US3708507A - Process for the epoxidation of unsaturated compounds - Google Patents

Process for the epoxidation of unsaturated compounds Download PDF

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Publication number
US3708507A
US3708507A US00060872A US3708507DA US3708507A US 3708507 A US3708507 A US 3708507A US 00060872 A US00060872 A US 00060872A US 3708507D A US3708507D A US 3708507DA US 3708507 A US3708507 A US 3708507A
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US
United States
Prior art keywords
acid
allyl
peracetic acid
water
unsaturated compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US00060872A
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English (en)
Inventor
G Schreyer
O Weiberg
A Kleemann
M Kruger
W Weigert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DEUTSCHE GOLD und SILBER SCHEIDEANSTALT DT
Evonik Operations GmbH
Original Assignee
Degussa GmbH
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Priority claimed from DE19691942557 external-priority patent/DE1942557C/de
Application filed by Degussa GmbH filed Critical Degussa GmbH
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Publication of US3708507A publication Critical patent/US3708507A/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals

Definitions

  • the olefinic compound to be epoxidized forms a minimum azeotrope with'water it is brought in excess amount, into contact with pure aqueous percarboxylic acid in a suitable distillation column equipped with a water trap in which case a water free solution of percarboxylic acid in the unsaturated compound collects in the 'sump while the water in the form of an azeotrope with the unsaturated compound is removed in vapor form overhead and after condensation of the vapors in the water trap is separated from the unsaturated compound which latter is again returned to the column.
  • FIGURE is a diagrammatic illustration of a continuous azeotropic distillation according to the invention.
  • a distillation column 1.
  • Percarboxylic acid solution is introduced by way of conduit 5 and the compound to be epoxidized is introduced via conduit 4.
  • the column is also equipped with heat exchanger 6 and thermometer 7.
  • the azeotrope of water and unsaturated compound is led via conduit 10 and heat exchanger 9 into water trap 2 whereby after the separation the recovered unsaturated compound is returned to the column via conduit 8 while the water leaves the system via conduit 11 and valve 12.
  • the solution ofpercarboxylic acid in the compound to be epoxidized collecting in the sump of column 1 is withdrawn via conduit 3.
  • the pressure in the column should be adjusted so that the sump temperature is the region in which no significant destruction takes place of the percarboxylic acid employed.
  • the temperature is between 20 and C. but it can be as low as 0 C. or as high as 110 C.
  • the sump product is subjected to a subsequent reaction at 30 100 C.
  • the percarboxylic acids can be extracted from their aqueous solution by the unsaturated compounds themselves which are to be epoxidized employing known processes for extraction.
  • known processes for extraction there can be used any of the processes disclosed in the article in Vauck-Miiller, Grundoperationen Chemischer Maschinenstechnik, (1966) pages 662, et seq. The entire disclosure of the article in Vauck- Muller is hereby incorporated by reference.
  • the solution of percarboxylic acid in the compound to be epoxidized is subjected to a subsequent reaction at 30 100 C.
  • the extraction like the azeotropic dehydration, can be carried out continuously or batchwise. If the percarboxylic acid extract still contains small amounts of water these can be easily removed by a subsequent azeotropic dehydration, for example in the manner described above.
  • aqueous solutions of percarboxylic acids employed can be used in any desired concentration of the percarboxylic acid.
  • they are pure aqueous solutions in the concentrations which are produced, for example by the processes described in German Pat. No. 1,165,576, German Auslegeschrift Pat. No. 1,170,926 and Weiberg US. Pat. No. 3,264,346, e.g., about 40 to 60 percent of lower peralkanoic acid and 60 to 40 per-, cent of water by weight although the water can vary from 20 to percent by weight.
  • suitable percarboxylic acids include peracetic acid, perpropionic acid, perbutyric acid, perisobutyric acid and pervaleric acid.
  • the molar proportions of olefinically unsaturated compound to the percarboxylic acid can be adjusted at pleasure and is not critical. Preferably the proportions range between 1.2 and 25 to l.
  • the working up of the reaction mixture obtained by the process of the invention can take place in known manner, for example by distillation or extraction.
  • Unsaturated hydrocarbons for example diisobutylene, styrene, para menthene, octadecene-l, nonene- 2, octylene, alpha-pinene, camphene, beta-pinene, stilbene, cycloheptene, alpha carotene, beta carotene,
  • limonene p-methyl styrene, l-vinyl cyclohexane
  • allyl and vinyl esters for example allyl acetate, allyl propionate, vinyl acetate, vinyl stearate, allyl stearate, allyl butyrate, vinyl hexanonate
  • unsaturated ethers for example, diallyl ether, 2-metha1lyl ethyl ether, di (Z-methallyl) ether, ethyl vinyl ether, divinyl ether, allyl Z-methyl propen-2-y1 ether, allyl methyl cyclohexen-3-y1 ether, allyl butene-Z-yl ether, allyl ethyl ether, allyl cyclopehten-Z-yl ether, allyl vinyl ether, allyl octyl ether, vinyl methyl ether, vinyl isobutyl ether,
