CA1059121A - Synthesis of higher polyol fatty acid polyesters - Google Patents
Synthesis of higher polyol fatty acid polyestersInfo
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- CA1059121A CA1059121A CA217,654A CA217654A CA1059121A CA 1059121 A CA1059121 A CA 1059121A CA 217654 A CA217654 A CA 217654A CA 1059121 A CA1059121 A CA 1059121A
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- Prior art keywords
- fatty acid
- polyol
- lower alkyl
- alkali metal
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
- C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
- C07H13/04—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals attached to acyclic carbon atoms
- C07H13/06—Fatty acids
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/20—Reducing nutritive value; Dietetic products with reduced nutritive value
- A23L33/21—Addition of substantially indigestible substances, e.g. dietary fibres
- A23L33/25—Synthetic polymers, e.g. vinylic or acrylic polymers
- A23L33/26—Polyol polyesters, e.g. sucrose polyesters; Synthetic sugar polymers, e.g. polydextrose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
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- Food Science & Technology (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
SYNTHESIS OF HIGHER POLYOL FATTY ACID POLYESTERS
Harry M. Taylor and George P. Rizzi ABSTRACT OF THE DISCLOSURE
A solvent-free transesterification comprising the steps of (1) heating a mixture of a polyol, a fatty acid lower alkyl ester, an alkali metal fatty acid soap, and a basic catalyst to form a homogenous melt; and (2) subsequently adding to the reaction product of step (1) excess fatty acid lower alkyl esters yields polyol fatty acid polyesters.
Harry M. Taylor and George P. Rizzi ABSTRACT OF THE DISCLOSURE
A solvent-free transesterification comprising the steps of (1) heating a mixture of a polyol, a fatty acid lower alkyl ester, an alkali metal fatty acid soap, and a basic catalyst to form a homogenous melt; and (2) subsequently adding to the reaction product of step (1) excess fatty acid lower alkyl esters yields polyol fatty acid polyesters.
Description
BACKGROUND OF THE INVENTION
This invention relates to a high yield synthesis of polyol fatty acid polyesters, sucrose polyesters in particular, via transesterification.
The food industry has recently focused attention on polyol polyesters for use as low calorie fats in food products. As a result of this attention, there is a current need for a high yield synthesis of polyol fatty acid polyesters. Historically, such syntheses have been conducted using a mutual solvent to solubilize a polyol and esters of long-chain fatty acids, thus providing a homogenous reactionmedium suitable for catalytic transesterification.
One variation o~ this process, known as the Snell synthesis, has been employed as a means for preparing both poly- and . .
.
.. . . , , . ,, , .. , .. .: , ,, : ,, - :,~ ,,, ;
, . . . .. ..
,. . . . . . . . . .
" ~059lZl lower esters. However, thc solv~nts heretofore employed in such processes are difficult to separate from the final product and are characteristically toxic, therefore limiting the usefulness of such syntheses in the foods industry.
Accordingly, recent efforts have been directed toward the discovery of a high yield synthesis of polyol fatty acid polyesters which does not employ toxic solvents~
Other solvent-free transesterification processes are known in the art.
U.S. Patent 3,521,827 discloses the preparation of sucrose polyesters by means of a solvent-free interesterification using phenyl esters. However, phenol is liberated during the reaction. Phenol is extremely toxic and caustic; c~ntaminates the product; and is difficult to separate. Accordingly, this process does not satisfy current needs for a synthesis of polyol fatty acid polyesters for use in the foods industry.
Feuge, et al., 'LPreparation of Sucrose Esters by Interesterification", Journal of the American Oil Chemical Societv, 47~s], 56-60 (1970), disclose a single stage solvent-free transesterification useful in synthesizing fatty acid esters of sucrose. However, this process is limited to the synthesis of lower esters. It has been experimentally determined that if the sucrose/methyl ester ratio of the Feuge, et al., reaction is lowered by use of excessmethyl esters in an effort to synthesize polyesters, the reactants will -- 2 ~
i.` 1059121 ; disproportionate and prccipitat~ sucrose which then caramelizes to form a brittle, charred waste product.
~urthermore, the Feuge, et al. article reports low yields using lower alkyl esters. The more successful Feuge, et al. synthesis uses fatty acid methyl carbitol esters as ; starting materials. Unfortunately, methyl carbitol is, itself, relatively toxic. Thus, the Feuge, et al. process also fails to satisfy current needs for a synthesis of polyol fatty acid polyesters useful in the foods industry.
It is therefore an object of this invention to provide a high yield syn';hesis of polyol fatty acid polyester.
It is a further object of this invention to provide a synthesis of polyol fatty acid polyesters which does not employ toxic solvent nor generate difficult-to-remove toxic contaminants.
It is a still further object of this invention to provide a synthesis of polyol fatty acid polyesters in which the reactants do not disproportionate thereby reducing caramelization of the polyol.
These and other objects are obtained herein as will be seen from the following disclosure.
. SUMMARY OF THE INVENTION
- It has now been found that high yields of polyol fatty acid polyesters can be prepared via a transesterifi-`~ cation process which can be carried out in the absence of solvents or other contaminants. Thus, the toxicity problems of the prior art are avoided.
, 5912~
The synthesis disclosed herein procceds in three ,: stages. In the first stage, a heterogenous mixture of a polyol, fatty acid lower alkyl esters, an alkali metal ; fatty acid soap, and a basic catalyst is reacted to form ; a homogenous melt consisting of partially esterified polyol ~ and unreacted starting materials. In the second stage, : excess fatt~ acid lower alkyl esters are added to the melt and react with the solubilized partial esters of the polyol and the remaining unesterified polyol to form polyol fatty acid polyester. In the third stage, the polyol fatty acid polyester is separated from the reaction product. The desired polyester product is obtained in high yield. The synthesis can be conveniently carried out at relatively low temperatures and, if desired, at atmospheric pressure.
~5 More specifically, the present invention encompasses } a high yield process for synthesizing polyol fatty acid polyesters comprising the steps of:
(1) heating a heterogenous mixture comprising: (i) from about 10% to about 50% by weight of a polyol;
~0 (ii) from about 40% to about 80% by weight of fatty acid lower alkyl esters; (iii) from about 1% to about 30% by weight of an alkali metal fatty acid soap; and (iv) from about 0.05% to about 5% by weight of a basic catalyst selected from the group consisting of alkali metals, alloys of two or more alkali metals, , alkali metal alkoxides and alkali metal hydrides to a temperature of from about 110C to about 180C under a pressure of from about O.lmm Hg to about 760mm Hg for a ?
time sufficient to form a homogenous melt of partially esteriicd polyol and unrcactcd starting materials;
i ` lOS9lZl ; (2) under the conditions of step 1, adding excess fatty acid lower alkyl esters to the reaction r.
7 product of step 1 to form the polyol fatty acid ~ polyester; and , i , (3) separating the polyol fatty acid polyester from .~ the reaction mixture.
DETAILED`'DESCRIPTION OF THE INVENTION
Objects of the present invention are achieved by ` providing a solvent-free process for synthesizing high yields ~` 10 of polyol fatty acid polyesters. The process is characterized ~' by a unique three step reaction procedure.
Step 1 In the first step of the present process, a hetero~-~i genous mixture of (i) a polyol, (ii) fatty acid lower alkyl '~' esters, (iii) an alkali metal fatty acid soap, and (iv) a basic ' catalyst is reacted to form a homogenous melt comprising .~, .
