US2992237A

US2992237A - Process for the production of com-

Info

Publication number: US2992237A
Authority: US
Publication date: 1961-07-11
Anticipated expiration: 1978-07-11

Description

United States Patent This invention relates to an improved process of producing epoxidized organic compounds and to the epoxideoxygen containing compounds so prepared.

I have found that technically valuable epoxide compounds can be obtained when olefinically-unsaturated compounds, preferably high-molecular weight olefin'ically-unsaturated compounds containing aliphatic hydrocar- .bon lipophilic radicals, are admixed with organic polyhydroxy compounds, such as monoor poly-saccharides or aliphatic hydrocarbon polyols, in the presence of acid activators, the mixture thus formed is treated with hydrogen peroxide and the epoxide-oxygen containing compounds formed thereby are isolated.

Examples of suitable olefinically-unsaturated starting compounds are: aliphatic olefinic hydrocarbons, such as pentene, octene, dodecene, octadecene, squalene, etc., del rivatives of olefinically-unsaturated high-molecular weight hydrocarbon alcohols, such as the esters of alcohols obtained by reduction of naturally occurring vegetable or animal olefinically-unsaturated fatty acids under reaction conditions whereby the double bond is preserved,

hereinafter sometimes referred to as olefinically-unsaturated fatty alcohols, or esters of olefinically-unsaturated al'coholswhich are obtained by saponifying natural wax esters, such as the esters of olefinically-unsaturated fatty 2,992,237 Patented July 11, 196 1 2 unsaturated fatty acids, may be used as starting materials, such as the amidation products of unsaturated'fatty acids or fatty acid mixtures with ammonia, dimethylamin'e, dodecylamine, oleylamine, ethylene diamine, cyclohexylamine, benzylamine, etc. Also nitriles such as tetradecenyl nitrile',,hexadecenyl nitrile or mixtures of alkylene-nitriles with 14 to 18 carbon atoms may be used.

The process is inherently applicable also to epoxidizable compounds of a non-aliphatic character, especially to unsaturated cycloaliphaticor heterocyclic compounds. Examples of suitable starting materials of this type are tetrahydrobenzoic acid derivatives and tetrahydrophthalic acid derivatives, or condensation products formedfby diene components with atleast two conjugated double bonds and philodiene components with at least one nosaturated bond. Q'-

In accordance with the invention, the above-mentioned starting materials are treated with an epoxidation mixture containing an organic polyhydroxy compound such as monoor poly-saccharides or aliphatic hydrocarbon polyols. Examples of monoor polysaccharides which may be used for this purpose are threose, erythrose, arabinose, ribose, xylose, glucose, mannose, fructose, galactose, gluconic acid, mannonic acid, mucic acid, ascorbic acid and other sugar acids. Examples of sugar-like polysacchrides are sucrose, gentiobiose, maltose, cello biose, tr'ehalose, lactose, and the like. In addition, polysaccharides not related to sugar may be used in degrad-af tion form, if desired, such as amylose, amylopectiri, dextn'ns, glycogens, inulin, pectins, alginates, celluloses, etc. Further suitable are aliphatic hydrocarbon polyols as glycerine, hexanetn'ols, pentites, hexites, heptites, pentaerythrite, dipentaerythn'te, and the like. It is also possialcohols with 14 to 18 carbon atoms, especially of oleyl alcohol, and other monoor polyolefinically-unsaturated alcohols formed with any desired lowor high-molecular weight carboxylic acids. Also suitable are the corresponding ethers of the above-mentioned unsaturated alcohols formed preferably with low-molecular weight alcohols.

Further suitable as starting materials are derivativesof olefinically-unsaturated high-molecular weight fatty acids, such as their esters, amides or nitriles. Especially suitable are naturally-occurring, glycerides, -'moiety of which may be monoor poly-unsaturated, such as the-semi-drying oils, primarily soybean oil, cottonseed oil and linseed oil. Further suitable are olive oil,

' neats-foot oil, sperm oil and other marine animal oils.

