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WO1991010368A1 - Succedanes de matieres grasses pauvres en calories, precurseurs desdits succedanes et leurs procedes de fabrication - Google Patents

Succedanes de matieres grasses pauvres en calories, precurseurs desdits succedanes et leurs procedes de fabrication Download PDF

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Publication number
WO1991010368A1
WO1991010368A1 PCT/US1991/000260 US9100260W WO9110368A1 WO 1991010368 A1 WO1991010368 A1 WO 1991010368A1 US 9100260 W US9100260 W US 9100260W WO 9110368 A1 WO9110368 A1 WO 9110368A1
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Prior art keywords
polyglycerol
oil
mixture
percent
composition
Prior art date
Application number
PCT/US1991/000260
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English (en)
Inventor
Kevin S. Dobson
Robert T. Jernigan
Clinton J. Boriack
Alan P. Croft
Original Assignee
The Dow Chemical Company
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Priority to JP3503399A priority Critical patent/JPH05504062A/ja
Publication of WO1991010368A1 publication Critical patent/WO1991010368A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/10—Saturated ethers of polyhydroxy compounds
    • C07C43/11—Polyethers containing —O—(C—C—O—)n units with ≤ 2 n≤ 10
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS OR COOKING OILS
    • A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
    • A23D7/01—Other fatty acid esters, e.g. phosphatides
    • A23D7/013—Spread compositions
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS OR COOKING OILS
    • A23D9/00—Other edible oils or fats, e.g. shortenings or cooking oils
    • A23D9/007—Other edible oils or fats, e.g. shortenings or cooking oils characterised by ingredients other than fatty acid triglycerides
    • A23D9/013—Other fatty acid esters, e.g. phosphatides
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/115—Fatty acids or derivatives thereof; Fats or oils
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond

