CA1296720C - Process for the post-hydrogenation of sucrose polyesters - Google Patents
Process for the post-hydrogenation of sucrose polyestersInfo
- Publication number
- CA1296720C CA1296720C CA000554673A CA554673A CA1296720C CA 1296720 C CA1296720 C CA 1296720C CA 000554673 A CA000554673 A CA 000554673A CA 554673 A CA554673 A CA 554673A CA 1296720 C CA1296720 C CA 1296720C
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- CA
- Canada
- Prior art keywords
- sucrose
- hydrogenation
- post
- polyesters
- polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- 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
PROCESS FOR THE POST-HYDROGENATION
OF SUCROSE POLYESTERS
Abstract of the Disclosure The invention is a process for post-hydrogenating sucrose polyesters with hydrogen gas in the presence of a catalytically effective amount of hydrogenation catalyst, at a temperature of from about 250°F (121°C) to about 450°F
(232°C), Post-hydrogenation can be used to make sucrose polyesters that are different from those made by esterification. Preferably, the hydrogen pressure is at least about 20 psig. Increased hydrogen pressure overcomes steric hindrance of certain kinds of sucrose polyester molecules, allowing more complete hydrogenation of the fatty acids.
OF SUCROSE POLYESTERS
Abstract of the Disclosure The invention is a process for post-hydrogenating sucrose polyesters with hydrogen gas in the presence of a catalytically effective amount of hydrogenation catalyst, at a temperature of from about 250°F (121°C) to about 450°F
(232°C), Post-hydrogenation can be used to make sucrose polyesters that are different from those made by esterification. Preferably, the hydrogen pressure is at least about 20 psig. Increased hydrogen pressure overcomes steric hindrance of certain kinds of sucrose polyester molecules, allowing more complete hydrogenation of the fatty acids.
Description
~LZ96720 , . .
PRO OESS ~OR T~ POST-~YDROGENATION
OF ~CROSE POLY~STERS
Field of the Invention The field of this invention is fatty acid esters of sucrose. In particular, the invention relates to a process for hydrogenating the unsaturated fatty acids of the sucrose polyesters after they have been esterified to the sucrose molecules.
Back~round of the Invention Hydrogenation consists of the addition of hydrogen to the double bonds of fatty acids, increasing the saturation of the fatty acids. In the hydrogenation of triglycerides, the reaction typically takes place by contacting triglyceride with gaseous hydrogen at a 15 temperature above about 302F (150C), in the presence of a solid catalyst. It ls known that increasing the pressure increa~es the rate o~ the triglyceride hydrogenation reaction. Swern, Bailey's Industrial Oil and Fat Products, Vol. 2, 4th ed., Interscience 20 Publishers, NY, pp. 5-69 (1982), discusses the hydrogenation process in general.
Fatty acid esters of sucrose ("sucrose polyesters") are usually synthesized by one of three methods:
transesterification of the sucrose with methyl, ethyl or glycerol fatty acid esters; acylation with a fatty acid chloride; or acylation with a fatty acid per se. As an example, the preparation of sucrose fatty acid polyesters is described in U.S. Patent Nos. 2,831,854 and 3,521/827.
More highly saturated sucrose polyesters are generally made by using more saturated fatty acids as the starting material prior to esterification. The present invention, on the other hand, concerns a method for increasing the saturation of sucrose polyesters by - 35 hydrogenating the polyesters after they have been synthesized from sucrose and fatty acids, i.e., "post-hydrogenation".
6~720 ,, It is, therefore, an object of an aspect of the present invention to provide an effective process for the post-hydrogenation of sucrose polyesters.
It is an object of an aspect of the present invention to use the post-hydrogenation process to make sucrose polyesters that are different from those made by esterification alone.
It is an object of an aspect of the present invention to provide a post-hydrogenation process that allows more complete hydrogenation of certain kinds of sucrose polyester molecules.
These and other objects of aspects of the invention will be made clear by the disclosure herein.
A11 percentages are by weight unless otherwise defined.
SummarY of the Invention The invention in one aspect is a process for post-hydrogenating sucrose polyesters with hydrogen gas in the presence of a catalytically effective amount of hydrogenation catalyst, at a temperature of from about 250F (121C) to about 450F (232C). Post-hydrogenation can be used to make sucrose polyesters that are different from those made by esterification.
Preferably, the hydrogen pressure is at least about 20 psig. Increased hydrogen pressure overcomes steric hindrance of certain kinds of sucrose polyester ; molecules, allowing more complete hydrogenation of the ; fatty acids.
Another aspect of this invention is as follows:
A process for post-hydrogenating sucrose polyesters comprising contacting sucrose polyesters having at least four fatty ester groups, wherein at least one of said fatty acid ester groups is unsaturated, with hydrogen gas in the presence of a catalytically effective amount of hydrogenation catalyst, at a temperature of from about 250F. (121C.) to about 450F. (232C.) to ~L2~6~
hydrogenate the unsaturated fatty acids of the sucrose polyesters.
Detailed DescriPtion of the Invention The present invention is concerned with the post-~5 hydrogenation of sucrose polyesters, i.e., hydrogenation ;of the fatty acids of sucrose polyesters after the fatty acids are already esterified to the sucrose molecules.
Post-hydrogenation of sucrose polyesters allows the synthesis of polyesters that are different from those made by esterification alone. When sucrose is esterified with fatty acids, different kinds of fatty acids will preferentially esterify to particular sites on the sucrose molecuIe depending on their degree of unsaturation and other factor~. When these fatty acids are post-hydrogenated, the resulting more saturated fatty acids often are positioned on the sucrose at positions different than would have resulted had these fatty acids been ffrst hydrogenated and then esterified to sucrose.
Hence, post~hydrogenation can produce sucrose polyesters with differently positioned fatty acids, giving the polyesters different physical attributes. In particular, sucrose polyesters with specific unique melt profiles can be produced.
Samples of sucrose polyester made by post-hydrogenation and by transesterification having similar iodine values were found to have very different Solid Fat (:ontent (SFC) curves.
