2,977,374 United States Patent Office Patented Miar. 28, 1961 2 pressure in a vessel large enough to contain all the material employed. Such batchwise operation, in order to per imit a reasonable degree of productivity, had to be of 2,977,374 considerable size. Moreover, at any given temperature, PROCESS FOR PREPARNG OXRANE the rate of epoxidation was controlled by the rate at COMPOUNDS which the peracid was fed into the vessel. Under such Benjamin Phillips and Paul S. Starcher, Charleston, conditions, once the reaction was completed with, for W. Va., assignors to Union Carbide Corparation, a example, the first amount of peracid fed to the entire corporation of New York charge of the contained ethylenic compound, the epoxide 0 so produced could not be removed as it was formed. No Drawing. Filed Mar. 7, 1958, Ser. No. 719,741 Rather, the entire-charge was retained in the vessel until the reaction was essentially complete. Among the dis 18 Claims. (C. 260-348.5) advantages of the foregoing procedure are the following: undue exposure of the excess ethylenic compound over the This invention relates to the preparation of oxirane 5 available peracid to temperatures above normal storage compounds. In one aspect this invention relates to the temperature thus inviting or enhancing polymerization epoxidation, in an elongated reaction zone, of ethyl of the excess ethylenic compound; undue exposure of enically unsaturated compounds with peracetic acid. the epoxide product to the effects of the resulting acetic This application is a continuation-in-part of copending acid by-product; the use of excessively long reaction times application Serial No. 439,878, now abandoned, entitled 20 with the upper reaction temperature limit controlled by “Manufacture of Aliphatic Chloroepoxides,' by B. Phil the atmospheric boiling point of the lowest boiling lips. and P. S. Starcher, filed June 28, 1954, and assigned material present in the reaction mixture; and others. to the: same assignee' as the instant application. . . The present invention is directed to epoxidation re In recent years. epoxide compounds have experienced actions which can be continuously carried out at reaction a growing utility in a wide variety of fields. As a con 25 rates, efficiencies, and/or yields heretofore unobtainable sequence, the epoxidation of ethylenically unsaturated. or contemplated. The epoxidation process of the instant compounds has become increasingly important as a means invention is effected by introducing an ethylenically un of synthesizing: such epoxides: For example; 12-epoxy Saturated compound and peracetic acid into an elongated 3-butene. has utility as a fumigaatgas: a source-of vinyl reaction zone under critically controlled conditions re ethylene. carbonate, as "as source of plastieizers, -etc.; 30. garding the operative pressure, the residence time of the a,b,b-trialkyl substituted glycidicesters have shown prom reaction rhixture; and the length and smallest diameter ise as agents to prevent stem ruston-oats; divinylbenzene ... or smaller cross-sectional area of said elongated reaction dioxide as a reactant with polycarboxylic acids, anhy zone to be described hereafter. The epoxidation reaction : drides, and polyfunctional amines to prepare composi is thus conducted at a temperature in the range of from . tions having utility in the fields of coating; laminating, 35 about: 0-C: to below about .150-C, preferably from about 20. C. to below about 130 G., with the maximum molding,In the bondingpast various and potting;methods and have so beenforth. employed ... :: for residence tirie of the reaction mixture in the eldingated the preparation of epoxide compounds. Darzens dis reaction zone not exceeding about 45 minutes Pressure closed the preparation of glycidicesters: by reacting-ke sufficient to maintain: the reaction mixture in the liquid tones or aldehydes with ethyl dichloroacetate and dilute 40 phase is necessary...... magnesium amalgan, followed by hydrolysis: of the The: elongated reaction zone is preferably a uniform product to produce a p-hydroxy-a-chloroester. Treat tubular reaction zone, the periphery of a perpendicular ment of this intermediate with sodium ethoxide provided cross-sectional view of which defines a circle. Thus, the the glycidic esters Pummerer and Reindel: reported diameter. (D) of the circular cross section of the tubular the preparation of 1,2-epoxy-3-butene by the reaction of 45 reaction zone must be between 0.25 inch to 5.0 inches, and butadiene with perbenzoic acid, in a sealed tube main the length (L) of the tubular reaction zone is from about tained under refrigeration for three to four days. Exist 100 to 10,000 times this diameter (D). The elongated ing processes for the preparation of chloroepoxides employ reaction zone also can be a tubular zone wherein the pe the halohydrin route: for the synthesis of these coma riphery of perpendicular cross-sectional views are circular pounds. The commercial process for the preparation of 50 throughout but not uniform in size, i.e., area, such as coni epichlorohydrin is an example of the halohydrin route and cal-shaped reaction zones. In such cases the diameter involves the addition of hypochlorous acid to allyl chlo (D) referred to above is the diameter of the smallest ride and subsequent dehydrohalogenation with sodium circular cross section, area-wise, of the reaction zone and

hydroxide to produce epichlorohydrin, salt, and water. the length (L) referred to above is the over-all length It is apparent that the foregoing. epoxidation routes 55 of the reaction zone." It is emphatically pointed out, suffer from several disadvantages. For example, among however, that the elongated reaction zone is not limited the disadvantages resulting from the use of Darzen's to uniform or non-uniform tubular reaction zones such process are included small yields, undesirable side re as those illustrated previously, but rather, the elongated actions, wide boiling point ranges of many reported gly reaction zones can be uniform and/or non-uniform in cidic esters indicating the presence of impurities, recom 60 perpendicular cross-sectional views taken along the length mended use of an inert atmosphere, and others. The of the reaction Zone, and the periphery of these perpen Pummerer et al. route is extremely limited and employs dicular cross-sectional views can define an ellipse, square, a most expensive source of oxygen in the epoxidation rectangle, triangle, quadrilateral, polygon, annulus, multi step... Lastly, the halohydrin route requires, for example, lateral planar figure, or other configurations. When the one mol of hypochlorous acid and one mol of base to 65 perpendicular cross-sectional view of the elongated reac produce epichlorohydrin from allyl chloride. tion zone defines an annulus (such as would be formed, Heretofore the interaction of a peracid and an ethyl for example, by a thermocouple well within a tubular re enically unsaturated compound to produce the corre action zone), the diameter (D) referred to above is the sponding epoxide was generally conducted at atmospheric diameter of the outer circle of a perpendicular cross-sec 70 tional view of the annulus taken at the narrowest point Organic Reactions, by Adams et al., volume. 