US2681282A

US2681282A - Fatty material stabilized against oxidation and stabilizers therefor

Info

Publication number: US2681282A
Application number: US266106A
Authority: US
Inventors: Noel H Kuhrt
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1952-01-11
Filing date: 1952-01-11
Publication date: 1954-06-15
Anticipated expiration: 1971-06-15

Description

UNITED STATES 3P FATTY MATERIAL STABILIZED AGAINST OXIDATION AND STABILIZER'SHHERE- *FOR .Noel H. Knhrt, Rochesterg N. ,Y., assignorto Eastman Kodak Company, Rochester, N. -Y., a corporation of New Jersey IENT OFFICE No Drawing. Application Ja nuary'1'1,i.1952,

Serial N0.'-266;106

10 Claims. (Cl. 991'63) 1 This invention relates tostabilized fatty comject to oxidation, including both solid fats and positions and to stabilizers for fatty material t y oils, a d pa t cu a ly the f tty materials normally subject to oxidation. consisting predominantly of fatty triglycerides Fatty materials, such assolid fats, fatt oils r fat-forming fatty acids containing unsatuand fatty acids, and particularly the fatty ma- 5 rated components and hence subject to oxi'daterials having unsaturated components are nort The a ty ly id si c udeanimal'fats mally subject to oxidation and resultant oxidasuch as lard, tallow and the like, andvegetable tive rancidity due, at least in part, to the deoils such as cottonseed oil, soybean oil, peanut yelopment of peroxides in such fatty materials. oil, coconut oil, corn oil and the like, Whether since the fatty materials such as the animal hy r s n or p t ly hy r n and fats and the vegetable oils, whether unhydroincluding the animal and vegetable shortenings.

:genated or partially hydrogenated, are widely Th f y ci i l ny f the rum r mixed usedas cooking fats, salad oils, shortenings and unsaturated fatty ac ds as yp fi d y o acid the like, the fatty materials must be stabilized and linoleic acid. against objectionable oxidation, The stabilizer composition embodying this'in- It is-accordingly an object of this invention vention comprises'asolution of glycineand p to provide new fattycompositions characterized D o c acid. i a hydroxy polyalky e o de 98118! by improved stability against deleterious per- Of a fa m a ty acid. Any of the well oxide formation and resultant oxidative ranknown hydroxy polyoxyalkyl ne ester 'of fatcidity. 2 forming fatty acids can be employed in prac- It is a further objectof theinvention to .protioing this invention D Vided such esters have vide nevr stabilizer compositions suitable for ina melting point not substantially hi her than corporation in fatty materials normally subject 100 C., and those esters having a melt ng point to oxidation and effective tostabilize suchfatty below 0 C. are preferred. The hydr y p materials against objectionable oxidation. xy ky ene est rs employ d in pr ct n th It is also an object of the invention to provide invention are obtained in accordance Withknown new stabilized compositions consistingpredomipractice by co ensing-a fat-forming fatty acid nantly of fatty triglycerides. With from 5 to 60 'molar proportions of an Another object of the invention is :to stabilize kyl ne oxide or by r ac in a fa y a id with edible fatty materials against development ,of alkylene oxide polyme The 'l o y y y e objectionable oxidative rancidity under normal de a ives are des ably emp oyed i practicin storage onditi ns, this invention although other oxyalkylene de- Another object of the invention is .toprovide rivatives such a 1;2propylene oxide or L13- improved animal fat or vegetable oil-composiopyl ne oxide deriv t ve ca be emp oy dif tions, including both unhydrogenated and pardesired. The ester can be a hydrOXy p0 y0Xytially hydrogenated compositions. alkylene ester of "any of the well-known fat- Another object of theinvention is 'tostabilize forming fatty acid with those fatty acids havfatty material against oxidationwithout impairing at least 12 carbon atoms in the fatty acid ment of the desirable physical and chemical molecule being vpreferred, as typified by lauric properties of such fatty material. 40 acid, stearic acid, oleic acid, ,palmitic acidand. Other objects will be apparent from the dethe like. Good results are obtained over a wide scription and claims which follow. range of esters as, for example, with hydroxy- These and. other objects are attained linsac- 8-cxyethylene monostearate and hydroxy-j40- cordance with this invention by incorporating oxyethylene monostearate, the number in each in .a fatty material normally subject to oxidacase referring to the molarproportions of ethyltion, a solution of glycine and phosphoric-acid ene oxide .for each molar proportion of fatty in a hydroxy polyoxyalkylene ester of a ,fatacid.

forming fatty acid. In preparing the stabilizer composition, glycine The inventionisapplicable for stabilizing any .and phosphoric acid are dissolved in the polyof the well-known fatty materials normally suboxyethylene fatty ester, either with such ester in liquid form or with the glycine and phosphoric acid in solution in a suitable mutual solvent such as glycerine. The concentration of glycine and phosphoric acid in the ester solution can be varied as desired up to the limit of solubility. The stabilizer composition is then incorporated in the fatty material to be stabilized, with best results being obtained by incorporation at a temperature of 40-95 C. and more desirably at 5090 C., temperatures above 95 C. being less desirable because of impairment of the effectiveness of stabilization. The glycine and phosphoric acid provide effective stabilization at concentrations of each of from 0.00005% to 0.02% by weight based on the total composition weight. Larger amounts of glycine and phosphoric acid can be employed if desired, with amounts as high as 0.5% or higher of each of such materials being suitable. Best results are obtained with the phosphoric acid present in an amount not greater than twice the weight of glycine, although larger proportions of glycine can be' used without adverse effect. The amount of hydroxy polyoxyalkylene fatty acid ester can be varied but is desirably present in an amount not greater than 5% by weight of the total weight of the stabilized fatty composition. In the preferred triglyceride compositions, the fatty triglycerides are present in an amount equal to at least 85% of the total composition weight.

