CA1134842A - Process for the preparation of epoxies - Google Patents
Process for the preparation of epoxiesInfo
- Publication number
- CA1134842A CA1134842A CA000316964A CA316964A CA1134842A CA 1134842 A CA1134842 A CA 1134842A CA 000316964 A CA000316964 A CA 000316964A CA 316964 A CA316964 A CA 316964A CA 1134842 A CA1134842 A CA 1134842A
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- CA
- Canada
- Prior art keywords
- olefin
- peracetic acid
- reaction mixture
- epoxidation
- acid containing
- 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.)
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Classifications
-
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/24—Peroxy compounds the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids
- C07C409/26—Peracetic acid
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
PROCESS FOR THE PREPARATION OF EPOXIES
ABSTRACT OF THE DISCLOSURE
A process for the preparation of an epoxide from an olefin having a boiling point above 40°C at pressures from 1 to 15 bar has been discovered. The present process has the advantage that the olefin may be directly reacted with a crude peracetic acid reaction medium containing impurities such as heavy metal oxidation catalysts without the necessity of first purifying the peracetic acid. In the process, the olefin is epoxidized by the crude reaction medium in the presence of a complexing agent for the catalyst, at a temperature from about 50 to about 150°C, at a pressure from about 1 to about 15 bar, while simultaneously dis-tilling off unreacted acetaldehyde, solvent, and acetic acid by-product, by passing an inert gas through the reaction medium.
(I)
ABSTRACT OF THE DISCLOSURE
A process for the preparation of an epoxide from an olefin having a boiling point above 40°C at pressures from 1 to 15 bar has been discovered. The present process has the advantage that the olefin may be directly reacted with a crude peracetic acid reaction medium containing impurities such as heavy metal oxidation catalysts without the necessity of first purifying the peracetic acid. In the process, the olefin is epoxidized by the crude reaction medium in the presence of a complexing agent for the catalyst, at a temperature from about 50 to about 150°C, at a pressure from about 1 to about 15 bar, while simultaneously dis-tilling off unreacted acetaldehyde, solvent, and acetic acid by-product, by passing an inert gas through the reaction medium.
(I)
Description
li3~B42 BACKGROUND OF THE INVENTION
The present invention refers to a process for the preparation of epoxides (oxiranes) by reacting compounds con-taining one or more olefinic double bonds with peracetic acid.
Heretofore, epoxidation with per acids has been carried out in such a way, that the per compound, which had been prepared first, was freed from reducing and decomposing substances, such as aldehydes and traces of heavy metals, by distillation, and finally reacted with the olefinic compound (cf. Ullman, Encyclo-pedie der Technischen Chemie, 4th Edition, vol. 10, p. 563 ff, publishing house Chemie, Weinheim/Bergstr., 1975). Such a pro-cess has the disadvantage that purification of the per acid is subject to a danger of explosion. It is not possible to do without the purification of the peracetic acid, which is pre-pared through oxidation of acetaldehyde with oxygen, because the unconverted acetaldehyde is converted with the peracetic acid to acetic acid through a redox reaction.
Thus an object of the present invention is to provide a process by which the dangerous distillation to obtain pure peracetic acid is not needed.
SUMMARY OF THE INVENTION
There has now been discovered a process for the preparation of an epoxide from an olefin which has a boiling point above 40C at 1 to 40 bar, comprising oxidizing acetalde-hyde with oxygen in the presence of an organic solvent, which boils below the boiling point of said olefin, and a heavy metal oxidation catalyst to form a peracetic acid containing reac-tion mixture, containing acetaldehyde, peracetic acid, said catalyst and said organic solvent and subsequently epoxidizing the olefin by contacting said olefin with the peracetic acid containing reaction mixture, said mixture being at a tempera-ture of from -10 to +10C prior to said contacting, in the presence of a complexing agent for the .E~
- 1 - f~
1134~4Z
catalyst, at a temperature from about 50 to about 150C, at a pressure from about 1 to about 15 bar, while simultaneously dis-~tilling off unreacted acetaldehyde, solvent, and acetic acid by-product, by pa~sing an inert yas through the reaction mixture.
DESCRIPTION OF THE PREFERRED E~!BODIMENTS
In the process of the present invention it is, of course, possible to vary the particular epoxidation conditions and thus epoxidation may be effected at any pressure from about 1 to about 15 bar. Also, any typical epoxidation catalyst may be employed. Likewise, the olefin may be brought into contact with ¦the peracetic acid reaction mixture in the form of the pure olefin ~or in the form of a solution of the olefin in an organic solvent.
IObviously, the oxygen may be introduced as pure oxygen or in the ¦form of an oxygen containing gas, such as air.
According to a preferred version of the process pursuant to the invention, the peracetic acid reaction mixture is cooled to -10 to +10C, the complexing agent and, if necessary, the epoxi-dation catalyst added to the peracetic acid reaction mixture, or to the olefin or olefin solution, and the peracetic acid reaction ¦
mixture is gradually added to the olefin, or olefin solution, kept under epoxidation conditions.