5, pages in the elongated reaction zone. When the elongated re 413-439; published by John Wiley and Sons, Inc., 1952. a Ber. 66B, 335-9 (1933). action zone is such that the perpendicular cross-sectional 2,977,874 3 4. view cannot be expressed in terms of diameter (D) such 120 percent per hour). It will be noted in operative . as in those cases where said view defines a multilateral Example 11 that ethyl crotonate was epoxidized to ethyl planar figure, for example, a triangle, quadrilateral, poly 2,3-epoxybutyrate in a pressurized system at 125 C. gon, or an ellipse, or other geometrical configurations, . Under the operative conditions employed in said Exam then the critical limits of the elongated reaction zone are ple 11 at least 91 percent of the peracetic acid (after expressed in terms of length (L) and the expression thermal decomposition reduced the original concentration: v4K/ar wherein K is the area of the figure obtained by from 25 weight percent to 17.5 weight percent solution in: the perpendicular cross-sectional view taken at a point ethyl acetate) was available for epoxidation and that at in the elg.gated reaction zone which represents the small least 96 percent of this available peracid was utilized in O the preparation of the epoxide. It should also be noted. est cross-sectional area. The expression v4.K/int is ar that the residence time of a unit mass of reaction mixture: rived at as follows: The area (K) of a circle equals arD2/4; in the reaction zone was approximately 9.9 minutes. It hence D is equal to V4K/ar. is short of astounding and highly unexpected and surpris Thus, in summary the elongated reaction zone is criti ing, indeed, that such efficiencies and yields are obtainable cally defined by the diameter (D) or the expression by the practice of the instant invention in view of the in v4K/ar and the length (L) wherein the diameter (D) is stability of peracetic acid and the heretofore unobtainable: the smallest diameter of a circle obtained by a perpendicu or contemplated fast reaction rates. Thirdly, the practice: lar cross-sectional view of the elongated reaction zone; of the instant invention results in substantially no diffusion: wherein K is the smallest area of the figure obtained by of product with the incoming reagents. In contrast to a perpendicular cross-sectional view of the elongated re 20 conventional batchwise epoxidation processes wherein per action zone (the expression v4.K/it being used when the acetic acid was introduced into an excess of an ethylenic appropriate cross-sectional view defines a figure not geo compound thus inviting, among other disadvantages, poly metrically measurable in trems of diameter); and where merization of the ethylenic compound, undue exposure of in L is the length of the elongated reaction zone. More the epoxide product to the ring opening effect of the: 25 acetic by-product, etc., the instant invention subjects the over, the diameter (D) or the expression V4K/ar must reaction mixture to residence times ranging from about fall between 0.25 to 5.0 inches and the length (L) is 100 seconds to below about 45 minutes after which the epoxide to 10,000 times the value assigned to D or v4K/r. product, unreacted reactants, by-product, etc., can be re It is also pointed out that a single elongated reaction covered by conventional means such as fractionation, dis Zone, or a plurality of elongated reaction zones, whether. 30 tillation, extraction, and the...like. Fourthly, the opera said zones are uniform or non-uniform and whether iden-i. tive temperature of the elongated reaction zone can be tical or dissimilar in design or structure, can be employed, 's The elongated reaction-zone:or-zones-can-be-arranged carefullychange equipment, and effectively for example, controlled -a-heat-exchange by means of heat jacket ex in parallel or series fashion to meet the thermal require encompassing the external surface of the reaction zone.. ments of the system employed. When the elongated re 35 Fifthly, it should be noted that at all times an excess of action zones...are arranged in series, the several zones, peracetic acid over-ethylenic material can be employed if considered as a unit, must conform to the same require desired, a procedure which in many. i ances would be Inents. It is also pointed out that the process of the in hazardousin batchwise-operation. stant invention must be conducted in the liquid phase Accordingly, one or more of the following objects will. and under pressure sufficient to maintain the reaction 40 beachieved by the practice of the instant invention. . . mixture in the liquid phase...... It is an object of this invention to provide a novel proc The residence time of the reaction mixture must not ess for epoxidizing ethylenically unsaturated compounds. exceed about 45 minutes. In other words, the entry of It is another object of this invention to provide a novel a unit mass of reaction mixture into the elongated reaction continuous process for effecting the epoxidation of ethyl zone exits from said zone in less than about 45 minutes. enically unsaturated compounds with peracetic acid Thus, though the diameter D or the expression v4K/ar through a critically defined elongated reaction zone pre and the length L are fixed within the boundaries previously viously, described. It is a further object of this inven set out, the criticality regarding the residence time further tion to provide a novel continuous epoxidation process: realistically defines the elongated reaction zone. When at reaction rates heretofore not contemplated or obtain the elongated reaction zones are arranged in parallel fash 50 able with an amazing and unexpected degree of efficiency ion, each individual elongated reaction zone must con and yield of product resulting. Another object of this form to the aforesaid requirements for diameter (D) or invention is to provide a continuous, liquid phase epoxi the expression v4K/ar and the length (L). Consequent dation process under controlled temperature conditions ly, modifications of the elongated reaction zone will be in an elongated reaction zone. Other objects will become 55 apparent to those skilled in the art in the light of the limited not, only by the variables D or V4K/ar and L instant specification...... - - . noted above, but also, by the ability of the pumping means As stated previously, the instant invention is directed to contemplated which must be sufficient to push or flow a the epoxidation of ethylenically unsaturated compounds. unit mass of the reaction mixture through the elongated By the term "ethylenically unsaturated compound,' as reaction zone in less than about 45 minutes. used herein (including the appended claims), is meant an The advantages accruing by the practice of the instant 60 organic compound which contains at least three carbon invention, are many, and, indeed, highly unexpected and atoms and which has one or more aliphatic double bonds, Surprising. In the first place, epoxide compounds can be i.e., DC=C-3, in which the atoms directly joined to the prepared from the corresponding ethylenically unsatu ethylenic carbon atoms are hydrogen or carbon. For sake rated compounds, e.g., propylene, butadiene, etc., which of brevity the above quoted term oftentimes will be re are too volatile to be converted economically into expox 65 ferred to as “ethylenic compound(s).' Stated in other ides by conventional batchwise nonpressurized methods. words, by the term "ethylenically unsaturated compound," Secondly, the epoxidation reaction is a liquid phase reac as used herein, which can be epoxidized by the process tion conducted under perssure sufficient to maintain the of this invention, are hydrocarbons, halogenated hydro reaction mixture in the liquid phase. Peracetic acid is carbons, alcohols, ethers, ketones, mono-unsaturated acet widely known to be a