The glycine and phosphoric acid are desirably employed in the form of the free acids. Materials furnishing glycine or phosphoric acid in the fatty composition can be employed, however, and are within the scope of the invention. Thus, for example, the phosphoric acid can be furnished by a salt of phosphoric acid such as sodium phosphate, and the glycine can be added hydrolysate within the scope of the invention.

The development of oxidative rancidity is usually evaluated by analysis of the peroxide content of a fatty composition, a peroxide value of 20 millimols of peroxide per kilogram of fatty composition usually being considered the maximum permissible value for commercial use. The stability of fatty compositions is evaluated by the accelerated Active Oxygen Method (AOM) wherein a sample of the composition being evaluated is heated on a steam bath at a temperature of 96 C. with air bubbling through the sample and the time necessary for attaining a peroxide value of 20 is determined by periodic analysis of the peroxide content and sonsidered the measure of stability.

The following specific examples illustrate certain preferred embomments of the invention, it being understood that such examples are illustrative and are not intended to limit the scope of the invention unless otherwise specifically indicated.

Example 1 A solution of i% by Weight of glycine and 4% by weight of phosphoric acid in glycerol was mixed with hydroxy 40 oxyethylene monostearate in an amount sufficient to give a solution of 0.02% by weight of each of the glycine and phosphoric acid in the monostearate. The resulting solution was stirred into oleic acid in an amount of 1.5% by weight of the glycine-phosphoric acid-monostearate composition based on the weight of oleic acid, at a temperature of approximately 60 C. The stabilized fatty composition obtained thereby was tested for stability under the accelerated AOM test conditions and it was found that the stability of the oleic acid with respect to the time necessary to reach a peroxide value of 20 had been increased 60% over the untreated control sample.

Example 2 A stabilized lard composition containing 0.0003% by weight of glycine, 0.0003% by weight of phosphoric acid, and 1.5% by weight of hydroxy-40-oxyethylene monostearate was evaluated by the AOM accelerated test. The stabilized composition required 29 hours to reach a peroxide value of 20 as compared to '7 hours for unstabilized lard.

Example 3 A partially hydrogenated cottonseed oil shortening was stabilized by admixing therewith 1.5% by weight of a solution of 0.02% by weight of glycine and 0.02% by weight of phosphoric acid in hydroxy-40-oxyethylene monostearate. The AOM stability of the shortening was increased 40% by such stabilization.

Similar results are obtained with other hydroxy polyalkylene fatty acid esters, with other fatty materials and with varying concentrations of glycine and phosphoric acid, and it will be understood that variations and modifications can be effected within the spirit and. scope of the invention as described hereinabove and defined in the appended claims.

I claim:

1. A fatty composition consisting predominantly of fatty material normally subject to oxidation and having incorporated in said fatty material a solution of glycine and phosphoric acid in a hydroxy polyalkylene oxide ester of a fatforming fatty acid.

2. A normally solid fat having incorporated therein a solution of glycine and. phosphoric acid in a hydroxy polyoxyethylene ester of a fatforming fatty acid.

3. A fatty oil having incorporated therein a solution of glycine and. phosphoric acid in a hydroxy polyoxyethylene ester of a fat-forming fatty acid.

4. A fatty compos'tion consisting predominantly of fatty triglycerides and having dispersed therein a minor amount of a solution of glycine and phosphoric acid in a hydroxy polyoxyethylene ester of a fat-forming fatty acid.

5. A fatty triglyceride composition having incorporated therein a solution of glycine and phosphoric acid in a hydroxy polyoxyethylene ester of a fatty acid having at least 12 carbon atoms in the fatty acid molecule, said glycine and said phosphoric acid each being present in an amount of not more than about 0.02% by weight based on the total weight of said composition, said phosphoric acid being present in an amount not greater than twice the weight of said glycine.

6. A fatty composition comprising at least by weight of fatty triglycerides, from 0.00005% to 0.02% by weight of glycine, and from 0.0005 to 0.02% by weight of phosphoric acid, all based on the total composition weight, said glycine and. phosphoric acid being present in solution in a hydroxy polyoxyethylene ester of a fatty acid having at least 12 carbon atoms in the fatty acid molecule.

'7. A shortening having incorporated therein a solution of glycine and phosphoric acid in a hydroxy polyoxyethylene ester of a fat-forming fatty acid.

8. A stabilizer composition suitable for incorporation in fatty material normally subject to 5 oxidation, said composition comprising a solumolecule, said phosphoric acid being present in tion of glycine and phosphoric acid in a, hydroxy an amount not greater than twice the weight of polyalkylene oxide ester of a fat-forming fatty said glycine.

acid.

9. A stabilizer for fatty material comprising 5 References Cited in e fi Of this Patent a solution of glycine and phosphoric acid in a UNITED STATES PATENTS hydroxy polyoxyethylene ester of a fatty acid Number Name Date having at least 12 carbon atoms 1n the fatty acid 2,511,804 Han June 13, 1950 molecule.

10. A stabilizer for fatty material comprising 10 2535910 Fonyo 1950 a solution of glycine and phosphoric acid in a OTHER REFERENCES hydroxy polyoxyethylene ester of a fatty acid Chem Abs; 40 (1945), 5

having at least 12 carbon atoms in the fatty acid

Claims

1. A FATTY COMPOSITION CONSISTING PREOMINANTLY OF FATTY MATERIAL NORMALLY SUBJECTED TO OXIDATION AND HAVING INCORPORATED IN SAID FATTY MATERIAL A SOLUTION OF GLYCINE AND PHOSPHORIC ACID IN A HYDROXY POLYALKYLENE OXIDE ESTER OF A FATFORMING FATTY ACID.