'~ partially esterified polyol and unreacted starting materials.
-; (i) As used herein, the term "polyol" is intended to include any aliphatic or aromatic compound containing at least !`, 20 two free hydroxyl groups. In practicing the process disclosed herein, the selection of a suitable polyol is simply a matter of choice. For example, suitable polyols may be selected from the following classes: saturated and unsaturated straight and `i~ branched chain linear aliphatics; saturated and unsatu~ated cyclic aliphatics including heterocyclic aliphatic6; or mono-' nuclear and polynuclear aromatics including heterocyclic . .
aromatics. Inasmuch as the present invention encompasses a . proce~s which does not employ toxic solvents nor generatedifficult-to-remove ~!toxic contaminants, preferred polyols are .,:
those which have utility in the foods industry. Accordingly, the carbohydrates and non-toxic glycols are preferred polyols.
Carbohydrates are polyhydroxy aldehydes or : i , - 5 -,, . . .
` ` 1059~21 . .
$ polyhydroxy ketonc~s, or substances that yield such compounds ~-` on hydrolysis. Thcy are distributcd universally in plants and animals, and make up one of the three important classes of animal foods. Carbohydrates may be sùbdivided into three ' i important classes; the monosaccharides, oligosaccharides, and the polysaccharides. Monosaccharides include those carbohydrates which do not hydrolyze. Accordingly, mono-saccharides suitable for use herein include, for example, glucose, mannose, galactose, arabinose, xylose, ribose, 0 apiose, rhamnose, psicose, fructose, sorbose, tagitose, ~`` ribulose, xylulose, and erythrulose. Oligosaccharides ~", are carbohydrates which yield only a few molecules of mono-saccharides on hydrolysis. Accordingly, oligosaccharides suitable for use herein include, for example, maltose, ;,,5 kojibiose, nigerose, cellobiose, lactose, melibiose, gentiobiose, . ., , turanose, rutinose, trehalose, sucrose, and raffinose.
Polysaccharides are those carbohydrates which yield a large ,` number of molecules of monosaccharides on hydrolysis.
Accordingly, polysaccharides suitable for use herein include, - O for example, amylose, glycogen, cellulose, chitin, inulin, agarose, zylans, mannan, and galactans. Another class of ,~ polyols preferred herein is the sugar alcohols. Although `~ sugar alcohols are not carbohydrates in a strict sense, the ~i '- naturally occurring sugar alcohols are so closely related '5 to the carbohydrates that they are also preferred for use herein.
The sugar alcohols most widely distributed in nature and suitable for use herein are sorbitol, mannitol, and galactitol.
Preferred carbohydrates and sugar alcohols suitable for use herein includc, for example, xylitol, sorbitol, and sucrose.
- G -p ~
~ ' ~
`; 1059121 , (ii) As uscd herein, thc tcrm "fatty acid lowcr alkyl esters" is intended to include the cland C2 esters of fatty acids containing about 8 or more carbon atoms, and mixtures :.:;
~`~ of such esters. Suitable esters can be prepared by the rcaction of diazoalkanes and fatty acids, or derived by alcoholysis , . .
from the fatty acids naturally occurring in fats and oils. If , .: . , the acids are derived from fats, saturated acids predominate, , ,;.,, ~
~ but if derived from oils, unsaturated acids predominate.
.. ~
Accordingly, suitable fatty acid lower alkyl esters can be ~10 derived from either saturated or unsaturated fatty acids. Suitable ~ ~ preferred saturated fatty acids include, for example, capric~
`;i` lauric, palmitic, stearic, behenic, isomyristic, isomargaric, ~ myristic, caprylic, and anteisoarachadic. Suitable preferred un-'~.,; - ' saturated fatty acids include, for exa~ple, maleic, linoleic, licanic, oleic, linolenic, and erythrogenic acids. Mixtures of fatty acids derived from soybean oil, sunflower oil, v safflower oil, and corn oil are especiallypreferred for use herein.
Unusually high yields, i.e., greater than 90%, of -j polyol fatty acid polyesters have been obtained where'~ ~0 methyl esters are used in accordance with the process herein. Accordingly, methyl esters are the preferred fatty acid lower alkyl esters.
- (iii) As used herein, the term "alkali metal fatty acid soap" is intended to include the alkali metal salts of saturated and unsaturated fatty acids having from about 8 to about 18 carbon atoms. Accordingly, suitable alkali metal fatty acids soaps include, for example, the lithium, . ....
,'':' ' ' ; ~ 7 -"
~:; lOS91Zl , -; sodium, potassium, rubidium, and cesium salts of fatty acids such as capric, lauric, myristic, palmitic, licanic, parinaric, and stearic acids. Mixtures of fatty acids .::
derived from soybean oil, sunflower oil, safflower oil, and corn oil are preferred for use herein. Accordingly, preferred alkali metal fatty acid soaps include, for .... ~ . .
~ example, the potassium soap made from soybean oil fatty .~.. . . .
acids and the sodium soap made from sunflower oil fatty ~` acids.
`;`10 (iv) The basic catalysts suitable for use herein are those selected from the group consisting of alkali metals such as sodium, lithium, and potassium; alloys of two or more alkali metals such as sodium-lithium a~;;.
sodium-potassium alloys; alkali metal hydrides such as ~5 sodium, lithium and potassium hydride; and alkali metal alkoxides such as potassium t-butoxide and sodium methoxide.
In a preferred embodiment of this invention, the catalyst is dispersed in a suitable carrier so as to . .. ; ~ .
- insure uniform distribution of the catalyst throughout the reaction mass. Suitable ca~riers or dispersing agents include, for example, mineral oil; hydrocarbon solvents, such as xylene; and polyol octaesters, such as sucrose octaesters. Octaesters derived from the polyol .
, . . .
, ., .
: 10591Zl - being esteriied are prefcrred carriers sincc thcir use avoids contamination or removal problems. Preferred . .; .
catalysts suitable for use herein include, for example, sodium hydride, potassium hydride, a dispersion of potassium in sucrose octaester, a dispersion of potassium in mineral oil, potassium t~butoxide, and sodium methoxide.
. In carrying out step 1, thè above-described " reactants are combined to form a heterogenous mixture.
m e precise ratio of reactants can be freely selected ~0 from within the guidelines set forth hereinafter.
However, routine experimentation may be necessary in ~ order to establish the optimum concentrations for a s given set of reactants. In general, the heterogenous r mixture comprises from about 10% to about 50%, `5 preferably from about 20% to about 30% by weight ` of a polyol; from about 40% to about 80%, preferably from about 50% to about 70% by weight of fatty acid lower alkyl esters; from about 1% to about 30%, preferably from about 5% to about 10% by weight of 0 an alkali metal fatty acid soap; and from about 0.05%
to about 5%, preferably from about 0.1% to about 0.5% by weight of a basic catalyst selected from Oe .
'. .
., 9 ,, .
`` 1059121 group consisting of alkali metals, alloys of two or more alkali metals, alkali metal alkoxides and alkali metal hydrides. The heterogenous mixture is heated to a temperature within the range of from about 110C to about 180C, preferably from about 130C -to about 145C under a pressure of from about 0.1 mm Hg to about 760 mm Hg, preferably from about 0.5 mm Hg to about 25 mm Hg. Within these temperature and pressure ranges a homogenous melt of partially esterified polyol and unreacted starting materials will form in from about 1 to about 4 hours.