highly elusive, explosive, degrada 70 als, acids, esters, amides, imides, nitriles, and phosphoric tive organic compound; moreover, the detonability and esters, which compounds are characterized by having at degradation of peracetic acid increases with increased tem least one aliphatic double bond and which are free of perature. At an operative temperature of 125° C. a solu Encyclonedia of Chemical Technology. First Supplement tion of 40 weight percent peracetic acid in acetic acid Wolume (1957), pages 623-626; published by the Inter decomposes at the rate of 3,000 percent per day (over science Encyclopedia, Inc., New York. 2,977,874 5 6 elements other than carbon, hydrogen, oxygen, nitrogen alkylene glycol bis(2-alkenoates); alkylene glycol 2-al in the form of amido, imido, or cyano groups, phosphorus kenoate 2,3-epoxyalkanoates; and the like. in the form of phosphoric esters, and halogens, and where Illustrative mono-unsaturated acetals include, for ex in the atoms joined to the ethylenic group, i.e., dC-FC<, ample, 1,2,5,6-tetrahydrobenzaldehyde diethyl acetal, to be epoxidized are of the group consisting of hydrogen paravinylbenzaldehyde dibutyl acetal; the dialkyl acetals and carbon atoms. of alkenals, such as the dimethyl, diethyl, dipropy, di Illustrative ethylenic hydrocarbons which can be em isopropyl, dibutyl, dihexyl, di-2-ethylhexyl, didecyl, etc. ployed as reagents in the epoxidation process include, acetals of unsaturated aliphatic aldehydes, for example, among others, propene, butenes, pentenes, hexenes, hep 2-, 3-, 4-, etc., alkenals, and the like. tenes, octenes, decenes, dodecenes, octadecenes, butadiene, O Typical unsaturated phosphoric esters which can be isoprene, pentadienes, hexadienes, heptadienes, octadienes, employed include, among others, di-(2-butenyl) 2-ethyl decadienes, dodecadienes, octadecadienes, styrene, divinyl hexyl phosphate, tri-(crotylphenyl) phosphate, allyl di benzenes, dihydronaphthalenes, indene-stilbene, 1-phenyl phenyl phosphate, dioctyl 3-pentenyl phosphate, and the 1 - propene, 1,1-diphenylene, cyclopentenes, cyclohex like. enes, cyclopentadiene, dicyclopentadiene, vinylcyclohex 5 The unsaturated halogenated hydrocarbons amenable enes, alkyl-substituted cycloalkenes, alkyl-substituted cy as starting material are those which do not contain halo cloalkadienes, aryl-substituted alkadienes, aryl-substituted gen atoms joined directly to the ethylenic-carbon atoms, cycloperatenes, unsaturated macromolecules such as buta >C=C-3. A particularly preferred class of unsaturated diene polymer and copolymers, and the like. halogenated hydrocarbons: are the aliphatic haloalkenes, Examples of alcohols and phenols containing ethylenic 20 e.g., aliphatic chloroalkenes which contain from 3 to 10 unsaturation therein are exemplified by compounds such carbon atoms in the alkene chain and in which no more as 3-cyclohexenylmethanol, p-allylphenol, p-crotylphenol, than two of the carbon atoms alpha to the ethylenic dicrotylphenols, p-(2-cyclopentenyl)phenol, 3-penten-1- group, >C=C-3, contain but a single halo substituent ol, 5-decen-1-ol, 9-octadecen-1-ol, 2-ethyl-2-hexenol, 3 thereon. cyclopentenol, 4-cyclohexenol, alkyl-substituted alkenols, 25 Illustrative unsaturated halogenated hydrocarbons aryl-Substituted alkenols, cycloalkenols, cycloalkadienols, which can be employed include allyl chloride, crotyl chlo alkyl-substituted cycloalkenols, cycloalkenyl-substituted ride, 1,4-dichloro-2-butene, 3,4-dichloro-1-butene, 3-chlo alkanols, alkenylphenols, and the like. . ro-1-butene, 2-chloro-3-pentene, 2-ethyl-2-hexenyl chlo Exemplary unsaturated ethers which are contemplated ride, methallyl chloride, crotyl fluoride, crotyl bromide, include, among others, diallyl ether of diphenylolmethane; 30 ortho-, meta, and para-chlorostyrene, ortho-, meta-, and diallyl ether-of-2,2-diphenylolpropane; diallyl ether; butyl para-chloromethylstyrene, 1-chloro-3-vinylcyclohexane, 4 crotyl ether;2-pentenylbutyl ether;4-pentenylbutyl ether; (trichloromethyl)-1-cyclohexene, tetra-(chloromethyl) 4-octenyl 3-pentenyl ether; ortho-allylphenyl ethyl ether; ethylene, 1-chloro 4-fluoro-2-butene, parabromobenzyl butyl 3-dodecenyl ether;-2,4-diallylphenyl ethylether:-3- ethylene, and the like. cyclohexenylmethyl alkyl ethers; 3-cyclohexenylmethyl 35 The epoxidation reaction can be conducted at a tem aryl ethers; 4-decenyl 2-propenyl ether; 14-pentadienyl perature in the range of from about 0 to below about alkyl-ether; 1,4-alkadienylalkenyl ether; and the-like. . 150° C., and preferably from about 20 to below about Illustrative -nitrogen-containing compounds, e.g., un 130° C. As a practical matter, the choice of the par Saturated amides, imides, nitriles, and the like, amenable ticular temperature at which to effect the epoxidation as:starting material include 3-pentenenitrile, 4-penteneni 40 reaction within the broad temperature range set out de trile, 4-cyanocyclohexene, ortho-, meta-, and para-vinyl pends, to an extent, on the nature of the ethylenic.com benzonitrile, 3-pentenamide, 4-pentenamide, oleamide, pound, the pressure employed, the residence. time (here ortho-, meta-, and para-vinylbenzamide, 3-cyclohexene-1- inafter described), and other factors. To maintain the carboxamide, N-crotylmaleimide, N-crotylphthalimide, N desired operating temperature the elongated reaction allyl phthalimide, and the like. 45 Zone, for example, can be suspended in or jacketed by Among the unsaturated carbonylic compounds, e.g., heat exchange media. Of course, other conventional unsaturated ketones, acids, esters, and the like, which means can be employed to maintain the desired operat can be employed in the instant process include, for ex ing temperature. sample, vinylacetic acid, oleic acid, cinnamic acid, soy The operative pressure should be sufficient to main bean oil, linseed oil, linoleic acid, mesityl oxide, allyl 50 tain a liquid phase epoxidation reaction. This factor will acetate, ally methacrylate, croty acrylate, ex-phenyl-6- be mainly governed by the boiling point of the lowest pentenyl ox-benzylcrotonate, 6-pentenyl az-ethyl-3-propyl boiling component comprising the reaction mixture at acrylate, octyl B,6-pentadienoate, croty or-cyclohexyl the operating temperature. . For example, when normal crotonate, 2-ethylhexyl oleate, 2-cyclopentenyl crotonate, ly gaseous butadiene is the ethylenic compound to be glycol dioleate, vinyl ox-ethyl-6-propyl-3-butylacrylate, 4 55 epoxidized and a reaction temperature of 60° C. is em "decenoic acid, methyl ally ketone, methyl 2-pentenyl ployed, it will be necessary to apply above about 8 at -ketone, dially maleate, vinyl cy-tolyl-8-ethylacrylate, 2 mospheres to the system to maintain a liquid phase re ethylhexyl a-methyl-8-ethylacrylate, propyl 1-cyclohex action. Should it be desirable to effect the epoxidation of butadiene at 115 C., then a pressure above about 23 enecarboxylate, butyl c, y-diethyl-ox,y-pentadienoate, meth atmospheres would be necessary to maintain a liquid yl az-phenyl-ay-hexadienoate, toly B-phenethyl-y-butyl: 60 phase reaction mixtue. By way of further illustration, oxy - heptadienoate, phenyl 1 - cyclopentenecarboxylate, normally gaseous propylene can be maintained in the tolyl 2-methyl-1-cycloheptenecarboxylate, 2-ethylhexyl liquid phase at 50 C. by applying above about 20 at 6-methyl-3-cyclohexenecarboxylate, butyl 2-phenyl-1-cy mospheres to the system; at a reaction temperature of clohexenecarboxylate, allyl 2-benzyl-2,3-epoxyhexanoate, 100 C. a pressure about 50 atmospheres is essential. 