CA1219859A - Synthesis of higher polyol fatty acid polyesters using high soap: polyol ratios - Google Patents
Synthesis of higher polyol fatty acid polyesters using high soap: polyol ratiosInfo
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- CA1219859A CA1219859A CA000457078A CA457078A CA1219859A CA 1219859 A CA1219859 A CA 1219859A CA 000457078 A CA000457078 A CA 000457078A CA 457078 A CA457078 A CA 457078A CA 1219859 A CA1219859 A CA 1219859A
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- Prior art keywords
- fatty acid
- polyol
- process according
- soap
- esters
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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
Abstract
SYNTHESIS OF HIGHER POLYOL
FATTY ACID POLYESTERS
USING HIGH SOAP:POLYOL RATIOS
ABSTRACT OF THE DISCLOSURE
An improved solvent-free transesterification process for producing higher polyol fatty acid polyesters is disclosed. In this process a mixture of a polyol, a fatty acid methyl, 2-methoxy ethyl or benzyl ester, an alkali metal fatty acid soap, and a basic catalyst, having a molar ratio of soap:polyol of from about 0.6:1 to about 1:1, preferably from about 0.75:1 to about 1:1.
is heated to form a homogeneous melt. To this melt is subsequently added excess fatty acid methyl, 2-methoxy ethyl or benzyl ester, yielding the desired polyol fatty acid polyesters.
FATTY ACID POLYESTERS
USING HIGH SOAP:POLYOL RATIOS
ABSTRACT OF THE DISCLOSURE
An improved solvent-free transesterification process for producing higher polyol fatty acid polyesters is disclosed. In this process a mixture of a polyol, a fatty acid methyl, 2-methoxy ethyl or benzyl ester, an alkali metal fatty acid soap, and a basic catalyst, having a molar ratio of soap:polyol of from about 0.6:1 to about 1:1, preferably from about 0.75:1 to about 1:1.
is heated to form a homogeneous melt. To this melt is subsequently added excess fatty acid methyl, 2-methoxy ethyl or benzyl ester, yielding the desired polyol fatty acid polyesters.
Description
121g8S9 SYNTHESIS OF HIG~ER POLYOL
FATTY ACID POLYESTERS
USING HIGH SOAP:POLYOL RATIOS
Robert A. Volpenhein TECHNICAL FIELD
This invention relates to an improved, high yield synthesis of higher polyol fatty acid polyesters, sucrose polyesters in particular, via transesterification.
BACKGROUND OF THE INVENTION
The food and pharmaceutical industries have recently focused attention on polyol polyesters for use as low calorie fats in food products and as pharmaceuti-cal agents, e.g., for the lowering of blood cholesterol levels. U.S. Patent 3,600,186, Mattson and Volpenhein, issued August 17, 1971, describes low calorie food com-positions formed by replacing at least a portion of the fat content of food products with higher polyol fatty acid polyesters. U.S. Patent 3,954,976, Mattson and Volpenhein, issued May 4, 1976, describes pharmaceutical compositions for inhibiting the absorption of cholesterol comprising effective unit dosage amounts of higher polyol fatty acid polyesters, as well as the method for treating hypercholesterolemia using these polyesters. Additional pharmaceutical uses are described in U.S. Patent 4,241,054, Volpenhein and Jandacek, issued December 23, 1980 (re-moval of halogenated toxins from the body), and U.S.
Patent 4,264,583, Jandacek, April 28, 1981 (treatment of gallstones).
As a result of these many uses for the higher polyol fatty acid polyesters, it would be desirable to have an efficient high yield synthesis for them. ~istori-cally, such syntheses have been conducted using a mutual solvent to solubili~e a polyol and esters of long chain fatty acids, thus providing a homogeneous reaction medium suitable for catalytic transesterification. One varia-tion of this process, known as the Snell synthesis, has been employed as a means for preparing both poly- and ~.
~i~
~21~BS~
lower esters. However, the solvents employed in such processes are difficult to separate from the final pro-duct and are characteristically toxic, therefore limiting the usefulness of such syntheses in the food and pharmaceutical industries. Accordingly, efforts have been directed toward the discovery of high yield syn-theses of polyol fatty acid polyesters which do not employ toxic solvents.
BACKGROUND ART
n U.S. Patent 3,963,699, Rizzi and Taylor, issued June 15, 1976, describes the basic solvent-free transes-terification process for synthesizing higher polyol fatty acid polyesters. In this three-step reaction, a mixture of a polyol (such as sucrose), a fatty acid lower alkyl ester (such as fatty acid methyl ester), an alkali metal fatty acid soap, and a basic catalyst is heated, forming a homogeneous melt, to which is added excess fatty acid lower alkyl ester to form the higher polyol fatty acid polyesters. The polyesters are then separated from the reaction mixture. The catalysts described in this patent as being useful include alkali metals, alloys of two or more alkali metals, alkali metal hydrides, and alkali metal alkoxides. The processes exemplified in this patent utilize sodium hydride, sodium hydroxide or dis-persions of potassium as catalysts, and soap:sucrose moleratios of about 0.3-0.4:1.
Rizzi and Taylor, Journal of the American Oil Chemists' Society _:398 (1978), further describe the reaction set forth in the above-referenced Rizzi and Taylor patent. Advantages are demonstrated for catalyzed reactions versus uncatalyzed reactions; sodium hydride and sodium-potassium alloy are taught to be effective catalysts. At page 400, the paper teaches that alkali metal carbonates and alkali metal alkoxides are rela-tively ineffective as catalysts.
U.S. Patent 4,334,061, Brossier, III, ~ssuedJune 8, 1982, describes a method for separating and ~2~9859 purifying the polyesters formed by the Rizzi and Taylor process. The procedure requires, in the separation step, an alkaline pH which is obtained by adding an alkali metal carbonate to the reaction mixture at the 5 conclusion of the transesterification reaction. Thus, the carbonate compounds added do not function as cata-lysts for the transesterfication reaction.
U.S. Patent 2,893,990, Hass, et al, issued July 7, 1959, describes a process for making carboxylic acid ~n l~wer esters of sucrose and raffinose; generally, mono- or diesters are formed. In the process, a non-sucrose ester of a fatty acid (e.g., methyl stearate or methyl palml-tate) is reacted with sucrose, preferably in a solvent.
A wide range of alkaline catalysts, including sodium 15 carbonate and potassium carbonate, are disclosed for use in the reaction.
It has now been found that by modifying the solvent-free transesterfication reaction described in the Rizzi and Taylor patent, discussed above, using potassium 20 carbonate, sodium carbonate or barium carbonate as the catalyst and/or using significantly higher soap:sucrose mole ratios than those originally envisioned, shorter reaction times, more complete utilization of the polyol component, and improved yields of the higher polyol 25 polyesters can be obtained.
