US2810733A - Peracid epoxidation of fatty acid esters - Google Patents
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
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- This application pertains to a novel type of epoxidized triglycerides and more particularly to a method of partially epoxidizing triglycerides such as occur in unsaturated oils.
- Such partially epoxidized oils furthermore require in their manufacture, reduced amounts of epoxidizing agent, such as peracid or hydrogen peroxide, because obviously partial epoxidation of a given quantity of a given oil requires less reactants than complete epoxidation.
- epoxidizing agent such as peracid or hydrogen peroxide
- partially epoxidized oils prepared in accordance with this invention have been found to be not only better in performance but also cheaper to manufacture than fully epoxidized oils.
- these novel partially epoxidized oils have various useful properties of interest in the manufacture of intermediate detergents, lubricant additives, etc.
- the amount of peracid used is calculated on the amount of ethylenic unsaturation present in thet oil. That is to say, that ordinarily at least 1 mole of peracid or hydrogen peroxide is employed for each double bond in each mole of the unsaturated fatty acid chains in the oil.
- suflicient peracid is available to transform substantially all double bonds present into the corresponding epoxy groups.
- Such epoxidation reactions may be carried out with prepared organic peracids such as peracetic acid, performic acid, perbutyric acid and others.
- reactions may also be carried out using the so-called in situ method, wherein peracid in formed during the course ofthe reaction in the reaction medium from calculated quantities of hydrogen peroxide and the corresponding organic acid.
- in situ methods wherein peracid in formed during the course ofthe reaction in the reaction medium from calculated quantities of hydrogen peroxide and the corresponding organic acid.
- epoxida- Patented Oct. 22, 1957 tion reactions using prepared peracids or peracids formed in situ, may be carried out with or without a solvent present in the reaction mixture, which solvents may be benzene, hexane or other inert solvents.
- the present invention pertains to a method resulting in a controlled and defined partial epoxidation.
- epoxidation is carried out in such a manner that substantially all of the ethylenic unsaturation in those chains of the oil that are mono-unsaturated fatty acid chains is epoxidized but only one double bond epoxidized in those chains that are poly-unsaturated fatty acid chains.
- This controlled epoxidation method and the resulting products are, therefore, distinct and different from methods which arbitrarily restrict degree epoxidation and produce a random distribution of epoxy groups and double bonds. Taking into account total unsaturation; that is total number of double bonds in a naturally occurring oil and taking into account the approximate per cent fatty acid composition of such oils, it becomes posible to calculate the amount of peracid required to produce a defined degree of partial epoxidation.
- the amount of peracid required for such partial epoxidation will, of course, vary with the unsaturated oil to be treated because the composition of such oils; that is, their content of mono-ethylenic unsaturated higher fatty acid, di-ethylenic unstaurated higher fatty acid and poly-ethylenic unsaturated higher fatty acid varies.
- Corn oil for instance, contains essentially only mono-and di-unsaturated acids aside from some saturated acids.
- Linseed oil on the other hand, contains mono-, di-, and triethylenic unsaturated fatty acids, together with some saturated acids.
- this composition of the oil, as well as the respective percentages of mono-, di-, and poly-ethylenic unsaturated acids have to be taken into account when calculating the amount of peracid required for defined partial epoxidation.
- the reaction has to be carried out in such a manner that substantially all double bonds in the mono-unsaturated fatty acids present are epoxidized and, therefore, disappear.
- the multiple double bonds in the double unsaturated and polyunsaturated fatty acids present substantially one double bond only in each fatty acid chain should be epoxidized. Therefore, the proper amount of peracid is calculated in every case so as to epoxidize all of the mono-unsaturated radicals and one double bond of the poly-unsaturates. Knowing the composition of a given natural oil, calculation of the proper amount of peracid, sulficient to give the desired percentage of reacted double bonds, is possible. Per cent double bonds reacted can also be expressed and checked by calculating the iodine number to be expected for a certain degree of partial epoxidation.
- the proper amount of peracid required for partial epoxidation in accordance with this invention is calculated on a molar basis and corresponds to 1-1.3 mole of peracid for each double bond in each mole of monounsaturated esterified acid and 1-1.3 mole of peroxide for one double bond in each mole of polyunsaturated esterified acid.
- An example for calculating the required amount of peracid may be given for the case of partial epoxidation of linseed oil.
- a typical commercial linseed oil will contain about 19% oleic acid containing 1 double bond in the chain, 24% linoleic acid containing 2 double bonds in the chain and 47% linolenic acid containing 3 double bonds in the chain.