Definitions

  • the invention is related to low caloric oil or fat substitutes and processes for making the low caloric oil or fat substitute.
  • fats provide essential nutrients, they have been linked to certain chronic diseases such as arteriosclerosis, heart disease, cancer and obesity. Thus, by reducing the amount of fat and calories in an individual's diet, the risk of disease may also be reduced.
  • Desirable properties attributable to fats include the richness in taste or textural characteristics that are associated with certain foods. It is important that these and other organoleptic properties associated with fats are maintained.
  • triglycerides which are the triesters of glycerine and various fatty acids.
  • the organoleptic characteristics which we associate with an oil depend upon the fatty acids of the triglycerides.
  • the fatty acids may be saturated, unsaturated, cyclic, acylic, oxygenated or non-oxygenated.
  • the properties of a fat substitute can be controlled by the choice of fatty acid groups comprising the oil.
  • sucrose polyester SPE
  • U.S. Patent 3,600,186 to Mattson et. al. and U.S. Patent 3.963*699 to 5 Rizzal et al...
  • RCU2 e methyl soybean fatty acid ester
  • SPE is prepared by solvent free interesterification using phenyl esters. Phenol is liberated during the process. A preparation process in which phenol is liberated is not generally attractive to the food industry.
  • EEEP epoxide- -extended polyols
  • the fat substitutes are prepared by treating polyols in the presence of a base catalyst with an epoxide to produce epoxide-extended polyols (EEP).
  • EEP is reacted with at least one fatty acid to produce an epoxide-extended polyol esters. Every hydroxyl group on the polyol is replaced with an ether linkage.
  • the end groups may be either secondary or primary and are esterified.
  • Said oil/fat substitute additionally should be produced using a wide variety of fatty acids to achieve desirable properties such as color, taste, mouthfeel without generating toxicity or adverse physiological difficulties upon consumption.
  • the invention is a linear polyglycerol composition that is a precursor for making a low caloric oil or fat substitute, said precursor having a high level of hydroxyl functionality permitting, upon further processing, esterification with a wide variety of fatty acids whereas an oil/fat substitute is achieved having a high content of secondary and tertiary esters which minimizes hydrolyzation or absorption by a mammal but enhances or retains desirable characteristics of an oil or fat.
  • the present invention is also a linear polyglycerol composition that has been esterified to produce a low caloric fat substitute.
  • the invention is also a method of making the polyglycerol composition.
  • This low caloric fat substitute is made by the esterification of a polyglycerol that is enriched in secondary and tertiary hydroxyls.
  • the polyglycerol is prepared by polymerizing glycidol in such a manner that a linear molecule is made.
  • the polyglycerol may also be reacted further with an alkylene oxide before esterification to further enhance secondary and tertiary ester content.
  • This polyglycerol has a narrow molecular weight distribution without further processing; is low in odor and color; and has greater than 50 percent of the hydroxyls present as secondary or tertiary groups.
  • the linear polyglycerol is reacted with an oxide having 3 to 6 carbon atoms prior to esterification.
  • linear it is meant that the pplyglycol is linear if 50 percent or less of its hydroxyl groups are primary groups.
  • the polyglycerol has less than 40 percent of its hydroxyl groups primary, more preferably, less than
  • linear polyglycerol composition of the invention corresponds to Formula I: H ( 0-CHR 1 -CH 2 ) n 0 (CH 2 -CHR ⁇ -0) n H
  • and R- are each independently alkyl groups of 1 to carbon atoms
  • n is an integer from 0 to 32 inclusive.
  • R 2 , R3, R4 R and R5 are each independently selected from hydrogen or an alkyl group having 1 to 3 carbon atoms and the composition is at least 50 weight percent linear polyglycerol moieties and contains less than 20 weight percent of compounds wherein m is 3 or less.
  • the polyglycerol is made by heating a basic catalyst and an initiator with agitation to a temperature in the range from 25° to 130°.
  • the initiator is selected from the group consisting of sugars, sugar alcohols, dihydroxy alcohol, polyhydroxy alcohol, polyether polyols, metal alkoxides or metal hydroxides. Preferred are sodium or potassium salts of methanol, ethanol, 1-propanol or sodium or potassium hydroxides. Glycerine is the preferred initiator.
  • a monomer is added to the catalyst and initiator at a rate such that the temperature is maintained between 100° to 160°C.
  • the monomer is of the general Formula II:
  • Ri R5 and R5 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms.
  • polyglycerol can be Q esterified to produce a low caloric fat substitute represented by the following Formula III:
  • m is 2 to 30 inclusive
  • and R ⁇ are each independently alkyl groups of 1 to 4 carbon atoms
  • n is an integer from zero to 32 inclusive
  • R4 R5 and R5 are 5 each independently hydrogen or an alkyl group having 1 to 3 carbon atoms
  • Rg» R9 and R-J Q are each independently acyl groups having 5 to 23 carbon atoms.
  • the fat substitute is useful to replace r - fats or oils in many different types of foods.
  • the fat substitute is useful as a cooking oil, in margarine spreads, baked goods and baking mixes, confections, frostings, salad dressings, frozen desserts and mixes, puddings and hard and soft candies. Fat is also 0 absorbed by foods while frying.
  • the snack industry uses a large amount of fats and oils in the production of potato chips, corn chips and other snack items.
  • a low calorie fat substitute that has acceptable oil properties could be useful for producing such snacks, thereby producing a low calorie snack.
  • polyglycerols In addition to these polyglycerols being used to make fat substitutes, they could also be employed in a number of other food applications.
  • the polyglycerol has a high viscosity so it could be used to improve the viscosity of the low calorie beverages and soft drinks.
  • the high viscosity and water solubility make it useful for applications which employ gum acacia. Due to the chemical stability and high viscosity of the polyglycerol, it can also be useful in acidic food preparations such as pickle relish, ketchup, citrus juices and the like.