The process of this invention for post-hydrogenating sucrose fatty acid polyesters comprises contacting the sucrose 1 a polyesters with hydrogen gas in the presence of a catalyt-ically effective amount of hydrogenation catalyst, at a temperature of from about 250F (121C) to about 450F
(232C). In ordinary practicc the hydrogen is first brought into contact with the polyesters, with the hydrogen-laden polyesters then brought into contact with the catalyst by mechanical means. ln the usual type of equipment, a suspension of catalyst and polyester is agitated in a closed vessel in an atmosphere OI hydrogen. Agitation of the catalyst-polyester mixture promotes dissolution of hydrogen in 2~ the polyester and continuously renews the polyester at the catalyst surface. For a thorough discussion of hydrogenation equipment, see Swern, Bailey's Industrial_Oil _and Fat Products, Vol. 2, 4th ed., Interscience Publishers, NY, pp. ~7-37 (1982).
PRO OESS ~OR T~ POST-~YDROGENATION
OF ~CROSE POLY~STERS
Field of the Invention The field of this invention is fatty acid esters of sucrose. In particular, the invention relates to a process for hydrogenating the unsaturated fatty acids of the sucrose polyesters after they have been esterified to the sucrose molecules.
Back~round of the Invention Hydrogenation consists of the addition of hydrogen to the double bonds of fatty acids, increasing the saturation of the fatty acids. In the hydrogenation of triglycerides, the reaction typically takes place by contacting triglyceride with gaseous hydrogen at a 15 temperature above about 302F (150C), in the presence of a solid catalyst. It ls known that increasing the pressure increa~es the rate o~ the triglyceride hydrogenation reaction. Swern, Bailey's Industrial Oil and Fat Products, Vol. 2, 4th ed., Interscience 20 Publishers, NY, pp. 5-69 (1982), discusses the hydrogenation process in general.
Fatty acid esters of sucrose ("sucrose polyesters") are usually synthesized by one of three methods:
transesterification of the sucrose with methyl, ethyl or glycerol fatty acid esters; acylation with a fatty acid chloride; or acylation with a fatty acid per se. As an example, the preparation of sucrose fatty acid polyesters is described in U.S. Patent Nos. 2,831,854 and 3,521/827.
More highly saturated sucrose polyesters are generally made by using more saturated fatty acids as the starting material prior to esterification. The present invention, on the other hand, concerns a method for increasing the saturation of sucrose polyesters by - 35 hydrogenating the polyesters after they have been synthesized from sucrose and fatty acids, i.e., "post-hydrogenation".
6~720 ,, It is, therefore, an object of an aspect of the present invention to provide an effective process for the post-hydrogenation of sucrose polyesters.
It is an object of an aspect of the present invention to use the post-hydrogenation process to make sucrose polyesters that are different from those made by esterification alone.
It is an object of an aspect of the present invention to provide a post-hydrogenation process that allows more complete hydrogenation of certain kinds of sucrose polyester molecules.
These and other objects of aspects of the invention will be made clear by the disclosure herein.
A11 percentages are by weight unless otherwise defined.
SummarY of the Invention The invention in one aspect is a process for post-hydrogenating sucrose polyesters with hydrogen gas in the presence of a catalytically effective amount of hydrogenation catalyst, at a temperature of from about 250F (121C) to about 450F (232C). Post-hydrogenation can be used to make sucrose polyesters that are different from those made by esterification.
Preferably, the hydrogen pressure is at least about 20 psig. Increased hydrogen pressure overcomes steric hindrance of certain kinds of sucrose polyester ; molecules, allowing more complete hydrogenation of the ; fatty acids.
Another aspect of this invention is as follows:
A process for post-hydrogenating sucrose polyesters comprising contacting sucrose polyesters having at least four fatty ester groups, wherein at least one of said fatty acid ester groups is unsaturated, with hydrogen gas in the presence of a catalytically effective amount of hydrogenation catalyst, at a temperature of from about 250F. (121C.) to about 450F. (232C.) to ~L2~6~
hydrogenate the unsaturated fatty acids of the sucrose polyesters.
Detailed DescriPtion of the Invention The present invention is concerned with the post-~5 hydrogenation of sucrose polyesters, i.e., hydrogenation ;of the fatty acids of sucrose polyesters after the fatty acids are already esterified to the sucrose molecules.
Post-hydrogenation of sucrose polyesters allows the synthesis of polyesters that are different from those made by esterification alone. When sucrose is esterified with fatty acids, different kinds of fatty acids will preferentially esterify to particular sites on the sucrose molecuIe depending on their degree of unsaturation and other factor~. When these fatty acids are post-hydrogenated, the resulting more saturated fatty acids often are positioned on the sucrose at positions different than would have resulted had these fatty acids been ffrst hydrogenated and then esterified to sucrose.
Hence, post~hydrogenation can produce sucrose polyesters with differently positioned fatty acids, giving the polyesters different physical attributes. In particular, sucrose polyesters with specific unique melt profiles can be produced.
Samples of sucrose polyester made by post-hydrogenation and by transesterification having similar iodine values were found to have very different Solid Fat (:ontent (SFC) curves.
The process of this invention for post-hydrogenating sucrose fatty acid polyesters comprises contacting the sucrose 1 a polyesters with hydrogen gas in the presence of a catalyt-ically effective amount of hydrogenation catalyst, at a temperature of from about 250F (121C) to about 450F
(232C). In ordinary practicc the hydrogen is first brought into contact with the polyesters, with the hydrogen-laden polyesters then brought into contact with the catalyst by mechanical means. ln the usual type of equipment, a suspension of catalyst and polyester is agitated in a closed vessel in an atmosphere OI hydrogen. Agitation of the catalyst-polyester mixture promotes dissolution of hydrogen in 2~ the polyester and continuously renews the polyester at the catalyst surface. For a thorough discussion of hydrogenation equipment, see Swern, Bailey's Industrial_Oil _and Fat Products, Vol. 2, 4th ed., Interscience Publishers, NY, pp. ~7-37 (1982).
3 o The sucrose polyesters employed in this invention comprise well-defined sucrose fatty acid esters. Sucrose has eight esterifiable hydroxyl groups. The sucrose fatty acid esters useful in this invention must contain at least four fatty acid ester groups. Sucrose fatty acid ester compounds that 3 5 contain three or less fatty acid ester groups tend to be digested in the intestinal tract in much the same manner as ~29~i72~
ordinary triglyceride fats, whereas the sucrose fatty acid ester compounds that contain four or more fatty acid ester groups are substantially non-absorbable and non-digestible by the human body. It is not necessary that all of the hydroxyl groups of the sucrose be esterified with fatty acid, but it is preferable that the sucrose polyester contain no more than three unesterified hydroxyl groups, and more prefera~ly no more than two unesterified hydroxyl groups. The fatty acid ester groups can be the same or mixed on the same sucrose 10polyester molecule.