- the equivalent of the total number of double bonds in a single average fatty acid' chain of the triglyceride can then be arrived at as follows:
- percent epoxidation reaction indicates how far the controlled partial epoxidation' has been carried. Variations.
- Example 3 1000 g. of safilower oil, equivalent to 5.5 mole ofv ethylenic unsaturation, of the same composition as used in Example 1, and 200 g. of benzene were put into the.
- reaction fiask To this were added 1.67 mole acetic acid (100 g. glacial acetic) and 6.7 g. of 50% sulfuric acid. Then 3.47 mole H202 (236.0 g. of 50% H202) were added over a period of 1 /2 hours while maintaining the temperature of the mixture between 40 and 54 C. The reaction was continued for a total reaction time of 13 hours maintaining the temperature at 60 to 65 C. After washing, the product was analyzed and found to contain:
- Example 4 1000 g. of safilower oil, equivalent to 5.5 mole of ethylenic unsaturation, of the same composition as in Example 1, 1.67 mole acetic acid (100.0 g. glacial acetic) and 14.8 g. of 50% sulfuric acid were put in the reaction flask. Then 3.97 mole H202 (270.0 g. of 50% H202) were added over a period of 1 hour while keeping the temperature between 53 and 65 C. Total reaction time was 9 hours at a temperature of 60 to 65 C. After washing, the product was analyzed and found to contain:
- Example 5 500 g. of safilower oil, corresponding to 2.75 mole of ethylenic unsaturation, of the same composition as used in Example 1, and 21.5 g. of anhydrous sodium acetate were placed in the reaction flask. Then 1.73 mole of perbutyric acid (430 g. of 42% perbutyric acid) were added over a period of 2 hours while maintaining the temperature at to C. The reaction was continued for any additional 2 hours at to C. to give a total reaction time of 4 hours. After washing, the product was analyzed and found to contain:
- Example 10 Percent epoxy Iodine number
- Percent epoxy Iodine number Yield percent 96 SwOOQO I-PWN .of 1 to 4 hours.
- the temperature of reaction is preferably low, from about 15 C. to 35 C. and the reaction time, on the order Where peroxide and lower aliphatic acid are employed, 'the'temperature of reaction is somewhat higher and the duration of 'the reaction longer.
- the method of ,epoxidizing unsaturated fatty acid esters contained in naturally occurring unsaturated oils which comprises. heating. said oilsunder epoxidizing conditions-with: a lower aliphatic peracid, the amount of which correspondsto Lto 1.? moles of peracid foreach double. bond in each moleof mono unsaturated esterified acidplus .1 to l.3 moles ofilowenaliphatic peracid for one. double. bond only of each mole of polymnsaturated '2.
- unsaturated fatty acid esters contained in naturally occurring unsaturated oils which comprises heating said oils under epoxidizing conditions with hydrogen peroxide; a lower aliphatic acid and sulfuric acid, the amount of the hydrogen peroxide corresponding to 1 to 1.3 moles, and the amount of lower aliphatic acid corresponding to about 0.25. to l mole'for' each double bond in each mole of mono-unsaturated esterified acid plus 1" to 1.3-rnoles of hydrogen peroxide, and theamountof sulfuric acid corresponding to about 0.5 to 5% of the total weight of lower aliphatic acid and hydrogen peroxide for one double bond only of each mole of poly-unsaturated esterified acid. 7
- the method of epoxidizing linseed oil which comprises heating the linseed oil under epoxidizing conditions with a lower aliphatic pefacid, the amount of which corresponds to about 43.3% of that required completely to epoxidize the oil. 5
- esters contained in naturally occurring'unsatiir'a'ted oils which comprises heating said oils under epoxidi zing' coii V
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Description
United States Patent i PERACID EPOXIDATION OF FATTY ACID ESTERS Frank P. Greenspan, Buffalo, N. Y., assignon'by'mesne assignments, to Food Machinery and Chemical Corporation, San Jose, Calif., a corporation of Delaware No Drawing. Application March 23, 1954, Serial No. 418,208
Claims. or. 260-3485) This application pertains to a novel type of epoxidized triglycerides and more particularly to a method of partially epoxidizing triglycerides such as occur in unsaturated oils.