  • the linear polyglycerol compound that has at least two secondary o tertiary hydroxyl groups is represented by Formula I.
  • the glycerine units are from 70 to 80 weight percent of the polyglycerol composition. More preferably, the glycerine units are greater than 80 percent of the polyglycerol composition.
  • m is 6 to 15 glycerine units, more preferably m is 8 to 12 glycerine units;
  • R- j and Ry are preferably each independently an alkyl group of 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms;
  • n is preferably an integer from 1 to 15 inclusive, more preferably, 1 to 5 inclusive.
  • R R5 and R5 are preferably each independently a methyl group, an ethyl group or hydrogen.
  • oligomers it is meant a polyglycerol having 3 or less repeating units of glycerine, that is, m is 1, 2 or 3.
  • the low calorie fat substitute can be made by substantially complete esterification of the above described linear polyglycerol.
  • the low caloric fat substitute is represented by Formula III hereinbefore.
  • m is an integer preferably from 6 to 15 inclusive, more preferably 8 to 12 inclusive.
  • R 2 , R3, Rj j , R5 and R5 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms, preferably a methyl or ethyl group or hydrogen.
  • R ⁇ , Rg and R 10 are acyl groups having from 5 to 23 carbon atoms.
  • the acyl group can advantageously be derived from the fatty acids found in common edible oils, including olive oil, soybean oil, coconut oil, palm oil, cotton seed oil and canola oil.
  • fatty acids may include oleic, octanoic, lauric, eicosanoic, stearic, palmitic, linoleic, myristic acid, and linolenic acids or the acyl j . group could be derived from a complex mixture of these fatty acids. Additionally, the acyl group is in one preferred embodiment derived from mixtures of natural oils that could be short, medium, or long chain, saturated or unsaturated, cis or trans. Examples of
  • short chain acyl derived from shorter chain aliphatic acids which could include, but are not limited to valeric, hexanoic, or octanoic acids.
  • Medium chain acyl group could be, but is not limited to caproic, caprylic, capric, lauroleic, lauric, and caproleic acid, -decenoic,
  • Long chain acyl groups include but are not limited to behenic, lignoceric, arachidic, myristoleic, palmitoleic, gadoleic, erucic, elaidic, vaccenic, archidonic, and eicosapentaenoic acid.
  • the 0 acyl group is preferably derived from one or more fatty acid types, and most preferably is derived from a complex mixture of the fatty acids that are derived from natural oils.
  • linear polyglycerol is made under conditions that are generally anhydrous.
  • generally anhydrous is meant that minor amounts of water can be present in glycerine, glycidol
  • Glycerine is reacted with glycidol to form a linear polyglycerol.
  • glycerine is mixed neat or solvent free with glycidol under anhydrous conditions.
  • the presence of water or a polar or protic solvent capable of hydrogen bonding generally has adverse effects upon the polymerization of polyglycerol. These adverse effects may include an increase in the primary hydroxyl content, an increase in the percentage of lower oligomers, broad molecular weight distribution, and inhibition of chain extension of the polyglycerol.
  • the concentration of glycidol In addition to certain solvents having an adverse effect upon the polymerization of glycerol, the concentration of glycidol, even though it is a reactant, could have an adverse effect upon the reaction. It.is important that the concentration of glycidol be controlled such that there is no build-up of glycidol in the reactor. It is not advantageous to have excess unreacted glycerine in the presence of the polyglycerol, because it is theorized that the unreacted glycerine will be converted to triglycerides upon esterification of the polyglycerol. Since triglycerides are hydrolyzed in the small intestines, the triglycerides can increase the caloric content of the oil.
  • the basic catalyst can be lithium; sodium; rubidium; magnesium; cesium; metal hydroxides such 'as sodium hydroxide, calcium hydroxide, and barium hydroxide; metal hydrides such as sodium, potassium, lithium, and calcium hydride, lithium aluminum hydri ' de, sodium borohydride; sodium carbonate; sodium amide or sodium sulfate.
  • the catalyst is potassium metal, sodium metal, sodium hydroxide, potassium t - hydroxide, calcium hydroxide or barium hydroxide.
  • the amount of catalyst heated with the glycerine is 0.001 mole percent to 10 mole percent, preferably 0.5 to 10 mole percent, more preferably 1 mole percent to 5 mole percent. .
  • the glycerine and catalyst are preferably 15 heated under nitrogen to a temperature in the range from 25° to 130°C. Agitation is desirable from about 40 to about 130°C.
  • Glycidol is added slowly to the glycerine.
  • glycidol is added to the glycerine below the liquid surface. The addition is carried out in such a 0 manner that the temperature during addition is maintained between 100° to 160°C.
  • the mixture is heated at a temperature from 100° to 160°C, preferably 115° to 125°C r - for a period of up to about 16 hours, preferably for about 3 to about 6 hours. Most preferably, the mixture is heated at about 120° to 125°C for about one hour.
  • the catalyst is any organic compound. Also, it is preferred that the catalyst is organic compound.
  • the stoichiometric ratio of glycidol to glycerine determines the polymer chain length.
  • a mole ratio of glycidol to glycerine of 4:1 to 1:1 is advantageous, preferably about a 2:1 ratio is employed.
  • a mole ratio of glycidol to glycerine of 6:1 to 2:1 is advantageous, preferably about a 4:1 ratio.
  • a mole ratio of glycidol to glycerine of 9:1 to 3:1 is advantageous, preferably a 6:1 ratio.
  • a mole ratio of glycidol to glycerine of 11:1 to 4:1 is advantageous, preferably a 7:1 ratio.
  • a mole ratio of glycidol to glycerine of 14:1 to 5:1 is advantageous, preferably a 9:1 ratio.
  • a mole ratio of glycidol to glycerine of 19:1 to 7:1 is advantageous, preferably a 12:1 ratio.
  • a mole ratio of glycidol to glycerine of 22:1 to 8:1 is advantageous, preferably a 14:1 ratio.
  • a mole ratio of glycidol to glycerine of 24:1 to 9:1 is advantageous, preferably a 16:1 ratio.