The sucrose starting material must be esteri~ed with fatty acids having from about eight to about 22 carbon atoms.
Examples of such fatty acids include capry]ic, capric, laurie, myristic, myristoleie, palmitic, palmitoleic, stearic, oleie, 15ricinoleic, linoleic, linolenic, eleostearie, arachidio, arachidonic, behenic, and erucie acid. The fatty acids can be derived from naturally oecurring or synthetie fatty acids;
they can be saturuted or unsaturated, including positional and geometrical isomers. Of course, at least one of the fatty 20acids must be unsaturated for the process of this invention to be useful.
Fatty acids per se or natura~y occurring fats and oils can serve as the source of the fatty acid component in the sucrose fatty aeid ester. For example, rapeseed oil provides g for C22 fatty aeid, C16-C18 fatty aeid can be provided by tallow, soybean oil, or cottonseed oil. Shorter chain fatty aeids can be provided by coconut, palm kernel, or babassu oils. Corn oil, lard, olive oil, palm oil, peanut oil, safflower seed oil, sesame seed oil, and sunflower seed oil, - 3 0are examples of other natural oils which can serve as the source of the fatty acid component.
The catalyst can be any standard hydrogenation catalyst. The preferred eatalyst is nickel metal, although minor amounts of copper, aluminum, ete., can be incorporated 3 5with the niekel for their "promoter" or seleetivity action .
Other catalysts include metals, alloys and compounds of, for .
~L2~ hi7~`~
'`
example, chromium, cobalt, copper, iron, lead, manganese, mercury, molybdenum, palladium, pla'dnum, thorium, titanium, vanadium, zinc and zirconium. Preferably, the catalyst is present in the amount of from about 0 . 01% to about 0 . 5% by 5 weight of the sucrose polyester. The amount of catalyst used is dependent upon the rate of reaction to be attained and other variables such as temperature and pressure, and the starting polyesters.
A preferred method for preparing the catalyst is to mix 10 from about 15% to about 28~ nickel cataly6t into ~i~uid triglyceride or liquid sucrose polyester.
Hydrogenation is carried out at a temperature of from about 250F (1~1C) to about 450F (~32C). The preferred temperature range i8 from about 340F (171C) to about 410F
15 (210C), and the most preferred range is from about 365F
(185C) to about 405F (207C).
The time of hydrogenaffon is a function of the temperature, pressurc, type of sucrose polyester, and most importantly, the type of catalyst. The sucrose polyester is 2~ hydrogenated to a parffcular Refractive Index endpoint (as an indicator of Iodine Value), depending on the kind of product dssired .
Triglycerides are genera~y hydrogenated until the product reaches a par'dcular Refractive Index, which is 2 5 correlated with Iodine Value, a Eneasure of the degree of unsaturation of the triglycerides. It was attempted to hydrogenate sucrose polyes ters at atmospheric pres~ure to a certain Refraetive Index. Surprisingly, it was ~ound that the Refracffve Index reached a pOiIlt beyond which it changed no 3 0 further, even with additional hydrogenation time . The problem, it has now been found, is that unlike the hydrogenation of triglycerides, the hydrogenation of sucrose polyesters is to a great extent affected by steric hindrance of the fatty acids on the sucrose molecules. The shape of 35 certain kinds of sucrose fatty acid ester molecules is such that it is impossible to hydrogenate some of the fatty acid ~:z~
unsaturation sites under normal conditions. For example, the hydrogenation process did not hydrogenate the 9-10 carbon double bond of a sucrose polyester, resulting in a polyester which was high in mono-unsaturates.
It has now been discovered that post-hydrogenating the sucrose polyesters under high pressure can overcome the problems caused by steric hindrance. This is an ; unexpected finding based on what is known of triglyceride hydrogenation because, while increased pressure increases the rate of hydrogenation of triglycerides, increased pressure does not change the extent of hydroyenation of the triglycerides. By contrast, post-hydrogenation of sucrose polyesters under high pressure can produce sucrose polyesters that are hydrogenated to a greater extent. For example, post-hydrogenation under pressure enabled hydrogenation of the 9-10 carbon double bond of the sucrose polyester fatty acids.
~' Hence, although the process of the present invention can be conducted at atmospheric pressure, a preferred embodiment of the present invention is to post-hydrogenate the sucrose polyesters under a hydrogen pressure of at least about 20 psig. More preferably, the hydrogen pressure will be at least about 40 psig, and mo~t preferably the pressure will be at least about 45 psig.
:`
AnalYtical Methods Solid Fat Content: The method for determining Solid Fat Content (SFC) values of a fat by PNMR is ` described in Madison and Hill, J. Amer. Oil Chem. Soc., Vol. 55 (1978), pp. 328-31. Before determining SFC
~.~
6a values, the fat materi l sample is heated to a temperature of 158F (70C) or higher for at least 0.5 hours or until the sample is complet~ely melted. The melted sample is then tempered at a temperature of 40F
(4C) for at least 72 hours. After tempering, the SFC
value of the fat material at a temperature of 100F
(38C) is determined by pulsed nuclear magnetic resonance (PNMR).
- ~L2~
Fatty Acid Composition: The fatty acid composition is determined by gas chromatography, utilizing a Hewlett-Packard Model S712A gas chromatograph equipped with a thermal conductivity detector and a Hewlett-Packard Model 7671A automatic sampler. The chromatographic method utilized is described in Official Methods and Recommended Practices of the American Oil Chemists Society, 3rd Ed., 1984, Procedure Ce 1-62.
The following e~amples are intended only to further illustrate the invention and are not intended to limit the scope of the invention which is defined by the claims.
Example 1 Forty pounds of a sucrose polyester made by transesterifying sucrose with soy-based methyl esters i8 placed into a 50-lb. stainless steel reaction ~ressel at 150F
( 66C) . The reaction vessel is sparged with nitrogen at atmospheric pressure and heated to a temperature of 350F
(177C) over a period of 65 minutes. Next, 80 g. of a slurry 2 0 made with 17 . 5 g. nickel metal catalyst and 62 . 5 g. coconut oil hardstock is added to the polyester. Then hydrogen is introduced into the reaction vessel at a pressure of 50 psig.