  • the reaction time is sharply reduced because of the increased concentration of both the peracid and unsaturated compound compared with the known processes using solutions of percarboxylic acids in inert solvents.
  • the yields are increased over those obtained with epoxidation processes with vapor form percarboxylic acids (for example compare British Pat. No. 1,053,972 Example 6).
  • the working up is simplified since besides the unsaturated compound added in excess and the carboxylic acid arising from the percarboxylic acid no materials need to be separated from the reaction product.
  • the capacity of an existing plant can be considerably increased and the expense for the apparatus necessary for the working up reduced. In carrying out the process in continuous fashion the water free mixture of percarboxylic acid and unsaturated compound are completely reacted,
  • EXAMPLE 1 A mixture of 500 grams moles) of allyl acetate and- 121.3 grams of aqueous peracetic acid (47.7 weight percent peracetic acid, 0.75 mol) was azeotropically dehydrated in a vacuum (42 Torr.) in a 1 meter Vigreux column having a water trap. The sump temperature of the column did not exceed 36 C. The separated water still contained 0.044 mol of peracetic acid which was returned to the column having an insufficient selectivity capacity. The sump product was subsequently held at normal pressure at a temperature of 50 C. whereby after 12 hours peracid was no longer detectable in the reaction mixture. By working up with a vacuum distillation to a maximum bath temperature of 50 C. there were obtained 67.7 grams of pure glycidyl acetate. This corresponds to a yield of 91 percent of theory based on the peracetic acid.
  • EXAMPLE 2 1n the apparatus shown in the drawing (effective column height 2 meters) 2.5 mols of a 50.8 weight percent aqueous peracetic acid together with 8 mols (800 grams) of allyl acetate were dehydrated in a vacuum at a sump temperature of 50 C. The subsequent reaction to quantitative peracetic acid reaction took 13 hours at 50 C. By working up in a distillation there were obtained 258 grams of glycidyl acetate which corresponds to a yield of 89 percent of theory based on the peracetic acid.
  • EXAMPLE 3 In a 50 mm. diameter 2.50 meter long glass column filled with Raschig rings and equipped with a water trap and a return line for the organic phase separated from the head of the column at normal pressure there were continuously added hourly between the upper and middle thirds of the column 127 grams of aqueous peracetic acid (46.9 weight percent peracetic acid, 0.785 mol), and between the middle and the lower third of the column 492 grams (6.43 mols) of allyl chloride. The peracetic acid was dehydrated azeotropically. The sump temperature did not exceed 48 C. The water separated per hour still contained 0.0024 mol of peracetic acid. The correspondingly drawn off sump product had a peracetic acid content of about 6.5 weight percent (or 0.47 mol/hour), i.e., there had already occurred about a 40 percent reaction of the peracetic acid.
  • the sump product was subsequently held in a glass flask for 6 hours with reflux boiling at normal pressure at 50 C.
  • gas chromatography and titrimetrical determination of the epoxide in the reaction mixture there were found 12.8 weight percent epichlorhydrin and by titrimetrical determination there was found 0.12 weight percent of peracetic acid. This corresponds to a 98.7 percent peracetic acid reaction and an analytically detected epichlorhydrin yield of 97 percent of theory based on the peracetic acid.
  • EXAMPLE 4 In a 50 mm. diameter extraction column having 30 perforated plates (20 percent passage) and having an outer mantle cooled to about 5 C. there were continuously fed in countercurrent flow 3,000 grams per hour (39.2 mol/hour) of allyl chloride and 407 grams per hour of aqueous peracetic acid (51.9 weight percent, 2.77 mol/hour). The continuously withdrawn organic phase (3,160 grams/hour) contained 5.0 weight percent of peracetic acid (2.08 mol/hour), and 0.16 weight percent'water (0.28 mol/hour).
  • a process for the liquid phase epoxidation of a difficulty epoxidizable liquid olefinically unsaturated compound selected from the group consisting of olefinically unsaturated hydrocarbons, allyl and vinyl esters, ally] and vinyl ethers, allyl halides and unsaturated alcohols with an organic peroxide comprising azeotropically distilling an aqueous solution consisting essentially of water, a lower peralkanoic acid having at least two carbon atoms and the compound to be epoxidized to separate the water from said per acid and then holding the solution of peralkanoic acid in liquid epoxidizable compound at 30 to 100 C until the epoxidation is completed, the molar proportion of olefinically unsaturated compound to peralkanoic acid being between 1.2 and 25 to l.
  • olefinically unsaturated compound is diisobutylene, styrene, allyl acetate, diallyl ether, 2-methallyl ether, 1- buten-S-ol or allyl chloride.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Compounds (AREA)
US00060872A 1969-08-21 1970-08-04 Process for the epoxidation of unsaturated compounds Expired - Lifetime US3708507A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19691942557 DE1942557C (de) 1969-08-21 Verfahren zur Herstellung von Epoxyden