It is, therefore, an object of this invention to provide an improved solvent-free high yield synthesis of polyol fatty acid polyesters.
SUMMARY OF THE INVENTION
The present invention encompasses an improved solvent-free transesterification process for synthesizing higher polyol fatty acid polyesters comprising the steps of:
91~59 (1) heating a mixture of (a) a polyol selected from the group consisting of monosaccha-rides, disaccharides and sugar alcohols, (b) a fatty acid ester selected from the group consisting of methyl esters, 2-methoxy ethyl esters, benzyl esters and mixtures thereof, (c) an alkali metal fatty acid soap, and (d) a basic catalyst, to a temperature of from about 110C to about 180C at a pressure of from about 0.1 mm to about 760 mm of mercury to form a homogeneous melt; and ~2) subsequently adding to the reaction product of step (1) excess fatty acid ester selected from the group consisting of methyl esters,
FATTY ACID POLYESTERS
USING HIGH SOAP:POLYOL RATIOS
Robert A. Volpenhein TECHNICAL FIELD
This invention relates to an improved, high yield synthesis of higher polyol fatty acid polyesters, sucrose polyesters in particular, via transesterification.
BACKGROUND OF THE INVENTION
The food and pharmaceutical industries have recently focused attention on polyol polyesters for use as low calorie fats in food products and as pharmaceuti-cal agents, e.g., for the lowering of blood cholesterol levels. U.S. Patent 3,600,186, Mattson and Volpenhein, issued August 17, 1971, describes low calorie food com-positions formed by replacing at least a portion of the fat content of food products with higher polyol fatty acid polyesters. U.S. Patent 3,954,976, Mattson and Volpenhein, issued May 4, 1976, describes pharmaceutical compositions for inhibiting the absorption of cholesterol comprising effective unit dosage amounts of higher polyol fatty acid polyesters, as well as the method for treating hypercholesterolemia using these polyesters. Additional pharmaceutical uses are described in U.S. Patent 4,241,054, Volpenhein and Jandacek, issued December 23, 1980 (re-moval of halogenated toxins from the body), and U.S.
Patent 4,264,583, Jandacek, April 28, 1981 (treatment of gallstones).
As a result of these many uses for the higher polyol fatty acid polyesters, it would be desirable to have an efficient high yield synthesis for them. ~istori-cally, such syntheses have been conducted using a mutual solvent to solubili~e a polyol and esters of long chain fatty acids, thus providing a homogeneous reaction medium suitable for catalytic transesterification. One varia-tion of this process, known as the Snell synthesis, has been employed as a means for preparing both poly- and ~.
~i~
~21~BS~
lower esters. However, the solvents employed in such processes are difficult to separate from the final pro-duct and are characteristically toxic, therefore limiting the usefulness of such syntheses in the food and pharmaceutical industries. Accordingly, efforts have been directed toward the discovery of high yield syn-theses of polyol fatty acid polyesters which do not employ toxic solvents.
BACKGROUND ART
n U.S. Patent 3,963,699, Rizzi and Taylor, issued June 15, 1976, describes the basic solvent-free transes-terification process for synthesizing higher polyol fatty acid polyesters. In this three-step reaction, a mixture of a polyol (such as sucrose), a fatty acid lower alkyl ester (such as fatty acid methyl ester), an alkali metal fatty acid soap, and a basic catalyst is heated, forming a homogeneous melt, to which is added excess fatty acid lower alkyl ester to form the higher polyol fatty acid polyesters. The polyesters are then separated from the reaction mixture. The catalysts described in this patent as being useful include alkali metals, alloys of two or more alkali metals, alkali metal hydrides, and alkali metal alkoxides. The processes exemplified in this patent utilize sodium hydride, sodium hydroxide or dis-persions of potassium as catalysts, and soap:sucrose moleratios of about 0.3-0.4:1.
Rizzi and Taylor, Journal of the American Oil Chemists' Society _:398 (1978), further describe the reaction set forth in the above-referenced Rizzi and Taylor patent. Advantages are demonstrated for catalyzed reactions versus uncatalyzed reactions; sodium hydride and sodium-potassium alloy are taught to be effective catalysts. At page 400, the paper teaches that alkali metal carbonates and alkali metal alkoxides are rela-tively ineffective as catalysts.
U.S. Patent 4,334,061, Brossier, III, ~ssuedJune 8, 1982, describes a method for separating and ~2~9859 purifying the polyesters formed by the Rizzi and Taylor process. The procedure requires, in the separation step, an alkaline pH which is obtained by adding an alkali metal carbonate to the reaction mixture at the 5 conclusion of the transesterification reaction. Thus, the carbonate compounds added do not function as cata-lysts for the transesterfication reaction.
U.S. Patent 2,893,990, Hass, et al, issued July 7, 1959, describes a process for making carboxylic acid ~n l~wer esters of sucrose and raffinose; generally, mono- or diesters are formed. In the process, a non-sucrose ester of a fatty acid (e.g., methyl stearate or methyl palml-tate) is reacted with sucrose, preferably in a solvent.
A wide range of alkaline catalysts, including sodium 15 carbonate and potassium carbonate, are disclosed for use in the reaction.
It has now been found that by modifying the solvent-free transesterfication reaction described in the Rizzi and Taylor patent, discussed above, using potassium 20 carbonate, sodium carbonate or barium carbonate as the catalyst and/or using significantly higher soap:sucrose mole ratios than those originally envisioned, shorter reaction times, more complete utilization of the polyol component, and improved yields of the higher polyol 25 polyesters can be obtained.
It is, therefore, an object of this invention to provide an improved solvent-free high yield synthesis of polyol fatty acid polyesters.
SUMMARY OF THE INVENTION
The present invention encompasses an improved solvent-free transesterification process for synthesizing higher polyol fatty acid polyesters comprising the steps of:
91~59 (1) heating a mixture of (a) a polyol selected from the group consisting of monosaccha-rides, disaccharides and sugar alcohols, (b) a fatty acid ester selected from the group consisting of methyl esters, 2-methoxy ethyl esters, benzyl esters and mixtures thereof, (c) an alkali metal fatty acid soap, and (d) a basic catalyst, to a temperature of from about 110C to about 180C at a pressure of from about 0.1 mm to about 760 mm of mercury to form a homogeneous melt; and ~2) subsequently adding to the reaction product of step (1) excess fatty acid ester selected from the group consisting of methyl esters,
2-methoxy ethyl esters, benzyl esters and mixtures thereof;
the improvement being obtained by using molar ratios of soap:polyol in step (1) of from about 0.6:1 to about 1:1, preferably from about 0.75:1 to about 1:1, more preferably from about 0.75:1 to about 0.85:1, most preferably about 0.75:1.
