DE1945470A1 - Process for the preparation of epoxides from aliphatic or cyclic olefins and molecular oxygen in the presence of catalysts - Google Patents

Description

Process for the production of epoxides from aliphatic or cyclic olefins and molecular oxygen in the presence of "catalysts" .

The present invention relates to a process for the preparation of 1,2-epoxides by direct oxidation of olefins with molecular oxygen in the presence of catalysts. Depending on the type of olefin and its vapor pressure under the reaction conditions , the reaction is carried out in the presence or absence of a solvent. The solvent can be inert towards oxygen or it can also take part in the oxidation reaction

From a schematic point of view, the implementation proceeds as follows equation

t3 «C = C + 1/2 O,

catalyst

Umsetzungetemperaturen of 20 to 25O ⁰ C ₁ is preferably between 60 and 180 ⁰ C ₁ are applied. The partial pressure of the oxygen can be between 0.050 and "60 kg / cm ² , but preferably between 0.05 and 20 kg / cm ²

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Oxygen, air, enriched air or diluted with nitrogen Air can be used. CO or COp can also be used in the Gas mixture be present; apart from the increase in the total pressure in the oxidation vessel, this does not pose any difficulties evoked.

Since the oxidation is carried out in a liquid medium, require some olefins the use of a solvent in order to be oxidized according to the invention without the total pressure im Reactor gets too high. The solvent must be recoverable and have sufficient solvent power for the olefin used. The solvents used are mainly aromatic, optionally substituted, hydrocarbons, alcohols, ethers, or polyethers and esters are used, the latter not having any particular advantages when used. As a suitable solvent are named for example:

Benzene, chlorobenzene, o-dichlorobenzene, diphenyl, Nitrobenzene, phenyloxide, phenyl polyoxide, e.g .:

or their homologues "

Among the esters, those will be used that are good Combine thermal stability with increased resistance to oxidation «Either monoesters or polyesters are used * Preferably the esters of acetic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid or the acids of the following formula are used:

CH, 0

I ³ IR ₁ -C _- -C-OH

R ₂ ; "■ - ■

009813/1801 \,

BATH

- sheet 3 -

where R ₁ and R ₂ & are alkyl radicals with 1 to 15 carbon atoms

Apart from alcohols such as methyl, ethyl and tertiary butyl alcohol, glycols such as propylene glycol and neopentyl glycol can be used as esterifying agents. «Pentaerythritol also provides esters, which are excellent solvents *

Various saturated hydrocarbons such as isooctane can also be used as solvents, as can certain ones Ketones and alcohols such as acetophenone or tertiary butanol. The aforementioned solvents can also be used in mixtures which are designed with the purpose of improved effectiveness

to get voted.

The solvent content of the oxidation mixture is most advantageously chosen between 5 and 70%; However, in order to limit the dilution effect, which has a retarding effect on the oxidation processes, a solvent content of between 5 and 65 % is preferred.

The catalyst of the present invention consists of certain Chelates of molybdenum, tungsten or vanadium or of cations that combine these metals with other elements contain, e.g. oxygen »

f.

The chelating agent is a nitrogen compound as follows general formal

R - N «N - R»

wherein R and R 'are the same or different; optionally sub- · \ etituierte alkyl, cycloalkyl: - or aryl felftd of which · \ ■ Each contains 1 to 30 carbon "tb" · · For example könntn. the diary! compounds result in the following formula

009813/1091

ORIGINAL BATHROOM *

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X Χ ·

in which X and X * can be identical or different radicals, for example H, OH, OR ", O-CH ₂ -COOH, COOR", NH ₂ , where R "has the ^{meaning given for R and R 1.} An aryl radical can also have the groups OH and COOH in 06, / 3 -position:

One and the same molecule can have several (eg 2 to 4) of these groups. Among the compounds that can occur with molybdenum and tungsten in the form of cations MoO ₂ and Wo ₂ , the following can be mentioned - without being limited to this list:

Dihydroxy-2,2-azobenzene; Diamino-2,4-sulfamido-4'-azobenzene; PPhenyl-azo] ^ -hydroxy-1-naphthalenine-diamino ^^ '- azobenzene; Diamino-2,4 azobenzene;

[Naphthyi-asoJ-1-hydroxy-2-naphthalene; Dihydroxy-2,6-azobenzene; [(SuIfamido-4-phenyl-1) azo] hydroxy-8-acetylamino-2-disulfo-3,6-naphthalene;

(Phenyl-azo) -3-dihydroxy-ll, 5-disulf 0-2,7-naphthalene; [(ChlQro-5-hydroxy-2-phenyl) azobis] ^{-3-dihydroxy-1,} 5-disulfo-2,7-naphthalene;

[(Hydroxy-1-naphthyl-2 -) - azo-] -1-sulfo-Jl-naphthol-2; [(Hydroxy-1-naphthyl-2) -az (1-4-hydroxy-3-nitro-7-sulfo-lnaphthaiine;

(Pyridyl-2-azo-) - 1-naphthol-2j
(Pyridyl-2-azo -) - ⁱ l-resorcinol;
Jj [SuIf ol-hydroxy-J-naphthyl- ^) -azo-J -it-phenyl-1-methyl-3-

pyrazolon-5; ■

0Q9813 / 1891 -5-

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[(Disulfo-6,8-hydroxy-2-naphthyl-1) -azo-1 -2-diethyl-sulfonamido-5? Anisole-1;

• sulfonamido-4-hydroxy-l-phenyl-

([NN · -Methyl- ( β -cyano-ethyl) -si 2] -azo-j-oC-aceto-acetanilide;

([NN »-Methyl- ( β- cyano-ethyl) -si 2J-azoi- JJ-phenyl-1-methyl-3-i

• sulfonamido-4-hydroxy-1-phenyl- • pyrazolone-5;

(Phenyl-azo -) -5 _r hydroxy-2-benzoic acid; _;

[Nitro-3-pher> yl- »l) -azoJ -5-hydroxy-2-benzoic acid; £ (Phenyl-azo-) -4-methyl-2-phenyl-1-J-azo-1-hydroxy-2-naphthalenine £ (Disulfo-2,4-hydroxy-1-napthyl-2) azo] I -4-methyl-1-benzene.

The list of the connections listed above is not exhaustive and also includes all compounds of the azo type with one or more azo groups, as well as all other groups, which enable chelation. One and the same compound can, for example, contain heterocycles of different types, the Heteroatoms can be e.g. oxygen, sulfur or nitrogen.

The azo compounds are metallized according to the classic ' sic method · The ratio of metal (expressed in g / atoms) to the azo compound (expressed in moles) is determined in each case by elemental analysis

The catalyst itself has the general formula (azo-) _n M,. where the azo group has already been described above and η is an integer 1, 2, 3 or 4, while H denotes molybdenum, tungsten, vanadium, or a compound of these metals) or an oxidized cation such as molybdyl, molybdenyl or vanadyl.

The catalyst content is most advantageously between 10 " ¹ and 10" ⁵ g-atoms of metal per kilogram of the charge.

\. The present invention relates to aliphatic olefins - or · on oyolliohe olefin ·, which may be branched

009815/1891 - * r * _ÄJ

t »■ \ ■.:; ■ '- ■' ■. · - '♦ i.

BAD ORlOINAL

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and which contain 1 to 16 carbon atoms The general formula of these olefins is:

R ₁ - CH - C = C - R ₀

¹ III ²

^R 5 ^R A ^R 3

wherein R ₁ to R 1 - are identical or different radicals, such as hydrogen or the alkyl, aryl, alkaryl, aralkyl radical. Two of these residues can also form a ring, as specific examples are to be mentioned:

the propylene, isobutene, butene-1, butene-2, methyl-2-butene-2-, Methyl-3-butene-l-, n-pentene, trimethyl ^^ j ^ -pentene-l-, trimethyl-2,4i, 4-pentene-2-, or the ethyl-2-hexen-i radical, as Cyclopenteh, cyclohexene, ethyl-Jj-cyclohexeia-l.