According to another preferred version of the process pursuant to the invention, the olefin, or olefin solution and, at the same time, the peracetic acid reaction mixture are continu-ously metered into a reactor kept at epoxidation conditions; unre-¦ acted acetaldehyde, solvent and, paxtly, acetic acid are continu-ously distilled off, by passing an inert gas through; and the ¦liquid reaction mixture containing the epoxy is continuously with-¦drawn from the reactor sump.
. I .
84;2 The first stage of the process, i.e. oxida~ion of the acetaldehyde with oxygen or gases containing oxygen, such as air, to peracetic acid, is carried out pursuant to known proc~sses, in which the-acetaldehyde diluted with a solvent is reacted with oxygen or air. In this connection, reference is made to D. Swern, Chemical Reviews, vol. 45 (1949), pp. 5 to 8.
In industry, preference is given to performing the reaction in the presence of a catalyst. In this respect, reference is e.g. made to German published patent application 1,165,009.
Suitable catalysts are, for example, FeC13, Fe(~03)2, Co(~O3)2, Co(CH3C00)2 and molybdenum acetonyl-acetonate. With respect to conversion rate and selectivity, there is practically no difference between the iron and cobalt salts. The selectivity in the formation of peracetic acid is more than 90% and the aldehyde conversion rate is about 60%.
The catalyst is employed in customary quantities, for example, in quantities from about 0.001 to about 0.01 percent, by weight, referred to the acetaldehyde. Oxidation is carried out at any customary temperature, such as from about O to about 30C, preferably between about 0 and about 20C.
Customarily, the reaction periods are from about 30 to about 120 minutes.
Solvents used in the oxidation of the acetal-dehyde may be, for example, acetone, acetic ester, chloro-benzene, methylethyl ketone, acetic acid, or methylene chloride, preferably, acetone or acetic ester. The quantity of solvent is chosen in such a way, that the concentration of acetaldehyde in the oxidation mixture is within a range of about 5 to about ~0 percent, preferably within a range from about 10 to about 20 percent.
-11348~Z
¦ It is an essential point of the invention, that the reaction mixture obtained in the oxidation of~the acetaldehyde is not processed to separate the pure peracetic acid, but the olefin is reacted with the reaction mixture containing acetaldehyde, solvent and catalyst. During this time, most of the organic sol-vent, as ~ell as part of the formed acetic acid and the unreacted acetaldehyde are distilled off with the addition of an inert gas.
Of course, this is possible only if, under the conditions of epoxidation, the boiling points of the inert organic solvents and 10 ¦ the acetaldehyde are lower than the boiling point of the olefin ¦used for epoxidation. Consequently, the process pursuant to the invention is only suitable for the conversion of such olefins, the boiling point of which, under the epoxidation conditions to be considered here, is higher than the boiling point of the acetaldehyde. Selection of a suitable organic solvent depends of course upon the boiling point of the olefin to be subjected to epoxidation, i.e. under the epoxidation conditions, the boiling point of the organic solvent has to be lower than the hoiling point of the olefin.
Olefins which may be epoxidized according to the processj puxsuant to the invention are, for example, normal and iso-alkenes, substituted alkenes,~oe~st,abu~nesaturated fatty acids and polyolefins`
with double bonds in middle and/or terminal position. The follow-ing may be mentioned as examples of such alkenes:
Hexene-l, octene-l, decene-l, undecene-l, dodecene-l, octadecene-l, polycyclopentadiene, polybutadiene-1,2 and!or polybutadiene-1,4, allyl chloride, propylene trimer, linseed oil and oleic acid.
~11 these olefins possess boiling points that are higher than the boiling point of acetaldehyde. Examples of . ~
~ _4_ ~
i olefins that cannot be converted accorclin~ to the process pursuant, to the invention because their boiling points are lower than the boiling point of acetaldehyde are ethene, propene and the butenes.l Epoxidation is typically carried out at temperatures in !
a range from about 50 to about 150C~ preferably from about 80 to about 110C, and at pressure of up to about 15 bar. Epoxidation is performed under pressure when a comparatively low-boiling sol-vent is used, which is necessary when the olefinic compound to be subjected to epoxidation also has a relatively low boiling point. !
Suitable solvents are, for example, acetone, acetic ester, methylene chloride, methyl chloride, chlorobenzene and methylethyl ketone. For reasons of economy ald processing tech-nology, the same solvent is used for epoxidation, as in the oxida-tion of the acetaldehyde, preferably acetone or acetic ester.
The followiny table shows by way of an example some of the possible and expedient process parameters:
Alkene Temperature Pressure Solvent (C) (bar) _ I
hexene-l 90 - 100 12 methylene chloride octene-l 90 - 100 3 acetone decene-l 90 - lO0 1 acetic ester polybutadiene-1.290 - l00 l acetic ester polybutadiene-1.490 - 100 1 acetic ester octadecene-l 90 - 100 1 acetic ester 25 undecene-l 90 - lO0 1 acetic ester propylene trimer90 - lO0 1 acetic ester oleic acid 90 - lO0 l acetic ester linseed oil 90 - 100 1 acetic ester allyl chloride90 - lO0 15 methylene chloride I '-5.