3 - cyclohexenylmethyl acetate, 3 - cyclohexenylmethy e In general, the pressure will be in the range of from acrylate, 3-cyclohexenylmethyl acylates, ethylene glycol about atmospheric pressure, preferably slightly above at bis(2-butenoate), propylene glycol bis(acrylate), 1,5- mospheric pressure, to about 1,500 p.s.i.g. depending, pentanediol bis(2 - butenoate), 1,3 - butylene glycol of course, on the nature of the ethylenic compound re crotonate 2,3-epoxybutyrate, ethylene glycol methacryl O agent and the operative temperature. It is evident, ate 2-methyl-2,3-epoxypropionate; aryl, alkenyl, cycloa therefore, that the instant invention provides a process kyl, cycloalkenyl, alkaryl, alkyl, and aralkyl alkenoates; for preparing epoxides from ethylenic compounds which aryl, alkenyl, cycloalkyl, alkyl, cycloalkenyl, alkaryl, and are too volatile to be converted into epoxides by conven aralkyl alkadienoates; aryl, alkyl, alkenyl, cycloalkyl, cy tional batchwise non-pressurized methods. Moreover, 'cloalkenyl, alkaryl, and aralkyl cycoolefin-1-carboxylates; 75 the unexpected and unobvious results obtained by con 2,977,874. 7 8 ducting the epoxidation reaction in the liquid phase is, in to that which remains at the termination of a batchwise deed, highly surprising especially when one considers the epoxidation process. Normally the effluent will comprise elusive, explosive and degradative nature of peracetic unreacted ethylenic compound reagent, epoxide product, acid under the operative conditions of the instant proc peracetic acid, acetic acid by-product, minor amounts of SS residual materials from degradation of the ethylenic com It has been observed that a faster and cleaner reac pound and/or epoxide product, solvent for the peracetic. tion is effected by employing the peracetic acid in an acid, is employed, and solvent for the ethylenic compound, inert organic medium such as ethyl acetate, acetone, and if employed. A preferable procedure for resolving the the like. It has also been noted that better control liquid effluent comprises continually removing said efflu and/or conversion can be achieved by employing a solu O ent from the elongated reaction zone into the lower half tion of peracetic acid. A solution comprising from about of a continuous still, and removing solvent, acetic acid, 5 to 50 weight percent of peracetic acid, based on the unreacted peracetic acid, and unreacted ethylenic com total weight of peracetic acid and inert organic medi pound as a heads fraction or distillate. The tails, or um, is satisfactory; from about 10 to 30 weight percent residual fraction, then can be continuously fed into a of peracetic acid, based on the solution weight, is pre 5 second similar still wherein the epoxide product is re fered. An inert organic diluent not containing active hy moved as a distillate. Of course, other recovery proce drogen can be employed with the ethylenic compound dures, whether a continuous or a batchwise operation, reagent, if desired, to provide moderation of the exo can be employed such as an intermittent batchwise dis thermic reaction, and also, said diluent can serve as an tillation of collected reactor product stream; single- or azeotroping agent in the product recovery stage. 20 multi-stage jacketed stripping coils suitable for isolation Theoretically, to effect substantially complete epoxi of a high boiling or residue product; crystallization tech dation of the ethylenic compound reagent, at least a niques; and other conventioal recovery means. stoichiometric quantity of peracetic acid per carbon to In the practice of the instant invention the apparatus carbon double bond of ethylenic compound should be setup is capable of various modifications with the excep employed. It has been observed, however, that the ratio 25 tion that the elongated reaction zone is restricted to the of peracetic acid to ethylenic compound will depend, to limits set out previously regarding the diameter (D) of an extent, on the nature of the ethylenic compound, i.e., the expression, V4K/ar, and the length (L), and further, on the number of carbon to carbon double bonds possessed by the fact that the residence time of any unit of the by said ethylenic compound, on the ease of oxidation of . reaction mixture does not exceed about 45 minutes. Thus, the ethylenic bond(s), on the ease of recovery of excess 30 for example, the ethylenic compound and peracetic acid ethylenic compound and/or peracetic acid, on the opera solution can be supplied to the elongated reaction zone tive temperature, and other factors. In general, a molar by means of controlled-volume positive-displacement ratio of peracetic acid to carbon to carbon double bond pumps. The pump controls can be regulated so that the ... of ethylenic compound of about 0.05 to 5.0 is satisfactory; predetermined ratio of peracetic acid to ethylenic com a molar ratio offeracetic acid to carbon to carbon double 35 pound entering the reaction zone is constant. As stated bond of ethylenic compound of about 0.2 to 2.0 is previously, the individual peracetic acid stream and eth preferred,3: - . . . ylenic compound stream can converge at the entrance of It is desirable to conduct the epoxidation reaction with the reaction zone or prior thereto. Alternatively, either equipment which will not foster the polymerization of the peracetic acid 'stream or the ethylenic compound the ethylenic compound or catalyze the decomposition of 'stream can be introduced at a plurality of evenly or un peracetic acid. The equipment should be of sufficient evenly 'spaced intervals in the system. Moreover, the strength to withstand the operating pressures contemplated peracetic acid solution and ethylenic compound can be by the practice of the instant invention. Equipment con premixed in the desired or predetermined ratios and main structed of stainless steel, aluminum and the like has been tained below the epoxidation reaction temperature, and observed to be adequate for this purpose. If desired, a 45 subsequently, the resulting premixed feed can be in polymerization inhibitor or retarder such as hydroquinone, troduced into the reaction zone. The rate at which the 2,4-dinitrophenol, 2,4-dinitro-m-cresol, pyrogallol, phenyl feed charge is pumped into the elongated reaction zone beta-naphthylamine, t-butylcatechol, and the like can be depends, in part, on the desired produciton rate, the ratio incorporated into the reaction mixture in an amount suffi of peracetic acid and ethylenic compound, the extent of cient to prevent possible polymerization of the ethylenic 50 thermal decomposition of peracetic acid which, though compound starting material. minor in extent, always takes place, the residence time The particular manner of adding or introducing the within the range stated previously, the over-all optimum reagents, i.e., the ethylenic compound and peracetic acid, conditions desired, and other factors. It should be noted, to the elongated reaction zone is not narrowly critical. however, the feed rate is sufficient to insure a residence One desirable procedure is to have one stream containing 55 time in the range of from seconds to less than about 45 ethylenic compound and another stream containing a solu minutes. Within the critical limits defining the elongated tion of peracetic acid converge at the entrance or prior reaction zone, it has been observed that a relatively longer to the entrance of the elongated reaction zone. Another reaction zone is desirable for expoxidation reactions which method which can be employed is, for example, to in take place at higher