 grams of the methyl ester of hydrogenated castor oil prepared as in Example I and cubic centimeters of Triton B was added. After 30 minutes, the mixture was placed under high vacuum at 100 C. and the temperature was increased very slowly to 150 to 160- C. during a period of about 2 hours whereby the solvent was distilled off. The sucrose ester product was water-Washed and recovered, and then the excess methyl esters were topped out of the product at 190 to 210 C. -by distillation.

Five grams of the above sucrose ester product was further esterified by reaction with ten grams palmitoyl chloride in the presence of cubic centimeters pyridine and 50 cubic centimeters toluene. The reaction mixture Acid value 27.5 Saponification value 204.9 Hydroxyl value 0 Total fatty .acid percent 95.6

When the above mixed sucrose ester of hydrogenated castor oil acids and palmitic acid was dissolved in the salad oil of Example I and held at 30 F., the chill test was extended beyond the 12 hours for the original salad oil without inhibitor as follows:

Percent added ester: Chill test, hours Example III A mixed sucrose ester was prepared from Sucrodet (a commercial sucrose dipalmitate-acid value 1.5; Saponification value 115.6; hydroxyl value 426; total fatty acid 58.8%) by methanolysis with the methyl ester of the hydrogenated castor oil of Example I as follows:

Sucrodet (32.7 grams) was reacted with the hydrogenated castor oil methyl esters (82.1 grams) in the presence of cubic centimeters dimethylformamide, 100 cubic centimeters cyclohexane and 5 cubic centimeters Triton B at 90 to C. for 3 to 4 hours. The solvents were stripped off under high vacuum at to C. and the product was water-washed and recovered from hexane. Excess methyl ester was then topped out of the product by distillation at 205 C. and 95 grams of purified product was recovered. Analysis:

Acid value 3.6 Saponification value 164.6 Hydroxyl value 86.1 Total fatty acid percent 91.5

When the above mixed sucrose ester of hydrogenated castor oil acids .and palmitic acid was dissolved in the salad oil of Example I and held at 30 F., thechill test was extended beyond the 12 hours for the original salad oil without inhibitor as follows:

Percent added ester: Chill test, hours When equivalent weights of sucrosedipalmitate monoacetate or sucrose dipalmitate monooleate are substituted for sucrose dipalmitate in the preparation and use of the mixed sucrose ester in the above example, substantially similar improvements in chill test results are obtained.

Example IV Fifty grams of the mixed palmitic and hydrogenated castor oil acid sucrose ester of Example III was further acylated with thirty-seven grams palmitoyl chloride in the presence of pyridine and toluene to yield eighty-four grams of esterified product. Analysis:

Acid value 5.3 Saponification value 190.4 Hydroxyl value 31.1 Total fatty acid percent 83.8

When the above mixed sucrose ester of hydrogenated castor oil acids and palmitic acid was dissolved in the salad oil of Example I and held at 30 F., the chill test was extended beyond the 12 hours for the original salad oil without inhibitor as follows:

Percent added ester: Chill test 0.0 hours 12 0.1 do 198 0.3 days 31 The chill tests described in Examples V to XIII, below, employed the same procedure and base salad oil described in Example I.

Example V (a) Sucrose (34 grams) was reacted with methyl ester of hydrogenated castor oil (135 grams) in the presence of dimethylformamide, cyclohexane, .and Triton B at 125 to 130 C. for 2 hours. After solvent-stripping, water-washing, and recovery from ethyl acetate, the product showed the following analysis:

Acid value 2.7 Saponification value 138.3 Hydroxyl value 192.9 Total fatty acid "percent" 97.0

Acid value 7.6 Saponification value 174.1 Hydroxyl value 7.8 Total fatty acid percent 95.1

Percent added ester: Chill test, hours 0.0 12 0.1 200 0.3 (slight haze) 375 Example Vl Example V(b) was repeated except that 45 grams of the sucrose ester of Example V(a) was reacted with 83 grams of stearoyl chloride instead of with palmitoyl chlo ride. An ester product (121 grams) was recovered with the following analysis and chill test:

Acid value 0.4 Saponification value 182.8 Hydroxyl value 23.1 Total fatty acid percent 95.5