~; 10 It may be desirable to initiate the reaction by ini-tially introducing from about 0.1% to about 1%, by weight, of catalyst and, thereafter, introducing additional catalyst as the reaction proce~ds.
Step 2 In the second step of the instant process, excesss fatty acid lower alkyl esters are added to the homogenous melt formed in Step 1. As used herein, the term "excess" is ~ -intended to include sufficient lower alkyl esters to raise - the overall ester:polyol mole ratio above 10:1, preferably ~.:
to about 16:1. Although ratios beyond 16:1 can be used, as --a general rule, such ratios do not noti¢eably decrease reaction time or improve the yield and are therefore impractical.
It should be noted that as the transesterification - proceeds, a lower alcohol is formed as a by-product. In order to promote the reaction, the alcohol by-product is preferably removed. Many removal techniques are known in the art, any - one of which can be used to effectively and efficiently remove ,.
.
lOS9121 ~ the lower alcohol. Vacuum removal both with and without :
an inert gas sparging has been found to promote the reaction.
~, - However, for practical purposes, simple distillation under atmospheric pressure has been found to be sufficient. In any ` event, the formation of a lower alcohol presents no significant ; obstacle to the use of the instant process by the foods industry.
` Step 3 In the third step of the process, the polyol fatty acid polyesters formed in step 2 are separated from the reaction product containing polyesters, alcohol, and unreacted :
` starting materials. Separation can be accompli~hed by any of the routinely used separation procedures. Distillation or solvent extraction are preferred due to their simplicity and t ~; economy.
.;
The following examples are intended to further clarify the invention and should not be construed as limitations.
EXAMPLE I
Rreparation-o Sucrose Polyesger from Sucrose and Methyl Esters "
A 1,000 milliliter resin kettle equipped with a ;
mechanical stirrer, thermometer,dropping funnel, and a distillation head arranged for vacuum take off was charged ; with finely powdered sucrose (25.5 gram, 0.0745 moles), soy .~ methyl esters (73.5 milliliters, 0.224 moles) and anhydrous . potassium-soap made from soy methyl esters (10.0 grams).
Heat was supplied via a large magnetic~lly stirred oil bath arranged below the kettle and the mixture was /
,, ' , . '' ~ ~
~ 1059121 deoxygenated undcr 15 millimeters vacuum for 1.25 hours at 95C. On cooling to 55C sodium hydride, 0.1%-(0.-178 grams of 56% dispersion in mineral oil~ was addea and the mixture was reacted at 145-148C/15 millimeters for 2 hours during which time the'mix'changed-from a white~s~lUrry~tO--a~light , brown translucent liquid. The mix was cooled to approximately ~;
90C,treated with a second 0.178 gram portion of sodium hydride dispersion,and reacted 1.5 hours at 150C/10 millimeters. The mixturè was cooled somewhat, dilu~ed with 297.0 milliliters of methyl esters from soybean oil, reheated to 150C/10 millimeters for one hour, cooled, treated with a third portion of sodium hydride (0.178 grams), reheated to 150C/10 mill~meters for three hours and finally cooled to room temperature. During 7.5 hours about 25-30 milliliters 'of liquid distillate collected in vacuum traps at dry ice-isopropanol temperature.__The crude reaction product was treated with 1 milliliter of acetic acid and washed by stir-ring and decantation with-5400 milliliters of methanol'(9 x 600-milliliters). Ice cooling prior to decantation greatly facilitated the separation of the lower, sucrose polyester phase. The clear brown sucrose polyester phase was freed of last traces of methanol by gentle heat under vacuum prior to bleaching with 10 grams of Filtrol clay at 100C/2.5 hours/l atmosphere. The neat mixture of sucrose polyester and clay was cooled, dissolved in hexane and the resulting ~urry was vacuum filtered. Evaporation of hexane under vacuum gave 143.2 grams of light yellow oil; having a hydroxyl value of 18.7. The yield based on sugar was 86%
sucrose polyesters.
* Trademark for acid-activated clays used as decolorizing adsorbent ,' '.~' ' ' ~
.
lOS9121 `` , .
In the above procedure, the sucrosc is replaccd by an ; equivalent amount of propylcne glycol, glycerol, penta-erythritol, glucose, xylitol and sorbitol, respectively, and ` the corresponding polyol fatty acid polyesters are obtained.
In the above procedure, the sodium hydride is replaced /.," .
by an equivalent amount of potassium metal, lithium metal, ~` ~odium-potassium alloy, potassium hydride, and lithium hydride, potassium methoxide, and potassium t-butoxide, ~` respectively, and equivalent results are secured.
~ EXAMPLE II
Preparation of Sucrose Polyester From ~..................... . .
Sucrose and Soybean Methyl Esters ~` Under Atmospheric Pressure ~..r A mixture containing powdered sucrose (2.52 grams), ;1s partially hardened (I.V. 57) soybean methyl esters (6.48 grams) and anhydrous potassium soap made from the same methyl esters ~, (1.0 grams) was homogenized for 10 minutes in a high shear Omni-mixer. The slurry was treated with 0.2% by weight of sodium hydride (56% dispersion mineral oil) and reacted 2 hours at 147C under nitrogen (provision was made for distillation of methanol evolved in the reaction). The one-phase mixture containing lower esters was treated with a second 0.2% of sodium hydride and 31.8 milliliters of additional methyl esters. After reacting another 6 hours at 147C, the final product was cooled and washed 5 limes with 100 milliliters of hot ethanol to remove soap and excess methyl esters. Final ,~ removal of ethanol under vacuum gave 15.7 grams of an off-white ,, ' .
. ,, - 13 _ ,. . .
, r r - -;` 1059~Zl solid; yield based on sucrose was 90%. Quantitative NMR
analysis indicated that the product contained less than 6%
`;~ methyl ester and TLC showed no free fatty acids present.As a preferred embodiment of this invention, it has been found that the alkali metal fatty acid soap used herein can be formed in situ by saponifying an alkali metal hydroxide using the fatty acid lower alkyl ester reactant. Accordingly, a preferred embodiment of the process disclosed herein comprises the steps of:
~10 (1) Heating a mixture of a fatty acid lower alkyl .j,~ . .
ester and an alkali metal hydroxide to a temperature of from about 100C to about 140C, preferably about 120C
under atmospheric pressure to form an emulsion comprising from about 5% to about 30%, preferably from about 7% to about 15% by weight of the corresponding alkali metal fatty acid soap and lower alkyl ester;
This invention relates to a high yield synthesis of polyol fatty acid polyesters, sucrose polyesters in particular, via transesterification.
The food industry has recently focused attention on polyol polyesters for use as low calorie fats in food products. As a result of this attention, there is a current need for a high yield synthesis of polyol fatty acid polyesters. Historically, such syntheses have been conducted using a mutual solvent to solubilize a polyol and esters of long-chain fatty acids, thus providing a homogenous reactionmedium suitable for catalytic transesterification.
One variation o~ this process, known as the Snell synthesis, has been employed as a means for preparing both poly- and . .
.
.. . . , , . ,, , .. , .. .: , ,, : ,, - :,~ ,,, ;
, . . . .. ..
,. . . . . . . . . .
" ~059lZl lower esters. However, thc solv~nts heretofore employed in such processes are difficult to separate from the final product and are characteristically toxic, therefore limiting the usefulness of such syntheses in the foods industry.