According to the present process, those with oxygen can too the olefins to be treated contain identical or higher molecular saturated homologues «For example, propylene can contain both propane and butane and isobutane. Small amounts of these hydrocarbons are converted during the reaction; the yield of epoxy is increased by the presence of these paraffins

Hydrocarbons or alkylated solvents can also be used as solvents aromatic hydrocarbons with 6 to 40 carbon atoms use, such as: toluene, xylenes, or their mixtures as well as ethylbenzene. These hydrocarbons can be pure or in solution can be used dissolved in a carboxylic acid, but not in Formic acid. Preferably acetic acid is used as it is only is weakly oxidizing and only has a moderate effect on the epoxides (I.SEREE de ROCH -Bull, Soc.Chim. 1965, p. 1981)

In this case the non-olefinic hydrocarbons are not just solvents, but be la course of the process

I "SÖ 13 / 18ί9ΐ ^:. " ⁷ ^

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also changed. Toluene is mainly converted to benzaldehyde, benzyl alcohol, and benzoic acid. The xylenes become mono- and Diacids, ethylbenzene becomes acetophenone and M ^ ethyl-phenylcarbi nol * This procedure is of particular interest because it at the same time the extraction of high-quality oxidation products is permitted «

The following non-exhaustive examples illustrate the above invention. The tests were carried out with a container made of stainless steel, which has a turbine agitator. The examples show that the yield of low molecular weight products (especially epoxypropane) in several cases goes well over 70 % . [

Example 1:

510 g of propylene in 800 g of benzene are at 150 ⁰ C under a

ο
Oxygen pressure of 12 kg / cm in the presence of various

Catalysts (see Table 1) treated, the metal content

Is 3.10 g-atom per kg batch.

Table I.

Structure of the catalyst metal Metal atoms abbreviation [Hn'-methyl- ( ß -cyano-ethyl) -
sulfonamido-4-hydroxy-l-
phenyl-2] -azo- ° ^ -aceto-
acetanilide (A.) Mon
W. Azo molecule A ₁ Mon
A ₁ W phenyl-2-azo] -4-phenyl-l-
methyl-3-pyrazolone-5 (A ₂ ) Mon
W. 1
1 A ₂ Mo
A ₂ W f (disulf O-6, 8-hydroxy-2-naph-
ethyl-l) -azo-] -2-diethyl-
sulfonamido-5-anisole-l (A,) .Mo:
W. 1
11th A-Mon
A, W . 1/2
1/2

(Molybdenum and tungsten are in the form of cations WO ₉ and MoOJ ⁺ ). ^c

00981 3/1891

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In each case a conversion of 7.5 % is achieved. The epoxypropane formed is quantitatively determined by gas chromatography «The molar yield of epoxide is determined in relation to the converted propylene« However, the yield can exceed 100% , which is due to the fact that one molecule of propylene can give 3 molecules of low molecular weight compounds such as methanol « The individual compounds are listed in Table 2.

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009813/1891

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Tabel

Methyl catalyst methanol epoxypropane acetone mono- and diformate mono- and Dlacetat of formate%%%%% of propylene glycol Propylene glycol%

A ₁ Mon 1.9 Ik 53 6.3 8.0 6.0 A ₂ Mo 2.6 17th 53 7.6 6.9 5.2 AJIo
j » 1.9 12th 70 7.8 2.0 1.5 A ₁ W 2.5 15th 60 7.6 3.3 A ₂ W 2.5 16 65 5.8 4, H. 3.3 A ₃ W. 2.2 17th 71 7.3 2.5 1.7

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Example 2;

510 g of propylene in 800 g of various solvents (see Table 3) are treated at 150 ° C. under an oxygen pressure of 12 kg / cm in the presence of the AW catalyst from Beispfel 1, the metal content being 3 · 10 ″ g-atom / kg of charge The conversion is 8 %. (The catalyst is obtained in the classic method by chelating the cation WOp ⁺ with the nitrogen derivative; the nitrogen derivative is formed by diazotizing diethylamine sulfone-ii-anisldin-2 and coupling with disulfo-6,8-naphthol -2-acid).