temperatures or with difficulty. Arel troduce the solution of peracetic acid, at a plurality of 60 atively narrower elongated reaction zone is often superior points or intervals, into the stream containing the ethyl to a reaction Zone of wider average cross-sectional area enic compound. By way of further illustration, the per in view of the greater efficient thermal control which acetic acid and ethylenic compound reagent can be pre can be achieved by the use of heat exchange jackets, mixed and maintained below that temperature at which baths, coils, etc. A thermocouple well in the interior of epoxidation occurs. The resulting feed mixture then can 5 the elongated reaction zone attached to a suitable tem be pumped into the elongated reaction zone, said zone perature recording device can serve to apprise the operator being maintained under the predetermined operative con of temperature variations, if any. ditions at which the epoxidation reaction is to be con As also noted previously, the instant process concerns dicted. epoxidation reactions in the liquid phase, and pressure In general, the resolution of the liquid effluent from 70 sufficient to maintain the reaction mixture in the liquid the reaction zone can be effected by conventional tech phase is employed. Conventional pressure maintaining niques such as distillation, fractionation, extraction, crys devices can be employed. They can be, for example, tallization, and the like. Once the reaction mixture leaves mechanical or hydraulic in operation and differ only in -from the elongated reaction zone and enters, for example, their details of construction. It is preferred to employ a pot or still, the reaction mixture is somewhat similar 75 a controlling type pressure device which will permit 2,977,874 9 O flow only when the reaction zone pressure exceeds the atmospheric pressure supplied by means of a motor valve desired and established operating level. Examples in at the effluent end of the elongated tubular reaction zone clude spring-loaded check valves, air-to-close diaphragm maintained the reaction mixture in the liquid phase at valves, and various types of pressure-activated motorized an operative temperature of 50° C. The residence time valves. As a safety device the reaction zone can also was 2.5 minutes. The major portion (69.2 weight per contain a pressure relief valve. It is emphatically pointed cent of the feed charge) of the effluent, taken under the out, however, that the instant invention is not to be operative conditions prevailing in said reaction Zone, was construed as limited to the various optional apparatuses introduced into a separate receiver under its own pres set forth above; those skilled in the art can readily de sure and then distilled in a Davis column. The na termine, for example, the particular heat exchanger, pres O terial boiling between 20 and 79°C., at atmospheric sure device, etc., which they choose to employ. pressure, was collected in one fraction. This fraction The following examples are illustrative. was analyzed for isobutylene oxide by the pyridine hy drochloride-pyridine method and was found to contain Example 84 weight percent of the theoretical amount of said iso A mixture of 1.15 mois of a 24.0 weight percent solu 5 butylene oxide. tion of peracetic acid (also containing 26.2 weight per Example 4 cent acetic acid and 49.8 weight percent ethylbenzene) In this experiment a reaction between butadiene and and 11.5 mols of propylene was placed in a pressure peracetic acid in ethyl acetate was carried out in a tubular ized vessel under refrigerated conditions (below about reaction zone under sufficient pressure to keep the re minus 20° C.) such that no interaction between peracid 20 actants liquefied. The tubular reaction Zone comprised and olefin took place. Subsequently, this mixture was a single length of /2 inch stainless steel pipe 12 feet pumped over an 83 minute period through a 4 inch long, with a 3% inch thermocouple well extending the stainless steel tube having a 150 milliliter volume, said full length. Temperature measurements were made by tube being suspended in a water bath maintained at 60° C. thermocouples located at several points in the thermo The reaction mixture in the elongated tubular reaction 25 couple well. zone was maintained in the liquid phase by Supplying All of the tubing and fittings, and other equipment 950-1050 p.si.g. pressure thereto. The reaction mix which came in contact with peracetic acid were made ture was exhausted under its own pressure into a re of 18-8 stainless steel. Peracetic acid solution was fed ceiver. The entire reaction product was diluted with 100 by volume under 30 p.s.i.g. nitrogen pressure from a milliliters of acetaldehyde to decompose unspent per 30 calibrated tank, and butadiene was fed by weight under acetic acid, and then the resulting mixture was added to 60 psi.g. nitrogen pressure. The pump was a Milton 200 milliliters of dry acetone. This mixture was dis Roy duplex reciprocating pump with cooling jackets on tilled in a Davis coluimn and a fraction distilling from the valve bodies. The reaction zone was jacketed; liquid 0 to 56° C. was analyzed for propylene oxide by as "Dowthernt A’ 6 circulating therein afforded the meats pyridine hydrochloride-pyridine method. The results for controlling the operative ternperature. Pressure in showed that 30 grams of propylene oxide were present the reaction zone was maintained essentially constant by which corresponded to a yield of 44.8 percent based on means of a motor valve at the outlet. The product was the peracetic acid charged. collected under its own vapor pressure in stainless steel cylinders sufficiently cooled to condense the components Example 2 4) of the reaction mixtures. A solution of 364 grams (1.5 mois of a 31.4 weight In this operation, 3510 grams of a 12.3 weight per percent solution) of peracetic acid in acetic acid contain cent solution of peracetic acid in ethyl acetate and 1674 ing 0.1 weight percent of Victor Stabilizer 53, based grams of butadiene were simultaneously fed into the re on the weight of the solution, and 622 grams (14.8 action zone over a period of 1.75 hours. The reaction mols) of propylene were placed in a pressurized feed 45 temperature was '68 C.; a pressure of 350 p.s.i.g. main tank and pumped through a 4 inch stainless steel coil tained the reaction mixture in the liquid phase; and the which had a volume equal to 150 milliliters. The op residence time was 7.4 minutes. The conversion of per erative temperature in the elongated tubular reaction acid was found to be 95.6 percent. Subsequent labora zone was 90° C.; the reaction mixture was maintained tory distillation of the reaction mixture gave 271 grams in the liquid phase under 950-1050 p.s.i.g. pressure, the 50 of butadiene monoxide having the following properties. residence time was 2.85 minutes. Once steady operat ing conditions were achieved 71.5 weight percent of Boiling point ------67.5-68 C./atin. the reaction mixture was taken under its own pressure in 30/D ------1.4120-1.4122. into a separate cylindrical receiver. This material was 55 The yield was 68 percent of the desired product. diluted with 100 grams of acetaldehyde and 200 grams of dry acetone and distilled in a Davis column. The Example 5 fraction boiling from 19 C. to 75° C. was analyzed for Butadiene monoxide (630 grams) and peracetic acid propylene oxide. A total of 53.5 grams was thus as (905 grams of a 25.2 weight percent solution in ethyl ace certained which represented a yield of 86 percent of the 60 