Percent added ester: Chill test, hours 0.0 12

0.1 150 0.3 (slight haze) 150 Example VII The ethanol insoluble fraction (at room temperature) of the product of Example VI yielded the following analysis and chill test:

Acid value 5.3 Saponification value 173.4 Hydroxyl value 9.8 Total fatty acid percent 96.4 Percent added ester: Chill test, hours Example VIII Sucrose (17.1 grams) was reacted with methyl palrnitate (81 grams) in 200 cubic centimeters dimethylformamide and cubic centimeters Triton B at 100 C. for /2 hour. Then 200 cubic centimeters of cyclohexane was 8 added and the methyl alcohol Was azeotropically distilled out of the mixture over a 3-hour period. Thirtyfive grams of the methyl ester of hydrogenated casto oil of Example I was added to the reaction mixture and agitated at C. for 2 hours. Five cubic centimeters Triton B was then added. After heating the mixture at to C., 200 cubic centimeters cyclohexane was added. The solvents were stripped off under high vacuum at 135 C. for about 2 hours, whereby 59 grams of product was recovered. Fifty grams of the product was reacted with 15 grams of palmitoyl chloride in 200 cubic centimeters cyclohexane and 10 cubic centimeters pyridine. The mixture was agitated and allowed to stand at room temperature for 2 days. An ester product (65 grams) was recovered with the following analysis and chill test:

Acid value 4.6 Saponification value 186.2 Hydroxyl value 93.2 Total fatty acid percent 87.8

Percent added ester: Chill test, hours 0.0 12 0.1 30 0.3 30

Example IX Fifty-six grams of the mixed sucrose ester of Example VIII was reacted with 15 grams of palmitoyl chloride in 100 cubic centimeters cyclohexane and 10 cubic centimeters pyridine. The reaction mixture was allowed to stand at room temperature for 2 days. An ester product (66 grams) was recovered from hexane. Analysis and chill test:

Acid value 0.3 Saponification value 186.0 Hydroxyl value 11.0 Total fatty acid percent 90.4

Percent added ester: Chill test, hours Example X A methyl ester of 12-hydroxystearic acid was prepared by reacting 40 grams of 12-hydroxystearic acid (acid value 185.5; melting point 79 to 81 C.) with 200 grams methanol, the reaction being catalyzed with sulfuric acid. The reaction mixture was refluxed one hour and then allowed to stand at room temperature for 12 hours. The product was water-washed and then recovered from hexane (41.5 grams). Analysis:

Acid value 2.0 Saponification value 178.0 Hydroxyl value 106.0

A sucrose ester was prepared by reacting 3.42 grams sucrose with 19.5 grams of the above methyl ester of 12-hydroxystearic acid in 25 cubic centimeters cyclohexane, and 2.5 cubic centimeters Triton B at about C. Ten grams of the sucrose ester product was then acylated with 13 grams palmitoyl chloride in the presence of cyclohexane and pyridine to yield 19 grams of the mixed sucrose ester. Analysis and chill test:

Acid value 0.9

Saponification value 181.0

Hydroxyl value 2.0

Total fatty acid percent- 96.6

Percent added ester: Chill test, hours 0.0 12 01 0 3 250 9 Example XI Trihydroxy acids were prepared after the method of Kass and Radlove, 64 J. Amer. Chem. Soc. 2253 (1942), by action of peracetic acid on castor oil followed by saponification and splitting. The trihydroxy acids were then crystallized from ethyl acetate.

Eighty-five grams of the above-formed trihydroxy acid was refluxed with 162 grams methanol and 2 grams sulfuric acid to form methyl ester. This methyl ester was used to form two surcro'se ester reparations as follows:

(a) Sucrose (8.5 grams) reacted with methyl ester (50 grams) in 50 cubic centimeters dimethylformamide and 50 cubic centimeters cyclohexaue and 10 cubic centimeters Triton B at 125 C.

(b) Sucrose (5.13 .grams) reacted with methyl ester 15.6 grams) in 50 cubic centimeters dimethylformamide, 50 cubic centimeters cyclohexane and 10 cubic centimeters Triton B at 125 C.