DETAILED DESCRIPTION OF THE INVENTION
The present invention encompasses improvements in the solvent-free transesterification reaction for forming higher polyol fatty acid polyesters described and claimed in U.S. Patent 3,963,699, Rizzi and Taylor, issued June 15, 1976. This process is characterized by a three-step reaction procedure, summarized below.
By utilizing the improvements taught her-in, the reac-tion described in the Rizzi and Taylor patent can beimproved by reducing excessive foaming, shortening re-action times, increasing the yields of the higher polyol fatty acid polyesters, and yielding products having better (lighter) color characteristics. In fact, the improvements herein permit the reaction to be ~21~8S~
formulated as a single step solvent-free reaction for the production of higher polyol fatty acid polyesters.
In the first step of the present process, a heterogeneous mixture of a polyol, fatty acid methyl, 2-methoxy ethyl or benzyl esters, an alkali metal fatty acid soap, and a basic catalyst is reacted to form a homogeneous melt comprising partially esterified polyol and unreacted starting materials.
' n As used herein, the term "polyol" is intended to include any aliphatic or aromatic compound containing at least two free hydroxyl groups. In practicing the pro-cess 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 branched chain linear aliphatics; saturated and unsaturated cyclic ali-phatics, including heterocyclic aliphatics; or mono-nuclear or polynuclear aromatics, including heterocyclic aromatics. Carbohydrates and nOn-tQXiC glycols are pre-ferred polyols. Monosaccharides suitable for use herein include, for example, mannose, galactose, arabinose, xylose, ribose, apiose, rhamnose, psicose, fructose, sorbose, tagitose, ribulose, xylulose, and erythrulose.
Oligosaccharides suitable for use herein include, for example, maltose, kojibiose, nigerose, cellobiose, lac-tose, melibiose, gentiobiose, turanose, rutinose, tre-halose, sucrose and raffinose. Polysaccharides suitable for use herein include, for example, amylose, glycogen, cellulose, chitin, inulin, agarose, zylans, mannan and galactans. Although sugar alcohols are not carbohydrates in a strict sense, the naturally occurring sugar alcohols are so closely related 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.
~2~9859 Particularly preferred classes of materials suitable for use herein include the monosaccharides, the dissacharides and sugar alcohols. Preferred carbohy-drates and sugar alcohols include xylitol, sorbitol and sucrose.
S As used herein, the term "fatty acid esters" is intended to include the methyl, 2-methoxy ethyl and benzyl esters of fatty acids containing about eight or more carbon atoms, and mixtures of such esters. Suitable ester~ ~an be prepared by the reaction of diazoalkanes 10 and fatty acids, or derived by alcoholysis fxom the fatty acids naturally occurring in fats and oils. Suitable fatty acid esters can be derived from either saturated or unsaturated fatty acids. Suitable preferred saturated fatty acids include, for example, capric, lauric, palmi-tic, stearic, behenic, isomyristic, isomargaric, my-ristic, caprylic, and anteisoarachadic. Suitable pre-ferred unsaturated fatty acids include, for example, maleic, linoleic, licanic, oleic, linolenic, and erythro-genic acids. Mixtures of fatty acids derived from soy-bean oil, palm oil, sunflower oil, safflower oil, and corn oil are especially preferred for use herein. Methyl esters are the preferred fatty acid esters for use herein, since their use in the process herein tends to result in unusually high yields of polyol fatty acid polyesters.
As used herein, the term "alkali metal fatty acid soap" is intended to include the alkali metal salts ofsaturated and unsaturated fatty acids having from about eight to about eighteen carbon atoms. Accordingly, suit-able alkali metal fatty acid soaps include, for example, the lithium, sodium, potassium, rubidium, and cesium salts of fatty acids such as capric, lauric, myristic, palmitic, licanic, parinaric, and stearic acids, as well as mixtures thereof. Mixtures of fatty acids derived from soybean oil, sunflower oil, safflower oil, and corn ~219~5C~
oil are preferred for use herein. Accordingly, preferred alkali metal ~atty acid soaps include, for example, the potassium soap made Erom soybean oil fatty acids and the sodium soap made from sunflower oil fatty acids.
The basic catalysts generally suitable for use herein are those selected from the group consisting of alkali metals, such as sodium, lithium and potassium; al-loys of two or more alkali metals, such as sodium-lithium and sodium-potassium alloys; alkali metal hydrides, such as sodium, lithium and potassium hydride; and alkali metal alkoxides, such as potassium t-butoxide and sodium methoxide.
In a particularly preferred embodiment of the present invention, the basic catalyst used in the reac-tion is potassium carbonate, sodium carbonate, bariumcarbonate, or mixtures of these compounds. It has been found that when these specific compounds are used as the catalyst, shorter reaction times and/or increased yields of the higher polyol polyesters are obtained when compared to essentially identical reactions carried out using more conventional catalysts, such as sodium hydride, potassium hydride, soap, or scdium methoxide. These pre-ferred catalysts may also be used in admixture with the more conventional basic catalysts, described above.
Potassium carbonate is the most preferred catalyst for use herein. The use of these catalysts is further dis-closed and claimed in Volpenhein, U.S. Patent 4,517,360 issued May 14, 1985.
In a preferred embodiment of this invention, the catalyst is dispersed in a suitable carrier so as to ensure uniform distribution of the catalyst through-out the reaction mass. Suitable carriers or dispersing agents include, for example, methanol and fatty acid methyl esters.
In carrying out step 1, the above-described re-actants are combined to form a heterogeneous mixture. The precise ratio of reactants can be Ereely selected from within the guidelines set forth hexeinafter. However, routine experimentation may be necessary in order to establish the optimum concentrations for a given set of reactants. In general, the heterogeneous mixture com-prises from about 10% to about 50%, preferably from about 15~ to about 30%, by weight of the polyol; from about 40%
to about 80%, preferably from about 55% to about 75%, by weight of the fatty acid esters; from about 1% to about 30%, preferably from about 5% to about 20%, by weight of the alkali metal fatty acid soap; and about from about 0.05~ to about 5%, preferably from about 0.1~ to about 0.5%, by weight of the basic catalyst component.
It has surprisingly been found that when this mix~ ~
ture is formed so as to include relatively high molar ratios of soap:polyol, increased yields of the higher polyesters ~e.g., the octaesters) are obtained when com-pared with similar reactions carried out using lower art-disclosed soap:polyol molar ratios (e.g., about 0.3-0.4:1). Specifically, these higher soap:polyol ratios result in increased yields of the higher polyols, more complete utilization of the polyol reaction component, and/or faster disappearance of free polyol from the re-action mixture. Soap:polyol molar ratios in step 1 of from about 0.6:1 to 1:1 are, therefore, preferred for use in the present invention. More preferred soap:polyol ratios fall in the range from about 0.75:1 to about 1:1, from about 0.75:1 to about 0.85:1, and most preferably about 0.75:1.