Examples of other esterifying components for the olefinically-unsaturated high-molecular weight fatty acids are the following alcohols; ethyl, isopropyl, n-bntyl', sec- .Ondary butyl, tertiary butyl, tertiary amyl,,n-octyl, .2- "ethylhexyl, dodecyl, octadecyl, octadecenyl, cyclohexyl, methylcyclohexyl, naphthenyl, benzyl and the like; polyhydroxy alcohols, such as' ethyleneglycol, 1,2-propylene glycol, 2-ethyl-hexanedi0l-1,3, butanediol-LB, butanediol-1,4, dodecanediol-l,l2, glycerine, pentaerythrite and polyalkyleneglycols, such diethylene glycol, and the like. Similarly, esters formedby the olefinically-unsaturated carboxylic acids and alooholrnixtures may be used as starting materials, as well as mixed esters formed by polyhydroxy alcohols and different olefinically-unsaturated fatty acids, such as the mixed esters formedby ethylene glycol with oleic acid and linseed oil fatty acid. Finally, the esters in which both the acid moiety as well as the alcohol moiety contain a high-molecular weight aliphatic monoor poly-unsaturated hydrocarbon radical may also be used.

In addition to the esters, the amides of olefinicallythe fatty acid ble to use mixtures of monoand poly-saccharidcs and polyols for the epoxidation.

, customary, inorganic or organic acids or acid halides are used as activators, for example, mineral acids, such as phosphoric acid, nitric acid, sulfuric, acid or per chloric acid, boron 'trifluon'de or boron trifludride-water adducts; organic acids, such as acid phosphoric acid esters, p-toluenesulfonic acid; and high-molecularweight synthetic resins containing sulfonic acid groups, such as those used as base exchangers, and the like. Some of these activators are commonly known as Lewis acids. The epoxid-ation probably proceeds by a reaction between the monoor poly-saccharides or polyols and the hydrogen peroxide,forming organic, complex, acid oxidation mixtures which effect the transfer of active oxygen to the doublefbond of the high-molecular weight olefinically-unsaturated compounds. Y t The quantitative ratios in which the reaction components according to the invention are employed, de-

pend'primarily on the number of double bonds in the starting materials which are to' be transformed into epoxide groups. The concentration of activeoxygen, that is, the content of hydrogen peroxide, should as a rule be between 1.1 and 2 mols per molar equivalent of double bonds present in the starting material. The hydrogen peroxide, however, may also 'be used in excess of this amount. The required maximum amount of monoor poly-saccharides or polyols and their activator should together be about 2.5 to 15% by weight of the unsaturated starting'material and should .not normally exceed these quantities. However, when a-base exchange resin containing sulfonic acid groups is used as the activator larger quantities of activator are sometimes recommended. The reaction temperatures to be employed are between 0 and 100 C. and preferably between 50 and C. I

The process is performed according to customary epoxidation procedures. For example, a mixture-of the olefinically-unsaturated fatty substance and the organic polyhydroxy compound is formed and then the calculated amount of hydrogen peroxide together with the acid activator is added to the mixture, accompanied by vigorous stirring. The process may also be carried out bysimultaneously adding the. organic polyhydroxy com pound and the mixture of hydrogen peroxide and acid activator, both while stirring. Finally, it is also possible, whenpolysaccharides unrelated to sugars are used, to first produce a mixture of the polysaccharides with the-acid activators and thereby bring about a partial degradation or hydrolysis ofthe poly-saccharides, and add this mixture, together with the hydrogen peroxide to the olefinic fatty compound in the reaction mixture.

The addition of the hydrogen peroxide is, as a rule, carried'out over. a period of several hours. At least a 30% "solution of hydrogen peroxide, and preferably a 50-60% solution, is used.

At the end of the reaction the acid components, which sometimes also contain small amounts of hydrogen peroxide, may be separated in accordance with known methods and may be re-admixed as a starting material with an volefinic substrate in a preliminary step or preliminary reaction or in accordance with the well-known counter-current flow principle.

In the present process, as in most known epoxidation processes, if the reaction is extended over longer periods of time, dihydroxy compounds are obtained in large amount from the epoxidized compounds due to bydrolysis of the epoxy-group. Accordingly, the present process alsoprovides a means for the production of such dihydroxy compounds.