Accordingly, recent efforts have been directed toward the discovery of a high yield synthesis of polyol fatty acid polyesters which does not employ toxic solvents~
Other solvent-free transesterification processes are known in the art.
U.S. Patent 3,521,827 discloses the preparation of sucrose polyesters by means of a solvent-free interesterification using phenyl esters. However, phenol is liberated during the reaction. Phenol is extremely toxic and caustic; c~ntaminates the product; and is difficult to separate. Accordingly, this process does not satisfy current needs for a synthesis of polyol fatty acid polyesters for use in the foods industry.
Feuge, et al., 'LPreparation of Sucrose Esters by Interesterification", Journal of the American Oil Chemical Societv, 47~s], 56-60 (1970), disclose a single stage solvent-free transesterification useful in synthesizing fatty acid esters of sucrose. However, this process is limited to the synthesis of lower esters. It has been experimentally determined that if the sucrose/methyl ester ratio of the Feuge, et al., reaction is lowered by use of excessmethyl esters in an effort to synthesize polyesters, the reactants will -- 2 ~
i.` 1059121 ; disproportionate and prccipitat~ sucrose which then caramelizes to form a brittle, charred waste product.
~urthermore, the Feuge, et al. article reports low yields using lower alkyl esters. The more successful Feuge, et al. synthesis uses fatty acid methyl carbitol esters as ; starting materials. Unfortunately, methyl carbitol is, itself, relatively toxic. Thus, the Feuge, et al. process also fails to satisfy current needs for a synthesis of polyol fatty acid polyesters useful in the foods industry.
It is therefore an object of this invention to provide a high yield syn';hesis of polyol fatty acid polyester.
It is a further object of this invention to provide a synthesis of polyol fatty acid polyesters which does not employ toxic solvent nor generate difficult-to-remove toxic contaminants.
It is a still further object of this invention to provide a synthesis of polyol fatty acid polyesters in which the reactants do not disproportionate thereby reducing caramelization of the polyol.
These and other objects are obtained herein as will be seen from the following disclosure.
. SUMMARY OF THE INVENTION
- It has now been found that high yields of polyol fatty acid polyesters can be prepared via a transesterifi-`~ cation process which can be carried out in the absence of solvents or other contaminants. Thus, the toxicity problems of the prior art are avoided.
, 5912~
The synthesis disclosed herein procceds in three ,: stages. In the first stage, a heterogenous mixture of a polyol, fatty acid lower alkyl esters, an alkali metal ; fatty acid soap, and a basic catalyst is reacted to form ; a homogenous melt consisting of partially esterified polyol ~ and unreacted starting materials. In the second stage, : excess fatt~ acid lower alkyl esters are added to the melt and react with the solubilized partial esters of the polyol and the remaining unesterified polyol to form polyol fatty acid polyester. In the third stage, the polyol fatty acid polyester is separated from the reaction product. The desired polyester product is obtained in high yield. The synthesis can be conveniently carried out at relatively low temperatures and, if desired, at atmospheric pressure.
~5 More specifically, the present invention encompasses } a high yield process for synthesizing polyol fatty acid polyesters comprising the steps of:
(1) heating a heterogenous mixture comprising: (i) from about 10% to about 50% by weight of a polyol;
~0 (ii) from about 40% to about 80% by weight of fatty acid lower alkyl esters; (iii) from about 1% to about 30% by weight of an alkali metal fatty acid soap; and (iv) from about 0.05% to about 5% by weight of a basic catalyst selected from the group consisting of alkali metals, alloys of two or more alkali metals, , alkali metal alkoxides and alkali metal hydrides to a temperature of from about 110C to about 180C under a pressure of from about O.lmm Hg to about 760mm Hg for a ?
time sufficient to form a homogenous melt of partially esteriicd polyol and unrcactcd starting materials;
i ` lOS9lZl ; (2) under the conditions of step 1, adding excess fatty acid lower alkyl esters to the reaction r.
7 product of step 1 to form the polyol fatty acid ~ polyester; and , i , (3) separating the polyol fatty acid polyester from .~ the reaction mixture.
DETAILED`'DESCRIPTION OF THE INVENTION
Objects of the present invention are achieved by ` providing a solvent-free process for synthesizing high yields ~` 10 of polyol fatty acid polyesters. The process is characterized ~' by a unique three step reaction procedure.
Step 1 In the first step of the present process, a hetero~-~i genous mixture of (i) a polyol, (ii) fatty acid lower alkyl '~' esters, (iii) an alkali metal fatty acid soap, and (iv) a basic ' catalyst is reacted to form a homogenous melt comprising .~, .
'~ partially esterified polyol and unreacted starting materials.
-; (i) As used herein, the term "polyol" is intended to include any aliphatic or aromatic compound containing at least !`, 20 two free hydroxyl groups. In practicing the process disclosed herein, the selection of a suitable polyol is simply a matter of choice. For example, suitable polyols may be selected from the following classes: saturated and unsaturated straight and `i~ branched chain linear aliphatics; saturated and unsatu~ated cyclic aliphatics including heterocyclic aliphatic6; or mono-' nuclear and polynuclear aromatics including heterocyclic . .
aromatics. Inasmuch as the present invention encompasses a . proce~s which does not employ toxic solvents nor generatedifficult-to-remove ~!toxic contaminants, preferred polyols are .,:
those which have utility in the foods industry. Accordingly, the carbohydrates and non-toxic glycols are preferred polyols.
Carbohydrates are polyhydroxy aldehydes or : i , - 5 -,, . . .
` ` 1059~21 . .
$ polyhydroxy ketonc~s, or substances that yield such compounds ~-` on hydrolysis. Thcy are distributcd universally in plants and animals, and make up one of the three important classes of animal foods. Carbohydrates may be sùbdivided into three ' i important classes; the monosaccharides, oligosaccharides, and the polysaccharides. Monosaccharides include those carbohydrates which do not hydrolyze. Accordingly, mono-saccharides suitable for use herein include, for example, glucose, mannose, galactose, arabinose, xylose, ribose, 0 apiose, rhamnose, psicose, fructose, sorbose, tagitose, ~`` ribulose, xylulose, and erythrulose. Oligosaccharides ~", are carbohydrates which yield only a few molecules of mono-saccharides on hydrolysis. Accordingly, oligosaccharides suitable for use herein include, for example, maltose, ;,,5 kojibiose, nigerose, cellobiose, lactose, melibiose, gentiobiose, . ., , turanose, rutinose, trehalose, sucrose, and raffinose.
Polysaccharides are those carbohydrates which yield a large ,` number of molecules of monosaccharides on hydrolysis.
Accordingly, polysaccharides suitable for use herein include, - O for example, amylose, glycogen, cellulose, chitin, inulin, agarose, zylans, mannan, and galactans. Another class of ,~ polyols preferred herein is the sugar alcohols. Although `~ sugar alcohols are not carbohydrates in a strict sense, the ~i '- naturally occurring sugar alcohols are so closely related '5 to the carbohydrates that they are also preferred for use herein.
The sugar alcohols most widely distributed in nature and suitable for use herein are sorbitol, mannitol, and galactitol.
Preferred carbohydrates and sugar alcohols suitable for use herein includc, for example, xylitol, sorbitol, and sucrose.