Reaction products from (a) and (b) were then separately acylated with palmitoyl chloride in the following proportions to form mixed sucrose esters:

Twenty grams of (a) reacted with 80 grams palmitoyl chloride in 50 cubic centimeters cyclohexane and 50 cubic centimeters pyridine, yielded a product of the following analysis and chill test:

Forty-five grams of (b) reacted With 5 0 grams palmitoyl chloride in 50 cubic centimeters cyclohexane and 50 cubic centimeters pyridine, yielded a product of the following analysis and chill test:

Acid value 0.7 Saponification value 206.0 Hydroxyl value 2.0 Total fatty acid per nt 99.2

Percent added ester: Chill test, hours Example XII Tetrahydroxy acids were prepared from linoleic acid by using the method of Hazura, 29 Biochem. J. 1554 (1935) according to which the potassium soap of linoleic acid was treated with potassium permanganate followed by treatment with S0 and HCl. The tetrahydroxy acids were then crystallized from ethyl acetate.

The tetrahydroxy acid (1100 grams) was refluxed with methanol (450 cubic centimeters) and sulfuric acid (2 cubic centimeters) to form the methyl ester thereof. A sucrose ester of the tetrahydroxy acid was prepared by reacting 3.42 grams of sucrose with 20 grams of the above methyl ester; and a mixed sucrose ester was prepared by reacting 8 grams of the methyl ester product with 50 grams palmitoyl chloride, both reactions being carried out in the manner described for the trihydroxy esters of Example XI. Analysis and chill test:

10 Example XIII A methyl ester of dihydroxystearic acid was prepared by refluxing 118 grams of 9, 10-dihydroxystearic acid (melting point to 92 C.; obtained by crystallization of 9,10 cis acids) with 375 cubic centimeters methanol and 2 grams sulfuric acid for 2 hours. A sucrose ester was prepared from this methyl ester by reacting 3.42 grams of sucrose with 18.2 grams of the methyl ester in dimethylformamide and cyclohexane in accordance with the procedure in Example XI for preparing the trihydroxy esters. The sucrose ester was acylated to form a mixed sucrose ester by reacting 10 grams of the ester with 24 grams of polymitoyl chloride in dimethylformamide and cyclohexane in substantial accordance with the acylation procedure described in Example XI. The alcohol insoluble portion of the reaction product had the following analysis and chill test:

When an equivalent weight of behenoyl chloride is substituted for the palmitoyl and stearoyl chlorides in the above examples, substantially equivalent chill test results are obtained.

If too large an amount of inhibitor is present in the salad oil, it will be precipitated out of the oil as the oilinhibitor mixture is cooled, and possibly even promote crystallization of high-melting solids in the oil. Too small an amount of inhibitor, of course, will be relatively ineffective. Amounts of ester in excess of 1%, by weight, are unnecessary as affording no significant added improvement of the oil; and it is preferred to use from about 0.05% to about 0.1%. A salad oil having dissolved therein about 0.1% sucrose fully esterified with hydroxy fatty acid and palmitic acid in a ratio of about 1:1 is a very desirable example of the invention herein defined.

What is claimed is:

1. A clear glyceride salad oil having improved resistance to deposition of high-melting solids and compirsing a base salad oil having dissolved therein from about 0.001% to about 1%, by weight, of esterified carbohydrate substance selected from the group consisting of oligosaccharides and polysaccharides having from 2 to about 15 saccharide units per molecule, said carbohydrate substance being from about 50% to about esterified, based on the total hydroxyl equivalency of carbohydrate substance and esterifying hydroxy fatty acid, from about 15% to about 85 of the esterifying carboxyl equivalency being contributed by material selected from the group consisting of saturated and unsaturated hydroxy fatty acids having from about 14 to about 22 carbon atoms and from 1 to about 8 hydroxyl groups, from about 15 to about 85% of the esterifying carboxyl equivalency being contributed by saturated fatty acids having from about 14 to about 22 carbon atoms, and any balance of the esterifying carboxyl equivalency being contributed by material selected from the group consisting of fatty acids having from 2 to about 12 carbon atoms and unsaturated fatty acids having from about 14 to about 22 carbon atoms.

2. The clear glyceride salad oil of claim 1 in which the carbohydrate substance is sucrose.

3. The clear glyceride salad oil of claim 1 in which the esterifying saturated fatty acid is palmitic.

4. The clear glyceride salad oil of claim 1 in which the esterifying hydroxy fatty acid is derived from hydrogenated castor oil.