The process according to my invention has a number of advantages over other known epoxidation processes. (1) It obviates the use of expensive low-molecular weight carboxylic acids. (2) The organic oxidation mixtures formed from the organic polyhydroxy compounds are far less explosive than performic acid or peracetic acid formed in the known epoxidation processes. (3) In contrast to known processes, in which the total required amount of hydrogen peroxide is added to the reaction mixture in the beginning, the present process, where thehydrogen peroxide is added gradually, has the advantage that the epoxidation process can be more easily controlled by control .of the exothermic course of reaction. (4) Because of the delayed course of reaction, the danger of formation of undesirable dihydroxy or acyloxy compounds due to cleavage of the epoxide ring is reduced. (5) In those cases where synthetic resins containing sul-fonic acid groups are used as acid activators, there is a further advantage in that these resins do not cause a cleavage of the epoxidegroups formed by the reaction even when present in amounts above 0.5 mol per molar equivalent of double bonds. The high-molecular weight epoxide compounds obtainable by the method of the invention are of versatile technical interest. For example, because of their compatibility and resistance to migration, they are useful as such, or in the form of their derivatives, as plasticizers and stabilizers for polyvinyl chloride and its copolymers and are thus important auxiliary agents in the production of synthetics. Furthermore, they are useful as lubricants, lubricating oil additives or textile oils.

The following examples will further illustrate the present invention and enable others skilled in the art to understand it more completely. .It will be understood,

however, that the invention is not limited to these particular examples. Example 1 200 parts by weight of a soybean oil (acid number 0.1; saponification number 187; iodine number 120) and 20 parts 'by weight of technical grade cane sugar were placed into a VA-steel vessel provided with a. stirring me ns. acoilheater and cooling means. Thereafter, the

temperature of the contents of the vessel was raised to 65 C. In the course of 3-4 hours parts by weight of a 50% by weight hydrogen peroxide solution containing 4 parts by weight of concentrated phosphoric acid were added to the contents of the vessel While stirring and-maintaining the temperature at 65 C. by cooling. The reaction product was stirred for another two hours at this temperature and was then washed with water until neutral. In order to remove small amounts of residual acid components, the reaction product was refined by washing with a dilute sodium hydroxide solution and again washed until neutral. By heating the product to 70-90 C. under reduced pressure to dehydrate, a dry soybean oil epoxide was obtained having an epoxide oxygen content of 5.1% (iodine number 31.5; acid number 0.)

Example 2 1000 parts by weight of a cotton seed oil fatty acidmethylcyclohexyl ester .(produced from the liquid components of a cottonseed oil fatty acid and methylcyclohexanol; saponification number 149.8; iodine number 94.9; acid number 0.95) were admixed with parts by weight of cane sugar and the mixture was raised to a temperature of 65 C. Thereafter 400 parts by weight of a 60% by volume hydrogen peroxide solution, to which 13.3 parts by weight of concentrated phosphoric acid and 6.66 parts by weight of concentrated sulfuric acid has been previously added, were stirred into the mixture over a. period of 3-4 hours, taking care that the temperature of 65 C. was accurately maintained. The reaction mixture was then stirred for about six additional hours. After cooling, the contents of the vessel were washed twice with a volume of distilled water corresponding to the reaction mixture, and the reaction product was de-acidified in a refining vessel. The epoxide ester was washed until neutral and subsequently freed from water under reduced pressure, The epoxide thus obtained has the following characteristic values:

When the procedure of Example 1 was altered by using in place of cane sugar an equal weight of glucose in the reaction, while operating under otherwise identical conditions, a soybean oil epoxide having an epoxide oxygen content of 5.33% was obtained after 15 hours.

Per ent Reaction Period Acid No. Iodine No. epoxide oxygen After 5.!ihours 0.17 80. 5 2. 67 After 9.5 hours 0.28 50. 6 4. 23 After 15.0 hours; 0. 23 27. 7 5. 33

Example 4 750.0 parts by weight of soybean oil having the charactcristic values:

Acid number 0.2 saponification No. 186.5 Hydroxyl No. 2

Iodine No. 122

were placed into a VA-steel vessel provided with a stirrer, together with 37.5 parts by weight of cane sugar and 10.0 parts by weight of a base exchanger of the type Lewatit S100 (ion exchanger of Farbenfabriken B yer AG based on sulfonated styrene resin) which had previously been treated with acid and then thoroughly washed until neutral. 400 parts by weight of a 50% by weight hydrogen peroxide solution was then added to the reaction mixture over a period of two to three hours at atemperature of 65 C; The heat of reaction formed thereby was withdrawn from the mixture sotha-t the temperature of the contents of the vessel did not rise above 65 C. The reaction was accompanied by thorough mechanical agitation. At the end of the exothermic reaction, the reaction mixture was maintained at a temperature of-65 C. with the aid of a heater for a total reaction period of 22 to 25 hours. The solid components of the base exchanger may be reused after filtration and regeneration.