- G -p ~
~ ' ~
`; 1059121 , (ii) As uscd herein, thc tcrm "fatty acid lowcr alkyl esters" is intended to include the cland C2 esters of fatty acids containing about 8 or more carbon atoms, and mixtures :.:;
~`~ of such esters. Suitable esters can be prepared by the rcaction of diazoalkanes and fatty acids, or derived by alcoholysis , . .
from the fatty acids naturally occurring in fats and oils. If , .: . , the acids are derived from fats, saturated acids predominate, , ,;.,, ~
~ but if derived from oils, unsaturated acids predominate.
.. ~
Accordingly, suitable fatty acid lower alkyl esters can be ~10 derived from either saturated or unsaturated fatty acids. Suitable ~ ~ preferred saturated fatty acids include, for example, capric~
`;i` lauric, palmitic, stearic, behenic, isomyristic, isomargaric, ~ myristic, caprylic, and anteisoarachadic. Suitable preferred un-'~.,; - ' saturated fatty acids include, for exa~ple, maleic, linoleic, licanic, oleic, linolenic, and erythrogenic acids. Mixtures of fatty acids derived from soybean oil, sunflower oil, v safflower oil, and corn oil are especiallypreferred for use herein.
Unusually high yields, i.e., greater than 90%, of -j polyol fatty acid polyesters have been obtained where'~ ~0 methyl esters are used in accordance with the process herein. Accordingly, methyl esters are the preferred fatty acid lower alkyl esters.
- (iii) As used herein, the term "alkali metal fatty acid soap" is intended to include the alkali metal salts of saturated and unsaturated fatty acids having from about 8 to about 18 carbon atoms. Accordingly, suitable alkali metal fatty acids soaps include, for example, the lithium, . ....
,'':' ' ' ; ~ 7 -"
~:; lOS91Zl , -; sodium, potassium, rubidium, and cesium salts of fatty acids such as capric, lauric, myristic, palmitic, licanic, parinaric, and stearic acids. Mixtures of fatty acids .::
derived from soybean oil, sunflower oil, safflower oil, and corn oil are preferred for use herein. Accordingly, preferred alkali metal fatty acid soaps include, for .... ~ . .
~ example, the potassium soap made from soybean oil fatty .~.. . . .
acids and the sodium soap made from sunflower oil fatty ~` acids.
`;`10 (iv) The basic catalysts suitable for use herein are those selected from the group consisting of alkali metals such as sodium, lithium, and potassium; alloys of two or more alkali metals such as sodium-lithium a~;;.
sodium-potassium alloys; alkali metal hydrides such as ~5 sodium, lithium and potassium hydride; and alkali metal alkoxides such as potassium t-butoxide and sodium methoxide.
In a preferred embodiment of this invention, the catalyst is dispersed in a suitable carrier so as to . .. ; ~ .
- insure uniform distribution of the catalyst throughout the reaction mass. Suitable ca~riers or dispersing agents include, for example, mineral oil; hydrocarbon solvents, such as xylene; and polyol octaesters, such as sucrose octaesters. Octaesters derived from the polyol .
, . . .
, ., .
: 10591Zl - being esteriied are prefcrred carriers sincc thcir use avoids contamination or removal problems. Preferred . .; .
catalysts suitable for use herein include, for example, sodium hydride, potassium hydride, a dispersion of potassium in sucrose octaester, a dispersion of potassium in mineral oil, potassium t~butoxide, and sodium methoxide.
. In carrying out step 1, thè above-described " reactants are combined to form a heterogenous mixture.
m e precise ratio of reactants can be freely selected ~0 from within the guidelines set forth hereinafter.
However, routine experimentation may be necessary in ~ order to establish the optimum concentrations for a s given set of reactants. In general, the heterogenous r mixture comprises from about 10% to about 50%, `5 preferably from about 20% to about 30% by weight ` of a polyol; from about 40% to about 80%, preferably from about 50% to about 70% by weight of fatty acid lower alkyl esters; from about 1% to about 30%, preferably from about 5% to about 10% by weight of 0 an alkali metal fatty acid soap; and from about 0.05%
to about 5%, preferably from about 0.1% to about 0.5% by weight of a basic catalyst selected from Oe .
'. .
., 9 ,, .
`` 1059121 group consisting of alkali metals, alloys of two or more alkali metals, alkali metal alkoxides and alkali metal hydrides. The heterogenous mixture is heated to a temperature within the range of from about 110C to about 180C, preferably from about 130C -to about 145C under a pressure of from about 0.1 mm Hg to about 760 mm Hg, preferably from about 0.5 mm Hg to about 25 mm Hg. Within these temperature and pressure ranges a homogenous melt of partially esterified polyol and unreacted starting materials will form in from about 1 to about 4 hours.
~; 10 It may be desirable to initiate the reaction by ini-tially introducing from about 0.1% to about 1%, by weight, of catalyst and, thereafter, introducing additional catalyst as the reaction proce~ds.
Step 2 In the second step of the instant process, excesss fatty acid lower alkyl esters are added to the homogenous melt formed in Step 1. As used herein, the term "excess" is ~ -intended to include sufficient lower alkyl esters to raise - the overall ester:polyol mole ratio above 10:1, preferably ~.:
to about 16:1. Although ratios beyond 16:1 can be used, as --a general rule, such ratios do not noti¢eably decrease reaction time or improve the yield and are therefore impractical.
It should be noted that as the transesterification - proceeds, a lower alcohol is formed as a by-product. In order to promote the reaction, the alcohol by-product is preferably removed. Many removal techniques are known in the art, any - one of which can be used to effectively and efficiently remove ,.
.
lOS9121 ~ the lower alcohol. Vacuum removal both with and without :
an inert gas sparging has been found to promote the reaction.
~, - However, for practical purposes, simple distillation under atmospheric pressure has been found to be sufficient. In any ` event, the formation of a lower alcohol presents no significant ; obstacle to the use of the instant process by the foods industry.
` Step 3 In the third step of the process, the polyol fatty acid polyesters formed in step 2 are separated from the reaction product containing polyesters, alcohol, and unreacted :
` starting materials. Separation can be accompli~hed by any of the routinely used separation procedures. Distillation or solvent extraction are preferred due to their simplicity and t ~; economy.
.;
The following examples are intended to further clarify the invention and should not be construed as limitations.
EXAMPLE I
Rreparation-o Sucrose Polyesger from Sucrose and Methyl Esters "
A 1,000 milliliter resin kettle equipped with a ;
mechanical stirrer, thermometer,dropping funnel, and a distillation head arranged for vacuum take off was charged ; with finely powdered sucrose (25.5 gram, 0.0745 moles), soy .~ methyl esters (73.5 milliliters, 0.224 moles) and anhydrous . potassium-soap made from soy methyl esters (10.0 grams).