The analysis is carried out as in the previous example by means of gas chromatography executed

Table 3

solvent Methyl-
formate
% Methanol
% Epoxy
propane
% acetone
% Propylene
glycol
formate % Propylene
glycol
acetate % benzene 2 14th 71 7th 3 2 tert-butyl
alcohol \ 12th 75 6th 3 2 Mix of
20 % benzene
m. 80 % ter.-
Butyl alcohol 3 12th 67 5 4th 2 Chlorobenzene 2 14th 73 6th 2 2 Dichloro
benzene 2 11th 70 5 5. 3 Propylene
giycoldiace- '
did it 12th 72 6th 4th 4th Qlycoldiace-
did 2 13th 71 6th 6th 3 toluene
p-xylene \ 10
14th 70
68 5
7th 4th
. 3 4th Dibutyl
phthalate • 2; 12th • 71 6th 2. 2

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Example 3:

500 g of trimethyl-2, l », il-pentene-l in 600 g of chlorobenzene are added. 125 C under a pressure of 10 kg / cm oxygen epoxidized. The AW catalyst from Example 1 is used with a concentration of 3.10 g-atom of metal per kg of charge. The conversion is 6.7 % Trimethy 1-2,4, * S-epoxy-1,2-pentane is formed with a yield of 58 %,

example k:

A mixture of 600 g propylene and 200 g propane in 800 g benzene is processed at 150 ° C. under an oxygen pressure of 15 / kg / cm. The AW catalyst from Example 1 is used in a concentration of 3.0 · 10 g-atom of metal per kg of charge. For a 92% conversion of propylene, the yield on epoxypropane is Ik%,

Example 5;

370 g of propylene and 100 g of propane in 500 g of toluene are used in Processed at l45 ° C under an oxygen pressure of 15 kg / cm. The catalyst A, W from Example 1 is used in a metal concentration of 3 * 10 g atom / kg batch.

For a propyl conversion of 12 % the yield of epoxypropane is 67 %.

Example 6;

510 g of propylene in 800 g of benzene are heated at 150 ° C under an acidic

2
substance pressure of 12 kg / cm in the presence of a catalyst of the formula f-azo-1 MoOo ⁺ treated, the agent for Che.latbildung -azo- L (disulfo-2, ¹ l-hydroxy-1-naphthyl-2) -azo -J »^ -methyl-1-benzene; the metal content is 2.7.10 g-atom / kg. Batch. The yield of 'Epoxypropah 76 5t contributes to a propylene ura conversion of 8 %.

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Claims (2)

Process for the production of epoxides from aliphatic or cyclic olefins and molecular oxygen in the liquid phase at temperatures from 20 to 25O ° C and one Oxygen pressure of 0.05 to 60 kg / cm in the presence of a catalyst, characterized in that the catalyst a.Chelate made of molybdenum, tungsten, vanadium or their compounds and an azo type chelating agent and is the formula [-azo-] _n M where M denotes molybdenum, tungsten, vanadium or a compound of these metals, η is an integer from 1 to k and -azo- is a compound of the formula RN = NR ', in which R and R ^{1 are} optionally substituted alkyl-, Cycloalkyl or aryl radicals with 1 to JO carbon atoms are. 2.) The method according to claim 1, characterized in that the content of catal;
Batch is. -1 -ζ content of catalyst 10 to 10 ^J g-atom of metal per kg 3 ·) Method according to claim 1 and 2, characterized in that the reaction is carried out in the presence of at least one aromatic hydrocarbon having 6 to 40 carbon atoms will. G 3 98 1 3 / 189-1