5. The clear glyceride salad oil of claim 1 in which the base salad oil is derived from cottonseed oil.

1 1 1 2 6. Theclear glyceride salad oil of claim 1 in which the References Cited base salad oil is derived from hydro enated soybean oil. UNITED STATES PATENTS 7. The clear glyceride salad oil of ilairn 1 in which the 6 esterified carbohydrate substance is present in an amount 2 3 2 Eckey et a1 99 of from about 0.05% to about 0.1% by weight. 5 9 [11/19 Baur et a1 99118 8. A clear glyceride salad oil comprising a base salad $158,490 11/1964 Baur et a1 99 118 oil having dissolved therein about 0.1% sucrose fully esterified with hydroxy fatty acid and palrnitic acid in a LOUIS MONACELL P'lmary Examine" ratio of about 1:1. MAURICE W. GREENSTEIN, Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2266591 *Oct 14, 1938Dec 16, 1941Procter & GambleProcess of improving salad oils
US3158489 *Mar 27, 1962Nov 24, 1964Procter & GambleSalad oils and method of making them
US3158490 *Mar 27, 1962Nov 24, 1964Procter & GambleSalad oils and method of making them
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5104674 *Apr 28, 1989Apr 14, 1992Kraft General Foods, Inc.Microfragmented ionic polysaccharide/protein complex dispersions
US5422131 *Oct 30, 1992Jun 6, 1995The Procter & Gamble CompanyNondigestible fat compositions containing relatively small nondigestible solid particles for passive oil loss control
US5424420 *Oct 5, 1993Jun 13, 1995Kraft Foods, Inc.Method for preparing saccharide polyesters by transesterification
US5440027 *Oct 5, 1993Aug 8, 1995Kraft General Foods, Inc.Method for preparing saccharide fatty acid polyesters by transesterification
US5451416 *Aug 10, 1994Sep 19, 1995Johnston; Robert W.Nondigestible fat compositions containing cocrystallized blend of polyol polyester hardstock and crystal modifier as a passive oil loss control agent
US5480667 *Oct 11, 1994Jan 2, 1996Corrigan; Patrick J.Nondigestible fat compositions containing diversely esterified polyol polyester for passive oil loss control
US5490995 *Oct 30, 1992Feb 13, 1996The Procter & Gamble CompanySolid nondigestible polyol polyesters containing esterified hydroxy fatty acids such as esterified ricinoleic acid
US5534284 *Sep 7, 1994Jul 9, 1996Corrigan; Patrick J.Nondigestible fat compositions containing solid polyol polyester polymer for passive oil loss control
US5596085 *Apr 11, 1995Jan 21, 1997Kraft Foods, Inc.Method for preparing polyol fatty acid polyesters by transesterification
US5767257 *Jul 19, 1996Jun 16, 1998The Procter & Gamble CompanyMethods for producing polyol fatty acid polyesters using atmospheric or superatmospheric pressure
US5945529 *Jul 19, 1996Aug 31, 1999The Procter & Gamble CompanySynthesis of polyol fatty acid polyesters using column with inert gas stripping
US6077556 *Sep 8, 1992Jun 20, 2000The Procter & Gamble CompanySolid, nondigestible, fat-like compounds
US6261628Dec 20, 1993Jul 17, 2001The Procter & Gamble CompanyNondigestible fat compositions containing solid polyglycerol ester particles for passive oil loss control
USRE33885 *Sep 29, 1989Apr 14, 1992The Procter & Gamble CompanyCompositions for inhibiting absorption of cholesterol
USRE33996 *May 3, 1989Jul 14, 1992The Procter & Gamble CompanyCompositions for treating hypercholesterolemia
USRE34617 *Dec 2, 1991May 24, 1994The Procter & Gamble CompanyVitaminized compositions for treating hypercholesterolemia
EP0272759A2 *Dec 18, 1987Jun 29, 1988THE PROCTER & GAMBLE COMPANYProcess for the post-hydrogenation of sucrose polyesters
EP0757031A2May 20, 1992Feb 5, 1997Pfizer Inc.Low calorie fat substitute
Classifications
U.S. Classification426/610, 426/330.6, 554/2, 426/598
International ClassificationA23D9/013, A23D9/007
Cooperative ClassificationA23D9/013
European ClassificationA23D9/013