Heat was supplied via a large magnetic~lly stirred oil bath arranged below the kettle and the mixture was /
,, ' , . '' ~ ~
~ 1059121 deoxygenated undcr 15 millimeters vacuum for 1.25 hours at 95C. On cooling to 55C sodium hydride, 0.1%-(0.-178 grams of 56% dispersion in mineral oil~ was addea and the mixture was reacted at 145-148C/15 millimeters for 2 hours during which time the'mix'changed-from a white~s~lUrry~tO--a~light , brown translucent liquid. The mix was cooled to approximately ~;
90C,treated with a second 0.178 gram portion of sodium hydride dispersion,and reacted 1.5 hours at 150C/10 millimeters. The mixturè was cooled somewhat, dilu~ed with 297.0 milliliters of methyl esters from soybean oil, reheated to 150C/10 millimeters for one hour, cooled, treated with a third portion of sodium hydride (0.178 grams), reheated to 150C/10 mill~meters for three hours and finally cooled to room temperature. During 7.5 hours about 25-30 milliliters 'of liquid distillate collected in vacuum traps at dry ice-isopropanol temperature.__The crude reaction product was treated with 1 milliliter of acetic acid and washed by stir-ring and decantation with-5400 milliliters of methanol'(9 x 600-milliliters). Ice cooling prior to decantation greatly facilitated the separation of the lower, sucrose polyester phase. The clear brown sucrose polyester phase was freed of last traces of methanol by gentle heat under vacuum prior to bleaching with 10 grams of Filtrol clay at 100C/2.5 hours/l atmosphere. The neat mixture of sucrose polyester and clay was cooled, dissolved in hexane and the resulting ~urry was vacuum filtered. Evaporation of hexane under vacuum gave 143.2 grams of light yellow oil; having a hydroxyl value of 18.7. The yield based on sugar was 86%
sucrose polyesters.
* Trademark for acid-activated clays used as decolorizing adsorbent ,' '.~' ' ' ~
.
lOS9121 `` , .
In the above procedure, the sucrosc is replaccd by an ; equivalent amount of propylcne glycol, glycerol, penta-erythritol, glucose, xylitol and sorbitol, respectively, and ` the corresponding polyol fatty acid polyesters are obtained.
In the above procedure, the sodium hydride is replaced /.," .
by an equivalent amount of potassium metal, lithium metal, ~` ~odium-potassium alloy, potassium hydride, and lithium hydride, potassium methoxide, and potassium t-butoxide, ~` respectively, and equivalent results are secured.
~ EXAMPLE II
Preparation of Sucrose Polyester From ~..................... . .
Sucrose and Soybean Methyl Esters ~` Under Atmospheric Pressure ~..r A mixture containing powdered sucrose (2.52 grams), ;1s partially hardened (I.V. 57) soybean methyl esters (6.48 grams) and anhydrous potassium soap made from the same methyl esters ~, (1.0 grams) was homogenized for 10 minutes in a high shear Omni-mixer. The slurry was treated with 0.2% by weight of sodium hydride (56% dispersion mineral oil) and reacted 2 hours at 147C under nitrogen (provision was made for distillation of methanol evolved in the reaction). The one-phase mixture containing lower esters was treated with a second 0.2% of sodium hydride and 31.8 milliliters of additional methyl esters. After reacting another 6 hours at 147C, the final product was cooled and washed 5 limes with 100 milliliters of hot ethanol to remove soap and excess methyl esters. Final ,~ removal of ethanol under vacuum gave 15.7 grams of an off-white ,, ' .
. ,, - 13 _ ,. . .
, r r - -;` 1059~Zl solid; yield based on sucrose was 90%. Quantitative NMR
analysis indicated that the product contained less than 6%
`;~ methyl ester and TLC showed no free fatty acids present.As a preferred embodiment of this invention, it has been found that the alkali metal fatty acid soap used herein can be formed in situ by saponifying an alkali metal hydroxide using the fatty acid lower alkyl ester reactant. Accordingly, a preferred embodiment of the process disclosed herein comprises the steps of:
~10 (1) Heating a mixture of a fatty acid lower alkyl .j,~ . .
ester and an alkali metal hydroxide to a temperature of from about 100C to about 140C, preferably about 120C
under atmospheric pressure to form an emulsion comprising from about 5% to about 30%, preferably from about 7% to about 15% by weight of the corresponding alkali metal fatty acid soap and lower alkyl ester;
(2) Adding to the reaction product of Step (1) from about 10% to about 50%, preferably from about 20% to about 30% by weight of a polyol and from about 0.05% to about 5%, preferably from about 0.1% to about 0.5% by weight of a basic catalyst selected from the group consisting of alkali metals, alloys of two or more alkali metals, alkali metal alkoxides, and alkali metal hydrides to form a heterogenous mixture;
(3) Heating the heterogenous mixture formed in Step (2) to a temperature of from about 110C to about 180C, preferably from about 130-C to about 145C under a pressure of ,, , ' .;, ' from about 0.1 mm lIg to about 760 mm Hg, prefera~ly from about 0.5 mm ~Ig to about 25 mm Hg to form a homogenous melt of partially esterified polyol and unreacted starting materials;
(4) Under the conditions of Step (3), adding excess fatty acid lower alkyl esters to the reaction product of Step (3) to form the polyol fatty acid polyester; and
(5) Separating the polyol fatty acid polyester from the reaction mixture.
The weight percentages of reactants used to form the fatty acid soap èmulsion in Step (1) obviously depend upon the molecular weight of the particular alkali metal hydroxide employed. Inasmuch as the alkali metals vary in molecular weight between about 7 (lithium) and about 133 (cesium), the reactant weight percentages vary appreciably. Notwithstand-ing this variability, calculation of the useful ranges of reactant weight percentages can be determined by routine methods. By way of example, it has been determined that when using potassium hydroxide (molecular weight of about 39), t the mixture of Step (1) comprises from about 94% to about 99% by weight fatty acid lower alkyl esters and from about 1% to about 6% by weight potassium hydroxide.
The following example is intended to further clarify the preferred embodiment and should not be construed as a limitation.
EXAMPLE III
Preparation of Sucrose Polyester from Sucrose and Soybean Methyl Esters Using Potassium Dispersion Soybean methyl esters (2.86 kilograms, I.V. - 132-135) were mixcd with potassium hydroxide (63 grams of 85% KOH
,. . .
"
, - 15 ~
` ~ ' ,: ' ` . `
, . . .
.
, ; 1059~21 - dissolved in 300 milliliters methanol) at atmospheric pressure and hcated to 120C with agitation. After 2 hours a smooth ;,,.~ .
textured emulsion was formed and powdered sucrose (1.04 kilogra~s~ was added to the mixture. M~e pressure was reduced to S millimeters Hg to remove any moisture and methanol and 30 grams of a potassium dispersion (30% potassium, 70% light mineral oil) was added. This mixture was reacted for 2 hours at 145C to form a one-phase mixture.
Excess soybean methyl esters (12.17 kilograms) were then , . .
~10 added and the reaction continued for 4 hours under the above -~; conditions. The system was then allowed to cool overnight ~h'~
and started up the following day by adding more potassium -~' dispersion (30 grams of 30/70 dispersion) and returning to 145C and 5 millimeters Hg for 4 hours. The reaction mixture was then acidified with glacial acetic acid (250 Milliliters).
NMR analysis showed the final mixture to contain 49.8%
~; methyl esters. Allowing for the soap formed during the first ,`~ portion of the reaction and by reaction of the catalyst, this , indicates a sucrose polyester yield of 97 to 98% based on 0 sucrose.
In the above procedure, sucrose polyester was prepared .
without significant caramelization of the sucrose reactant.
In the above procedure, the soybean methyl esters ~: are replaced by an equivalent amount of sunflower oil ...~
-'5 methyl esters, safflower oil methyl esters, and corn oil methyl ~ esters and the corresponding sucrose fatty acid polyesters are ,, obtained.
' .
;
,, .
~,. . .
" .
, . .
