WO1996016140A1 - Solution antioxydante translucide - Google Patents

Solution antioxydante translucide Download PDF

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Publication number
WO1996016140A1
WO1996016140A1 PCT/US1995/015277 US9515277W WO9616140A1 WO 1996016140 A1 WO1996016140 A1 WO 1996016140A1 US 9515277 W US9515277 W US 9515277W WO 9616140 A1 WO9616140 A1 WO 9616140A1
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WO
WIPO (PCT)
Prior art keywords
weight percent
antioxidant solution
carnosic acid
natural antioxidant
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1995/015277
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English (en)
Inventor
Greg Alan King
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Chemical Co
Original Assignee
Eastman Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Chemical Co filed Critical Eastman Chemical Co
Priority to AU42875/96A priority Critical patent/AU4287596A/en
Publication of WO1996016140A1 publication Critical patent/WO1996016140A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/34—Anti-oxidant compositions; Compositions inhibiting chemical change containing plant or animal materials of unknown composition
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0085—Substances of natural origin of unknown constitution, f.i. plant extracts

Definitions

  • the present invention relates to a translucent natural antioxidant solution which is used to prolong the shelf life of animal fats and vegetable oils.
  • Oxidation of unsaturated fats and oils is essentially a degradation process which occurs at the double—bond sites in glyceride molecules. Glyceride molecules are the building blocks of edible fats and oils.
  • the degradation process proceeds via a "free—radical" mechanism in which the initiation step is the formation of a fatty free radical when hydrogen departs from the a—methylenic carbon in the unsaturated fatty acid group of the oil molecule.
  • the resultant free radical becomes very susceptible to attack by oxygen to form an unstable peroxide free radical.
  • Antioxidants such as butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA) are widely used in many foods to prevent fat rancidity. These compounds are added at concentrations ranging from 50 to 200 ppm to suppress the development of peroxides during food storage.
  • the antioxidative activities of these synthetic substances stem from the phenolic configuration of their molecular structures. These phenolic substances function as free radical acceptors which can terminate fat or oil oxidation at the initiation stage.
  • the antioxidant free radical that forms is stable and, most importantly, does not initiate or promote further oxidation of the glyceride.
  • tocopherol molecules which have the phenolic configuration, exhibit antioxidant properties.
  • Vitamin E activity is attributed mainly to ⁇ —tocopherol, which also provides some oxidation inhibition effect in oil, but the and ⁇ forms are more effective antioxidants.
  • Tocopherols are widely distributed in many vegetable matters from which commercial edible oils are extracted. Moreover, a high proportion of these "natural" antioxidants survive commercial oil processing to end up in the finished oils at levels as high at 500—1,000 ppm. These "residual" tocopherols are largely responsible for the oxidative stability inherent in finished vegetable oils.
  • Common acid—type antioxidants include citric, phosphoric, propionic, ascorbic, and tartaric acids. Because these acids are generally insoluble in vegetable oils, they cannot be used directly with the primary antioxidants. Instead, it has been found that certain derivatives of these acids are effective. These include isopropyl citrate, didodecyl thiodipropionate, dilauryl thiodipropionate, dioctadecyl thiodipropionate, and ascorbyl palmitate. Sherwin, E. R. , "Antioxidants for Vegetable Oils", JAOCS, 53, 1976 (430-436).
  • a number of compounds have been isolated from herbs and spices which exhibit antioxidant activity.
  • An effective stabilizer for preventing oxidation of animal and vegetable fats and oils is an extract from oil of rosemary (rosmarinus officinalis) .
  • Rosemary extract is commonly available as a somewhat colored solid which contains numerous impurities and exhibits low solubility in common fats and oils, properties which frequently make it undesirable for fat stabilization.
  • U. S. Pat. No. 5,102,659 discloses an antioxidant composition containing rosemary extract which is added to mineral supplements. In addition to rosemary extract, the compositions contained ascorbyl palmitate and a mixed tocopherol concentrate. A disadvantage of the antioxidant is that it is not translucent and is in the form of a dispersion.