Methods for epoxidizing unsaturated oils by means of an organic peracid have been described previously. In these methods the ethylenic unsaturated material is treated with a quantity of organic peracid suflicient to epoxidize substantially all double bonds present in the material. In other words, previously published epoxidation methods, starting out with an oil possessing a certain degree of ethylenic unsaturation, were performed in such a way as to result in a fully epoxidized oil possessing essentially no ethylenic unsaturation. Such fully epoxidized oils were found to be suitable as plasticizers for polymeric substances, such as polyvinyl chloride, either as such or in form of their derivatives.
Because unepoxidized oils, possessing original unsaturation, are not compatible with plastics which it is desired to plasticize, previous epoxidation methods all aimed at complete epoxidation so as to leave only a marginal amount of unsaturation. I have now found that under certain conditions, oils which have not been fully epoxidized are not only compatible with plastics but actually have better performance characteristics than fully epoxidized oils. However, such partially epoxidized oils cannot be produced by arbitrarily restricting the extent of epoxidation, but have to be produced by a strictly controlled epoxidation process. Such partially epoxidized oils furthermore require in their manufacture, reduced amounts of epoxidizing agent, such as peracid or hydrogen peroxide, because obviously partial epoxidation of a given quantity of a given oil requires less reactants than complete epoxidation. Thus partially epoxidized oils prepared in accordance with this invention have been found to be not only better in performance but also cheaper to manufacture than fully epoxidized oils. Moreover, these novel partially epoxidized oils have various useful properties of interest in the manufacture of intermediate detergents, lubricant additives, etc.
I have now found that such partially epoxidized oils can be produced by a critically modified epoxidation process. In epoxidation methods designed. to produce fully epoxidized oils, the amount of peracid used is calculated on the amount of ethylenic unsaturation present in thet oil. That is to say, that ordinarily at least 1 mole of peracid or hydrogen peroxide is employed for each double bond in each mole of the unsaturated fatty acid chains in the oil. Thus suflicient peracid is available to transform substantially all double bonds present into the corresponding epoxy groups. Such epoxidation reactions may be carried out with prepared organic peracids such as peracetic acid, performic acid, perbutyric acid and others. These reactions may also be carried out using the so-called in situ method, wherein peracid in formed during the course ofthe reaction in the reaction medium from calculated quantities of hydrogen peroxide and the corresponding organic acid. Furthermore, such epoxida- Patented Oct. 22, 1957 tion reactions, using prepared peracids or peracids formed in situ, may be carried out with or without a solvent present in the reaction mixture, which solvents may be benzene, hexane or other inert solvents.
In contrast to epoxidation methods resulting in complete epoxidation, the present invention pertains to a method resulting in a controlled and defined partial epoxidation. Here epoxidation is carried out in such a manner that substantially all of the ethylenic unsaturation in those chains of the oil that are mono-unsaturated fatty acid chains is epoxidized but only one double bond epoxidized in those chains that are poly-unsaturated fatty acid chains. There results a defined epoxy compound con taining saturated fatty acid chains, saturated epoxy fatty acid chains and unsaturated epoxy fatty acid chains. This controlled epoxidation method and the resulting products are, therefore, distinct and different from methods which arbitrarily restrict degree epoxidation and produce a random distribution of epoxy groups and double bonds. Taking into account total unsaturation; that is total number of double bonds in a naturally occurring oil and taking into account the approximate per cent fatty acid composition of such oils, it becomes posible to calculate the amount of peracid required to produce a defined degree of partial epoxidation.
The amount of peracid required for such partial epoxidation will, of course, vary with the unsaturated oil to be treated because the composition of such oils; that is, their content of mono-ethylenic unsaturated higher fatty acid, di-ethylenic unstaurated higher fatty acid and poly-ethylenic unsaturated higher fatty acid varies. Corn oil, for instance, contains essentially only mono-and di-unsaturated acids aside from some saturated acids. Linseed oil, on the other hand, contains mono-, di-, and triethylenic unsaturated fatty acids, together with some saturated acids. As pointed out above, this composition of the oil, as well as the respective percentages of mono-, di-, and poly-ethylenic unsaturated acids have to be taken into account when calculating the amount of peracid required for defined partial epoxidation.