tate) were fed simultaneously from individual positive theoretical amount. displacement controlled-volume pumps at a molar ratio Example 3 of 3 mois of butadiene monoxide to 1 of peracid into a tubular reaction zone. The reaction zone was fabricated A charge of 850 grams of isobutylene (15 mols) and from a 48 inch length of 38 inch stainless steel tubing 509 grams of a 22.4 weight percent solution of peracetic 65 jacketed with a one inch iron pipe through which a heat acid in ethyi acetate (1.5 mois) was placed in a stain exchange fluid (dioctyl phthalate) was circulated. The less steel cylinder and maintained under refrigerated con total volume of the reaction Zone was 47 milliliters. The ditions (below about minus 20 C.) such that no epoxi reaction Zone was operated at a jacket temperature of dation reaction took place. Subsequently, this mixture 110 C.; a system pressure of 80 to 115 p.s.i.g. applied by was pumped through a 4 inch stainless steel (; 8-8) 70 an air operated diaphragm-controlled valve maintained the reaction mixture in the liquid phase. The reactants coil which had a volume equal to 150 milliliters. Super were fed over a period of 134 hours into said Zone; the 4A distillation column incorporating a silver coated vac residence time was 3.0 minutes. The effluent from the uum jacket throughout the length of the column. . 5 Victor Chemical Co. tradenark for Nas (2-ethylhexyl) 5 Dow Chemical Co. trademark for a eutectic mixture of (P3010)2, an anionic wetting agent. 5 diphenyl and diphenyl ether. 2,977,874 2 reaction zone was exhausted to atmospheric pressure loaded check valve provided a liquid phase reaction mix through a cooling condenser and continuously fed into a ture. The effluent from the reaction zone was fed con stirred slurry comprising 11 mols of anhydrous sodium tinuously into the middle of the column of a continuous carbonate in 500 cc. of ethyl acetate which was main still containing styrene inhibited with 1 weight percent of tained over a temperature range of 20 to 25 C. At dinitrochlorophenol at the start of the operation. With the termination of the feed period the slurry was filtered; this still operating at 25-30 mm. of Hg pressure with a subsequent analysis of the filtrate showed it to be essen calandria temperature of 125 C. (supplied by a circulat tially free of the acetic acid by-product. Distillation of ing heat exchange fluid), the crude product stream was the filtrate at 300 mm. of Hg pressure served to remove withdrawn from the base of the still while the other the ethyl acetate therefrom. Subsequent fractionation O volatiles were removed as a distillate. The crude product through a packed column gave recovered excess butadiene stream was continuously flash distilled from polymer and smonoxide and 113 grams of butadiene dioxide having a other residual materials by pumping the material into a boiling point of 65-66 C. at 50 mm. of Hg pressure flash evaporator at 200 C. at 4-5 mm. of Hg pressure. and an in 30/D equal to 1.4265-1.4270. This represented An 81 percent yield of styrene oxide was continuously ob a yield of 43.8 percent. 15 tained from the overall operation. Example 6 Example 9 Epichlorohydrin was prepared continuously by passage of a mixture of allyl chloride and peracetic acid solution In a reaction zone similar to that employed in Example through a /8 inch stainless steel coil which had a volume 8, an equimolar mixture of vinylcyclohexene and vinyl of 67 milliliters. The feed charge consisted of 530 grams 20 cyclohexene monoxide was allowed to react with peracetic of allyl chloride, 0.95 cc. of a 35 weight percent solution acid in ethyl acetate solution such that total consumption of Victawet 35B in acetic acid, and 451 grams of a 27.4 of peracid would provide a mixture of vinylcyclohexene weight percent solution of peracetic acid in acetone. The dioxide and vinylcyclohexene monoxide. The latter ma reaction mixture was maintained in the liquid phase by terial was used in subsequent operations since the use of applying 75 psi.g. nitrogen pressure at an operative tem 25 a stream comprising vinylcyclohexene and vinylcyclo perature of 100° C.; the residence time was 36.5 minutes. hexene monoxide was found to be more efficient than use Subsequent stripping under reduced pressure of the effluent of vinylcyclohexene alone. Thus, at a reaction tempera from the reaction zone (to remove the excess chloro ture of 69 C. and a contact time of 4 minutes, yields of alkene and acetone), followed by dilution of the residue 80.5 percent of vinylcyclohexene dioxide based on the with 500 grams of carbon tetrachloride and then water 30 peracid used were achieved. Operative pressures of washing, removed the acetic acid. The resulting oil phase 21-24 psi.g. were employed to maintain the reaction was then distilled under reduced pressure. The yield mixture in the liquid phase...... of epichlorohydrin was 86 percent based on the available. - - - - - Example 10 ------peracetic acid consumed (96.2 percent). 35 Solutions of commercial divinylbenzene (diluted with Example 7 an equal weight of ethyl acetate) and peracetic acid (28.4 Epichlorohydrin was prepared continuously by passage weight percent in ethyl acetate) were fed by controlled of a mixture of allyl chloride and peracetic acid solution volume positive-displacement pumps into the elongated through a 6 inch stainless steel coil which had a volume tubular reaction zone described in Example 5. Over a of 67 milliliters. The feed charged consisted of 530 34 hour period, peracetic acid was fed at the rate of grams of allyl chloride, 0.95 cc. of a 35 weight percent 940 ml/hr. while the divinylbenzene solution was fed at solution of Victawet 35B in acetic acid, and 451 grams of a rate of 474 ml./hr. During this period 2,000 grams a 27.4 weight percent solution of peracetic acid in acetone. of divinylbenzene-ethyl acetate solution (with 4 grams of The reaction mixture was maintained in the liquid phase 2,4-dinitrochlorobenzene as a polymerization inhibitor) by supplying 75 p.s.i.g. nitrogen pressure at an operative 45 and 3784 grams of the peracetic acid solution had been pressure of 100 C.; the residence time as 17.4 minutes. Supplied to the reaction zone. The reaction zone jacket Subsequent stripping under reduced pressure of the effiu temperature was maintained at 70° C.; the pressure was ent from the reaction zone (to remove the excess chloro between about 80-115 p.s.i.g.; the residence time was 2 alkene and acetone), followed by dilution of the residue minutes. The reaction was sufficiently exothermic to ele with 500 grams of carbon tetrachloride and then water 50 vate the liquid reaction mixture to 98-102 C. in transit washing, removed the acetic acid. The resulting oil layer through the reaction zone. Analysis of the effluent showed was then distilled under reduced pressure. Based on 89 a conversion of 95 weight percent based on the period percent of the available peracetic acid consumed, an 81.5 actually consumed. percent yield of epichlorohydrin was obtained. The effluent from the reaction zone was passed con 55 tinuously into a steam-jacketed coil type stripper equipped Example 8 with a cyclone separator operated at 98 C. at 75 mm. of Hg. This equipment effectively removed the major A tubular reactor for the continuous preparation of part of the volatile materials present which were pre styrene oxide was set up according to the following dis dominantly ethyl acetate and acetic acid. This was fol cussion. Peracetic acid (24.8 weight percent in ethyl 60 lowed by a second stripper