The temperature is raised to 400F (204C) over a 45-minute - period, ~nd then the hydrogenation reacffon is contlnued at 2~ this temperature for 1 hour and 10 minutes until the Refractive Index of the product is 51. 9 . After the reaction is completed, the vessel is depressurized to atmospheric pressure and sparged with nitrogen gas, and the reacffon mixture is quickly cooled to 200F (93C) and then filtered.
3 0 The hydrogenated sucrose polyester product has the following fatty aeid composition and Solid Fat Content:
~.
FAC: G12 0.1~
C14 0 . 1%
C16 1û . 2~
C18 24.5%
C18-1 56 . 1%
C18-2 7.4%
C18-3 0.6%
C20 0,7%
C22 0 . 396 SFC: 50F (10C): 47.9g6 70F (21C): 24.79c 80F (27C): 20 . 6%
92F ( 33C): 13 . 2%
105F (41C): 6.8g6 The product's Refrac'dve Index is 51.9, and its Iodine Value is 62.2.
1~ Fxnmple 2 Two samples of sucrose polyester are made. The first sample is synthesized by transesterification. The second sample is also made by transesterification, but the polyester is also post-hydrogenated after esterification:
20 A. First sucrose polyester, made by_transesterification:
Soy-based methyl esters with an Iodine Value of 40 . 4 (227.3 kg.), and 36 kg. of an 18 wt. percent solution of potassium hydroxide in methanol are mixed in a stainless steel batch reactor. This mixture is then heated to 122F (50C) 2 $ with agit~ltion for 1 to 2 hours at atmospheric pressure .
During this time, a portion of the methyl esters are saponified. A vacuum is then pulled on the system to remove the last traces of methanol.
Granular sucrose (45.5 kg.) is added to the soap/ester 3 ~ mixture to give a 5 :1 molar ratio of estar to sucrose .
Potassium carbonate is then added to the mixture (approx.
.~
û . 5 wt . percent of the reaction mix) to catslyze the transesterification. This mixture is agitsted and heated under ~7acuum at about 275F (135C) for up to 8 hours to form the mono-, di- and trisucrose esters. Small quantities ~Z~67~Q
of tetra- and pent~esters are also formed during this stage.
Additional methyl ester (276.7 kg.) which has been preheated to 275F (135C) is added to bring and maintain the molar ratio of the esters to sucrose to 12 :1. When the reaction condiffons stabi~ze at 275F (135C), a nitrogen sparge is used to improve agitation and promote methanol stripping. As the reaction occurs, the reaction mixture becomes viscous and then thins out. This second reaction stage lasts approximately 24 to 36 hours.
After the reaction mixture has become thin, it is cooled to between 149F (65C) and 185F (85C). The crude reaction mixture is agitated with a dilute soluffon of methanol, sodium chloride and water . The volume of this wash solu ~on i8 equal to 20% to 40~6 of the reac~on mixture volume. The-mixed phases are then allowed to settle for approximately 30 to 60 minutes. The lower settled phase which contains the soaps, excess sugars and methanol is drawn off and disc~rd~d. The settled phase whi~h comprises the refined sucrose polyesters is washed again. Usually 2 to 4 washes ;20 are used.
The sucrose polyesters are then washed with a 1% glacial acetic acid in water solution at 10% to 20g6 of the volume of the reaction mix. This is followed by water wash of the same volume .
;2~ The reaction mix is then dried under vacuum. The reaction mixture is then treated with an oil bleaching agent and filtered. The bulk of the unreacted methyl esters are removed by distillation at 374F (190C) to 482F (250C) under approximately 5 mm Hg of vacuum.
3 0 The sucrose polyester i8 then deodorized in a stainless steel batch deodorizer or other suitable device at 374F
(190C) to 482F (250C) under a vacuum of about 5 mm Hg with steam sparging. Deodorization is continued until the . methyl ester content is below 200 ppm. The deodorizer 3~ contents are then cooled to 149F (65C) while using inert ~` :
'd ~2~67;~
gas sparging. The sucrose polyester is stored in clean stainless steel drums.
This produces a sucrose polyester product hav~ng the fo!lowing proper1ies:
FAC: C12 0~6 C14 o%
C16 13 . 2 18 42 . 8%
C18-1 40. 1%
C18-2 3.9g6 C18-3 o~6 C20 o%
C22 0%
SFC: 50F (10C): 72.9%
70F (21C~: 59.3%
80F (27C): 45.3%
92F (33C~: 22.99 105F (41C): 9.296 The product's Iodine Value is 41.3.
B. Second sucrose polyester, made by post-hydrogenation after transesterification:
Twenty-six pounds of a sucrose polyester made by transesterifying sucrose with soy-based methyl esters having an Iodine Value of about 107 is placed into a stainless steel reaction vessel. The reaction vessel is sparged with nitrogen at atmospheric pressure and heated to a temperature of 360F
2j (182C) over a period of 85 minutes. Next, 60 g. of a slurry made with 13 . 2 g . nickel metal catalyst and 46 . 8 g . of a melted coconut oil hardstock is added to the polyester. Then hydrogen is introduced into the reaction vessel at atmospheric pressure. The temperature is raised to 400F (204C), and 3 then the hydrogenation reaction is continued at this temperature for 6 hours and 30 minutes until the Refractive Index of the product is 46 . 3 . After the reaction is completed, the hydrogen is shut off and the vessel is sparged with nitrogen gas, and the reaction mixture is quickly cooled 3~ to 200F ~93C) and then filtered.
6~
The post-hydrogenated sucrose polyester product has the following fatty acid composition and Solid Fat Content:
FAC: C12 0 . 3%
C14 o%
C 16 11 . 9 C18 42.9 C1~ 4.9g6 C18-2 o%
C18-3 o%
~::22 0%
SFC: 50F ~10C): greater than 85%
70F ( 21C):
80F (27C):
92F ~33C): " " "
105P (41C): " " "
15 The Solid Fat Content of the sucrose polyester is too solid for measurement at all temperature~. The product's Refractive Index is 46.3 and its Iodlne Value is 38.6.