In any case of partial epoxidation of a naturally occurring oil, the reaction has to be carried out in such a manner that substantially all double bonds in the mono-unsaturated fatty acids present are epoxidized and, therefore, disappear. However, the multiple double bonds in the double unsaturated and polyunsaturated fatty acids present, substantially one double bond only in each fatty acid chain should be epoxidized. Therefore, the proper amount of peracid is calculated in every case so as to epoxidize all of the mono-unsaturated radicals and one double bond of the poly-unsaturates. Knowing the composition of a given natural oil, calculation of the proper amount of peracid, sulficient to give the desired percentage of reacted double bonds, is possible. Per cent double bonds reacted can also be expressed and checked by calculating the iodine number to be expected for a certain degree of partial epoxidation.
The proper amount of peracid required for partial epoxidation in accordance with this invention is calculated on a molar basis and corresponds to 1-1.3 mole of peracid for each double bond in each mole of monounsaturated esterified acid and 1-1.3 mole of peroxide for one double bond in each mole of polyunsaturated esterified acid.
An example for calculating the required amount of peracid may be given for the case of partial epoxidation of linseed oil. A typical commercial linseed oil will contain about 19% oleic acid containing 1 double bond in the chain, 24% linoleic acid containing 2 double bonds in the chain and 47% linolenic acid containing 3 double bonds in the chain. The equivalent of the total number of double bonds in a single average fatty acid' chain of the triglyceride can then be arrived at as follows:
19.0% oleic acid with 1 double bondequivalent to-0.'1901 24.1% linoleic acid with '2 double 7 bonds equivalent;to-0.482 47.4% linolenic acid with 3 double V a 7 bonds equivalent to 1.422 Total number of double bonds equivalent to 2.094
In the controlled :partial' epoxidation of linseed oil all of the double bonds of the oleic acid chains, ne of the 2 double bonds'in the linoleic acid chains and one-of the 3 double bonds in the linolenic .acidchains are. to be epoxidized. Therefore, the equivalent to .the number of double bonds to'be reacted can be represented astollows:
19.0% oleic acid with 1 double bond equivalent to 0.190
24.1% linoleic acid with 1 double bond equivalent-$0.241 47.4% 'linolenic acid with 1 double bond -equivalent1to 0.474 a Total number of double bonds to be reacted equivalent to 0.905
The percent double bondsto betheoretically"reacted-in linseed oil is then On this basis the theoretical amount of epoxidation rea gent required can be calculated. 1000 gram linseed oil with an iodine number of 171 corresponds to- 6.74 mole of ethylenic unsaturation and to epoxidize 43.37 th'ere-' of requires 43.3% of 6.74 mole or 2.91 mole of reagent.
The'percent'double bonds to be reacted can be cal-' culated in the same way for other oils, whereby the fol"- lowing percent figures are obtained:
Percent Corn oil 68.0 Menhaden oil 33.2
Safllower oil v 55.0
Soybean oil 57.7
t This sample calculation will sufiice to indicate how the proper amount of peracid is to be calculated for different natural oils and for different peracids. The following examples, although not restrictive, are intended to show partial epoxidation procedures for different naturally occurring unsaturated oils, different 'peracids as epoxidizing agents and different epoxidation techniques. Sample techniques are described for the use of prepared peracids, for use of in situ techniques and,'furthermore, with and without the useof a solvent. It should be pointed out that in allcases, substantially quantitative yields of the desired partially epoxidized oil were obtained in relatively' very short reaction times and in a highly economical way. The various oils were subjected to controlled partial epoxidation; that is, epoxidation was carried up to In the following Table 1, percent epoxidation reaction is given.
av percentage lower than. 100% epoxidation.
for'the different oils inthe different examples. The term,
percent epoxidation reaction" indicates how far the controlled partial epoxidation' has been carried. Variations.
in the figures given for percent epoxidation are essentially due to the fact that specific oil sampleswill frequently show a composition different from the average cOmposi: tion published for such oils. Moreover, as in organic reactions generally, a. certain excess o f'epoxidizing rea gent is used in carrying out the reaction to take care of unavoidable losses and experimental errors. In general, the amount of epoxidizing agent on a mole basis i s 1 to 1.3 moles per mole of desired double bond to be'reacted upon.
Before giving the actual experimental data and figures, the general procedure will be described here. All the following experimental exarnples were carried out by Weighing the proper amount of the-oil to be treated into a three-neck flask equipped'with a condenser, thermometer and stirrer. To. the oil was then added the proper amount of solvent, if a solvent was used. Where prepared peracids were employed, a quantity of a buffer, such as anhydrous sodium acetate, was then added in an amount sufiicient to neutralize the mineral acid catalyst used in preparing the. peracid and. present in the product as used. This addition wasca'rried. but slowly over a period of time while maintaining temperature between'approxi-' mately 15 and 35 C. For in situ operation, no anhydrous sodium acet'ate need be used and the calculated amount of" hydrogen peroxide-and concentrated organic acid. is added. In all'the experiments, the temperature was kept near theupper. limit of the'temperature range after. all reagents have been added to the reaction flaskJ In each experiment the composition of the oilis given in termsof the constituent fatty acid.