For purposes of the formation of complex compounds with the heavy metal catalysts present from the oxidation of the alde-hyde to per acid, as well as to prevent decomposition of the per acid through a wall reaction with meta]lic materials (see M. Andoh let al., Nippon Ragaku Kai Shi (1975), No. 8, 1383), a complexing agent is used in the epoxidation stage. Suitable complexing agents are, for example, polyphosphoric acid, pyromellitic acid and pyridinecarboxylic acids.
If desired, one of the customary epoxidation catalysts can be used during epoxidation. Among those which are useful are sulfuric acid, trifluoroacetic acid, tungstic and molybdic acid, alkanesul~onic acids, cation exchange resins and zinc phosphate.
The compounds polyphosphoric acid and pyromellitic acid, effective as complexing agents, also exert a catal~tic influence on epoxi-dation.
The epoxidation catalysts, or complexing agents, aretypically used in quantities o ahout 0.01 to about 1 percent, by weight, preferably in quantities of about 0.1 to about 0.3 percent, by weight, Leferred to the per acid. Preferably, use is made of polyphosphoric acid or pyromellitic acid as complexing agent in epoxidation and as epoxidation catalyst, or of sulfuric acid as epoxidation catalyst and ofla pyridinecarboxylic acid as com- !
plexing agent.
In contrast to the known process, the catalyst used in the oxidation of the acetaldehyde remains in the reaction mixture. !
It influences the progress of epoxidation to a decisive extent.
It has, for example, been found, that some of the catalysts used in the oxidation of acetaldehyde exert a negative influence on selectivity during e~oxidation. This is, for example, the case 113~8~Z
with feriferous an organic catalysts and can be explained as follows: as is known, an intermediary, dicyclic,addition complex is formed during epoxidation (see Bartlett, Rec. Chem.
Proc., 11, 51, (1960)).
¦¦ + ¦ C - R ~ C - R~
C H ..., 0 H------0 As was shown by our investigations, this addition complex can break down in two directions and into different reaction products:
r~o~--.C~
a. b.
¦ / 0+ ~ C - R ¦l + 0 + C - R ~ -Path a. ch?racterizes normal decomposition to the epoxide, path b. is strongly catalysed, for example, by heavy metal ions, thus the decline in selectivity is only in part due to a direct decomposition of the per acid since, in the absence of olefinic double bonds, due to the presence of heavy metal ions, it breaks down more slowly under the same reaction con-ditions. merefore, metals present in the form of inorganic salts during the oxidation of the acetaldehyde have to be rendered harmless by precipitation or complex formation. Among others, the compounds mentioned above are suitable for that purpose.
Compared with the known process, the process pursuant to the invention has the advantage, that distillation of the 11348~2 'peracetic acid, which is subject to explosion hazards, as well as the processing steps connecte~ therewith, are eliminated. In addition, in the process pursuant to the invention, the concentra-tion of peracetic acid in the epoxidation reaction mixture can always be kcpt low, but reaction with the olefinic com~ound will nevertheless proceed rapidly. Since, in the process pursuant to the invention, unreacted acetaldehyde is largely distilled off, there is practically no reaction of this compound with the per-acetic acid. This fact, as well as the simultaneous distilling ¦off of the solvents re~uired for oxidation, but harmful for epoxidation, leads to a very high selectivity for the epoxy com-¦pounds.
¦ The following nonlimiting examples further demonstrate ¦the present invention.
15 ¦ Example I
¦ A reactor of enamelled steel and e~uipped with a coolingjacket, a gas supply and a gas discharge line, as well as a mag-netic stirrer, was charged with 200 g acetaldehyde and 1800 g ethyl acetate, to which 0~01~ by weight, referred to the acetalde-hyde, of FeC13 was added as catalyst. For 2 hours, 1 normalliter/hr. of oxygen was introduced into the mixture cooled to ~10C, under a pressure of albout 4 bar.
Analysis of the reaction mixture showed an aldehyde conversion rate of 63% and a peracetic acid selectivity of 97%.
The reaction mixture was used in the epoxidation described in the following without any further processing.
For epoxidation of decene-l, 100 g of this material were placed in a pipe reactor (bubble column) and heated to 100C by means of jacket heating. After that, nitrogen was conducted ~1348~2 through the decene-l at a flow speed of 20 lit. per hour. In the following, 285 g of the reaction mixture containing per-acetic acid and prepared in the manner described above were cooled to 0C, mixed with polyphosphoric acid and fed into the heated reactor within 15 minutes. Continuing the bubbling through of nitrogen, the reaction was continued for another 5 minutes; the preponderant part of the low-boiling components was distilled off and condensed in a cooler. In addition to acetic ester, acetic acid and acetaldehyde, the distillate still contained 29% of the charged peracetic acid.