The first sucrose polyester, made by transesterification alone, has an Iodine Value of ~1. 3 and the second sucrose 20 polyester, made by post-hydrogenation fo~owing transesteri-fication, has an lodine Value of 46 . 3 . This is true even though the polyesters were synthesized from soy-based methyl esters having Iodine Values of about 40 and about 107, respecffvely. While the Iodine Values for the two sucrose 25 polyester products are similar, the Solid Fat Content cur~es of the polyesters are very different~
ordinary triglyceride fats, whereas the sucrose fatty acid ester compounds that contain four or more fatty acid ester groups are substantially non-absorbable and non-digestible by the human body. It is not necessary that all of the hydroxyl groups of the sucrose be esterified with fatty acid, but it is preferable that the sucrose polyester contain no more than three unesterified hydroxyl groups, and more prefera~ly no more than two unesterified hydroxyl groups. The fatty acid ester groups can be the same or mixed on the same sucrose 10polyester molecule.
The sucrose starting material must be esteri~ed with fatty acids having from about eight to about 22 carbon atoms.
Examples of such fatty acids include capry]ic, capric, laurie, myristic, myristoleie, palmitic, palmitoleic, stearic, oleie, 15ricinoleic, linoleic, linolenic, eleostearie, arachidio, arachidonic, behenic, and erucie acid. The fatty acids can be derived from naturally oecurring or synthetie fatty acids;
they can be saturuted or unsaturated, including positional and geometrical isomers. Of course, at least one of the fatty 20acids must be unsaturated for the process of this invention to be useful.
Fatty acids per se or natura~y occurring fats and oils can serve as the source of the fatty acid component in the sucrose fatty aeid ester. For example, rapeseed oil provides g for C22 fatty aeid, C16-C18 fatty aeid can be provided by tallow, soybean oil, or cottonseed oil. Shorter chain fatty aeids can be provided by coconut, palm kernel, or babassu oils. Corn oil, lard, olive oil, palm oil, peanut oil, safflower seed oil, sesame seed oil, and sunflower seed oil, - 3 0are examples of other natural oils which can serve as the source of the fatty acid component.
The catalyst can be any standard hydrogenation catalyst. The preferred eatalyst is nickel metal, although minor amounts of copper, aluminum, ete., can be incorporated 3 5with the niekel for their "promoter" or seleetivity action .
Other catalysts include metals, alloys and compounds of, for .
~L2~ hi7~`~
'`
example, chromium, cobalt, copper, iron, lead, manganese, mercury, molybdenum, palladium, pla'dnum, thorium, titanium, vanadium, zinc and zirconium. Preferably, the catalyst is present in the amount of from about 0 . 01% to about 0 . 5% by 5 weight of the sucrose polyester. The amount of catalyst used is dependent upon the rate of reaction to be attained and other variables such as temperature and pressure, and the starting polyesters.
A preferred method for preparing the catalyst is to mix 10 from about 15% to about 28~ nickel cataly6t into ~i~uid triglyceride or liquid sucrose polyester.
Hydrogenation is carried out at a temperature of from about 250F (1~1C) to about 450F (~32C). The preferred temperature range i8 from about 340F (171C) to about 410F
15 (210C), and the most preferred range is from about 365F
(185C) to about 405F (207C).
The time of hydrogenaffon is a function of the temperature, pressurc, type of sucrose polyester, and most importantly, the type of catalyst. The sucrose polyester is 2~ hydrogenated to a parffcular Refractive Index endpoint (as an indicator of Iodine Value), depending on the kind of product dssired .
Triglycerides are genera~y hydrogenated until the product reaches a par'dcular Refractive Index, which is 2 5 correlated with Iodine Value, a Eneasure of the degree of unsaturation of the triglycerides. It was attempted to hydrogenate sucrose polyes ters at atmospheric pres~ure to a certain Refraetive Index. Surprisingly, it was ~ound that the Refracffve Index reached a pOiIlt beyond which it changed no 3 0 further, even with additional hydrogenation time . The problem, it has now been found, is that unlike the hydrogenation of triglycerides, the hydrogenation of sucrose polyesters is to a great extent affected by steric hindrance of the fatty acids on the sucrose molecules. The shape of 35 certain kinds of sucrose fatty acid ester molecules is such that it is impossible to hydrogenate some of the fatty acid ~:z~
unsaturation sites under normal conditions. For example, the hydrogenation process did not hydrogenate the 9-10 carbon double bond of a sucrose polyester, resulting in a polyester which was high in mono-unsaturates.
It has now been discovered that post-hydrogenating the sucrose polyesters under high pressure can overcome the problems caused by steric hindrance. This is an ; unexpected finding based on what is known of triglyceride hydrogenation because, while increased pressure increases the rate of hydrogenation of triglycerides, increased pressure does not change the extent of hydroyenation of the triglycerides. By contrast, post-hydrogenation of sucrose polyesters under high pressure can produce sucrose polyesters that are hydrogenated to a greater extent. For example, post-hydrogenation under pressure enabled hydrogenation of the 9-10 carbon double bond of the sucrose polyester fatty acids.
~' Hence, although the process of the present invention can be conducted at atmospheric pressure, a preferred embodiment of the present invention is to post-hydrogenate the sucrose polyesters under a hydrogen pressure of at least about 20 psig. More preferably, the hydrogen pressure will be at least about 40 psig, and mo~t preferably the pressure will be at least about 45 psig.
:`
AnalYtical Methods Solid Fat Content: The method for determining Solid Fat Content (SFC) values of a fat by PNMR is ` described in Madison and Hill, J. Amer. Oil Chem. Soc., Vol. 55 (1978), pp. 328-31. Before determining SFC
~.~
6a values, the fat materi l sample is heated to a temperature of 158F (70C) or higher for at least 0.5 hours or until the sample is complet~ely melted. The melted sample is then tempered at a temperature of 40F
(4C) for at least 72 hours. After tempering, the SFC
value of the fat material at a temperature of 100F
(38C) is determined by pulsed nuclear magnetic resonance (PNMR).
- ~L2~
Fatty Acid Composition: The fatty acid composition is determined by gas chromatography, utilizing a Hewlett-Packard Model S712A gas chromatograph equipped with a thermal conductivity detector and a Hewlett-Packard Model 7671A automatic sampler. The chromatographic method utilized is described in Official Methods and Recommended Practices of the American Oil Chemists Society, 3rd Ed., 1984, Procedure Ce 1-62.
The following e~amples are intended only to further illustrate the invention and are not intended to limit the scope of the invention which is defined by the claims.