  • the ester derivatives of the polyglycerol are expected to be less susceptible to enzymatic hydrolysis and absorption, although a lower molecular weight linear polyglycerol might be useful in applications which the high molecular weights are not desirous. Additionally, the molecular weight of the polyglycerol will depend on whether a diglycerol, triglycerol, tetraglycerol and the like are produced. The higher molecular weight polyglycerols are preferred for the preparation of a low caloric fat substitute. The molecular weight distribution is also important, since the presence of lower molecular weight oligomers may affect the over all performance of the derived polyglycerol oils as low caloric fat substitutes.
  • any conventional means of esterifying the polyglycerol is operable to produce the low caloric fat substitute.
  • the polyglycerol may be transesteri ied by using one of the transesterification catalysts known in the art. Examples of such catalysts include organic titanates, organic * acids, or mineral acids.
  • esterification of the polyglycerol is accomplished by stirring the polyglycerol with a catalyst used in esterification processes such as, pyridine, cyclohexyl- -carbodiimide or p-toluene sulfonic acid at 15°C to 60°C, preferably from 20°C to 40°C.
  • a fatty acid or a fatty acid equivalent that is, a fatty acyl halide, an ester of fatty acid, or a fatty acyl anhydride is added to the polyglycerol mixture, and these reactants have the acyl group corresponding to Rg, Rg and R-
  • the polyglycerol may be esterified with a low molecular weight acyl halide or equivalent and then the ester groups exchanged with an excess of fatty acid.
  • a solvent may be added at any time, to aid in the proper mixing of the reaction mixture. If a solvent is added, any non-polar, aprotic solvent may be used. However, hydrocarbon solvents, such as hexane, are preferred.
  • the resulting unpurified oil can be filtered and extracted with any number of polar solvents. Water, ethanol, methanol, isopropanol or any combination of these is preferred. Salts such as sodium chloride, potassium chloride or alkaline materials such as sodium hydroxide, potassium hydroxide may be added to the aqueous extracting phase to aid in extraction of free fatty acids and separation of phases.
  • the solvent may be removed from the oil by a number of means, but is conveniently done in the laboratory using a rotary 0 evaporator.
  • the oil can be deodorized if desired by steam stripping or treated further in any manner that normal oils are treated. Additives may or may not e' added, as thought necessary.
  • the polyglycerol is made, it is esterified with a fatty acid acyl derivative to produce the low caloric fat substitute.
  • the resulting low caloric fat substitute if diglycerol tetraoleate, has a molecular weight of 1226.
  • Triglycerols esterified 0 result in triglycerol pentaoleate having a molecular weight of 1565; tetraglycerol results in tetraglycerol hexaoleate having a molecular weight of 1904; pentaglycerol results in pentaglycerol septaoleate _- having a molecular weight of 2242; hexaglycerol results in hexaglycerol octaoleate having a molecular weight of 2582; octaglycerol results in an octaglycerol decaoleate having a molecular weight of 3260; and nonaglycerol results in a nonaglycerol undecaoleate having a 0 molecular weight of 3599.
  • the polyglycerol in order to assure the polymerization of a polyglycerol having high secondary or tertiary content greater than about 85 percent, the polyglycerol is "capped" or reacted with an oxide under alkaline conditions. By capping the polyglycerol the existing primary hydroxyls become secondary or tertiary hydroxyls.
  • the oxides which can be employed to cap the polyglycerol have the following formula:
  • R is an alkyl group.
  • the R is methyl, ethyl or propyl.
  • the polyglycerol is reacted with propylene oxide, and most preferably polyglycerol is reacted with butylene oxide.
  • the polyglycerol is - stirred with a catalyst, preferably as nitrogen is flushed through the system.
  • the catalyst is similar to the catalyst used herein to make the polyglycerol.
  • the temperature is raised from 20°C to 110°C, preferably 20° to 100°C, then the oxide is slowly added to the polyglycerol and reacted until the oxide vapor pressure ceases to drop.
  • the resulting compound can be esterified to form the low calorie oil.
  • the crude capped oil can be further processed or cleaned-up if so desired, by the procedures discussed herein for uncapped crude oils.
  • a mole ratio of polyglycerol to oxide respectively of 1:0.01 to 1:4 ratio is advantageous, preferably a 1:2 ratio is employed.
  • a mole ratio of 1:0.1 to 1:4 ratio is advantageous, preferably a 1:2 ratio is employed.
  • a 1:0.1 to a 1:6 is advantageous, preferably a 1:2 ratio is employed.
  • a mole ratio of 1:0.1 to 1:7 is advantageous, preferably a 1:3 ratio is employed.
  • a mole ratio of 1:0.1 to 1:8 is advantageous, preferably 1:3 ratio is employed.
  • a mole ratio of 1:0.1 to 1:10 is advantageous, preferably a 1:3 ratio is employed.
  • a mole ratio of 1:0.1 to 1:11 is advantageous, preferably a 1:3 ratio is employed.
  • a ratio of 1:0.1 to 1:12 is advantageous, preferably a 1:3 ratio is employed.
  • the capped polyglycerol can be esterified as described herein for uncapped polyglycerol to produce the low caloric oil.
  • Glycidol was distilled at 42°C, under 2 mm of Hg. Potassium metal that was stored in mineral oil, was rinsed with hexane before being weighed into a tared beaker of mineral oil, rinsed with hexane and dried under a stream of nitrogen before being added to glycerine.
  • a three-neck round-bottom flask (50 ml) was charged with 3.15 g (0.034 mol) of glycerine and 0.120 g of 87 percent pure potassium hydroxide (1.86 mmol of assay). The mixture was stirred and heated under nitrogen to approximately 80°C. At this point a high vacuum (0.5 mm Hg) was applied and the mixture was heated for an additional 30 minutes. The vacuum was then removed and the nitrogen pad was restored, taking care to ensure that the atmosphere inside the flask remained dry. The homogeneous mixture was heated to 115°C and 20.75 ml (0.313 mol) of glycidol was added dropwise through a constant addition funnel.