After termination of the reaction, the product was washed with warm water to remove residual free acid, and
acid: removal, where necessary, promoted by filtering through-anhydrous sodium carbonate. Finally, the product was. dried with anhydrous magnesium sulfate and.
filtered.
* Example 1' SAFFIJOWER =0IL Oil composition:
'Oleic acid percent 16.4
'Linoleic' acid do 77.7" 'Linolenic'acid do 0.3 Saturated acids do 6.6-
Iodine number 7.00 g. of safiiower oil, equivalent to 3.85 moles of ethylenic unsaturation, were reacted .in presence of 23 1 g.'of.anhydrous sodium acetate with 2.41 mole peracetic acid (459.0 g. peracetic acid 40%). This was added 7 over a period ofl hour and 50 minutes at 15 to 20 C.
and temperature then maintained at 20 to'30 C. for-a total reaction time of 3 /2 hours. product was analyzed-and found to contain:
Percent epoxy Iodine number 1 700g. of safilower oil, equivalent"to 3185' moles'of ethylenic unsaturation of the 's'amecompositionas used} in Example 1, were reacted in presence'of 23.1 g. of an hydrous sodium acetate and'of 700 g. of benzenewitn 2.41 mole peracetic acid' (459.0 g. peracetic acid 40%)., This was added over a period of 1' hour and 50 minutes at 15.10.20.- C. and temperature then maintained at20 to 30C. for atotalreaction time of 3 /2 hours. After wash-' ing, the product was analyzed and found to contain:
Percent epoxy Iodine num er mumwcoiziurenm After washing, the
ExampIe Z i m Example 3 1000 g. of safilower oil, equivalent to 5.5 mole ofv ethylenic unsaturation, of the same composition as used in Example 1, and 200 g. of benzene were put into the.
reaction fiask. To this were added 1.67 mole acetic acid (100 g. glacial acetic) and 6.7 g. of 50% sulfuric acid. Then 3.47 mole H202 (236.0 g. of 50% H202) were added over a period of 1 /2 hours while maintaining the temperature of the mixture between 40 and 54 C. The reaction was continued for a total reaction time of 13 hours maintaining the temperature at 60 to 65 C. After washing, the product was analyzed and found to contain:
Percent oxirane oxygen 4.1 Iodine number 67 Example 4 1000 g. of safilower oil, equivalent to 5.5 mole of ethylenic unsaturation, of the same composition as in Example 1, 1.67 mole acetic acid (100.0 g. glacial acetic) and 14.8 g. of 50% sulfuric acid were put in the reaction flask. Then 3.97 mole H202 (270.0 g. of 50% H202) were added over a period of 1 hour while keeping the temperature between 53 and 65 C. Total reaction time was 9 hours at a temperature of 60 to 65 C. After washing, the product was analyzed and found to contain:
Percent epoxy 4.3
Iodine number Example 5 500 g. of safilower oil, corresponding to 2.75 mole of ethylenic unsaturation, of the same composition as used in Example 1, and 21.5 g. of anhydrous sodium acetate were placed in the reaction flask. Then 1.73 mole of perbutyric acid (430 g. of 42% perbutyric acid) were added over a period of 2 hours while maintaining the temperature at to C. The reaction was continued for any additional 2 hours at to C. to give a total reaction time of 4 hours. After washing, the product was analyzed and found to contain:
Percent epoxy 4 4 Iodine number 56 Example 6 CORN OIL O11 composition:
Oleic a id perc nt 46.3 Linoleic acid do 41.7 Saturated acids d0 12.0 Iodine number 119 1500 g. of corn oil, equivalent to 7.03 moles of ethylenic unsaturation, were reacted in presence of 55.0 g. of anhydrous sodium acetate with 5.27 mole of peracetic acid (1005.0 g. peracetic acid This was added over a period of 2 hours and minutes at 15 to 20 C. and the temperature was then permitted to rise slowly over a total reaction time of 4 hours and 15 minutes to C. After washing, the product Was analyzed and found to contain:
Percent epoxy 5.3
Iodine number--- 24 Example 7 LINSEED OIL Oil composition:
Oleic acid percent 19.0 Linoleic acid do 24.1 Linolenic acid do 47.4 Saturated acids do 9.5 Iodine number 171 1000 g. of linseed oil, equivalent to 6.74 moles of ethylenic unsaturation, were reacted in presence of 32.0 of anhydrous sodium acetate with 3.34 mole peracetic acid (635.3 g. peracetic acid 40%). This was added over a period of 1 hour and 10 minutes at a temperature of 17 to 20 C. and the temperature then maintained at 17 to 33 C. for a total reaction time of 3 hours and 1 5 minutes.- After washing, the product was analyzed and 600 g. of manhaden oil, equivalent to 4.12 moles of ethylenic unsaturation, were reacted in presence of 14.3 g.