An epoxydecane solution free from peracetic acid was withdrawn from the sump of the reactor and the solvent distilled off. Referred to the decene-L, the reaction con-version was 33%, referred to the peracetic acid it was 71%.
Referred to the epoxydecane, the selectivity was 98%, while referred to the peracetic acid it was 92%.
ExamPle II
A pipe reactor was used for the continuous pre-paration of epoxyoctadecane. The interior of that reactor was equipped with a steam-heated, coiled spiral tube provided with a supply tube and a gas discharge tube at the upper end, and a gas supply tube at the lower end, while the exterior was equipped with a coil, a gas supply tube at the lower end and a gas dis-charge tube at the upper end, with the lower discharge tube of the inner spiral tube ending in the lower part, and the upper gas discharge tube of the inner spiral tube ending in the upper part of the external part of the reactor. 1540 g/hr. of a liquid reaction mixture cooled to 0C and consisting of 765 g octadecene-l and a reaction mixture containing peracetic acid mixed with polyphosphoric acid as ' .
1134~
!
described in ~xample I, were metered into the upper supply tube llf the ir~ner spiral coil. The reaction mixture containing per-¦¦acetic acid consi'sted of 115 g peracetic acid; 40.4 g acetalde-!I hyde, 2.~3 g acetic acid, 98~ g acetic ester, 0.1 ~ FeC13 and j 0.35 g polyphosphoric acid.
The reaction mixture went from top to bottom in the team-heated spiral coil. It fillefl its volume to a~out 20%. A
stream of inert gas was introduced at the lower end of the spiral coil, in a counter-current with the reaction mixture. On this o !j occasion, the biggest part of the low-boiling components (acetic ¦ester, acetic acid, acetaldehyde ana unreacted peracetic acid) ~¦evaporated and, going through the upper gas supply tube, reached llthe upper space of the external part of the re~ctor, which func-¦!tions asvapor space of the after-reaction zone. The epoxydecane 1l solution free from peracetic acid went through the lower discharge tube of the spiral coil to the lower part of the external part of the reactor, which functions as after-reaction space. Inert gas was supplied in this part of the reactor as well. There, the Iremainder of the low-boiling components evaporated, and, together with the low-boiling components evaporated in the spiral coil, was withdrawn at the upper end of the external part of the reactor via a cooler and ~ed to a condenser. The epoxydecane solution was ¦withdrawn from the after-reaction space and then processed hy means of distillation. I
The conversion, referred to the octadecene-l, was 42~, ¦
referred to the peracetic acid it was 92%. The selectivity re-l ferred to the epoxyoctadecane was 97%, referred to the per acid I it was 90~.
.` ` . ,
The present invention refers to a process for the preparation of epoxides (oxiranes) by reacting compounds con-taining one or more olefinic double bonds with peracetic acid.
Heretofore, epoxidation with per acids has been carried out in such a way, that the per compound, which had been prepared first, was freed from reducing and decomposing substances, such as aldehydes and traces of heavy metals, by distillation, and finally reacted with the olefinic compound (cf. Ullman, Encyclo-pedie der Technischen Chemie, 4th Edition, vol. 10, p. 563 ff, publishing house Chemie, Weinheim/Bergstr., 1975). Such a pro-cess has the disadvantage that purification of the per acid is subject to a danger of explosion. It is not possible to do without the purification of the peracetic acid, which is pre-pared through oxidation of acetaldehyde with oxygen, because the unconverted acetaldehyde is converted with the peracetic acid to acetic acid through a redox reaction.
Thus an object of the present invention is to provide a process by which the dangerous distillation to obtain pure peracetic acid is not needed.
SUMMARY OF THE INVENTION
There has now been discovered a process for the preparation of an epoxide from an olefin which has a boiling point above 40C at 1 to 40 bar, comprising oxidizing acetalde-hyde with oxygen in the presence of an organic solvent, which boils below the boiling point of said olefin, and a heavy metal oxidation catalyst to form a peracetic acid containing reac-tion mixture, containing acetaldehyde, peracetic acid, said catalyst and said organic solvent and subsequently epoxidizing the olefin by contacting said olefin with the peracetic acid containing reaction mixture, said mixture being at a tempera-ture of from -10 to +10C prior to said contacting, in the presence of a complexing agent for the .E~
- 1 - f~
1134~4Z
catalyst, at a temperature from about 50 to about 150C, at a pressure from about 1 to about 15 bar, while simultaneously dis-~tilling off unreacted acetaldehyde, solvent, and acetic acid by-product, by pa~sing an inert yas through the reaction mixture.
DESCRIPTION OF THE PREFERRED E~!BODIMENTS
In the process of the present invention it is, of course, possible to vary the particular epoxidation conditions and thus epoxidation may be effected at any pressure from about 1 to about 15 bar. Also, any typical epoxidation catalyst may be employed. Likewise, the olefin may be brought into contact with ¦the peracetic acid reaction mixture in the form of the pure olefin ~or in the form of a solution of the olefin in an organic solvent.