  • the addition was carried out in such a manner that the temperature was maintained between 115° and 125°C. After the glycidol addition was complete, the mixture was heated at 115°C for one hour. On cooling, a light brown viscous material was obtained. The resulting material was analyzed using gas chromatography for the presence of unreacted glycidol, gel permeation for determining molecular weight and a 13C nuclear magnetic resonance (NMR) for secondary hydroxyl content.
  • NMR nuclear magnetic resonance
  • hexaglycerol The theoretical value of hexaglycerol is 75 percent secondary hydroxyls. To determine the 25 percent secondary hydroxyls of the hexaglycerol made in Example 1, analysis of the resulting material was done via 13C NMR. it was determined that the resulting material had 70 percent secondary hydroxyl content.
  • Glycerine (108.8 g, 1.18 mol) was stirred with potassium metal (0.93 g, 0.024 mol) under nitrogen. The mixture was heated gradually to 123°C. Glycidol was added at a rate of approximately 0.4 mL/min (474.52 g,
  • the mixture was stirred at 123°C for 12 hours after all of the glycidol had been added.
  • the molecular weight was determined to be 414.7.
  • the yield of recoverable polyglycerol after transferral was,..581 g or 99.5 percent.
  • the percent of secondary hydroxyls in the 15 pentagylcerol is 64.
  • the brown polymer had a molecular weight (M n ) of 839.
  • the yield of recoverable polyglycerol after transferal was 457 g or
  • glycerine 25.53 g, 0.277 mol
  • potassium (0.58 g, 0.015 mol
  • glycerine 25.63 g, 0.278 mol
  • 0.55 g (0.014 mol) of potassium metal catalyst 0.55 g (0.014 mol)
  • Glycidol 310.8 g, 4.17 mol
  • the polymer had a molecular weight of 702 g.
  • the yield of recoverable polyglycerol after transfer was 260 g or 99.5 percent.
  • the percent of secondary hydroxyls is 75.
  • the viscous mixture was stirred for an additional.3 and 1/2 hours at 120°C. The mixture was then made neutral with phosphoric acid and allowed to cool to 70°C before pouring into glass jars for storage. On cooling to room temperature the material was a light brown, very viscous liquid.
  • a glycidol to glycerol ratio of 20 to 1 was used .
  • the next example illustrates the esterification of a polyglycerol, hexaglycerol to make hexaglyceroloctaoleate.
  • Example 13 Preparation of Hexaglyceroloctaoleate from a Polyglycerol Backbone of 70 percent Secondary Hydroxyls by Esterification With Oleoyl Chloride -.
  • the crude oil mixture was diluted with hexanes and then pyridine was added in excess, as determined by the lack of formation of pyridinium hydrochloride.
  • Hexaglycerol (32.6 g, 0.0706 mol) with 71 percent secondary hydroxyl content was heated in a three-neck flask on a water bath at 45° to 50°C.
  • the flask was fitted with a mechanical stirrer, nitrogen inlet and hydrogen chloride scrubber.
  • Oleoyl chloride (163 g > 0.54 mol) was added to the warmed polymer and the mixture stirred for 4 hours.
  • the oil was diluted with hexane, stirred with alumina, and passed twice through a WGRTM anion exchange resin column. After evaporation of solvent, 105.62 g of the hexaglycerol octaoleate was recovered.
  • Octaglycerol 188.5g, 0.309 mol
  • pyridine a mixture of pyridine
  • Oleoyl chloride 939.4 g (93.12 mol)
  • the mixture was stirred overnight.
  • the pyridinium salt was filtered from the oil and the oil extracted with a mixture of ethanol, water, sodium ⁇ hydroxide. Residual solvent was stripped from the oil and it was deodorized by steam stripping. 865 Grams of oil was recovered.
  • the flask and contents were heated to reflux, and water was azeotroped at 167°-170°C, over 55 hours (25 mL).
  • the oil was dissolved in hexane and extracted with aqueous NaOH, followed by extraction with hot water to reduce the level of free fatty acids and remove the catalyst.
  • the oil was concentrated by removal of solvent under vacuum, 381.34 g was recovered (72.5 percent yield).
  • Propoxynonaglycerol (549.0 g, 0.716 mol) was stirred with pyridine (630.4 g, 7.98 mol) oleoyl chloride (2393.0 g, 7.95 mol) was added to the mixture.
  • the temperature was kept between 40° to 50°C during the addition. Hexane was added to the stirred suspension.
  • the mixture was stirred for 12 hours after all of the oleoyl chloride was added.
  • the reaction mixture was filtered and the volatiles were removed under reduced pressure.
  • the crude oil was extracted with ethanol to less than one percent free fatty acid. Residual ethanol and other volatiles were removed under reduced pressure.
  • Butoxynonaglycerol (371.1 g, 0.531 mol) was stirred in a mixture of hexane (1 L) and pyridine.
  • the reaction mixture was filtered and the filter cake r- washed with hexane.
  • the hexane was combined with the crude oil and the volatiles were stripped on the rotary evaporator.
  • the crude concentrated oil was extracted with ethanol to less than one percent free fatty acid. Volatiles were removed under reduced pressure.
  • Butoxynonoglycerol (685.5 g, 0.800 mol) was stirred in a 6 L roundbottom flask with pyridine 15 (705.3 g, 8.93 mol). Oleoyl chloride (2674.9 g, 8.89 mol) was added slowly. The temperature was maintained within 40° to 50°C. Hexane was added to the thick suspension. The mixture was stirred for an
  • Octaglycerol 50.36 g, 0.0862 mol was warmed and stirred with 0.3 g of potassium metal, in a three-necked round bottom flask. The flask was fitted with a thermometer, nitrogen inlet, and short path vacuum distillation column. Stirring was continued until the metal was completely reacted. Soybean oil (240.0 g) (0.275 mol) was added to the mixture and the temperature was raised to 100°C. Nitrogen purge was stopped and vacuum applied as the temperature was increased steadily to greater than 200°C. Distillate j- was collected (150°C, 481.3 cm) as the temperature of the mixture increased from 210° to 250°C. The reaction was completed in one hour. Heating was discontinued and the crude oil was allowed to cool to room temperature before being diluted to twice its volume with heptane.
  • the next examples, 21 and 22 illustrate the lipase hydrolysis testing and the results of the feeding tests for the low calorie oils.
  • the polyglycerol oils were submitted to a lipase assay, which has been used as a screening test for feeding studies.
  • test oil emulsion is incubated with lipase and buffer of pH 8.0 overnight.
  • 4 ml vial are combining the following: 0.5 ml H 2 0; 0.5 ml of 7 percent (w/v) gum acacia (gum arabic); 0.5 ml of candidate oil and 0.2 ml of 0.2 M tris buffer pH 8.0 (tris(hydroxymethyl)- aminomethane which can be purchased from Sigma Chemical Co., St. Louis, M0).