  • U. S. Pat. No. 4,877,635 discloses a process for producing a natural antioxidant extract of a Labiatae herb also known as the mint family which includes herbs such as sage, rosemary, thyme, and peppermint.
  • a disadvantage of the oil—soluble antioxidant is that it is dark in color and is difficult or impossible to obtain in a soluble form for convenient addition to fats and oils. In addition to problems with solubility, those extracts which have been available heretofore contain impurities derived from the original plant which impart an unpleasant taste and/or odor to food products in which they are used.
  • the present invention is directed to a translucent natural antioxidant solution comprising 3 to 20 weight percent of camosic acid, 20 to 70 weight percent of distilled monoglyceride, and 30 to 70 weight percent of propylene glycol wherein the antioxidant solution is miscible with fats and oils up to a concentration of 500 ppm of carnosic acid.
  • the present invention provides a natural antioxidant solution for fats and oils of both animal and vegetable origin.
  • the natural antioxidant solution contains carnosic acid, distilled monoglyceride, and propylene glycol.
  • the carnosic acid may be obtained from any natural source.
  • the carnosic acid is obtained as an extract from rosemary ( rosmarinus offi cinalis) .
  • Rosemary extracts are available from Hauser Chemical Company, located in Boulder, Colorado, as a colored solid in powder form which exhibits low solubility in common fats and oils.
  • the rosemary should contain at least 70 weight percent of carnosic acid when analyzed by high pressure liquid chromatography, using a 4.6 X 250 mm column packed with "Hypersil ODS, 5 ⁇ " at a flow rate of 1.5 ml/triin, using an ultraviolet detector.
  • the rosemary may contain other ingredients such as 12—methoxycarnosic acid, carnosol, and rosemanol.
  • the natural antioxidant solution contains 3 to 20 weight percent of carnosic acid, preferably 5 to 10 weight percent. More preferably, the natural antioxidant solution contains 5 to 6 weight percent of carnosic acid.
  • Component (B) of the antioxidant solution is a distilled monoglyceride.
  • the distilled monoglyceride is a monoglyceride and/or diglyceride derived from a vegetable oil which contains saturated and monounsaturated carboxylic acids containing 12 to 22 carbon atoms, preferably 16 to 20 carbon atoms. More preferably, the distilled monoglyceride contains at least 90% of a monoglyceride having 18 carbon atoms and an iodide value of 90 to 95, since these monoglycerides have lower melting points and better oil and propylene glycol compatibility.
  • Representative vegetable oils include, but are not restricted to, canola oil, sunflower oil, cottonseed oil, and soybean oil.
  • a preferred distilled monoglyceride is derived from canola oil and is available as Myverol ® 18-99 from Eastman Chemical Company, Kingsport, TN.
  • Myverol ® 18-99 contains approximately 61% oleic and 21% linoleic acid, together with much smaller amounts of saturated and unsaturated carboxylic acids.
  • An acetylated monoglyceride derived from partially hydrogenated soybean oil (Myvacet 9—45 available from Eastman Chemical Co.) has also been found to be effective, although the unacetylated material is preferred.
  • Component (C) of the antioxidant solution is propylene glycol.
  • food grade propylene glycol is used which has been certified Rabbinically Kosher.
  • the antioxidant solutions are prepared by mixing the distilled monoglyceride and propylene glycol at a temperature of 20°C to 100°C to form a homogeneous solution. Preferably, a temperature of 40°C to 100°C is employed, more preferably 60°C to 70 °C.
  • the carnosic acid in the form of a rosemary extract powder is added with stirring to the homogenous solution. Agitation is continued until the rosemary extract is solubilized, usually 15 to 30 minutes.
  • the resulting antioxidant solution is a transluscent solution which is completely miscible with fats and oils up to a concentration of 500 ppm of carnosic acid.
  • the antioxidant solution of this invention is useful for inhibiting the oxidation and resulting rancidity of a wide variety of animal and vegetable fats and oils.
  • oils in which the stabilizers of this invention may be used include corn oil, olive oil, rapeseed oil, cottonseed oil, palm oil, and the like.
  • Animal oils and fats in which the stabilizers may be used include, but are not restricted to, lard, fish oil, tallow, butter, and the like.