The heterogeneous mixture is heated to a temperature within the range of from about 110C to about 180C, pre-ferably from about 130C to about 145C, under a pressure of from about 0.1 mm to about 760 mm, preferably from g about 0.5 mm to about 25 mm, of mercury. Within these temperature and pressure ranges, a homogeneous melt of partially esterified polyol and unreacted starting materials will form in from about 1 to 4 hours.
In the second step of the instant process, excess fatty acid methyl, 2-methoxy ethyl, or benzyl esters are added to the homogeneous melt formed in step 1. As used herein, the term "excess" is intended to include suf-icient fatty acid esters to raise the overall ester:
polyol mole ratio above about 8:1, preferably to about 12:1. Although ratios beyond 12:1 can be used, as a general rule, such ratios do not noticeably decrease reaction time or improve the yield and, therefore, tend 15 to be impractic~l. When fatty acid methyl esters are used, it is preferred that after the excess ester is added to the reaction mixture, the mixture be heated to a temperature of from about 120C to about 160C, pre-ferably about 135C, at a pressure from about 0.1 mm to 20 about 10 mm, preferably from about 0.5 mm to about 2 mm, of mercury to form the polyol fatty acid polyester material. The reaction time for step 2 is preferably less than about 10 hours, and generally is between about 2 and 8 hours.
It should be noted that as the transesterification reaction 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 techni-ques are known in the art, any one of which can be used 30 to effectively and efficiently remove the lower alcohol.
Vacuum removal both with and without an inert gas sparging has been found to promote the reaction. In any event, the formation of a lower alcohol presents no significant obstacle to the use of the process in the food or pharma-35 ceutical industries.
~219859 The use of the preferred catalysts and soap:polyolratios, defined herein, permit the combination of steps 1 and 2 into a single reaction step. In this single step approach, a mixture of (a) a polyol selected from mono-5 saccharides, disaccharides and sugar alcohols; (b) analkali metal fatty acid soap; (c) a basic catalyst selected from potassium carbonate, sodium carbonate and barium carbonate; and (d) an excess of fatty acid methyl, 2-methoxy ethyl or benzyl ester (wherein the soap:polyol 10 molar ratio is from about 0.6:1 to about 1:1, preferably from about 0.75:1 to about 1:1, more preferably from about 0.75:1 to about 0.85:1, most preferably about 0.75:1), is heated to a temperature of from about 100C
to about 180C at a pressure of from about 0.1 mm to 15 about 760 mm of mercury, thereby forming higher polyol fatty acid polyesters.
In the third step of the process, the polyol fatty acid polyesters formed in step 2 are separated from the 20 reaction mix containing polyesters, soap, and unreacted starting materials. Separation can be accomplished by any of the separation procedures routinely used in the art. Distillation, water washing, conventional refining techniques or solvent extraction are preferred due to 25 their simplicity and economy.
The following non-limiting examples are intended to further clarify the invention, but should not be con-strued as limiting thereof.
Each of the following reactions was carried out in 30 a 1 liter 3-neck flask containing a stirrer, thermometer, reflux condensor, and vacuum outlet.
EXAMPLE I
Two Stage Reaction Step (1): 3.6 g 85% KOH pellets (0.055 moles) dis-35 solved in some methanol and 103 g (0.347 moles) soybean lZ19859 oil fatty acid methyl esters (FAME) were heated and stir-red at reflux for two hours. 25 g sucrose (0.073 moles) and 1 g potassium carbonate were added and the condensor removed. The soap:sucrose molar ratio of the mixture was S 0.75:1. The methanol was evaporated from the mixture under a gentle stream of nitrogen. When the reaction reached 100C, a vacuum was applied and the temperature brought to 135C. Conditions were maintained for two hours .
tep (2): 174 g additional FAME (0.585 moles) was drawn into the reactor. The final molar ratio of FAME to sucrose was 12:1. The temperature was allowed to recover to 135C and stirring under vacuum was con-tinued for three hours. The vacuum slowly decreased in this time to from 5.0 to 0.5 mm Hg, as the methanol formed during the reactions was removed.
The reaction was cooled to 90-100C and 200 ml 80:20:2 (by weight) water:alcohol:salt added and the mix stirred for 10 minutes at 80C. The reaction mix was transferred to a separatory funnel and the phases allowed to separate. The lower ac~ueous soap solution was discarded and the lipid phase returned to the reac-tor ~or additional washes: first with a second 80:20:2 water:alcohol:salt wash and then with 2~ aqueous acetic acid and two water washes (all at 80C). The lipid was dried under vacuum, bleached with 1-5~ Filtrol~ 105 (a bleaching earth), filtered and steam deodorized at 205C to remove excess FAME. The sample was weighed and the yield calculated as percent sucrose recovered as octaester.
The octaester content of the reaction product was determined by separating the mix on a silica gel column and weighing the relative amount of octaester and partial esters recovered. The product formed com-prised a mixture of the higher polyesters of sucrose,having a high octaester content.
12~ 9859 Substantially similar results are obtained when the potassium carbonate catalyst is replaced, in whole or in part, by sodium carbonate, barium carbonate or mix-tures thereof. Similar results are also obtained when the sucrose is replaced, in whole or in part, by sorbitol, xylitol, mannitol or galactitol. The FAME is replaced, in whole or in part, with soybean oil benzyl esters, soybean oil 2-methoxy ethyl esters or the methyl esters of palm oil, sunflower oil, safflower oil, or corn oil;
similar results are obtained. Similar results are also obtained when the potassium soybean oil fatty acid soaps used in the above example are replaced, in whole or in part, by the lithium, sodium, rubidium or cesium salts of fatty acids derived from sunflower oil, safflower oil or corn oil.
EXAMPLE II
Single Stage Reaction
the improvement being obtained by using molar ratios of soap:polyol in step (1) of from about 0.6:1 to about 1:1, preferably from about 0.75:1 to about 1:1, more preferably from about 0.75:1 to about 0.85:1, most preferably about 0.75:1.
DETAILED DESCRIPTION OF THE INVENTION
The present invention encompasses improvements in the solvent-free transesterification reaction for forming higher polyol fatty acid polyesters described and claimed in U.S. Patent 3,963,699, Rizzi and Taylor, issued June 15, 1976. This process is characterized by a three-step reaction procedure, summarized below.