  • 0.5 ml H 2 0 0.5 ml of 7 percent (w/v) gum acacia (gum arabic); 0.5 ml of candidate oil and 0.2 ml of 0.2 M tris buffer pH 8.0 (tris(hydroxymethyl)- aminomethane which can be purchased from Sigma Chemical Co., St. Louis, M0).
  • the water, gum acacia, and buffer are combined into a stock solution (10-20 ml) and a sample of 1.2 ml of this mixture is added to 500 microliters of test oil in the vial.
  • Each test run will contain a sample of olive oil
  • the probe is wiped between samples with a Kimwipe moistened with
  • the result is a stable creamy white emulsion.
  • Eight each 135 microliter samples are distributed to 21x70 mm, 16 ml sc vials.
  • the four test vials receive 10 uL each of ⁇ .a mixture containing 10 percent w/v of each of the following lipases in deionized water: lipase N, lipase G and lipase D (which can be purchased from Amano International Enzyme Co., Inc., P.O. Box 1000, Troy, Virginia 22974).
  • the blanks receive no enzyme at this stage.
  • All of the vials are capped and incubated at 37°C overnight.
  • the unused lipase stock is also capped and incubated at 37°C overnight. This allows any enzymatic reactions which might alter pH to take place.
  • a fresh one liter batch of 0.05 N NaOH is prepared by diluting 1:10 a 100 ml sample of purchased reagent 0.5 N NaOH.
  • the 0.05 N NaOH is also standardized against a 0.1 N HC1 sample by titration to pH 7.0. All of these steps ensure the accuracy of the titration data.
  • the eight tubes are removed from the 37°C incubator. Each tube receives the addition of a 3/8 inch diameter TFE starburst stirring head (which can be purchased from Fisher Scientific Co.) magnetic stirrer and 4.0 ml of H 2 0 to increase the volume and allow the pH electrode to be submerged.
  • the four "blank" tubes receive 10 microliters of the overnight incubated lipase stock solution immediately prior to titration.
  • a value of lipase liberated milliequivalents of acid per gram of oil is computed. This value is divided by the value for total available acid determined by saponification of a measured mass of test oil. From this ratio, a value for percent lipase hydrolysis is computed.
  • the polyglycerol oil is not substantially hydrolyzed.
  • Example 21 Some of oils submitted for lipase testing in Example 21 were submitted for rat feeding studies. For two weeks rats were fed diets containing various levels of test oils.
  • the polyglycerol is not digested in animals.
  • Undecaglycerol (323.14 g, 0.385 mol) was warmed and poured into a 2-liter stainless steel autoclave fitted with a heating coil and a dip tube for subsurface addition. Potassium (1.62 g, 0.041 mol) was added, and the mixture stirred for two hours at 60°C as nitrogen was flushed through the reactor. The mixture was heated to 90°C, the system closed and pressured to 38 psig (365 kPa) with nitrogen. Propylene oxide (428 g, 7.38 mol) was pumped into the reactor, a maximum pressure of 84 psig (682 kPa) being recorded.
  • Propoxylated undecaglycerol (708.2 g, 0.526 mol) was mixed with 2008 g, (7.10 mol) of oleic acid, stirred vigorously in a 5-liter flask under nitrogen for several hours. Approximately 6 mL of phosphoric acid was added to the mixture. The flask was fitted with a Dean-Stark trap with watercooled condenser. Toluene (885 g, total) was added to the flask and trap. p-Toluene sulfonic acid monohydrate (22.8 g, ca 2 mol percent of the oleic acid) was added and the mixture heated to reflux ("135°C). After three hours, 75 mL of water had been trapped.
  • the hexane was extracted with two 50 mL portions of a solution of 10 g of NaOH in 50 percent saturated NaCl. A sample of the oil was titrated for free fatty acid content. The oil was found to have a Fatty Acid Value (FAV) of 54.54 mg KOH per gram sample (27.4 percent oleic acid). The oil (1324.1 g) was saturated with anhydrous ethanol and extracted with (12) 300 mL portions of same. The ethanol washes were saved. Ethanol was stripped from the oil on the rotavap (578.8 g recovered). Titration of a sample indicated that the oil had a FAV of 2.15 (1.08 percent oleic). This oil was not processed further.
  • FAV Fatty Acid Value
  • Decaglycerol (283.76 g, 0.376 mol) was stirred in a 2-liter autoclave with 1.45 g (0.0376 mol) of potassium for two hours with nitrogen flush. Over this time period the temperature was raised gradually from 50° to 90°C. The system was closed and propylene oxide was added over a 25-minute period (74.84 g, 1.29 mol). A maximum pressure of 40 psig (380 kPa) was reached, and this pressure dropped to atmospheric pressure over the next 4-1/2-hours. The mixture stirred for an additional two hours at 90°C. The viscous liquid was stripped of volatiles on the rotavap, and samples were analyzed for molecular weight and secondary hydroxyl content.
  • Example 26 Esterification of the Propoxylated jEtecaglycerol produced in Example 25
  • the amount of water azeotroped indicated that 10 of 12 hydroxyls were esterified.
  • Examples 27-30 illustrate the capping of the polyglycerol.
  • Nonaglycerol (535.3 g» 0.809 mol) was poured into a 2-liter stainless-steel pressure reactor. Potassium metal (1.59 g, 0.0407 mol) was added and the mixture was stirred while the system was flushed with nitrogen. The temperature of the mixture was raised gradually from 23° to 90°C over a period of four hours. The nitrogen purge was stopped, the vents closed and propylene oxide (140.4 g, 2.42 mol) was pumped, subsurfacely, into the mixture. The pressure inside the reactor dropped from 48 psig to 1 psig over a 2 and 1/2-hour period. The mixture was stirred for an additional 11 hours.
  • Decaglycerol (303 g» 0.416 mol) was poured into a 2-liter stainless-steel reactor. Potassium metal (0.77 g, 0.020 mol) was added and the mixture stirred under an atmosphere of nitrogen. The temperature was raised from 45° to 90°C over a three-hour period. At this temperature, butylene oxide (90 g, 1.25 mol) was added over a 2 and 1/2 hour period. The mixture was stirred for an additional 12 hours. At this point, the pressure inside the reactor was equal to atmospheric pressure.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Nutrition Science (AREA)
  • Mycology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Edible Oils And Fats (AREA)
  • Fats And Perfumes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyethers (AREA)