  • Acid synergists such as citric acid, asorbic acid, phosphoric acid, lactic acid, ascorbyl palmitate, and the like may be added to the antioxidant solutions of the present invention to enhance the performance of the antioxidant solutions. Acid synergists and their amounts are well known in the art.
  • the materials and testing procedures used for the results shown herein are as follows: The carnosic concentrate was determined by high pressure liquid chromatography, using a 4.6 X 250 mm column packed with 5 ⁇ HYPERSIL ODS. The mobile phase was a mixture of 75% acetonitrile and 25% of l mM ethylenediaminetetraacetic acid containing 0.1% phosphoric acid. The flow rate through the column was 1.5 ml/min. The detector measured ultraviolet absorption of the effluent at 230 nm.
  • Antioxidant Effectiveness was based on the Oil Stability Index ("OSI") as determined by American Oil Chemists Society Official Method Cd 12b-92 at 100°C.
  • the method involved passing air successively through heated oil, then deionized water. Oxidation of the oil released formic acid, which vaporized in the air stream and dissolved in the water. The resulting increase in the conductivity of the water was measured as an indication of the rate of formic acid evolution, hence of the rate of breakdown of the oil.
  • the OSI is defined as the number of hours required to reach the point of maximum change in rate of oxidation. The greater the OSI, the more effective the antioxidant.
  • the OSI was measured using a "RANCIMAT - Model 617 from Brinkman Instruments, Inc., subsidiary of Sybron Corp., Cantiague Road, Westbury, NY.
  • Example II show that as the level of carnosic acid increases, the oil stability index (OSI) increases.
  • the control sample without carnosic acid was the least stable.
  • Example III show that as the level of carnosic acid increases, the oil stability index (OSI) increases. Note that control sample without carnosic acid was the least stable.
  • Palm olein was treated with the antioxidant solution prepared in Example I to determine the stabilizing effect of the antioxidant solution.
  • Example IV show that as the level of carnosic acid increases, the oil stability index (OSI) increases. Note that control sample without carnosic acid was the least stable.
  • Example V clearly illustrates the superiority of the antioxidant of the present invention to stabilize the oil as compared to competitive antioxidants, not only at equivalent concentrations of antioxidant solution, but even when compared at a solution level of 1000 ppm with higher concentrations of competitive materials.
  • EXAMPLE VI This example compares the effectiveness of 95% carnosic acid with equal amounts of the commercial antioxidants, butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA) in soybean oil, available under the TENOX trademark as TENOX BHT and TENOX BHA, respectively. Two control samples were evaluated using 100% soybean oil and no antioxidant. The OSI was determined as described in Example II.
  • Example VI clearly show that the samples containing the 95% carnosic acid exhibited superior antioxidant activity at all antioxidant concentrations as determined by their higher OSI values.
  • Example VII This example compares the effectiveness of the carnosic acid concentrate of this invention with that of a commercial "rosemary antioxidant”.
  • Example II The antioxidant solution prepared in Example I which contained 7.4% of carnosic acid, 0.15 grams (equivalent to approx. 0.01 grams of carnosic acid) was added to 100 ml of soybean oil. For comparison, 0.06 grams of STABEX Rosemary Antioxidant was added to 100 ml of soybean oil. Both samples were evaluated in the Ranci at apparatus at 100° C.
  • the OSI value for the sample containing the carnosic acid concentrate was 21.0.
  • the OSI value for the sample containing the STABEX Rosemary Antioxidant was 15.5. The results clearly demonstrate the superior effectiveness of the antioxidant solution of the present invention as compared to commercially available rosemary extracts.
  • the natural antioxidant solution of the present invention is completely miscible in vegetable oils and animal fats and remains effective even in the presence of minerals and metals.
  • the natural antioxidant solution is translucent and imparts minimal taste or odor to the oils or fats in which it is used.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Botany (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Fats And Perfumes (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)