Example 1 Forty pounds of a sucrose polyester made by transesterifying sucrose with soy-based methyl esters i8 placed into a 50-lb. stainless steel reaction ~ressel at 150F
( 66C) . The reaction vessel is sparged with nitrogen at atmospheric pressure and heated to a temperature of 350F
(177C) over a period of 65 minutes. Next, 80 g. of a slurry 2 0 made with 17 . 5 g. nickel metal catalyst and 62 . 5 g. coconut oil hardstock is added to the polyester. Then hydrogen is introduced into the reaction vessel at a pressure of 50 psig.
The temperature is raised to 400F (204C) over a 45-minute - period, ~nd then the hydrogenation reacffon is contlnued at 2~ this temperature for 1 hour and 10 minutes until the Refractive Index of the product is 51. 9 . After the reaction is completed, the vessel is depressurized to atmospheric pressure and sparged with nitrogen gas, and the reacffon mixture is quickly cooled to 200F (93C) and then filtered.
3 0 The hydrogenated sucrose polyester product has the following fatty aeid composition and Solid Fat Content:
~.
FAC: G12 0.1~
C14 0 . 1%
C16 1û . 2~
C18 24.5%
C18-1 56 . 1%
C18-2 7.4%
C18-3 0.6%
C20 0,7%
C22 0 . 396 SFC: 50F (10C): 47.9g6 70F (21C): 24.79c 80F (27C): 20 . 6%
92F ( 33C): 13 . 2%
105F (41C): 6.8g6 The product's Refrac'dve Index is 51.9, and its Iodine Value is 62.2.
1~ Fxnmple 2 Two samples of sucrose polyester are made. The first sample is synthesized by transesterification. The second sample is also made by transesterification, but the polyester is also post-hydrogenated after esterification:
20 A. First sucrose polyester, made by_transesterification:
Soy-based methyl esters with an Iodine Value of 40 . 4 (227.3 kg.), and 36 kg. of an 18 wt. percent solution of potassium hydroxide in methanol are mixed in a stainless steel batch reactor. This mixture is then heated to 122F (50C) 2 $ with agit~ltion for 1 to 2 hours at atmospheric pressure .
During this time, a portion of the methyl esters are saponified. A vacuum is then pulled on the system to remove the last traces of methanol.
Granular sucrose (45.5 kg.) is added to the soap/ester 3 ~ mixture to give a 5 :1 molar ratio of estar to sucrose .
Potassium carbonate is then added to the mixture (approx.
.~
û . 5 wt . percent of the reaction mix) to catslyze the transesterification. This mixture is agitsted and heated under ~7acuum at about 275F (135C) for up to 8 hours to form the mono-, di- and trisucrose esters. Small quantities ~Z~67~Q
of tetra- and pent~esters are also formed during this stage.
Additional methyl ester (276.7 kg.) which has been preheated to 275F (135C) is added to bring and maintain the molar ratio of the esters to sucrose to 12 :1. When the reaction condiffons stabi~ze at 275F (135C), a nitrogen sparge is used to improve agitation and promote methanol stripping. As the reaction occurs, the reaction mixture becomes viscous and then thins out. This second reaction stage lasts approximately 24 to 36 hours.
After the reaction mixture has become thin, it is cooled to between 149F (65C) and 185F (85C). The crude reaction mixture is agitated with a dilute soluffon of methanol, sodium chloride and water . The volume of this wash solu ~on i8 equal to 20% to 40~6 of the reac~on mixture volume. The-mixed phases are then allowed to settle for approximately 30 to 60 minutes. The lower settled phase which contains the soaps, excess sugars and methanol is drawn off and disc~rd~d. The settled phase whi~h comprises the refined sucrose polyesters is washed again. Usually 2 to 4 washes ;20 are used.
The sucrose polyesters are then washed with a 1% glacial acetic acid in water solution at 10% to 20g6 of the volume of the reaction mix. This is followed by water wash of the same volume .
;2~ The reaction mix is then dried under vacuum. The reaction mixture is then treated with an oil bleaching agent and filtered. The bulk of the unreacted methyl esters are removed by distillation at 374F (190C) to 482F (250C) under approximately 5 mm Hg of vacuum.
3 0 The sucrose polyester i8 then deodorized in a stainless steel batch deodorizer or other suitable device at 374F
(190C) to 482F (250C) under a vacuum of about 5 mm Hg with steam sparging. Deodorization is continued until the . methyl ester content is below 200 ppm. The deodorizer 3~ contents are then cooled to 149F (65C) while using inert ~` :
'd ~2~67;~
gas sparging. The sucrose polyester is stored in clean stainless steel drums.
This produces a sucrose polyester product hav~ng the fo!lowing proper1ies:
FAC: C12 0~6 C14 o%
C16 13 . 2 18 42 . 8%
C18-1 40. 1%
C18-2 3.9g6 C18-3 o~6 C20 o%
C22 0%
SFC: 50F (10C): 72.9%
70F (21C~: 59.3%
80F (27C): 45.3%
92F (33C~: 22.99 105F (41C): 9.296 The product's Iodine Value is 41.3.
B. Second sucrose polyester, made by post-hydrogenation after transesterification:
Twenty-six pounds of a sucrose polyester made by transesterifying sucrose with soy-based methyl esters having an Iodine Value of about 107 is placed into a stainless steel reaction vessel. The reaction vessel is sparged with nitrogen at atmospheric pressure and heated to a temperature of 360F
2j (182C) over a period of 85 minutes. Next, 60 g. of a slurry made with 13 . 2 g . nickel metal catalyst and 46 . 8 g . of a melted coconut oil hardstock is added to the polyester. Then hydrogen is introduced into the reaction vessel at atmospheric pressure. The temperature is raised to 400F (204C), and 3 then the hydrogenation reaction is continued at this temperature for 6 hours and 30 minutes until the Refractive Index of the product is 46 . 3 . After the reaction is completed, the hydrogen is shut off and the vessel is sparged with nitrogen gas, and the reaction mixture is quickly cooled 3~ to 200F ~93C) and then filtered.