By utilizing the improvements taught her-in, the reac-tion described in the Rizzi and Taylor patent can beimproved by reducing excessive foaming, shortening re-action times, increasing the yields of the higher polyol fatty acid polyesters, and yielding products having better (lighter) color characteristics. In fact, the improvements herein permit the reaction to be ~21~8S~
formulated as a single step solvent-free reaction for the production of higher polyol fatty acid polyesters.
In the first step of the present process, a heterogeneous mixture of a polyol, fatty acid methyl, 2-methoxy ethyl or benzyl esters, an alkali metal fatty acid soap, and a basic catalyst is reacted to form a homogeneous melt comprising partially esterified polyol and unreacted starting materials.
' n As used herein, the term "polyol" is intended to include any aliphatic or aromatic compound containing at least two free hydroxyl groups. In practicing the pro-cess 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 branched chain linear aliphatics; saturated and unsaturated cyclic ali-phatics, including heterocyclic aliphatics; or mono-nuclear or polynuclear aromatics, including heterocyclic aromatics. Carbohydrates and nOn-tQXiC glycols are pre-ferred polyols. Monosaccharides suitable for use herein include, for example, mannose, galactose, arabinose, xylose, ribose, apiose, rhamnose, psicose, fructose, sorbose, tagitose, ribulose, xylulose, and erythrulose.
Oligosaccharides suitable for use herein include, for example, maltose, kojibiose, nigerose, cellobiose, lac-tose, melibiose, gentiobiose, turanose, rutinose, tre-halose, sucrose and raffinose. Polysaccharides suitable for use herein include, for example, amylose, glycogen, cellulose, chitin, inulin, agarose, zylans, mannan and galactans. Although sugar alcohols are not carbohydrates in a strict sense, the naturally occurring sugar alcohols are so closely related 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.
~2~9859 Particularly preferred classes of materials suitable for use herein include the monosaccharides, the dissacharides and sugar alcohols. Preferred carbohy-drates and sugar alcohols include xylitol, sorbitol and sucrose.
S As used herein, the term "fatty acid esters" is intended to include the methyl, 2-methoxy ethyl and benzyl esters of fatty acids containing about eight or more carbon atoms, and mixtures of such esters. Suitable ester~ ~an be prepared by the reaction of diazoalkanes 10 and fatty acids, or derived by alcoholysis fxom the fatty acids naturally occurring in fats and oils. Suitable fatty acid esters can be derived from either saturated or unsaturated fatty acids. Suitable preferred saturated fatty acids include, for example, capric, lauric, palmi-tic, stearic, behenic, isomyristic, isomargaric, my-ristic, caprylic, and anteisoarachadic. Suitable pre-ferred unsaturated fatty acids include, for example, maleic, linoleic, licanic, oleic, linolenic, and erythro-genic acids. Mixtures of fatty acids derived from soy-bean oil, palm oil, sunflower oil, safflower oil, and corn oil are especially preferred for use herein. Methyl esters are the preferred fatty acid esters for use herein, since their use in the process herein tends to result in unusually high yields of polyol fatty acid polyesters.
As used herein, the term "alkali metal fatty acid soap" is intended to include the alkali metal salts ofsaturated and unsaturated fatty acids having from about eight to about eighteen carbon atoms. Accordingly, suit-able alkali metal fatty acid soaps include, for example, the lithium, sodium, potassium, rubidium, and cesium salts of fatty acids such as capric, lauric, myristic, palmitic, licanic, parinaric, and stearic acids, as well as mixtures thereof. Mixtures of fatty acids derived from soybean oil, sunflower oil, safflower oil, and corn ~219~5C~
oil are preferred for use herein. Accordingly, preferred alkali metal ~atty acid soaps include, for example, the potassium soap made Erom soybean oil fatty acids and the sodium soap made from sunflower oil fatty acids.
The basic catalysts generally suitable for use herein are those selected from the group consisting of alkali metals, such as sodium, lithium and potassium; al-loys of two or more alkali metals, such as sodium-lithium and sodium-potassium alloys; alkali metal hydrides, such as sodium, lithium and potassium hydride; and alkali metal alkoxides, such as potassium t-butoxide and sodium methoxide.
In a particularly preferred embodiment of the present invention, the basic catalyst used in the reac-tion is potassium carbonate, sodium carbonate, bariumcarbonate, or mixtures of these compounds. It has been found that when these specific compounds are used as the catalyst, shorter reaction times and/or increased yields of the higher polyol polyesters are obtained when compared to essentially identical reactions carried out using more conventional catalysts, such as sodium hydride, potassium hydride, soap, or scdium methoxide. These pre-ferred catalysts may also be used in admixture with the more conventional basic catalysts, described above.
Potassium carbonate is the most preferred catalyst for use herein. The use of these catalysts is further dis-closed and claimed in Volpenhein, U.S. Patent 4,517,360 issued May 14, 1985.
In a preferred embodiment of this invention, the catalyst is dispersed in a suitable carrier so as to ensure uniform distribution of the catalyst through-out the reaction mass. Suitable carriers or dispersing agents include, for example, methanol and fatty acid methyl esters.
In carrying out step 1, the above-described re-actants are combined to form a heterogeneous mixture. The precise ratio of reactants can be Ereely selected from within the guidelines set forth hexeinafter. However, routine experimentation may be necessary in order to establish the optimum concentrations for a given set of reactants. In general, the heterogeneous mixture com-prises from about 10% to about 50%, preferably from about 15~ to about 30%, by weight of the polyol; from about 40%
to about 80%, preferably from about 55% to about 75%, by weight of the fatty acid esters; from about 1% to about 30%, preferably from about 5% to about 20%, by weight of the alkali metal fatty acid soap; and about from about 0.05~ to about 5%, preferably from about 0.1~ to about 0.5%, by weight of the basic catalyst component.
It has surprisingly been found that when this mix~ ~
ture is formed so as to include relatively high molar ratios of soap:polyol, increased yields of the higher polyesters ~e.g., the octaesters) are obtained when com-pared with similar reactions carried out using lower art-disclosed soap:polyol molar ratios (e.g., about 0.3-0.4:1). Specifically, these higher soap:polyol ratios result in increased yields of the higher polyols, more complete utilization of the polyol reaction component, and/or faster disappearance of free polyol from the re-action mixture. Soap:polyol molar ratios in step 1 of from about 0.6:1 to 1:1 are, therefore, preferred for use in the present invention. More preferred soap:polyol ratios fall in the range from about 0.75:1 to about 1:1, from about 0.75:1 to about 0.85:1, and most preferably about 0.75:1.
The heterogeneous mixture is heated to a temperature within the range of from about 110C to about 180C, pre-ferably from about 130C to about 145C, under a pressure of from about 0.1 mm to about 760 mm, preferably from g about 0.5 mm to about 25 mm, of mercury. Within these temperature and pressure ranges, a homogeneous melt of partially esterified polyol and unreacted starting materials will form in from about 1 to 4 hours.