Abstract

Nouvelle composition de polyglycérol linéaire, procédé de fabrication de la composition et nouveaux succédanés de matières grasses pauvres en calories, dérivés par estérification de la composition de polyglycérol. Ladite composition de polyglycérol est, facultativement, coiffée d'un oxyde d'akylène avant l'estérification. Le polyglycérol a une répartition de masse moléculaire étroite, il a peu d'odeur et de couleur et il comporte essentiellement des groupes hydroxyle secondaires ou tertiaires.
PCT/US1991/000260 1990-01-16 1991-01-11 Succedanes de matieres grasses pauvres en calories, precurseurs desdits succedanes et leurs procedes de fabrication WO1991010368A1 (fr)

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JP3503399A JPH05504062A (ja) 1990-01-16 1991-01-11 低カロリー脂肪代替物質、代替物質の製法およびその前駆体

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0571219A3 (fr) * 1992-05-20 1994-01-12 ARCO Chemical Technology, L.P. Compositions de substituant de graisse comprenant une glycerine estérifiée propoxylée et resistant aux effets gastroentériques secondaires
US5288884A (en) * 1992-10-22 1994-02-22 Arco Chemical Technology, L.P. Process for producing a reduced calorie fat mimetic composition
US5298637A (en) * 1992-10-22 1994-03-29 Arco Chemical Technology, L.P. Process for producing a reduced calorie lipid composition
WO1994009638A1 (fr) * 1992-10-30 1994-05-11 The Procter & Gamble Company Composition lipidique non digestible contenant des particules solides d'ester de polyglycerol pour controler les pertes huileuses anales
WO1994009640A1 (fr) * 1992-10-30 1994-05-11 The Procter & Gamble Company Compositions lipidiques non digestibles contenant un melange cocristallise de polyesters de polyol totalement hydrogenes et un modificateur cristallin en tant qu'agent de controle des pertes huileuses anales
WO1994009641A1 (fr) * 1992-10-30 1994-05-11 The Procter & Gamble Company Compositions lipidiques non digestibles contenant des particules solides non digestibles relativement petites pour controler les pertes huileuses anales
US5376398A (en) * 1993-10-22 1994-12-27 Arco Chemical Technology, L.P. Reduced calorie food compositions containing fatty acid-esterified polytetramethylene ether glycol fat substitutes
US5431949A (en) * 1991-03-29 1995-07-11 Curtice-Burns Foods, Inc. Fat substitute compositions having reduced laxative effects at low levels of inclusion
EP0706328A4 (fr) * 1993-06-17 1996-05-08
US6504003B1 (en) 1998-03-23 2003-01-07 The Procter & Gamble Co. Synthesis of higher polyol fatty acid polyesters by transesterification
US6566124B1 (en) 1998-03-23 2003-05-20 The Procter & Gamble Co. Processes for synthesis and purification of nondigestible fats
US6995232B2 (en) 2001-01-31 2006-02-07 Procter & Gamble Synthesis of polyol medium fatty acid polyesters
US7879384B2 (en) 2007-11-08 2011-02-01 Kraft Foods Global Brands Llc Structured glycerol esters useful as edible moisture barriers
US8206772B2 (en) 2007-11-08 2012-06-26 Kraft Foods Global Brands Llc Structured lipid compositions and methods of formulation thereof
US8236869B2 (en) 2006-10-31 2012-08-07 Mitsui Chemicals, Inc. Polyether polyol, rigid polyurethane foam and processes for production thereof
CN102695831A (zh) * 2010-01-05 2012-09-26 纳尔科公司 用于扬克涂层的改善的改性剂
US8486478B2 (en) 2007-11-08 2013-07-16 International Great Brands LLC Structured lipid compositions