of anhydrous sodium acetate with 1.50 mole of peracetic acid (285.0 g. peracetic acid 40%). This was added over'a period of 1 hour and 5 minutes at about 20 C.
and the temperature then maintained at 24 to 32 C. for. a total reaction time of 3 hours and 45 minutes. After washing, the product was analyzed and found to contain::
Percent epoxy 3.7 Iodine number 100 Example9 SOYBEAN OIL Oil composition: i Palmitoleic acid percent 0.4 Oleic a id d 29.7- Linoleic acid do 50.4 Linolenic acid do 6.5 Saturated acids do 13.0: Iodine number"; 135;
.600g..of soybean oil, equivalent to 3.19 moles bf ethylenic unsaturation, were reacted in presence of 18.3
g. of anhydrous sodium acetate with 1.92 mole of per-J;
acetic acid (365.0 g. peracetic acid 40%). This was added over a period of 1 hour and 10 minutes at 20 to 25 C. and temperature then maintained at 26 to 33 C,
After washing, the product was analyzed and found to contain:
for a total reaction time of 3 hours and 20 minutes.
Percent epoxy Iodine number Example 10 SAFFLOWER OIL 100g. of safllower oil, corresponding to 0.550 moleof ethylenic unsaturation, of the same composition as used in Example 1, and 0.165 mole of formic acid (8.46 g.
of formic acid) were placed in the reaction flask. Then 0.396 mole of H202 (27.0 g. 50% H202) were added over a 5 minute period at 26 C. and the tempera-f ture. then maintained between 26 and 35 C. foradditional 22 /2 hours. After washing, the product was analyzed and found to contain:
The over-all efiiciency of the method of this invention is further indicated by the very high and, in some cases, theoretical yield of partially epoxidized triglyceride obtained. These yields were: Example:
Percent epoxy Iodine number Yield percent 96 SwOOQO I-PWN .of 1 to 4 hours.
' esterified acid.
:From the foregoing 3 description and examples;
be seen that there is outlined a" method for obtaining stated'partially epoxidized ethylenic unsaturated higher fatty "ciiIs'inperi'ods' oftimeshorter than; required for complete" epoxidation." 'By limiting the amount of epoxidizing reagent to substantially that required to epoxidize the ethylenic unsaturatiorrin a mono-unsaturated chain,
' and to that required to epoxidize one. only of the ethylenic 7 acid,,suc-h as per'acetic acid, or may :he hydrogen peroxide and the lower-aliphatic acid in the presence of from about 0.5%..Jto 51% sulfuric acid.. Where the peracid .is employed, the temperature of reaction is preferably low, from about 15 C. to 35 C. and the reaction time, on the order Where peroxide and lower aliphatic acid are employed, 'the'temperature of reaction is somewhat higher and the duration of 'the reaction longer.
What is claimed is: J
'1. The method of ,epoxidizing unsaturated fatty acid esters contained in naturally occurring unsaturated oils which comprises. heating. said oilsunder epoxidizing conditions-with: a lower aliphatic peracid, the amount of which correspondsto Lto 1.? moles of peracid foreach double. bond in each moleof mono unsaturated esterified acidplus .1 to l.3 moles ofilowenaliphatic peracid for one. double. bond only of each mole of polymnsaturated '2. Themethod .of .epoxidizing. unsaturated fatty acid esters: contained in naturally occurring unsaturated oils which comprises heating said oils under epoxidizing conditions with hydrogen peroxide; a lower aliphatic acid and sulfuric acid, the amount of the hydrogen peroxide corresponding to 1 to 1.3 moles, and the amount of lower aliphatic acid corresponding to about 0.25. to l mole'for' each double bond in each mole of mono-unsaturated esterified acid plus 1" to 1.3-rnoles of hydrogen peroxide, and theamountof sulfuric acid corresponding to about 0.5 to 5% of the total weight of lower aliphatic acid and hydrogen peroxide for one double bond only of each mole of poly-unsaturated esterified acid. 7
'3.:The method of epoxidizing unsaturated fattyacid esters contained in naturally, occurring unsaturated oils whichcomprises heating said oils under epoxidizing conditions with peracetic acid, the amount of which corresponds to 1 to 1.3 moles of peracid for each double bond in each mole of mono-unsaturated esterified acid plus onlyof eachimole of poly-unsaturated esterifiedlacid.