In the second step of the instant process, excess fatty acid methyl, 2-methoxy ethyl, or benzyl esters are added to the homogeneous melt formed in step 1. As used herein, the term "excess" is intended to include suf-icient fatty acid esters to raise the overall ester:
polyol mole ratio above about 8:1, preferably to about 12:1. Although ratios beyond 12:1 can be used, as a general rule, such ratios do not noticeably decrease reaction time or improve the yield and, therefore, tend 15 to be impractic~l. When fatty acid methyl esters are used, it is preferred that after the excess ester is added to the reaction mixture, the mixture be heated to a temperature of from about 120C to about 160C, pre-ferably about 135C, at a pressure from about 0.1 mm to 20 about 10 mm, preferably from about 0.5 mm to about 2 mm, of mercury to form the polyol fatty acid polyester material. The reaction time for step 2 is preferably less than about 10 hours, and generally is between about 2 and 8 hours.
It should be noted that as the transesterification reaction 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 techni-ques are known in the art, any one of which can be used 30 to effectively and efficiently remove the lower alcohol.
Vacuum removal both with and without an inert gas sparging has been found to promote the reaction. In any event, the formation of a lower alcohol presents no significant obstacle to the use of the process in the food or pharma-35 ceutical industries.
~219859 The use of the preferred catalysts and soap:polyolratios, defined herein, permit the combination of steps 1 and 2 into a single reaction step. In this single step approach, a mixture of (a) a polyol selected from mono-5 saccharides, disaccharides and sugar alcohols; (b) analkali metal fatty acid soap; (c) a basic catalyst selected from potassium carbonate, sodium carbonate and barium carbonate; and (d) an excess of fatty acid methyl, 2-methoxy ethyl or benzyl ester (wherein the soap:polyol 10 molar ratio is from about 0.6:1 to about 1:1, preferably from about 0.75:1 to about 1:1, more preferably from about 0.75:1 to about 0.85:1, most preferably about 0.75:1), is heated to a temperature of from about 100C
to about 180C at a pressure of from about 0.1 mm to 15 about 760 mm of mercury, thereby forming higher polyol fatty acid polyesters.
In the third step of the process, the polyol fatty acid polyesters formed in step 2 are separated from the 20 reaction mix containing polyesters, soap, and unreacted starting materials. Separation can be accomplished by any of the separation procedures routinely used in the art. Distillation, water washing, conventional refining techniques or solvent extraction are preferred due to 25 their simplicity and economy.
The following non-limiting examples are intended to further clarify the invention, but should not be con-strued as limiting thereof.
Each of the following reactions was carried out in 30 a 1 liter 3-neck flask containing a stirrer, thermometer, reflux condensor, and vacuum outlet.
EXAMPLE I
Two Stage Reaction Step (1): 3.6 g 85% KOH pellets (0.055 moles) dis-35 solved in some methanol and 103 g (0.347 moles) soybean lZ19859 oil fatty acid methyl esters (FAME) were heated and stir-red at reflux for two hours. 25 g sucrose (0.073 moles) and 1 g potassium carbonate were added and the condensor removed. The soap:sucrose molar ratio of the mixture was S 0.75:1. The methanol was evaporated from the mixture under a gentle stream of nitrogen. When the reaction reached 100C, a vacuum was applied and the temperature brought to 135C. Conditions were maintained for two hours .
tep (2): 174 g additional FAME (0.585 moles) was drawn into the reactor. The final molar ratio of FAME to sucrose was 12:1. The temperature was allowed to recover to 135C and stirring under vacuum was con-tinued for three hours. The vacuum slowly decreased in this time to from 5.0 to 0.5 mm Hg, as the methanol formed during the reactions was removed.
The reaction was cooled to 90-100C and 200 ml 80:20:2 (by weight) water:alcohol:salt added and the mix stirred for 10 minutes at 80C. The reaction mix was transferred to a separatory funnel and the phases allowed to separate. The lower ac~ueous soap solution was discarded and the lipid phase returned to the reac-tor ~or additional washes: first with a second 80:20:2 water:alcohol:salt wash and then with 2~ aqueous acetic acid and two water washes (all at 80C). The lipid was dried under vacuum, bleached with 1-5~ Filtrol~ 105 (a bleaching earth), filtered and steam deodorized at 205C to remove excess FAME. The sample was weighed and the yield calculated as percent sucrose recovered as octaester.
The octaester content of the reaction product was determined by separating the mix on a silica gel column and weighing the relative amount of octaester and partial esters recovered. The product formed com-prised a mixture of the higher polyesters of sucrose,having a high octaester content.
12~ 9859 Substantially similar results are obtained when the potassium carbonate catalyst is replaced, in whole or in part, by sodium carbonate, barium carbonate or mix-tures thereof. Similar results are also obtained when the sucrose is replaced, in whole or in part, by sorbitol, xylitol, mannitol or galactitol. The FAME is replaced, in whole or in part, with soybean oil benzyl esters, soybean oil 2-methoxy ethyl esters or the methyl esters of palm oil, sunflower oil, safflower oil, or corn oil;
similar results are obtained. Similar results are also obtained when the potassium soybean oil fatty acid soaps used in the above example are replaced, in whole or in part, by the lithium, sodium, rubidium or cesium salts of fatty acids derived from sunflower oil, safflower oil or corn oil.
EXAMPLE II
Single Stage Reaction
3.6 g 85% KOH pellets (0.055 moles) dissolved in 50 ml methanol and 278 g (0.933 moles) soybean oil fatty acid methyl esters were refluxed for two hours. 25 g (0.073 moles) sucrose and 1 g potassium carbonate were added. The soap:sucrose molar ratio of the mixture was 0.75:1. The methanol was evaporated from the mixture under nitrogen. When the reaction reached 100C, a vacuum was applied and the temperature raised to 135C.
Reaction conditions were maintained for four hours. The reaction was cooled, 15 ml. of water added, stirred 5 minutes and certrifuged (45 minutes, 8000 RPM). The mix-ture of higher sucrose polyesters was then decanted from the soap. The mixture was then bleached with 1-5%
Filtrol 105, filtered and steam deodorized at 205C to remove excess FAME.
The product formed comprised a mixture of the higher polyesters of sucrose, having a high (about 85%) octaester content.
~219859 Substantially similar results are obtained when the potassium carbonate catalyst is replaced, in whole or in part, by sodium carbonate or barium carbonate. Similar results are also obtained when the sucrose is replaced, 5 in whole or in part, by sorbitol, xylitol, mannitol or galactitol. The FAME is replaced, in whole or in part, with soybean oil benzyl esters, soybean oil 2-methoxy ethyl esters or the methyl esters of palm oil, sunflower oil, safflower oil, or corn oil; similar results are 10 obtained. Similar results are also obtained when the potassium soybean oil fatty acid soaps used in the above example are replaced, in whole or in part, by the lithium, sodium, rubidium or cesium salts of fatty acids derived from sunflower oil, safflower oil or corn oil.