The filtration was washed with water and the raw epoxide, which was obtained by allowing the mixture to Example 6 A black marine animal oil of mediocre quality and unpleasant oder was bleached in accordance with the previously described process using the following reaction mixture:

settle, was refined by a wash with dilute sodium hydroxide, I

washed until neutral and dried.

106.9; saponifica-tion No. 105.8; hydroxyl No. 21.9 parts by weight cane sugar 150 parts by weight of a 50% hydrogen peroxide solution 10 parts by weight concentrated phosphoric acid Reaction temperature 65 C. a Reaction period 7 hours After purification a light yellow fish oil having the follow- Acid number h t 'sti a1 w obtained:

Iodine number 27.9 (after 16 hours) mg c arac en 0 v as Epoxide oxygen 5.1% (after 16 hours) Add Ep oxygen -8% e 16 u Iodine No. 70.7

h I I i Id Example 5 20 Epoxr e oxygen percen I g If in :place of the reaction mixture of the preceding Example 7 example the Ramon camed out When other monoor polysaccharides are substituted, the previously described process yielded fatty epoxides 1500 parts by welght soybean 011 (same l u with the following epoxide content values; in each case parts byweight sugar 15 parts by weight base exchanger (Lewatit S100), aciditied and washed until neutral and 700 parts by weight of a 5 0% hydrogen peroxide solution 750 parts by weight soybean oil (acid No. 0.2; saponification No. 186.5; iodine No. 122) were used. The reaction temperature was 65 C. and the reaction period. 15.17 hours. i

l Pretreated with theactlvator in dilute phase.

the peroxide being added over a periodof one and the temperature held at 65 C.; a fatty epoxide having Example 8 g V I The following results were obtained with the indicated starting materials "having the indicated characteristic values! p vSapon, Gm. Gm. Reae Reac- Epox- H I Substance Acid ifica- Iodine amount Gm. activator Gm H202 tion tion ide Acid Iodine No. tion 'gNo. used sugar temp. period oxygen 'No." -No;".':

No. in O. in hrs. percent Agcotfontsxeed oil-methylcyclo- 0.45 149.7 94.0 750 s Lewatlt $100..-- 20 s20 is 3.37 0. 0' "17.5

e es 1'.

A 0. 45 149. 7 94. 9 750 8 Lcwatit 5100..-; 40 350 65 22 4. 01 0. 6 8. 77 0.42 152 88.3 750 NaHS04. 16 350 65 12 3.70 0.6 12.4 0.2 186.5 122 750 400 65 35 5.60 0.4 12.3

the following characterstic values was obtained afterthe Example 9 indicated period of reaction.

1018 parts by weight of anaryloxy-alkyl carboxylic I 65 acid ester or an aryl carboxylic acid ester or an alkyl I Percent carboxylic acid ester respectively as described in the fol? Reaction Perm mime 9 2 3; lowing table are placed into an epoxidation apparatus according to Example 1. 70 parts by weight of cane Af 15 o M 4 50 v sugar are added and the mixture is heated up'to 70 C. After '70 During three hours a solution of 700 parts by weight igg 32 233;; 8:59 3' 2 23 of hydrogen peroxide, 50% by weight and 50 parts by 3.; 53.? Egg weight of concentrated phosphoric acid are gradually added. The heat of reaction is removed and the reaction 0.28 7 18-89 temperature is maintained at about 60 C. The mixture 7Y5 is vigorously stirred for 15-23 hours and after that'th 7 aqueous parts are drawn elf and the reaction product is worked up in a usual manner.

foot oil, marine animal oil, aliphatic hydrocarbons, low molecular weight carboxylic acid esters of aliphatic hydro- Oharacteristic numbers of the parent Characteristic numbers of the material epoxides Reaction Reaction Substance erlod temp. in

Saponl- Hydroxyl Iodine Iodine Percent hrs. 0. Acid No. ficlartion No. No. Acid No. No. epoxide Example 10 carbon alcohols, natural wax esters, low molecular weight Oleic acid esters are prepared from oleic acids by esterification under pressure with methyl alcohol, raflination and distillation. In such manner the following esters are obtained:

(a) Fluid parts of a C coconut oil fatty acid methyl ester (once pressed at 17 C.), (b) Fluid parts of a C coconut ester (twice pressed at 17 C.), (c) Fluid parts of a cotton seed oil fatty acid methyl ester, (d) Fluid parts of a tallow fatty acid methyl ester, (e) Sperm oil fatty acid methyl ester (C -C oil fatty acid methyl These esters were epoxidized according to the process described in Example 9, using the following charges:

After working up the epoxidized mixtures methyl ester epoxides are obtained having the following characteristic numbers:

carboxylic acid esters of lower alkoxy substituted aliphatic hydrocarbon alcohols, low molecular weight monohydroxy alcohol esters of fatty acids, dihydroxy alcohol esters of fatty acids, and unsubstituted amides of fatty acids, and (b) low molecular weight monohydroxy alcohol esters of tetrahydrobenzene :canboxylic acids which comprises the steps of (1) mixing said olefinically unsaturated compounds with (a) an organic polyhydroxy compound selected from the group consisting of aliphatic hydrocarbon polyols containing from 3 to 10 carbon atoms, monosaccharides, monosaccharidic acids, sugar polysaccharides, amylose, amylopectin, dextrins, glycogens, inulin, pectins, alginates, and acid degraded cellulose, and (b) an acid activator capable of accelerating peracid formation selected from the group consisting of phosphoric acid, nitric acid, sulfuric acid, sodium acid sulfate, perchloric acid, boron trifluoride, boron trifiuoride-water adducts, acid phosphoric acid alkyl esters, p-toluenesulfonic acid and high molecular weight synthetic cation exchange resins containing sulfonic acid groups, (2) adding from 1.1 to 2.0 moles per molar equivalent of the olefinic bonds of said high molecular weight compound of an aqueous hydrogen peroxide solution containing from about 30 to by weight of hydrogen peroxide during a period of from about 1 to 4 hours to said mixture while stirring vigorously and maintaining the reaction temperature between 0 C. and 100 (3., and (3) isolating the epoxidized olefinically-unsaturated compounds.

2. The process of claim 1 where said organic poly- Parent material Ep xi e Epoxlde Epoxlde Fromoxygen Saponl- Iodine Iodine percent Acid No. fic a tiou No. Acid No. No.

Methyl e o stearate Coconut 0ll- 0. 95 193. 9 70.7 0 3.9 3. Dix-9" do 0. 9 190. 2 75. 0 0 4. 0 3. 84 Do Cottonseed oil. 0.3 193. 2 114 0 11.2 5-23 Do Tallow 0. 4 191. 0 s4 0 4- 8 4.35 Methyl epoxystearate 18/22. Sperm oil 0. 9 184. 2 81. 1 0 2- 8 4.26

In like manner other high-molecular weight fatty acid derivatives such as the fatty acid amides and fatty acid nitriles and the esteiified high-molecular weight fatty alcohols can also be epoxidized by my invention.

While I have disclosed various specific embodiments of my invention, it will be apparent to persons skilled in the art that the present invention is not limited to these specific embodiments and that various changes and modifications may be made without departing from the spirit of the invention or the scope of the appended claims.

I claim:

1. A process for the introduction of epoxide groups into olefinically unsaturated compounds selected from the group consisting of (a) high molecular weight olefinically unsaturated compounds containing aliphatic hydrocarbon lipophilic radicals selected from the group consisting of linseed oil, soybean oil, cottonseed oil, olive oil, neatshydroxy compound and said acid activator are added in an amount in combination of from 7 to 15% by weight of said olefinically-unsaturated compound.

3. The process of claim 1 wherein said acid activator is sulfuric acid.

4. The process of claim lwherein said acid activator is phosphoric acid.

5. The process of claim 1 wherein said acid activator is a high molecular weight synthetic ion-exchange resin containing free sulfonic acid groups.