IObviously, the oxygen may be introduced as pure oxygen or in the ¦form of an oxygen containing gas, such as air.
According to a preferred version of the process pursuant to the invention, the peracetic acid reaction mixture is cooled to -10 to +10C, the complexing agent and, if necessary, the epoxi-dation catalyst added to the peracetic acid reaction mixture, or to the olefin or olefin solution, and the peracetic acid reaction ¦
mixture is gradually added to the olefin, or olefin solution, kept under epoxidation conditions.
According to another preferred version of the process pursuant to the invention, the olefin, or olefin solution and, at the same time, the peracetic acid reaction mixture are continu-ously metered into a reactor kept at epoxidation conditions; unre-¦ acted acetaldehyde, solvent and, paxtly, acetic acid are continu-ously distilled off, by passing an inert gas through; and the ¦liquid reaction mixture containing the epoxy is continuously with-¦drawn from the reactor sump.
. I .
84;2 The first stage of the process, i.e. oxida~ion of the acetaldehyde with oxygen or gases containing oxygen, such as air, to peracetic acid, is carried out pursuant to known proc~sses, in which the-acetaldehyde diluted with a solvent is reacted with oxygen or air. In this connection, reference is made to D. Swern, Chemical Reviews, vol. 45 (1949), pp. 5 to 8.
In industry, preference is given to performing the reaction in the presence of a catalyst. In this respect, reference is e.g. made to German published patent application 1,165,009.
Suitable catalysts are, for example, FeC13, Fe(~03)2, Co(~O3)2, Co(CH3C00)2 and molybdenum acetonyl-acetonate. With respect to conversion rate and selectivity, there is practically no difference between the iron and cobalt salts. The selectivity in the formation of peracetic acid is more than 90% and the aldehyde conversion rate is about 60%.
The catalyst is employed in customary quantities, for example, in quantities from about 0.001 to about 0.01 percent, by weight, referred to the acetaldehyde. Oxidation is carried out at any customary temperature, such as from about O to about 30C, preferably between about 0 and about 20C.
Customarily, the reaction periods are from about 30 to about 120 minutes.
Solvents used in the oxidation of the acetal-dehyde may be, for example, acetone, acetic ester, chloro-benzene, methylethyl ketone, acetic acid, or methylene chloride, preferably, acetone or acetic ester. The quantity of solvent is chosen in such a way, that the concentration of acetaldehyde in the oxidation mixture is within a range of about 5 to about ~0 percent, preferably within a range from about 10 to about 20 percent.
-11348~Z
¦ It is an essential point of the invention, that the reaction mixture obtained in the oxidation of~the acetaldehyde is not processed to separate the pure peracetic acid, but the olefin is reacted with the reaction mixture containing acetaldehyde, solvent and catalyst. During this time, most of the organic sol-vent, as ~ell as part of the formed acetic acid and the unreacted acetaldehyde are distilled off with the addition of an inert gas.
Of course, this is possible only if, under the conditions of epoxidation, the boiling points of the inert organic solvents and 10 ¦ the acetaldehyde are lower than the boiling point of the olefin ¦used for epoxidation. Consequently, the process pursuant to the invention is only suitable for the conversion of such olefins, the boiling point of which, under the epoxidation conditions to be considered here, is higher than the boiling point of the acetaldehyde. Selection of a suitable organic solvent depends of course upon the boiling point of the olefin to be subjected to epoxidation, i.e. under the epoxidation conditions, the boiling point of the organic solvent has to be lower than the hoiling point of the olefin.
Olefins which may be epoxidized according to the processj puxsuant to the invention are, for example, normal and iso-alkenes, substituted alkenes,~oe~st,abu~nesaturated fatty acids and polyolefins`
with double bonds in middle and/or terminal position. The follow-ing may be mentioned as examples of such alkenes:
Hexene-l, octene-l, decene-l, undecene-l, dodecene-l, octadecene-l, polycyclopentadiene, polybutadiene-1,2 and!or polybutadiene-1,4, allyl chloride, propylene trimer, linseed oil and oleic acid.
~11 these olefins possess boiling points that are higher than the boiling point of acetaldehyde. Examples of . ~
~ _4_ ~
i olefins that cannot be converted accorclin~ to the process pursuant, to the invention because their boiling points are lower than the boiling point of acetaldehyde are ethene, propene and the butenes.l Epoxidation is typically carried out at temperatures in !
a range from about 50 to about 150C~ preferably from about 80 to about 110C, and at pressure of up to about 15 bar. Epoxidation is performed under pressure when a comparatively low-boiling sol-vent is used, which is necessary when the olefinic compound to be subjected to epoxidation also has a relatively low boiling point. !