similarly constructed and op acetate solution) was fed from one positive displacement terated at 5 mm. of Hg pressure at 98 C. The residual controlled volume pump while styrene containing 0.5 liquid was rapidly flash distilled from the residue material weight percent of dinitrochlorophenol as a polymerization and analyzed for epoxide content. In all, 572 grams of inhibitor was fed from a similar pump into a tubular distillate were collected. Analyses by the pyridine hydro reaction zone consisting of a coiled length of /8 inch stain 65 chloride-pyridine showed the presence of 59 weight per less steel tube having a volume of 66 milliliters. The cent of divinylbenzene dioxide in the product mixture. pump rates were adjusted to provide a molar ratio of On the knowledge that the starting material contained peracetic acid to styrene into the reaction zone of 0.678 55 percent divinylbenzene, this represented a process yield at a contact time of 4 minutes. The temperature of the of 49.3 percent of divinylbenzene dioxide. reaction zone was maintained at 60° C. by suspension of said zone into vapors of a refluxing azeotrope of water 70 Example 11 and methyl acetate (80 weight percent methyl acetate). In this example the equipment described in Example 5 A reaction pressure of 21.5 psi.g. maintained by a spring was employed. At a jacket temperature of 125° C. and Yictor Chemical Co. trademark for Nas(2-ethylhexyl)- a system pressure of 100 psi.g., peracetic acid and ethyl P:Oia)s. - -75 Crotonate were fed into the reaction zone at rates of 160 2 977,sa cc./hr. and 125 cc./hr., respectively. After six hours, A total weight of 670 grams of solid product analyzing 701 grams (6.15 mols) of ethyl crotonate and 945 grams 88 percent purity as epoxystearic acid (by the conven (3.10 mols of a 25 weight percent solution in ethyl ace tional pyridine hydrochloride in pyridine procedure) was tate) of peracetic acid had been fed into said zone. The obtained, representing a yield of 91.1 percent of the theo residence time was 9.9 minutes. Analysis, at the opera retical amount of product. An iodine value of 3.93 es tive temperature, showed that thermal decomposition tablished that the major part of the residue product was, reduced the peracetic acid to an effective concentration indeed, non-olefinic in nature. of 17.5 percent and that a conversion of 91 percent of Example 14 peracid to other products was observed. Conventional Using the equipment described in Example 13, 3-cyclo distillation under reduced pressure gave 275 grams of O hexenecarbonitrile was converted into 3,4-epoxycyclohex ethyl 2,3-epoxybutyrate having a boiling point of 96° C. anecarbonitrile. The candidate ethylenic reagent was at 50 mm. of Hg; in 30/D equal to 1.4154; and purity by introduced into the reaction zone which was maintained saponification analysis equal to 98.7 percent. This repre at 79 C. at a feed rate of 275 cc./hr. over a 2-hour sented a yield, based on the peracid fed and consumed, period. In all, 4.87 mols (521 grams) of said ethylenic of 96.2 percent. 5 reagent was thus supplied. Simultaneously, peracetic Example 12 acid (30.0 weight percent in ethyl acetate) was intro Utilizing the equipment described in Example 5, the duced into the reaction zone at a feed rate of 665 cc./hr. epoxidation of 6-methyl-3-cyclohexenylmethyl 6-methyl- . over the same period of time. In all 5.25 mols (1327 3-cyclohexenecarboxylate was carried out as follows. At 20 grams) of the peracid solution was utilized. The opera an average reaction temperature of 64 C. and a system tive pressure was 110-120 p.s.i.g. and the residence time pressure of 120 p.s.i.g., peracetic acid in ethyl acetate was 2 minutes. Analyses indicated that total conversion (26.7 percent by weight) was fed at a rate of 695 cc./hr. of the ethylenic reagent was achieved under these con simultaneously with the above mentioned ethylenic re ditions. The liquid effluent was passed through a steam agent at a feed rate of 253 cc./hr. over a 2 hour and 45 25 jacketed stripping coil at 45 mm. of Hg operating pres minute period. The residence time was 3 minutes. Anal Sure to remove the volatile components from the reac ysis of the effluent indicated that an amount of per tion mixture. The mixture was then diluted with 500 acetic acid sufficient to convert all of the ethylenic re milliliters of ethyl benzene and repassed through the agent to epoxide had been consumed. The liquid, efflu stripping coil to complete the removal of acetic acid. ent from the tubular reaction zone was continuously in 30 Finally, the remaining material was distilled under re -troduced into a steam-jacketed stripping, coil equipped duced pressure to obtain the product. In all, 452 gm. with a cyclone separator at an operating pressure of 24 of 3,4-epoxycyclohexanecarbonitrile was obtained having mm. of:Hg.". This served to remove the majority of the the following properties: boiling point of 67° C./0.3 ethyl acetate, acetic acid, and unspent peracetic acid. The . mm. of Hg to 80 C./0.4 mm. of Hg; in 30/D equal to effluent from this equipment was also continuously fed 35 1.4719-14723; purity by pyridine hydrochloride method into a second similar piece of equipment operated at equal to 98.7 percent. This represented a yield of 75.6 steam temperature and 1 mm. of Hg pressure. Analyses percent of the theoretical amount. of the residue product gave a purity of 88.7 weight per Example 15 cent as 6-methyl-3,4-epoxycyclohexylmethyl 6-methyl-, The equipment described in Example 13 was employed 3,4-epoxycyclohexanecarboxylate. The product was ob 40 to prepare bis(2,3-epoxycyclopentyl) ether. Bis(2-cyclo tained in quantitative yield. pentenyl) ether was fed into the reaction zone at a rate Example 13 of 154 cc./hr. over a three-hour and ten-minute period Such that 2.76 mols (417 grams) of the unsaturated The tubular reaction zone in Example 5 was modified ether reagent were consumed in the operation. Peracetic by applying two jacketed sections to the length of the re 45 acid (29.3 weight percent in ethyl acetate) was fed action zone instead of only one jacket applied over the simultaneously to the reaction zone at a feed rate of entire length of said zone. This permitted application 600 cc./hr. until 7.33 mols (1900 grams) of the solution of cooling to the terminal reaction zone or the applica had been utilized over the same period of time. The tions of circulated heat exchange fluid at a temperature operative temperature was 76. C. and the pressure was different from that maintained around the first stage of 50 maintained at 110-120 p.s.i.g. The residence time was the reaction zone. In addition, the reaction zone was re 1.6 minutes. Volatile materials were removed from the fabricated from a 48 inch section of /2 inch stainless steel liquid effluent by means of a conventional steam-jacketed tubing equipped with a 4 inch stainless steel thermowell stripping coil equipped with a cyclone separator. The extending the entire length of the zone. This allowed for resulting crude product was rapidly distilled from non observation of thermal conditions at any point in said 55. distillable residue material and then carefully redistilled zone. No modifications were made in the feed or pres to remove any unconverted ether reagent or monoepoxi sure regulating systems. The working volume of the reac dized ether. The material distilling in the range from tion zone was found to be 79 milliliters. Normal operat 105 C./2 mm. of Hg to 120° C./2.5 mm. of Hg was ing pressure for this equipment was 110-120 p.s.i.g. collected as product. In all, 316 grams of material Using the equipment described above, 2.17 mols (602 60 analyzing 94 percent as bis(2,3-epoxycyclopentyl) ether grams) of oleic acid diluted with 235 grams of ethyl was collected. This represented a yield of 63.7 percent acetate was fed into the reaction Zone over a 2 hour and of bis(2,3-epoxycyclopentyl) ether. 