~059lZl '. Polyol fatty acid polyesters prepared in accordance ~ with the above disclosure are suitable for use as low .`, calorie fats in various food products. For example, . U. S. Patent 3,600,186, granted August 17, 1971, teaches the use of polyol fatty acid polyesters as low calorie i~ fats in cooking and salad oils. The following example - illustrates low calorie fat-containing food compositions wherein the fat comprises a polyol fatty acid polyester prepared according to the process of the present invention.
; 10 EXAMPLE IV
ii Food Compositions Containing Polyol Fatty Acid Polyesters ~ :
Salad oils are prepared as follows~
(A) ~.
Ingredients Percent by Weight . :
.. Refined, bleached and lightly hydrogenated soybean oil 50 , . -' Sucrose octaester of soybean ~ oil fatty acid 50 :~:
" . .
(B) Refined cottonseed oil go ;
~, 20 Sor~itol pentaoleate 10 (C) :`
Sucrose octaoleate 100 ' (D) . Erythritol polyester of olive oil fatty acid 100 ~;
3 (E~ 6 ::
i 50/50 Blend of cottonseed oil and soybean oil 50 ~ :
Olive oil 25 Erythritol polyester of sunflower oil 25 ,' ,~. .
, , ~ ,
The weight percentages of reactants used to form the fatty acid soap èmulsion in Step (1) obviously depend upon the molecular weight of the particular alkali metal hydroxide employed. Inasmuch as the alkali metals vary in molecular weight between about 7 (lithium) and about 133 (cesium), the reactant weight percentages vary appreciably. Notwithstand-ing this variability, calculation of the useful ranges of reactant weight percentages can be determined by routine methods. By way of example, it has been determined that when using potassium hydroxide (molecular weight of about 39), t the mixture of Step (1) comprises from about 94% to about 99% by weight fatty acid lower alkyl esters and from about 1% to about 6% by weight potassium hydroxide.
The following example is intended to further clarify the preferred embodiment and should not be construed as a limitation.
EXAMPLE III
Preparation of Sucrose Polyester from Sucrose and Soybean Methyl Esters Using Potassium Dispersion Soybean methyl esters (2.86 kilograms, I.V. - 132-135) were mixcd with potassium hydroxide (63 grams of 85% KOH
,. . .
"
, - 15 ~
` ~ ' ,: ' ` . `
, . . .
.
, ; 1059~21 - dissolved in 300 milliliters methanol) at atmospheric pressure and hcated to 120C with agitation. After 2 hours a smooth ;,,.~ .
textured emulsion was formed and powdered sucrose (1.04 kilogra~s~ was added to the mixture. M~e pressure was reduced to S millimeters Hg to remove any moisture and methanol and 30 grams of a potassium dispersion (30% potassium, 70% light mineral oil) was added. This mixture was reacted for 2 hours at 145C to form a one-phase mixture.
Excess soybean methyl esters (12.17 kilograms) were then , . .
~10 added and the reaction continued for 4 hours under the above -~; conditions. The system was then allowed to cool overnight ~h'~
and started up the following day by adding more potassium -~' dispersion (30 grams of 30/70 dispersion) and returning to 145C and 5 millimeters Hg for 4 hours. The reaction mixture was then acidified with glacial acetic acid (250 Milliliters).
NMR analysis showed the final mixture to contain 49.8%
~; methyl esters. Allowing for the soap formed during the first ,`~ portion of the reaction and by reaction of the catalyst, this , indicates a sucrose polyester yield of 97 to 98% based on 0 sucrose.
In the above procedure, sucrose polyester was prepared .
without significant caramelization of the sucrose reactant.
In the above procedure, the soybean methyl esters ~: are replaced by an equivalent amount of sunflower oil ...~
-'5 methyl esters, safflower oil methyl esters, and corn oil methyl ~ esters and the corresponding sucrose fatty acid polyesters are ,, obtained.
' .
;
,, .
~,. . .
" .
, . .
~059lZl '. Polyol fatty acid polyesters prepared in accordance ~ with the above disclosure are suitable for use as low .`, calorie fats in various food products. For example, . U. S. Patent 3,600,186, granted August 17, 1971, teaches the use of polyol fatty acid polyesters as low calorie i~ fats in cooking and salad oils. The following example - illustrates low calorie fat-containing food compositions wherein the fat comprises a polyol fatty acid polyester prepared according to the process of the present invention.
; 10 EXAMPLE IV
ii Food Compositions Containing Polyol Fatty Acid Polyesters ~ :
Salad oils are prepared as follows~
(A) ~.
Ingredients Percent by Weight . :
.. Refined, bleached and lightly hydrogenated soybean oil 50 , . -' Sucrose octaester of soybean ~ oil fatty acid 50 :~:
" . .
(B) Refined cottonseed oil go ;
~, 20 Sor~itol pentaoleate 10 (C) :`
Sucrose octaoleate 100 ' (D) . Erythritol polyester of olive oil fatty acid 100 ~;
3 (E~ 6 ::
i 50/50 Blend of cottonseed oil and soybean oil 50 ~ :
Olive oil 25 Erythritol polyester of sunflower oil 25 ,' ,~. .
, , ~ ,
Claims (13)
1. A solvent-free, low temperature process for synthesizing polyol fatty acid polyesters comprising the steps of:
(1) Heating a mixture comprising (i) a polyol selected from the group consisting of monosaccharides, disaccharides and sugar alcohols, (ii) a fatty acid lower alkyl ester, (iii) an alkali metal fatty acid soap, and (iv) a basic catalyst to a temperature of from about 110°C to about 180°C
at a pressure of from about 0.1mm of Hg to about 760mm of Hg to form a homogenous melt of partially esterified polyol and unreacted starting materials;
(2) under the conditions of Step (1) adding excess fatty acid lower alkyl esters to the reaction product of Step (1) to form the polyol fatty acid polyester; and (3) Separating the polyol fatty acid polyester from the reaction product of Step (2).
(1) Heating a mixture comprising (i) a polyol selected from the group consisting of monosaccharides, disaccharides and sugar alcohols, (ii) a fatty acid lower alkyl ester, (iii) an alkali metal fatty acid soap, and (iv) a basic catalyst to a temperature of from about 110°C to about 180°C
at a pressure of from about 0.1mm of Hg to about 760mm of Hg to form a homogenous melt of partially esterified polyol and unreacted starting materials;
(2) under the conditions of Step (1) adding excess fatty acid lower alkyl esters to the reaction product of Step (1) to form the polyol fatty acid polyester; and (3) Separating the polyol fatty acid polyester from the reaction product of Step (2).
2. A process according to claim 1 wherein the polyol is a disaccharide.
3. A process according to claim 1 wherein the polyol is selected from the group consisting of sucrose, xylitol, and sorbitol.
4. A process according to claim 1 wherein the temperature is from about 135°C to about 145°C.
5. A process according to claim 1 wherein the fatty acid lower alkyl esters are fatty acid methyl esters.
6. A process according to claim 5 wherein the methyl esters are derived from natural oils selected from the group consisting of soybean oil, sunflower oil, safflower oil and corn oil.
7. A process according to claim 1 wherein the catalyst is selected from the group consisting of potassium hydride, sodium hydride, a dispersion of potassium in sucrose octaester, a dispersion of potassium in mineral oil, potassium t-butoxide and sodium methoxide.