Suitable solvents are, for example, acetone, acetic ester, methylene chloride, methyl chloride, chlorobenzene and methylethyl ketone. For reasons of economy ald processing tech-nology, the same solvent is used for epoxidation, as in the oxida-tion of the acetaldehyde, preferably acetone or acetic ester.
The followiny table shows by way of an example some of the possible and expedient process parameters:
Alkene Temperature Pressure Solvent (C) (bar) _ I
hexene-l 90 - 100 12 methylene chloride octene-l 90 - 100 3 acetone decene-l 90 - lO0 1 acetic ester polybutadiene-1.290 - l00 l acetic ester polybutadiene-1.490 - 100 1 acetic ester octadecene-l 90 - 100 1 acetic ester 25 undecene-l 90 - lO0 1 acetic ester propylene trimer90 - lO0 1 acetic ester oleic acid 90 - lO0 l acetic ester linseed oil 90 - 100 1 acetic ester allyl chloride90 - lO0 15 methylene chloride I '-5.
For purposes of the formation of complex compounds with the heavy metal catalysts present from the oxidation of the alde-hyde to per acid, as well as to prevent decomposition of the per acid through a wall reaction with meta]lic materials (see M. Andoh let al., Nippon Ragaku Kai Shi (1975), No. 8, 1383), a complexing agent is used in the epoxidation stage. Suitable complexing agents are, for example, polyphosphoric acid, pyromellitic acid and pyridinecarboxylic acids.
If desired, one of the customary epoxidation catalysts can be used during epoxidation. Among those which are useful are sulfuric acid, trifluoroacetic acid, tungstic and molybdic acid, alkanesul~onic acids, cation exchange resins and zinc phosphate.
The compounds polyphosphoric acid and pyromellitic acid, effective as complexing agents, also exert a catal~tic influence on epoxi-dation.
The epoxidation catalysts, or complexing agents, aretypically used in quantities o ahout 0.01 to about 1 percent, by weight, preferably in quantities of about 0.1 to about 0.3 percent, by weight, Leferred to the per acid. Preferably, use is made of polyphosphoric acid or pyromellitic acid as complexing agent in epoxidation and as epoxidation catalyst, or of sulfuric acid as epoxidation catalyst and ofla pyridinecarboxylic acid as com- !
plexing agent.
In contrast to the known process, the catalyst used in the oxidation of the acetaldehyde remains in the reaction mixture. !
It influences the progress of epoxidation to a decisive extent.
It has, for example, been found, that some of the catalysts used in the oxidation of acetaldehyde exert a negative influence on selectivity during e~oxidation. This is, for example, the case 113~8~Z
with feriferous an organic catalysts and can be explained as follows: as is known, an intermediary, dicyclic,addition complex is formed during epoxidation (see Bartlett, Rec. Chem.
Proc., 11, 51, (1960)).
¦¦ + ¦ C - R ~ C - R~
C H ..., 0 H------0 As was shown by our investigations, this addition complex can break down in two directions and into different reaction products:
r~o~--.C~
a. b.
¦ / 0+ ~ C - R ¦l + 0 + C - R ~ -Path a. ch?racterizes normal decomposition to the epoxide, path b. is strongly catalysed, for example, by heavy metal ions, thus the decline in selectivity is only in part due to a direct decomposition of the per acid since, in the absence of olefinic double bonds, due to the presence of heavy metal ions, it breaks down more slowly under the same reaction con-ditions. merefore, metals present in the form of inorganic salts during the oxidation of the acetaldehyde have to be rendered harmless by precipitation or complex formation. Among others, the compounds mentioned above are suitable for that purpose.
Compared with the known process, the process pursuant to the invention has the advantage, that distillation of the 11348~2 'peracetic acid, which is subject to explosion hazards, as well as the processing steps connecte~ therewith, are eliminated. In addition, in the process pursuant to the invention, the concentra-tion of peracetic acid in the epoxidation reaction mixture can always be kcpt low, but reaction with the olefinic com~ound will nevertheless proceed rapidly. Since, in the process pursuant to the invention, unreacted acetaldehyde is largely distilled off, there is practically no reaction of this compound with the per-acetic acid. This fact, as well as the simultaneous distilling ¦off of the solvents re~uired for oxidation, but harmful for epoxidation, leads to a very high selectivity for the epoxy com-¦pounds.
¦ The following nonlimiting examples further demonstrate ¦the present invention.
15 ¦ Example I
¦ A reactor of enamelled steel and e~uipped with a coolingjacket, a gas supply and a gas discharge line, as well as a mag-netic stirrer, was charged with 200 g acetaldehyde and 1800 g ethyl acetate, to which 0~01~ by weight, referred to the acetalde-hyde, of FeC13 was added as catalyst. For 2 hours, 1 normalliter/hr. of oxygen was introduced into the mixture cooled to ~10C, under a pressure of albout 4 bar.
Analysis of the reaction mixture showed an aldehyde conversion rate of 63% and a peracetic acid selectivity of 97%.
The reaction mixture was used in the epoxidation described in the following without any further processing.