Abstract

L'invention porte sur une solution antioxydante translucide naturelle permettant de prolonger la durée de conservation des graisses animales et des huiles végétales. Plus précisément ladite solution comporte de 3 à 20 % d'acide carnosique, de 20 à 70 % de monoglycéride distillé et de 30 à 70 % de propylène glycol. Cette solution est miscible aux graisses et huiles jusqu'à une concentration de 500 ppm d'acide carnosique.
PCT/US1995/015277 1994-11-21 1995-11-13 Solution antioxydante translucide Ceased WO1996016140A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU42875/96A AU4287596A (en) 1994-11-21 1995-11-13 A natural antioxidant solution

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US34293394A 1994-11-21 1994-11-21
US08/342,933 1994-11-21

Publications (1)

Publication Number Publication Date
WO1996016140A1 true WO1996016140A1 (fr) 1996-05-30

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/015277 Ceased WO1996016140A1 (fr) 1994-11-21 1995-11-13 Solution antioxydante translucide

Country Status (4)

Country Link
AU (1) AU4287596A (fr)
IL (1) IL116079A0 (fr)
WO (1) WO1996016140A1 (fr)
ZA (1) ZA959873B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2178589A1 (es) * 2000-01-27 2002-12-16 Goodyear Tire & Rubber Uan base de goma de mascar conteniendo caucho estabilizado con acido carnosico.
EP2229064A2 (fr) 2007-12-10 2010-09-22 Vitiva D.D. Stabilisation par antioxydant de noix et de semences et de produits les contenant

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115281366A (zh) * 2022-06-28 2022-11-04 深圳市艾普生物科技有限公司 一种抗氧化尼古丁盐的制备方法及应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0454097A1 (fr) * 1990-04-25 1991-10-30 Norac Technologies Inc. Composition antioxydante obtenue à partie de labiatae
JPH03293001A (ja) * 1990-04-11 1991-12-24 Chisso Corp 天然源抗酸化成分の脱臭方法
WO1993006190A1 (fr) * 1991-09-20 1993-04-01 Norac Technologies Inc. Compositions oleoresineuses antioxydantes et procede de preparation
EP0560291A1 (fr) * 1992-03-11 1993-09-15 SKW Trostberg Aktiengesellschaft Procédé de préparation d'antioxydants naturels

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03293001A (ja) * 1990-04-11 1991-12-24 Chisso Corp 天然源抗酸化成分の脱臭方法
EP0454097A1 (fr) * 1990-04-25 1991-10-30 Norac Technologies Inc. Composition antioxydante obtenue à partie de labiatae
WO1993006190A1 (fr) * 1991-09-20 1993-04-01 Norac Technologies Inc. Compositions oleoresineuses antioxydantes et procede de preparation
EP0560291A1 (fr) * 1992-03-11 1993-09-15 SKW Trostberg Aktiengesellschaft Procédé de préparation d'antioxydants naturels

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE FSTA INTERNATIONAL FOOD INFORMATION SERVICE (IFIS), FRANFURT/MAIN, DE; DUXBURY: "EXTRACT OF ROSEMARY PROVIDES NATURAL SOLUTION TO DEHYDRATED PRODUCTS" *
DATABASE WPI Week 9206, Derwent World Patents Index; AN 92-046375 *
FOOD PROCESSING, vol. 53, no. 5, USA, pages 102 - 104 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2178589A1 (es) * 2000-01-27 2002-12-16 Goodyear Tire & Rubber Uan base de goma de mascar conteniendo caucho estabilizado con acido carnosico.
EP2229064A2 (fr) 2007-12-10 2010-09-22 Vitiva D.D. Stabilisation par antioxydant de noix et de semences et de produits les contenant

Also Published As

Publication number Publication date
ZA959873B (en) 1996-06-03
IL116079A0 (en) 1996-01-31
AU4287596A (en) 1996-06-17

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