8. A solvent-free, low temperature process for synthesizing polyol fatty acid polyesters comprising the steps of:
(1) heating a mixture comprising (i) from about 10%
to about 50% by weight of a polyol selected from the group consisting of monosaccharides, disaccharides and sugar alcohols, (ii) from about 40% to about 80% by weight of fatty acid lower alkyl esters, (iii) from about 1% to about 30% by weight of an alkali metal acid soap, and (iv) from about 0.05% to about 5% by weight of a basic catalyst selected from the group consisting of alkali metals, alloys of two or more alkali metals, alkali metal alkoxides, and alkali metal hydrides to a temperature from about 110°C to about 180°C at a pressure of from about 0.1mm Hg to about 760 mm of Hg to form a homogenous melt of partially esterified polyol and unreacted starting materials;
(2) Under the conditions of Step (1) adding excess fatty acid lower alkyl esters to the reaction product of Step (1) to form the polyol fatty acid polyester; and (3) Separating the polyol fatty acid polyester from the reaction product of Step (2).
(1) heating a mixture comprising (i) from about 10%
to about 50% by weight of a polyol selected from the group consisting of monosaccharides, disaccharides and sugar alcohols, (ii) from about 40% to about 80% by weight of fatty acid lower alkyl esters, (iii) from about 1% to about 30% by weight of an alkali metal acid soap, and (iv) from about 0.05% to about 5% by weight of a basic catalyst selected from the group consisting of alkali metals, alloys of two or more alkali metals, alkali metal alkoxides, and alkali metal hydrides to a temperature from about 110°C to about 180°C at a pressure of from about 0.1mm Hg to about 760 mm of Hg to form a homogenous melt of partially esterified polyol and unreacted starting materials;
(2) Under the conditions of Step (1) adding excess fatty acid lower alkyl esters to the reaction product of Step (1) to form the polyol fatty acid polyester; and (3) Separating the polyol fatty acid polyester from the reaction product of Step (2).
9. A process according to claim 8 wherein the polyol is sucrose.
10. A solvent-free, low temperature process for synthesizing polyol fatty polyesters comprisng the steps of:
(1) Heating a mixture of a fatty acid lower alkyl ester and an alkali metal hydroxide to a temperature of from about 100°C to about 140°C under atmospheric pressure to form an emulsion comprising from about 5% to about 30% by weight, of the corresponding alkali metal fatty acid soap and lower alkyl ester;
(2) Adding to the reaction product of Step (1) from about 10% to about 50% by weight of a polyol selected from the group consisting of monosaccharides, disaccharides and sugar alcohols, and from about 0.05% to about 5% by weight of a basic catalyst selected from the group consisting of alkali metals, alloys of two or more alkali metals, alkali metal alkoxides, and alkali metal hydrides to form a heterogenous mixture:
(3) Heating the heterogenous mixture formed in Step (2) to a temperature of from about 110°C to about 180°C
under a pressure of from about 0.1 mm Hg to about 760mm Hg to form a homogeneous melt of partially esterified polyol and unreacted starting materials;
(4) Under the conditions of Step (3), adding excess fatty acid lower alkyl esters to the reaction product of Step (3) to form the polyol fatty acid polyester; and (5) Separating the polyol fatty acid polyester from the reaction mixture.
(1) Heating a mixture of a fatty acid lower alkyl ester and an alkali metal hydroxide to a temperature of from about 100°C to about 140°C under atmospheric pressure to form an emulsion comprising from about 5% to about 30% by weight, of the corresponding alkali metal fatty acid soap and lower alkyl ester;
(2) Adding to the reaction product of Step (1) from about 10% to about 50% by weight of a polyol selected from the group consisting of monosaccharides, disaccharides and sugar alcohols, and from about 0.05% to about 5% by weight of a basic catalyst selected from the group consisting of alkali metals, alloys of two or more alkali metals, alkali metal alkoxides, and alkali metal hydrides to form a heterogenous mixture:
(3) Heating the heterogenous mixture formed in Step (2) to a temperature of from about 110°C to about 180°C
under a pressure of from about 0.1 mm Hg to about 760mm Hg to form a homogeneous melt of partially esterified polyol and unreacted starting materials;
(4) Under the conditions of Step (3), adding excess fatty acid lower alkyl esters to the reaction product of Step (3) to form the polyol fatty acid polyester; and (5) Separating the polyol fatty acid polyester from the reaction mixture.
11. A process according to claim 10 wherein the alkali metal hydroxide is potassium hydroxide.
12. A process according to claim 10 wherein the polyol is sucrose.
13. A process according to claim 10 wherein the fatty acid lower alkyl esters are fatty acid methyl esters derived from natural oils selected from the group consisting of soybean oil, sunflower oil, safflower oil, and corn oil.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/432,386 US3963699A (en) | 1974-01-10 | 1974-01-10 | Synthesis of higher polyol fatty acid polyesters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1059121A true CA1059121A (en) | 1979-07-24 |
Family
ID=23715946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA217,654A Expired CA1059121A (en) | 1974-01-10 | 1975-01-09 | Synthesis of higher polyol fatty acid polyesters |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3963699A (en) |
| CA (1) | CA1059121A (en) |
| GB (1) | GB1455804A (en) |
Families Citing this family (174)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IE44458B1 (en) * | 1976-02-12 | 1981-12-02 | Procter & Gamble | Compositions for treating hypercholesterolemia |
| US4264583A (en) * | 1979-07-25 | 1981-04-28 | The Procter & Gamble Company | Gallstone dissolution compositions and method |
| US4334061A (en) * | 1979-10-29 | 1982-06-08 | Ethyl Corporation | Process for recovery of polyol fatty acid polyesters |
| IE50028B1 (en) * | 1979-12-19 | 1986-02-05 | Tate & Lyle Plc | Process for the production of a surfactant containing sucrose esters |
| JPS6026399B2 (en) * | 1980-07-31 | 1985-06-24 | 第一工業製薬株式会社 | Method for producing sucrose fatty acid ester |
| EP0100382B1 (en) * | 1982-08-02 | 1986-11-20 | Unitika Ltd. | An intravenous nutrient |
| US4665057A (en) * | 1983-03-22 | 1987-05-12 | Deanna Nelson | Nutrient monoesters |
| US4701443A (en) * | 1983-03-22 | 1987-10-20 | Baxter Travenol Laboratories, Inc. | Nutrient polyesters |
| US4517360A (en) * | 1983-06-23 | 1985-05-14 | The Procter & Gamble Company | Synthesis of higher polyol fatty acid polyesters using carbonate catalysts |
| US4518772A (en) * | 1983-06-23 | 1985-05-21 | The Proctor & Gamble Company | Synthesis of higher polyol fatty acid polyesters using high soap:polyol ratios |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1643795A1 (en) * | 1967-08-04 | 1971-07-01 | Cassella Farbwerke Mainkur Ag | Process for the production of sugar esters |
| US3597417A (en) * | 1968-07-23 | 1971-08-03 | Procter & Gamble | Process for the preparation of fatty acid esters of sugar glycosides |
| US3714144A (en) * | 1969-05-29 | 1973-01-30 | Us Agriculture | Process for the production of sucrose esters of fatty acids |
-
1974
- 1974-01-10 US US05/432,386 patent/US3963699A/en not_active Expired - Lifetime
-
1975
- 1975-01-09 CA CA217,654A patent/CA1059121A/en not_active Expired
- 1975-01-09 GB GB91075A patent/GB1455804A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| US3963699A (en) | 1976-06-15 |
| GB1455804A (en) | 1976-11-17 |
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