For epoxidation of decene-l, 100 g of this material were placed in a pipe reactor (bubble column) and heated to 100C by means of jacket heating. After that, nitrogen was conducted ~1348~2 through the decene-l at a flow speed of 20 lit. per hour. In the following, 285 g of the reaction mixture containing per-acetic acid and prepared in the manner described above were cooled to 0C, mixed with polyphosphoric acid and fed into the heated reactor within 15 minutes. Continuing the bubbling through of nitrogen, the reaction was continued for another 5 minutes; the preponderant part of the low-boiling components was distilled off and condensed in a cooler. In addition to acetic ester, acetic acid and acetaldehyde, the distillate still contained 29% of the charged peracetic acid.
An epoxydecane solution free from peracetic acid was withdrawn from the sump of the reactor and the solvent distilled off. Referred to the decene-L, the reaction con-version was 33%, referred to the peracetic acid it was 71%.
Referred to the epoxydecane, the selectivity was 98%, while referred to the peracetic acid it was 92%.
ExamPle II
A pipe reactor was used for the continuous pre-paration of epoxyoctadecane. The interior of that reactor was equipped with a steam-heated, coiled spiral tube provided with a supply tube and a gas discharge tube at the upper end, and a gas supply tube at the lower end, while the exterior was equipped with a coil, a gas supply tube at the lower end and a gas dis-charge tube at the upper end, with the lower discharge tube of the inner spiral tube ending in the lower part, and the upper gas discharge tube of the inner spiral tube ending in the upper part of the external part of the reactor. 1540 g/hr. of a liquid reaction mixture cooled to 0C and consisting of 765 g octadecene-l and a reaction mixture containing peracetic acid mixed with polyphosphoric acid as ' .
1134~
!
described in ~xample I, were metered into the upper supply tube llf the ir~ner spiral coil. The reaction mixture containing per-¦¦acetic acid consi'sted of 115 g peracetic acid; 40.4 g acetalde-!I hyde, 2.~3 g acetic acid, 98~ g acetic ester, 0.1 ~ FeC13 and j 0.35 g polyphosphoric acid.
The reaction mixture went from top to bottom in the team-heated spiral coil. It fillefl its volume to a~out 20%. A
stream of inert gas was introduced at the lower end of the spiral coil, in a counter-current with the reaction mixture. On this o !j occasion, the biggest part of the low-boiling components (acetic ¦ester, acetic acid, acetaldehyde ana unreacted peracetic acid) ~¦evaporated and, going through the upper gas supply tube, reached llthe upper space of the external part of the re~ctor, which func-¦!tions asvapor space of the after-reaction zone. The epoxydecane 1l solution free from peracetic acid went through the lower discharge tube of the spiral coil to the lower part of the external part of the reactor, which functions as after-reaction space. Inert gas was supplied in this part of the reactor as well. There, the Iremainder of the low-boiling components evaporated, and, together with the low-boiling components evaporated in the spiral coil, was withdrawn at the upper end of the external part of the reactor via a cooler and ~ed to a condenser. The epoxydecane solution was ¦withdrawn from the after-reaction space and then processed hy means of distillation. I
The conversion, referred to the octadecene-l, was 42~, ¦
referred to the peracetic acid it was 92%. The selectivity re-l ferred to the epoxyoctadecane was 97%, referred to the per acid I it was 90~.
.` ` . ,
Claims (8)
1. A process for the preparation of an epoxide from an olefin which has a boiling point about 40°C at 1 to 15 bar, comprising oxidizing acetaldehyde with oxygen in the presence of an organic solvent, which boils below the boiling point of said olefin, and a heavy metal oxidation catalyst to form a peracetic acid containing reaction mixture, containing acetal-dehyde, peracetic acid, said catalyst and said organic solvent and subsequently epoxidizing the olefin by contacting said olefin with the peracetic acid containing reaction mixture, said mixture being at a temperature of from -10 to +10°C prior to said contacting, in the presence of a complexing agent for the catalyst at a temperature from about 50 to about 150°C at a pressure from about 1 to about is bar, while simultaneously distilling off unreacted acetaldehyde, solvent, and acetic acid by-product, by passing an inert gas through the epoxida-tion mixtures.
2. The process as in claim 1 wherein a solution of the olefin in an organic solvent is contacted with the peracetic acid containing reaction mixture.
3. The process as in claim 1 wherein the oxygen is present in the form of air.
4. The process of claims 1, 2 or 3 wherein the heavy metal oxidation catalyst complexing agent is admixed with the olefin and wherein the epoxidation reaction is conducted by maintaining the olefin-complexing agent mixture at said epoxida-tion conditions while gradually adding the peracetic acid containing reaction mixture thereto.
5. The process as in claims 1, 2 or 3 wherein the olefin and peracetic acid containing reaction mixture are simultaneously and continuously metered into and contacted in a reactor maintained under said epoxidation conditions while liquid reaction mixture containing the epoxide product of the epoxidation reaction is continuously withdrawn from the reactor.