EXAMPLE III
The general procedure described in Example I was used to compare the effectiveness of various catalysts.
Those tested included potassium carbonate (K2CO3), sodium carbonate (Na2CO3), sodium methoxide (NaOMe), sodium 20 hydride (Na.H) and potassium hydroxide (KOH), all at 10 mole percent of the sucrose in the reaction. K2CO3, NaOMe, and potassium hydride (K.H) were also compared at four weight percent of the sucrose. The results are summarized in the table below.
Effect of Various Catalvsts on the Synthesis of Sucrose Polye_ters Concentration % Octa-Catalyst (Sucrose Basls) % Yield Ester K2CO3 10 mole ~ 90 75 30 Na.H 10 mole % 76 36 NaOMe 10 mole % 85 63 KOH 10 mole % 58Not determined Na2C3 10 mole % 79 40 None -- 45 5 2C3 4 weight % 92 79 NaOMe 4 weight % 79 79 K.H 4 weight % 80 80 12~9~359 E~AMPLE IV
To assess the effect of soap level on the reaction, the reaction as described in Example I was utilized. The concentration of soap in the reaction mix was controlled 5 by either varying the amount of KOH added at the be-ginning or by adding varying amounts of preformed po-tassium soaps.
Two analytical methods were used to monitor the effect of soap on the reaction. In the first, varying 10 amounts of KOH and radiolabelled sucrose were used. At the end of the first two hours, before the second addition of FAME, the reaction was stopped and partitioned between hot water and ethyl acetate. The amount of 14C activity found in the water relative to that added as free sucrose 15 at the beginning of the reaction was a measure of un-reacted sucrose. These results are summarized below.
Effect of Soap Concentration On Sucrose Reaction Grams KOH Molar Ratio Unreacted Sucrose 20 Added Soap:Sucrose Remaining after 2 hrs.
3.6 0.75 1.2 2.4 0.5 3.6 1.4 0.3 14.0 o 0 100 In the second test, varying amounts of pre-formed potassium soap were added to the mixture in place of KOH.
The effect of the soap was judged by measuring yield of sucrose polyesters and octaester content. The results obtained are as follows.
Effect of_Soap Concentration On Yield of Sucrose Polyester .
Grams Potassium Molar Ratio Soap_dded Soap:Sucrose % Yield % Octaester
Reaction conditions were maintained for four hours. The reaction was cooled, 15 ml. of water added, stirred 5 minutes and certrifuged (45 minutes, 8000 RPM). The mix-ture of higher sucrose polyesters was then decanted from the soap. The mixture was then bleached with 1-5%
Filtrol 105, filtered and steam deodorized at 205C to remove excess FAME.
The product formed comprised a mixture of the higher polyesters of sucrose, having a high (about 85%) octaester content.
~219859 Substantially similar results are obtained when the potassium carbonate catalyst is replaced, in whole or in part, by sodium carbonate or barium carbonate. Similar results are also obtained when the sucrose is replaced, 5 in whole or in part, by sorbitol, xylitol, mannitol or galactitol. The FAME is replaced, in whole or in part, with soybean oil benzyl esters, soybean oil 2-methoxy ethyl esters or the methyl esters of palm oil, sunflower oil, safflower oil, or corn oil; similar results are 10 obtained. Similar results are also obtained when the potassium soybean oil fatty acid soaps used in the above example are replaced, in whole or in part, by the lithium, sodium, rubidium or cesium salts of fatty acids derived from sunflower oil, safflower oil or corn oil.
EXAMPLE III
The general procedure described in Example I was used to compare the effectiveness of various catalysts.
Those tested included potassium carbonate (K2CO3), sodium carbonate (Na2CO3), sodium methoxide (NaOMe), sodium 20 hydride (Na.H) and potassium hydroxide (KOH), all at 10 mole percent of the sucrose in the reaction. K2CO3, NaOMe, and potassium hydride (K.H) were also compared at four weight percent of the sucrose. The results are summarized in the table below.
Effect of Various Catalvsts on the Synthesis of Sucrose Polye_ters Concentration % Octa-Catalyst (Sucrose Basls) % Yield Ester K2CO3 10 mole ~ 90 75 30 Na.H 10 mole % 76 36 NaOMe 10 mole % 85 63 KOH 10 mole % 58Not determined Na2C3 10 mole % 79 40 None -- 45 5 2C3 4 weight % 92 79 NaOMe 4 weight % 79 79 K.H 4 weight % 80 80 12~9~359 E~AMPLE IV
To assess the effect of soap level on the reaction, the reaction as described in Example I was utilized. The concentration of soap in the reaction mix was controlled 5 by either varying the amount of KOH added at the be-ginning or by adding varying amounts of preformed po-tassium soaps.
Two analytical methods were used to monitor the effect of soap on the reaction. In the first, varying 10 amounts of KOH and radiolabelled sucrose were used. At the end of the first two hours, before the second addition of FAME, the reaction was stopped and partitioned between hot water and ethyl acetate. The amount of 14C activity found in the water relative to that added as free sucrose 15 at the beginning of the reaction was a measure of un-reacted sucrose. These results are summarized below.
Effect of Soap Concentration On Sucrose Reaction Grams KOH Molar Ratio Unreacted Sucrose 20 Added Soap:Sucrose Remaining after 2 hrs.
3.6 0.75 1.2 2.4 0.5 3.6 1.4 0.3 14.0 o 0 100 In the second test, varying amounts of pre-formed potassium soap were added to the mixture in place of KOH.
The effect of the soap was judged by measuring yield of sucrose polyesters and octaester content. The results obtained are as follows.
Effect of_Soap Concentration On Yield of Sucrose Polyester .