1, to 1.3'moles of perac etic acid for one double bond 4. Themethod of epoxidizingunsaturated fatty ditionswithperfor'mic acid, the amount of whieneone;
sponds to l to 1.3 molesofperacid for each-double bond in each mole of mono-unsaturated esterified 'acidplus 1' to 1.3 moles ofperfortnic acid for one double bond'o'nly of each mole of'pol'y-unsaturated esterified acid.
5. The method of epoxidizing unsaturated fatty acid esters contained in naturally occurring unsaturated oils whichcomprises Qheating said oils under epoxidizing con= ditions with perbntyrie acid, the amount of which corre-' sponds to 1 to'1.3 moles of peracid for each double bond in each mole of mono-unsaturated esterified acid plus' 1 to l.3.moles ofperbutyric acid for one doublebond only of each mole oftpoly-unsaturated esterified acid.
6. The method of epoxidizing safflower oil which com- 7 corresponds to .about 33.2% of that required completely to epoxidize the oil.
9; Th'e method of epoxidizing soybean oil which com-- prises heating'the soybean oil under epoxidizing conditions with alower aliphatic per'acid, the amount of which corresponds to about 57.7% of that required completely to epoxidize the oil. V
10. The method of epoxidizing linseed oilwhich comprises heating the linseed oil under epoxidizing conditions with a lower aliphatic pefacid, the amount of which corresponds to about 43.3% of that required completely to epoxidize the oil. 5
References Cited in the file of this patent UNITED STATES PATENTS 2,312,535 Fieser "Mar. 2, 1943 2,485,160 Ni'ederhauser et a1 Oct. 18, 1949 2,569,502 Swern a a1. Oct. 2, 1951 OTHER REFERENCES Findley et aL: J. Am. Chem. Soc. 672412 (19 Ralston: Fatty Acids and Their Deriv., p. 414 (1948), John Wiley and Sons.
a esters contained in naturally occurring'unsatiir'a'ted oils which comprises heating said oils under epoxidi zing' coii V
Claims (1)
1. THE METHOD OF EPOXIDIZING UNSATURATED FATTY ACID ESTER CONTAINED IN NATURALLY OCCURING UNSATURATED OILS WHICH COMPRISES HEATING SAID OILS UNDER EPOXIDIZING CONDITIONS WITH A LOWER ALIPHATIC PERACID, THE AMOUNT OF WHICH CORRESPONDS TO 1 TO 1.3 MOLES OF PERACID FOR ACID DOUBLE BOND IN EACH MOLE OF MONO-UNSATURATED ESTERIFIED ACID PLUS 1 TO 1.3 MOLES OF LOWER ALIPHATIC PERACID FOR ONE DOUBLE HOND ONLY OF EACH MOLE OF POLY-UNSATURATED ESTERIFIED ACID.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US418208A US2810733A (en) | 1954-03-23 | 1954-03-23 | Peracid epoxidation of fatty acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US418208A US2810733A (en) | 1954-03-23 | 1954-03-23 | Peracid epoxidation of fatty acid esters |
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| Publication Number | Publication Date |
|---|---|
| US2810733A true US2810733A (en) | 1957-10-22 |
Family
ID=23657152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US418208A Expired - Lifetime US2810733A (en) | 1954-03-23 | 1954-03-23 | Peracid epoxidation of fatty acid esters |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2810733A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2972595A (en) * | 1957-12-17 | 1961-02-21 | Pfizer & Co C | Dialkyl tin epoxy-succinate stabilizers for polymers of polyvinyl chloride |
| US3008911A (en) * | 1958-09-30 | 1961-11-14 | Union Carbide Corp | Reactive poly(vinyl chloride) resinreactive plasticizer compositions |
| US3047415A (en) * | 1959-02-26 | 1962-07-31 | Swift & Co | Vinyl resin-epoxy fatty acid coating composition, method and article |
| US3055778A (en) * | 1960-03-23 | 1962-09-25 | Swift & Co | Method for applying a mixture of a vinyl halide polymer and an epoxidized triglyceride on a wire and the resulting article |