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US3708507A true US3708507A (en) 1973-01-02

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Country Link
US (1) US3708507A (de)
JP (1) JPS5118406B1 (de)
AT (1) AT300748B (de)
BE (1) BE755100A (de)
CA (1) CA967166A (de)
CH (1) CH539629A (de)
FR (1) FR2056465A5 (de)
GB (1) GB1323335A (de)
SE (1) SE370234B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4071541A (en) * 1975-02-04 1978-01-31 Interox Chemicals Limited Epoxidation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1012484B (it) * 1974-05-17 1977-03-10 Snam Progetti Processo per la preparazione di epossidi di vinilesteri

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2877266A (en) * 1957-06-04 1959-03-10 Columbia Southern Chem Corp Preparation of peracids
US2903465A (en) * 1959-09-08 Epoxidation
CA594167A (en) * 1960-03-08 Phillips Benjamin Process for producing peracids from aliphatic carboxylic acids
DE1083797B (de) * 1958-12-17 1960-06-23 Huels Chemische Werke Ag Verfahren zur Herstellung von Epoxyden
GB975715A (en) * 1962-02-01 1964-11-18 Degussa A process for the preparation of solutions of pure percarboxylic acids

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2903465A (en) * 1959-09-08 Epoxidation
CA594167A (en) * 1960-03-08 Phillips Benjamin Process for producing peracids from aliphatic carboxylic acids
US2877266A (en) * 1957-06-04 1959-03-10 Columbia Southern Chem Corp Preparation of peracids
DE1083797B (de) * 1958-12-17 1960-06-23 Huels Chemische Werke Ag Verfahren zur Herstellung von Epoxyden
GB975715A (en) * 1962-02-01 1964-11-18 Degussa A process for the preparation of solutions of pure percarboxylic acids

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4071541A (en) * 1975-02-04 1978-01-31 Interox Chemicals Limited Epoxidation

Also Published As

Publication number Publication date
SE370234B (de) 1974-10-07
CH539629A (de) 1973-07-31
CA967166A (en) 1975-05-06
FR2056465A5 (de) 1971-05-14
GB1323335A (en) 1973-07-11
AT300748B (de) 1972-08-10
JPS5118406B1 (de) 1976-06-09
DE1942557A1 (de) 1971-03-18
BE755100A (fr) 1971-02-01

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