6~
The post-hydrogenated sucrose polyester product has the following fatty acid composition and Solid Fat Content:
FAC: C12 0 . 3%
C14 o%
C 16 11 . 9 C18 42.9 C1~ 4.9g6 C18-2 o%
C18-3 o%
~::22 0%
SFC: 50F ~10C): greater than 85%
70F ( 21C):
80F (27C):
92F ~33C): " " "
105P (41C): " " "
15 The Solid Fat Content of the sucrose polyester is too solid for measurement at all temperature~. The product's Refractive Index is 46.3 and its Iodlne Value is 38.6.
The first sucrose polyester, made by transesterification alone, has an Iodine Value of ~1. 3 and the second sucrose 20 polyester, made by post-hydrogenation fo~owing transesteri-fication, has an lodine Value of 46 . 3 . This is true even though the polyesters were synthesized from soy-based methyl esters having Iodine Values of about 40 and about 107, respecffvely. While the Iodine Values for the two sucrose 25 polyester products are similar, the Solid Fat Content cur~es of the polyesters are very different~
Claims (10)
1. A process for post-hydrogenating sucrose polyesters comprising contacting sucrose polyesters having at least four fatty ester groups, wherein at least one of said fatty acid ester groups is unsaturated, with hydrogen gas in the presence of a catalytically effective amount of hydrogenation catalyst, at a temperature of from about 250°F. (121°C.) to about 450°F. (232°C.) to hydrogenate the unsaturated fatty acids of the sucrose polyesters.
2. A process according to Claim 1 wherein the temperature is from about 340°F. (171°C.) to about 410°F. (210°C.).
3. A process according to Claim 2 wherein the temperature is from about 365°F. (185°C.) to about 405°F. (207°C.).
4. A process according to Claim 1 wherein the amount of catalyst is from about 0.01% to about 0.5% by weight of the sucrose polyester.
5. A process according to Claim 1 wherein the catalyst is nickel metal.
6. A process according to Claim 1 wherein the hydrogen is under a pressure of at least about 20 psig.
7. A process according to Claim 6 wherein the pressure is at least about 40 psig.
8. A process according to Claim 7 wherein the pressure is at least about 45 psig.
9. The product of the process of Claim 1 having an Iodine Value of from 38.6 to 62.2.
10. The product of the process of Claim 6 having an Iodine Value of from 38.6 to 62.2.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/947,062 US4806632A (en) | 1986-12-29 | 1986-12-29 | Process for the post-hydrogenation of sucrose polyesters |
US947,062 | 1986-12-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1296720C true CA1296720C (en) | 1992-03-03 |
Family
ID=25485453
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000554673A Expired - Lifetime CA1296720C (en) | 1986-12-29 | 1987-12-17 | Process for the post-hydrogenation of sucrose polyesters |
Country Status (8)
Country | Link |
---|---|
US (1) | US4806632A (en) |
EP (1) | EP0272759B1 (en) |
JP (1) | JP2510642B2 (en) |
AT (1) | ATE101614T1 (en) |
AU (1) | AU607956B2 (en) |
CA (1) | CA1296720C (en) |
DE (1) | DE3789098T2 (en) |
DK (1) | DK690787A (en) |
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US5498708A (en) * | 1989-07-18 | 1996-03-12 | Montefiore Medical Center | Method of synthesizing polyesters |
US5194281A (en) * | 1989-10-16 | 1993-03-16 | The Procter & Gamble Company | Polyol fatty acid polyesters with reduced trans double bond levels and process for making |
TR25051A (en) * | 1989-10-16 | 1992-11-01 | Procter & Gamble | ADVANCED POLIOL OILY ACID POLIESTERS. |
CA2027419C (en) * | 1989-10-16 | 1997-12-16 | Robert W. Johnston | Polyol fatty acid polyesters |
US5596085A (en) * | 1995-04-11 | 1997-01-21 | Kraft Foods, Inc. | Method for preparing polyol fatty acid polyesters by transesterification |
WO1997042826A1 (en) * | 1996-05-14 | 1997-11-20 | Mlp Operating Company | Refrigerated yeast-raised pizza dough |
US5945529A (en) * | 1996-07-19 | 1999-08-31 | The Procter & Gamble Company | Synthesis of polyol fatty acid polyesters using column with inert gas stripping |
US5767257A (en) * | 1996-07-19 | 1998-06-16 | The Procter & Gamble Company | Methods for producing polyol fatty acid polyesters using atmospheric or superatmospheric pressure |
US6465642B1 (en) | 1997-02-07 | 2002-10-15 | The Procter & Gamble Company | Lower alkyl ester recycling in polyol fatty acid polyester synthesis |
DE69827330T2 (en) * | 1997-08-22 | 2006-02-02 | Unilever N.V. | Stanol ester-containing composition |
US6965043B1 (en) | 1997-11-10 | 2005-11-15 | Procter + Gamble Co. | Process for making high purity fatty acid lower alkyl esters |
US20030191274A1 (en) * | 2001-10-10 | 2003-10-09 | Kurth Thomas M. | Oxylated vegetable-based polyol having increased functionality and urethane material formed using the polyol |
US20020058774A1 (en) | 2000-09-06 | 2002-05-16 | Kurth Thomas M. | Transesterified polyol having selectable and increased functionality and urethane material products formed using the polyol |
US7063877B2 (en) | 1998-09-17 | 2006-06-20 | Urethane Soy Systems Company, Inc. | Bio-based carpet material |
US6180686B1 (en) * | 1998-09-17 | 2001-01-30 | Thomas M. Kurth | Cellular plastic material |
US6979477B2 (en) | 2000-09-06 | 2005-12-27 | Urethane Soy Systems Company | Vegetable oil-based coating and method for application |
US7595094B2 (en) | 1998-09-17 | 2009-09-29 | Urethane Soy Systems, Co. | Vegetable oil-based coating and method for application |
US6962636B2 (en) * | 1998-09-17 | 2005-11-08 | Urethane Soy Systems Company, Inc. | Method of producing a bio-based carpet material |
CN1183124C (en) | 1999-10-15 | 2005-01-05 | 丹尼斯科卡尔特美国公司 | Method for direct esterification of sorbitol with fatty acids |