| US3141027A (en) * | 1959-03-12 | 1964-07-14 | Union Carbide Corp | Alkanediol bis |
| US3147285A (en) * | 1956-07-20 | 1964-09-01 | M & T Chemicals Inc | Epoxy organotin compounds |
| US3150153A (en) * | 1962-06-15 | 1964-09-22 | Gen Mills Inc | Stability of epoxidized oils by oxidation and naturalization |
| US3187019A (en) * | 1964-01-24 | 1965-06-01 | Abbott Lab | Brominated oils |
| US3207743A (en) * | 1963-08-16 | 1965-09-21 | Hercules Powder Co Ltd | Epoxidation of tall oil fatty acids and esters |
| US3328430A (en) * | 1964-11-16 | 1967-06-27 | Archer Daniels Midland Co | Epoxidation process |
| US20080103073A1 (en) * | 2006-10-31 | 2008-05-01 | Atanu Adhvaryu | Anti-friction anti-wear lubricant additive |
| WO2012038811A1 (en) | 2010-09-23 | 2012-03-29 | Council Of Scientific & Industrial Research | An improved process for the epoxidation of fatty acids, their esters and mixtures thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2312535A (en) * | 1940-07-23 | 1943-03-02 | Research Corp | Naphthoquinone oxides and method of preparing the same |
| US2485160A (en) * | 1948-10-23 | 1949-10-18 | Rohm & Haas | Process for the epoxidation of esters of oleic and linoleic acids |
| US2569502A (en) * | 1945-02-07 | 1951-10-02 | Swern Daniel | Epoxidized oils |
-
1954
- 1954-03-23 US US418208A patent/US2810733A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2312535A (en) * | 1940-07-23 | 1943-03-02 | Research Corp | Naphthoquinone oxides and method of preparing the same |
| US2569502A (en) * | 1945-02-07 | 1951-10-02 | Swern Daniel | Epoxidized oils |
| US2485160A (en) * | 1948-10-23 | 1949-10-18 | Rohm & Haas | Process for the epoxidation of esters of oleic and linoleic acids |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3147285A (en) * | 1956-07-20 | 1964-09-01 | M & T Chemicals Inc | Epoxy organotin compounds |
| US2972595A (en) * | 1957-12-17 | 1961-02-21 | Pfizer & Co C | Dialkyl tin epoxy-succinate stabilizers for polymers of polyvinyl chloride |
| US3008911A (en) * | 1958-09-30 | 1961-11-14 | Union Carbide Corp | Reactive poly(vinyl chloride) resinreactive plasticizer compositions |
| US3047415A (en) * | 1959-02-26 | 1962-07-31 | Swift & Co | Vinyl resin-epoxy fatty acid coating composition, method and article |
| US3141027A (en) * | 1959-03-12 | 1964-07-14 | Union Carbide Corp | Alkanediol bis |
| US3055778A (en) * | 1960-03-23 | 1962-09-25 | Swift & Co | Method for applying a mixture of a vinyl halide polymer and an epoxidized triglyceride on a wire and the resulting article |
| US3150153A (en) * | 1962-06-15 | 1964-09-22 | Gen Mills Inc | Stability of epoxidized oils by oxidation and naturalization |
| US3207743A (en) * | 1963-08-16 | 1965-09-21 | Hercules Powder Co Ltd | Epoxidation of tall oil fatty acids and esters |
| US3187019A (en) * | 1964-01-24 | 1965-06-01 | Abbott Lab | Brominated oils |
| US3328430A (en) * | 1964-11-16 | 1967-06-27 | Archer Daniels Midland Co | Epoxidation process |
| US20080103073A1 (en) * | 2006-10-31 | 2008-05-01 | Atanu Adhvaryu | Anti-friction anti-wear lubricant additive |
| WO2012038811A1 (en) | 2010-09-23 | 2012-03-29 | Council Of Scientific & Industrial Research | An improved process for the epoxidation of fatty acids, their esters and mixtures thereof |
| US9062019B2 (en) | 2010-09-23 | 2015-06-23 | Council Of Scientific And Industrial Research | Process for the epoxidation of fatty acids, their esters and mixtures thereof |
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