6. The process of claims 1, 2 or 3 wherein the solvent present is acetone or an acetic ester.
7. The process of claims 1, 2 or 3 wherein the solvent present is acetone or an acetic ester, the heavy metal oxida-tion catalyst complexing agent is admixed with the olefin and wherein the epoxidation reaction is conducted by maintaining the olefin-complexing agent mixture at said epoxidation con-ditions while gradually adding the peracetic acid containing reaction mixture thereto.
8. The process of claims 1, 2 or 3 wherein the solvent present is acetone or an acetic ester, and the olefin and peracetic acid containing reaction mixture are simultaneously and continuously metered into and contacted in a reactor maintained under said epoxidation conditions while liquid reaction mixture containing the epoxide product of the epoxi-dation reaction is continuously withdrawn from the reactor.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2752920.0 | 1977-11-26 | ||
| DE19772752920 DE2752920A1 (en) | 1977-11-26 | 1977-11-26 | PROCESS FOR THE MANUFACTURING OF EPOXIDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1134842A true CA1134842A (en) | 1982-11-02 |
Family
ID=6024747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000316964A Expired CA1134842A (en) | 1977-11-26 | 1978-11-27 | Process for the preparation of epoxies |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5479212A (en) |
| CA (1) | CA1134842A (en) |
| DE (1) | DE2752920A1 (en) |
| FR (1) | FR2409995A1 (en) |
| GB (1) | GB2008593A (en) |
| NL (1) | NL7811087A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3528007A1 (en) * | 1985-08-05 | 1987-02-05 | Degussa | METHOD FOR PRODUCING EPOXIDIZED POLYBUTADIENES |
| DE3528002A1 (en) * | 1985-08-05 | 1987-02-05 | Degussa | METHOD FOR PRODUCING A CYCLOALIPHATIC DIEPOXID |
| JP4663893B2 (en) * | 2001-03-23 | 2011-04-06 | ダイセル化学工業株式会社 | Method for producing epoxy compound |
| JP5226162B2 (en) * | 2001-05-14 | 2013-07-03 | 株式会社ダイセル | Liquid epoxy resin composition and use thereof |
| US20030059618A1 (en) * | 2001-03-23 | 2003-03-27 | Hideyuke Takai | Method of producing epoxy compound, epoxy resin composition and its applications, ultraviolet rays-curable can-coating composition and method of producing coated metal can |
| JP2004099467A (en) * | 2002-09-05 | 2004-04-02 | Daicel Chem Ind Ltd | Method for producing alicyclic epoxy compound |
| TWI312800B (en) * | 2002-09-05 | 2009-08-01 | Daicel Chem | Process for the preparation of an alicyclic diepoxy compound, a curable epoxy resin composition, an epoxy resin composition for encapsulating electronics parts, a stabilizer for electrically insulating oils, and an epoxy resin composition for casting |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR383547A (en) * | 1907-11-02 | 1908-03-11 | Paul Charles Brossier | Oyster knife |
| FR397879A (en) * | 1908-11-30 | 1909-05-19 | Victor Joseph Felix Boulanger | Advanced spoon |
| FR398187A (en) * | 1908-12-24 | 1909-05-28 | Eugene Arnould | Oyster pallet |
| GB274951A (en) * | 1926-04-28 | 1927-07-28 | Ada Jane Dancy | Improvements in or relating to spoons |
| US1781973A (en) * | 1929-01-28 | 1930-11-18 | Bolton Edith Mary | Spoon |
| US1827780A (en) * | 1930-05-29 | 1931-10-20 | Delos A Alig | Fruit spoon |
| US2778109A (en) * | 1956-07-26 | 1957-01-22 | James L Haynes | Citrus fruit spoon |
| FR1236600A (en) * | 1959-06-05 | 1960-07-22 | Compound cover | |
| US3121951A (en) * | 1960-12-12 | 1964-02-25 | Green Martin | Eating utensils |
| FR1419794A (en) * | 1964-10-20 | 1965-12-03 | Advanced spoon | |
| US3967376A (en) * | 1974-02-05 | 1976-07-06 | Foley Donald E | Clean up/cut spoon |
-
1977
- 1977-11-26 DE DE19772752920 patent/DE2752920A1/en not_active Withdrawn
-
1978
- 1978-11-08 NL NL7811087A patent/NL7811087A/en not_active Application Discontinuation
- 1978-11-16 JP JP14054078A patent/JPS5479212A/en active Pending
- 1978-11-23 GB GB7845771A patent/GB2008593A/en not_active Withdrawn
- 1978-11-24 FR FR7833300A patent/FR2409995A1/en not_active Withdrawn
- 1978-11-27 CA CA000316964A patent/CA1134842A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2752920A1 (en) | 1979-05-31 |
| FR2409995A1 (en) | 1979-06-22 |
| NL7811087A (en) | 1979-05-29 |
| JPS5479212A (en) | 1979-06-25 |
| GB2008593A (en) | 1979-06-06 |
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