WO2002060975A1 (en) | 2001-01-31 | 2002-08-08 | The Procter & Gamble Company | Synthesis of polyol medium fatty acid polyesters |
EP1856023A4 (en) | 2005-03-03 | 2010-08-04 | South Dakota Soybean Processor | Novel polyols derived from a vegetable oil using an oxidation process |
US11840670B2 (en) * | 2020-12-22 | 2023-12-12 | Applied Technology Limited Partnership | Hydrogenation of oleochemical derivatives and systems |
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US2013034A (en) * | 1932-06-22 | 1935-09-03 | Niacet Chemicals Corp | Sugar acylation |
US2831854A (en) * | 1955-05-24 | 1958-04-22 | Procter & Gamble | Method for preparing fatty esters of non-reducing oligosaccharides in the presence of an amide |
US2812324A (en) * | 1955-06-10 | 1957-11-05 | Procter & Gamble | Method for preparing fatty esters of non-reducing oligosaccharides in the presence of sulfoxides |
NL111638C (en) * | 1955-12-12 | |||
US2831855A (en) * | 1955-12-15 | 1958-04-22 | Procter & Gamble | Method for preparing fatty esters of non-reducing oligosaccharides in the presence of pyridine |
US2831856A (en) * | 1955-12-15 | 1958-04-22 | Procter & Gamble | Method for preparing fatty esters of non-reducing oligosaccharides in the presence of an amide |
US3021324A (en) * | 1958-01-28 | 1962-02-13 | Drew Chem Corp | Preparation of sugar esters |
US2948717A (en) * | 1959-01-14 | 1960-08-09 | Drew & Co Inc E F | Sugar ester preparation and purification |
US3054789A (en) * | 1959-02-06 | 1962-09-18 | Ledoga Spa | Process for the preparation of pure sucrose esters |
DE1200276B (en) * | 1959-10-08 | 1965-09-09 | Bayer Ag | Process for the preparation of carboxylic acid esters of non-reducing sugars |
US3096324A (en) * | 1960-08-24 | 1963-07-02 | Eastman Kodak Co | Process for manufacturing sugar esters |
US3248381A (en) * | 1961-11-21 | 1966-04-26 | Ledoga Spa | Process for the preparation of watersoluble and water-insoluble sucrose esters and products obtained thereby |
US3349081A (en) * | 1963-06-26 | 1967-10-24 | Ledoga Spa | Process for preparing sucrose esters of high molecular weight fatty acids |
US3353966A (en) * | 1964-03-27 | 1967-11-21 | Procter & Gamble | Salad oils and method of making them |
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DE1643795A1 (en) * | 1967-08-04 | 1971-07-01 | Cassella Farbwerke Mainkur Ag | Process for the production of sugar esters |
US3600186A (en) * | 1968-04-23 | 1971-08-17 | Procter & Gamble | Low calorie fat-containing food compositions |
US3886219A (en) * | 1969-01-14 | 1975-05-27 | Huels Chemische Werke Ag | Process for preparing saturated alcohols |
US3714144A (en) * | 1969-05-29 | 1973-01-30 | Us Agriculture | Process for the production of sucrose esters of fatty acids |
BE757846A (en) * | 1969-10-23 | 1971-04-01 | Dai Ichi Kogyo Seiyaku Cy Ltd | PROCESS FOR SYNTHESIS OF SACCHAROSE ESTERS OF FATTY ACIDS |
US3775503A (en) * | 1970-07-06 | 1973-11-27 | Sun Research Development | Branched hydrocarbons in the c16-c40 range having maximally crowded geminal methyl groups |
GB1399053A (en) * | 1973-03-16 | 1975-06-25 | Tate & Lyle Ltd | Process for the production of surface active agents comprising sucrose esters |
US3954976A (en) * | 1973-12-14 | 1976-05-04 | The Procter & Gamble Company | Pharmaceutical compositions for inhibiting absorption of cholesterol |
US3963699A (en) * | 1974-01-10 | 1976-06-15 | The Procter & Gamble Company | Synthesis of higher polyol fatty acid polyesters |
US4034083A (en) * | 1975-11-03 | 1977-07-05 | The Procter & Gamble Company | Compositions for inhibiting absorption of cholesterol |
US4005196A (en) * | 1976-02-12 | 1977-01-25 | The Procter & Gamble Company | Vitaminized compositions for treating hypercholesterolemia |
US4005195A (en) * | 1976-02-12 | 1977-01-25 | The Procter & Gamble Company | Compositions for treating hypercholesterolemia |
US4241054A (en) * | 1978-12-08 | 1980-12-23 | The Procter & Gamble Company | Detoxifying lipophilic toxins |
US4368213A (en) * | 1981-06-23 | 1983-01-11 | The Procter & Gamble Company | Emulsion concentrate for palatable polyester beverage |
US4461782A (en) * | 1982-02-16 | 1984-07-24 | The Procter & Gamble Company | Low calorie baked products |
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 |
JPS6115893A (en) * | 1984-06-29 | 1986-01-23 | Dai Ichi Kogyo Seiyaku Co Ltd | Purification of sucrose fatty acid ester |
US4705690A (en) * | 1985-11-18 | 1987-11-10 | The Procter & Gamble Co. | Weighting oil substitutes |
-
1986
- 1986-12-29 US US06/947,062 patent/US4806632A/en not_active Expired - Lifetime
-
1987
- 1987-12-17 CA CA000554673A patent/CA1296720C/en not_active Expired - Lifetime
- 1987-12-18 DE DE3789098T patent/DE3789098T2/en not_active Expired - Lifetime
- 1987-12-18 AT AT87202576T patent/ATE101614T1/en not_active IP Right Cessation
- 1987-12-18 EP EP87202576A patent/EP0272759B1/en not_active Expired - Lifetime
- 1987-12-24 AU AU83070/87A patent/AU607956B2/en not_active Ceased
- 1987-12-28 JP JP62336781A patent/JP2510642B2/en not_active Expired - Lifetime
- 1987-12-29 DK DK690787A patent/DK690787A/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
EP0272759B1 (en) | 1994-02-16 |
JP2510642B2 (en) | 1996-06-26 |
JPS63239293A (en) | 1988-10-05 |
EP0272759A3 (en) | 1990-06-06 |
US4806632A (en) | 1989-02-21 |
AU8307087A (en) | 1988-06-30 |
AU607956B2 (en) | 1991-03-21 |
DE3789098T2 (en) | 1994-08-11 |
DE3789098D1 (en) | 1994-03-24 |
ATE101614T1 (en) | 1994-03-15 |
DK690787D0 (en) | 1987-12-29 |
EP0272759A2 (en) | 1988-06-29 |
DK690787A (en) | 1988-06-30 |
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