6. The process of claim 1 wherein said compound is technical cane sugar.

7. The process of claim 1 wherein said polyhydroxy compound is glucose.

8. The process of claim 1 wherein said olefinically-nus saturated compound is soybean oil.

polyhydroxy (References on following page) References Cited in the file of this patent UNITED STATES PATENTS Terry et al. Jan. 4, 1949 Niederhauser et al. Oct. 18, 1949 6 Swern et al. Oct. 2, 1951 Greenspan et al. Dec. 18, 1956 Payne et al. Jan. 1, 1957 10 Phillips et al. Jan. 29, 1957 Greenspan et a1 July 30, 1957 Greenspan et al. Oct. 22, 1957 Wallace May 6, 1958 FOREIGN PATENTS Canada Oct. 2, 1956 UNITED STATES PATENT. OFFICE CERTIFICATE OF CORRECTION Patent No. 2392 237 July 11 1961 Gerhard Dii ckelmann It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below Column 5 line 19 for "(after 16 hours)" read we (after 25 hours) column 7, line 38 for concphosphoric acid" read con. phosphoric acid Signed and sealed this 30th day of January 1962.,

(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents

Claims

1. A PROCESS FOR THE INTRODUCTION OF EPOXIDE GROUPS INTO OLEFINICALLY UNSATURATED COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF (A) HIGH MOLECULAR WEIGHT OLEFINICALLY UNSATURATED COMPOUNDS CONTAINING ALIPHATIC HYDROCARBON LIPOPHILIC RADICALS SELECTED FROM THE GROUP CONSISTING OF LINSEED OIL, SOYBEAN OIL, COTTONSEED OIL, OLIVE OIL, NEAT''SFOOT OIL, MARINE ANIMAL OIL, ALIPHATIC HYDROCARBONS, LOW MOLECULAR WEIGHT CARBOXYLIC ACID ESTERS OF ALIPHATIC HYDROCARBON ALCOHOLS, NATURAL WAX ESTERS, LOW MOLECULAR WEIGHT CARBOXYLIC ACID ESTERS OF LOWER ALKOXY SUBSTITUTED ALIPHATIC HYDROCARBON ALCOHOLS, LOW MOLECULAR WEIGHT MONOHYDROXY ALCOHOL ESTERS OF FATTY ACIDS, DIHYDROXY ALCOHOL ESTERS OF FATTY ACIDS, AND UNSUBSTITUTED AMIDES OF FATTY ACIDS, AND (B) LOW MOLECULAR WEIGHT MONOHYDROXY ALCOHOL ESTERS OF TETRAHYDROBENZENE CARBOXYLIC ACIDS WHICH COMPRISES THE STEPS OF (1) MIXING SAID OLEFINICALLY UNSATURATED COMPOUNDS WITH (A) AN ORGANIC POLYHYDROXY COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC HYDROCARBON POLYOLS CONTAINING FROM 3 TO 10 CARBON ATOMS, MONOSACCHARIDES, MONOSACCHARIDIC ACIDS, SUGAR POLYSACCHARIDES, AMYLOSE, AMYLOPECTIN, DEXTRINS, GLYCOGENS, INULIN, PECTINS, ALGINATES, AND ACID DEGRADED CELLULOSE, AND (B) AN ACID ACTIVATOR CAPABLE OF ACCELERATING PERACID FORMATION SELECTED FROM THE GROUP CONSISTING OF PHOSPHORIC ACID, NITRIC ACID, SULFURIC ACID, SODIUM ACID SULFATE, PERCHLORIC ACID, BORON TRIFLUORIDE, BORON TRIFLUORIDE-WATER ADDUCTS, ACID PHOSPHORIC ACID ALKYL ESTERS, P-TOLUENESULFONIC ACID AND HIGH MOLECULAR WEIGHT SYNTHETIC CATION EXCHANGE RESINS CONTAINING SULFONIC ACID GROUPS, (2) ADDING FROM 1.1 TO 2.0 MOLES PER MOLAR EQUIVALENT OF THE OLEFINIC BONDS OF SAID HIGH MOLECULAR WEIGHT COMPOUND OF AN AQUEOUS HYDROGEN PEROXIDE SOLUTION CONTAINING FROM ABOUT 30 TO 60% BY WEIGHT OF HYDROGEN PEROXIDE DURING A PERIOD OF FROM ABOUT 1 TO 4 HOURS TO SAID MIXTURE WHILE STIRRING VIGOROUSLY AND MAINTAINING THE REACTION TEMPERATURE BETWEEN 0*C. AND 100*C., AND (3) ISOLATING THE EPOXIDIZED OLEFINICALLY-UNSATURATED COMPOUNDS.