Citations (1)

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US4861613A (en) * 1986-07-25 1989-08-29 Arco Chemical Technology, Inc. Non-digestible fat substitutes of low-caloric value

Patent Citations (1)

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US4861613A (en) * 1986-07-25 1989-08-29 Arco Chemical Technology, Inc. Non-digestible fat substitutes of low-caloric value

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Title
BABAYAN, V.K., "Polyglycerol Esters: Unique Additives for the Bakery Industry", Cereal Foods World, October 1982, Vol. 27, No. 10, pages 510-512, see the entire article. *
See also references of EP0510070A4 *

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5431949A (en) * 1991-03-29 1995-07-11 Curtice-Burns Foods, Inc. Fat substitute compositions having reduced laxative effects at low levels of inclusion
EP0571219A3 (fr) * 1992-05-20 1994-01-12 ARCO Chemical Technology, L.P. Compositions de substituant de graisse comprenant une glycerine estérifiée propoxylée et resistant aux effets gastroentériques secondaires
US5288884A (en) * 1992-10-22 1994-02-22 Arco Chemical Technology, L.P. Process for producing a reduced calorie fat mimetic composition
US5298637A (en) * 1992-10-22 1994-03-29 Arco Chemical Technology, L.P. Process for producing a reduced calorie lipid composition
CN1051206C (zh) * 1992-10-30 2000-04-12 普罗格特-甘布尔公司 不能消化型脂肪组合物及其食物制品和用途
WO1994009638A1 (fr) * 1992-10-30 1994-05-11 The Procter & Gamble Company Composition lipidique non digestible contenant des particules solides d'ester de polyglycerol pour controler les pertes huileuses anales
WO1994009640A1 (fr) * 1992-10-30 1994-05-11 The Procter & Gamble Company Compositions lipidiques non digestibles contenant un melange cocristallise de polyesters de polyol totalement hydrogenes et un modificateur cristallin en tant qu'agent de controle des pertes huileuses anales
WO1994009641A1 (fr) * 1992-10-30 1994-05-11 The Procter & Gamble Company Compositions lipidiques non digestibles contenant des particules solides non digestibles relativement petites pour controler les pertes huileuses anales
US6261628B1 (en) 1992-10-30 2001-07-17 The Procter & Gamble Company Nondigestible fat compositions containing solid polyglycerol ester particles for passive oil loss control
US5422131A (en) * 1992-10-30 1995-06-06 The Procter & Gamble Company Nondigestible fat compositions containing relatively small nondigestible solid particles for passive oil loss control
US5451416A (en) * 1992-10-30 1995-09-19 Johnston; Robert W. Nondigestible fat compositions containing cocrystallized blend of polyol polyester hardstock and crystal modifier as a passive oil loss control agent
EP0706328A4 (fr) * 1993-06-17 1996-05-08
US5376398A (en) * 1993-10-22 1994-12-27 Arco Chemical Technology, L.P. Reduced calorie food compositions containing fatty acid-esterified polytetramethylene ether glycol fat substitutes
US6504003B1 (en) 1998-03-23 2003-01-07 The Procter & Gamble Co. Synthesis of higher polyol fatty acid polyesters by transesterification
US6566124B1 (en) 1998-03-23 2003-05-20 The Procter & Gamble Co. Processes for synthesis and purification of nondigestible fats
US6995232B2 (en) 2001-01-31 2006-02-07 Procter & Gamble Synthesis of polyol medium fatty acid polyesters
US8236869B2 (en) 2006-10-31 2012-08-07 Mitsui Chemicals, Inc. Polyether polyol, rigid polyurethane foam and processes for production thereof
US7879384B2 (en) 2007-11-08 2011-02-01 Kraft Foods Global Brands Llc Structured glycerol esters useful as edible moisture barriers
US8206772B2 (en) 2007-11-08 2012-06-26 Kraft Foods Global Brands Llc Structured lipid compositions and methods of formulation thereof
US8486478B2 (en) 2007-11-08 2013-07-16 International Great Brands LLC Structured lipid compositions
US8911813B2 (en) 2007-11-08 2014-12-16 Intercontinental Great Brands Llc Structured lipid compositions
CN102695831A (zh) * 2010-01-05 2012-09-26 纳尔科公司 用于扬克涂层的改善的改性剂

Also Published As

Publication number Publication date
EP0510070A1 (fr) 1992-10-28
JPH05504062A (ja) 1993-07-01
CA2073868A1 (fr) 1991-07-17
EP0510070A4 (en) 1992-12-09

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