35 minute period at a rate of 330 cc./hr. Simultaneously, 2.95 mols of peracetic acid in ethyl acetate (778 grams Example 16 of a 28.9 weight percent solution were fed into the reac 65 The equipment described in Example 13 was employed tion zone over the same period at a rate of 300 cc./hr. in the preparation of 2,3-epoxy-2-ethylhexanol. At a The residence time was 1.3 minutes. At a reaction tem reaction temperature of 90° C. and a pressure of 110 perature of 75 C., analyses showed that essentially 98 120 p.s.i.g., 2-ethyl-2-hexenol and peractic acid (29.8 percent of the theoretical amount of peracid had reacted weight percent in ethyl acetate) were simultaneously with said oleic acid. The liquid effluent was introduced 70 introduced into the reaction zone over a 2 hour and 35 into a steam jacketed stripping coil at 50 mm. of Hg minute period. In all, 4.50 mols (577 grams of 2-ethyl pressure to remove the volatile material therefron. The 2-hexenol were supplied at a feed rate of 268 cc./hr., residual product from this operation was diluted with an while 5.13 mols (1307 grams) of the peracid solution equal volume of ethyl benzene and repassed through the were utilized at a feed rate of 509 cc./hr. The residence stripping equipment twice at 1-2 mm. of Hg pressure. 75 time was 1.65 minutes. The liquid effluent was ex 2,977,874 15 16 hausted into a still operating at 50 mm. of Hg pressure conducted at a temperature in the range of from about and containing refluxing ethylbenzene in order to facili --20 to below about --130 C. tate azeotropic removal of the acetic acid by-product 6. The process of claim 5 wherein said ethylenic com from the reaction mixture. Continued reduced pressure pound is a hydrocarbon which contains ethylenic un distillation gave 498 grams of pure 2,3-epoxy-2-ethyl saturation. hexanol distilling at 58 C. at 0.3 mm. of Hg. Other 7. The process of claim 5 wherein ethylenic compound properties determined were: n 30/D=1.4375; purity by is an alcohol which contains ethylenic unsaturation. analysis with pyridine hydrochloride in chloroforms=93 8. The process of claim 5 wherein said ethylenic com percent minimum. The yield of 2,3-epoxy-2-ethylhexanol pound is an alkenyl-substituted phenol. was 76.6 percent based on the peracetic acid charge. O 9. The process of claim 5 wherein said ethylenic com Reasonable variations and modifications of the instant pound is an ether which contains ethylenic unsaturation. invention can be made without departing from the spirit 10. The process of claim 5 wherein said ethylenic and scope thereof. compound is nitrogen-containing compound selected from What is claimed is: the group consisting of amides, imides and nitriles which 1. A process which comprises continuously introduc compounds contain ethylenic unsaturation. ing an ethylenically unsaturated compound and peracetic 11. The process of claim 5 wherein said ethylenic acid into an elongated reaction zone; said ethylenically. compound is an ethylenically unsaturated phosphoric unsaturated compound containing at least 3 carbon atoms ester. and at least one ethylenic double bond in which the 12. The process of claim 5 wherein said ethylenic atoms directly joined to the ethylenic carbon atoms are 20 compound is a halogen-substituted hydrocarbon which of the group consisting of hydrogen and carbon; said contains ethylenic unsaturation, the ethylenic carbon elongated reaction zone having a length in the range of atoms of which are free from halogen substituents. from 100 V4K/it to 10,000 V4K/ar, wherein K is the 13. The process of claim 5 wherein said ethylenic minimum area obtainable from a perpendicular cross compound is an epoxyalkyl-substituted hydrocarbon sectional view of said zone, and wherein the expression 25 which contains ethyenic unsaturation. V4K/ar is in the range of from 0.25 to 5.0 inches; under 14. The process of claim 5 wherein said ethylenic pressure sufficient to maintain a liquid phase reaction compound is divinylbenzene. mixture; and for a residence time at least sufficient to 15. The process of claim 5 wherein said ethylenic introduce oxirane oxygen at the site of a carbon to car compound is propylene. bon ethylenic bond of said ethylenically unsaturated 30 16. The process of claim 5 wherein said ethylenic compound, said residence time not exceeding about 45 compound is butylene. minutes. 17. The process of claim 5 wherein said ethylenic 2. The process of clairn 1 wherein the reaction is compound is styrene. conducted at a temperature in the range of from about 18. The process of claim 5 wherein said ethylenic com --20 to below about --130 C. 35 pound is vinylcyclohexene. 3. The process of claim 2 wherein said peracetic acid is employed as a solution in an inert organic medium. References Cited in the file of this patent 4. A process which comprises continuously introduc UNITED STATES PATENTS ing an ethylenically unsaturated compound and peracetic 2,414,385 Milas ------Jan. 14, 1947 acid into an elongated tubular reaction zone; said eth 40 2,457,328 Swern ------Dec. 28, 1948 ylenically unsaturated compound containing at least 3 2,458,484 Terry ------Jan. 4, 1949 carbon atoms and at least one ethylenic double bond 2,567,237 Scanlan ------Sept. 11, 1951 in which the atoms directly joined to the ethylenic car 2,567,930 Findley------Sept. 18, 1951 bon atoms are of the group consisting of hydrogen and 2,583,569 Herzfeld ------Jan. 29, 1952 carbon; said peracetic acid being employed as a solution 45 2,692,271 Greenspan ------Oct. 19, 1954 in an inert organic medium; said elongated reaction 2,783,250 Payne et al. ------Feb. 26, 1957 zone having a length in the range of from 100 D to 2,785,185 Phillips ------Mar. 12, 1957 10,000 D, wherein D is in the range of from 0.25 to 5.0 2,838,524 Wilson ------June 10, 1958 inches and is the diameter of the circle obtained by a 50 2,873,283 Yang ------Feb. 10, 1959 perpendicular cross section taken at the narrowest point FOREIGN PATENTS along said zone; under pressure sufficient to maintain 525,888 Canada ------June 1956 a liquid phase reaction mixture; and for a residence time. 769,127 Great Britail------Feb. 27, 1957 at least sufficient to introduce oxirane oxygen at the site of a carbon to carbon ethylenic bond of said eth 55 OTHER REFERENCES ylenically unsaturated compound, said residence time not Boeseken et al.: Rec. Trav. Chim, voi. 52, pages 874 exceeding about 45 minutes. 880 (1933). 5. The process of claim 4 wherein the reaction is Swern: JACS, vol. 69, pages 1692-98 (1947). UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent No. 2,977,374 Marcia 28, 1961 Benjamin Philiips et al. It is hereby certified that error appears in the above numbered pat entcorrected requiring below. correction and that the said Letters Patent should read as Column 3 line 23, for "trems" read r terms - line 68 for "pers sure read -- pressure -- colurer 8s line 22 for "conventioal" read -- conventional -- line 48 for "produciton" read -- production -- ; line 58, for "expoxidation" read ----.. perticidepoxidation --. ... ; column 12 line 52, for "period" read Signed and sealed this 5th day of September 196i.

(SEAL) Attest:

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