Grams Potassium Molar Ratio Soap_dded Soap:Sucrose % Yield % Octaester
4.7 0.2 Foamed & charred too badly during reaction to recover 7.7 0.33 75 47 15.0 0.64 90 80 17.6 0.75 93 77 23.5 1.0 91 74 WHAT IS CLAIMED IS:
Claims (18)
1. In a solvent-free transesterification pro-cess for synthesizing higher polyol fatty acid polyesters comprising the steps of:
(1) heating a mixture of (a) a polyol selected from a group consisting of monosaccharides, disaccharides and sugar alcohols, (b) a fatty acid ester selected from the group consisting of methyl esters, 2-methoxy ethyl esters, benzyl esters, and mixtures thereof, (c) an alkali metal fatty acid soap, and (d) a basic catalyst, to a temperature of from about 110°C to about 180°C at a pressure of from about 0.1 mm to about 760 mm of mercury to form a homogeneous melt; and (2) subsequently adding to the reaction pro-duct of step (l) excess fatty acid ester selected from the group consisting of methyl esters, 2-methoxy ethyl esters, benzyl esters, and mixtures thereof;
the improvement wherein the molar ratio of soap:polyol in step (l) is from about 0.6:1 to about 1:1,
(1) heating a mixture of (a) a polyol selected from a group consisting of monosaccharides, disaccharides and sugar alcohols, (b) a fatty acid ester selected from the group consisting of methyl esters, 2-methoxy ethyl esters, benzyl esters, and mixtures thereof, (c) an alkali metal fatty acid soap, and (d) a basic catalyst, to a temperature of from about 110°C to about 180°C at a pressure of from about 0.1 mm to about 760 mm of mercury to form a homogeneous melt; and (2) subsequently adding to the reaction pro-duct of step (l) excess fatty acid ester selected from the group consisting of methyl esters, 2-methoxy ethyl esters, benzyl esters, and mixtures thereof;
the improvement wherein the molar ratio of soap:polyol in step (l) is from about 0.6:1 to about 1:1,
2. The process according to claim l wherein the molar ratio of soap:polyol is from about 0.75:1 to about 1:1.
3. The process according to claim 2 wherein the polyol is a disaccharide.
4. The process according to claim 2 wherein the polyol is selected from the group consisting of sucrose, xylitol, sorbitol, and mixtures thereof.
5. The process according to Claim 2 wherein the fatty acid esters are fatty acid methyl esters.
6. The process according to Claim 5 wherein the methyl esters are derived from materials selected from the group consisting of soybean oil, safflower oil, palm oil, sunflower oil, corn oil and mixtures thereof.
7. The process according to Claim 2 wherein the mixture of step (1) is heated to a temperature of from about 130°C to about 145°C.
8. The process according to Claim 2 wherein the basic catalyst is selected from the group consisting of alkali metals, alloys of alkali metals, alkali metal hydrides, alkali metal alkoxides, and mixtures thereof.
9. The process according to Claim 2 wherein the reaction mixture of step (1) comprises from about 10% to about 50% by weight of the polyol, from about 40%
to about 80% by weight of the fatty acid ester, from about 1% to about 30% by weight of the alkali metal fatty acid soap, and from about 0.05% to about 5% by weight of the catalyst component.
to about 80% by weight of the fatty acid ester, from about 1% to about 30% by weight of the alkali metal fatty acid soap, and from about 0.05% to about 5% by weight of the catalyst component.
10. The process according to Claim 9 wherein the polyol is sucrose.
11. The process according to Claim 10 wherein the fatty acid esters are fatty acid methyl esters.
12. The process according to Claim 11 wherein the methyl esters are derived from a material selected from the group consisting of soybean oil, safflower oil, palm oil, sunflower oil, corn oil, and mixtures thereof.
13. The process according to Claim 12 wherein the mixture of step (1) is heated to a temperature of from about 130°C to about 145°C.
14. The process according to Claim 13 wherein the catalyst is selected from the group consisting of alkali metals, alloys of alkali metals, alkali metal hydrides, alkali metal alkoxides, and mixtures thereof.
15. The process according to Claim 14 wherein after the addition of the ester in step (2), the reaction mixture is heated to a temperature of from about 120°C
to about 160°C at a pressure of from about 0.1 mm to about 10 mm of mercury to form the higher polyol fatty acid polyesters.
to about 160°C at a pressure of from about 0.1 mm to about 10 mm of mercury to form the higher polyol fatty acid polyesters.
16. The process according to Claim 14 wherein the molar ratio of soap:polyol in step (1) is from about 0.75:1 to about 0.85:1.
17. The process according to Claim 16 wherein the molar ratio of soap:polyol in step (1) is about 0.75:1.
18. The process according to Claim 9 wherein water is added to the mixture of step (2), said mixture is centrifuged and the higher polyol fatty acid polyesters are separated therefrom.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/507,826 US4518772A (en) | 1983-06-23 | 1983-06-23 | Synthesis of higher polyol fatty acid polyesters using high soap:polyol ratios |
| US507,826 | 1983-06-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1219859A true CA1219859A (en) | 1987-03-31 |
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ID=24020295
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000457078A Expired CA1219859A (en) | 1983-06-23 | 1984-06-21 | Synthesis of higher polyol fatty acid polyesters using high soap: polyol ratios |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4518772A (en) |
| EP (1) | EP0132293B1 (en) |
| CA (1) | CA1219859A (en) |
| DE (1) | DE3484575D1 (en) |
| ES (1) | ES533629A0 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL111638C (en) * | 1955-12-12 | |||
| DE1200276B (en) * | 1959-10-08 | 1965-09-09 | Bayer Ag | Process for the preparation of carboxylic acid esters of non-reducing sugars |
| DE1643795A1 (en) * | 1967-08-04 | 1971-07-01 | Cassella Farbwerke Mainkur Ag | Process for the production of sugar esters |
| GB1399053A (en) * | 1973-03-16 | 1975-06-25 | Tate & Lyle Ltd | Process for the production of surface active agents comprising sucrose esters |
| US3963699A (en) * | 1974-01-10 | 1976-06-15 | The Procter & Gamble Company | Synthesis of higher polyol fatty acid polyesters |
| GB1499989A (en) * | 1974-10-17 | 1978-02-01 | Tate & Lyle Ltd | Production of a surface active material containing sucrose esters |
| US4334061A (en) * | 1979-10-29 | 1982-06-08 | Ethyl Corporation | Process for recovery of polyol fatty acid polyesters |
| GB2065634B (en) * | 1979-12-19 | 1983-07-13 | Tate & Lyle Ltd | Process for the production of a surfactant containing sucrose esters |
-
1983
- 1983-06-23 US US06/507,826 patent/US4518772A/en not_active Expired - Lifetime
-
1984
- 1984-06-19 DE DE8484304128T patent/DE3484575D1/en not_active Expired - Lifetime
- 1984-06-19 EP EP84304128A patent/EP0132293B1/en not_active Expired
- 1984-06-21 CA CA000457078A patent/CA1219859A/en not_active Expired
- 1984-06-22 ES ES533629A patent/ES533629A0/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| ES8506067A1 (en) | 1985-06-16 |
| EP0132293A2 (en) | 1985-01-30 |
| DE3484575D1 (en) | 1991-06-20 |
| US4518772A (en) | 1985-05-21 |
| EP0132293A3 (en) | 1985-03-06 |
| EP0132293B1 (en) | 1991-05-15 |
| ES533629A0 (en) | 1985-06-16 |
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