PREPARATION OF EPOXIDATION CATALYST SOLUTION

MINISTRY

THE INDUSTRIAL DEVELOPMENT

SCIENTIFIC AND

SERVICE

iNTELLECTUAL INDUSTRIELLE PATENT of the P.V. On PROBLEMS it 134,216 No. 1.583.189 internation Classification has the: B 01 j // C 07 d

Society said: [...] INTERNATIONAL, INC. residing in the United States of America.

Demanded 29 December 1967, to 10^{11 42m,} to Paris.

Issued by stopped 15 September 1969.

(Bulletin official A property industrial, no. 43 of the 24 October 1969.) (Patent application deposited in the United States of America 3 January 1967,

under the no. 606,535, on behalf of John m. Kollar.)

The present invention relates to the preparation

structure by the incorporation of

inorganic forms of certain elementary and

a hydroperoxide catalysts aralkyl, to

produce a solution of catalyst

for the production of compounds [...]. The In-

prevention also relates to the use of the said solution-

the purification catalyst for the production of compound^

[...].

The preparation method of catalyst solutions

[...] of the of the invention deviates from the tech-

nic front. For the production

[...] compounds using [...] -

organic oxides, reference is made to the patents

belgian n^{bone 663,859}, 665.082,644,090 657,838 and,

which describe in detail the reaction conditions

and catalytic materials used. A problem

which has been in the prior art is the

price of the catalyst employed. Be

the shapes also be possible to use the least

expensive catalyst, but difficulties have

been encountered for obtaining an amount of

lowest cost solution of the catalyst sufficient

to be able to successfully conduct epoxidation.

The invention provides a solution to this problem

by permitting the use of forms of catalyst

and inexpensive the solubilization of these forms

to such a degree that the catalyst solutions

resulting can be used for the production

[...] compounds.

An object of the invention is to provide a pro-

supplied for the preparation of said solution a-

the purification catalyst for use in

epoxidation reactions employing hydro-

aralkyl peroxides as epoxidation of agents.

The invention also relates to the use of the

solution to the production of compounds

[...].

According to the invention, are mixed forms [...] -

[...] or elementary metals capable of in-

9 210341 7-φ-

take efficiently at the reaction of unsaturated olefinic compounds with hydroperoxides to produce compounds with a hydroperoxide [...] aralkyl, and the mixture is kept, during a practical time frame, at a temperature capable of providing a solution containing the epoxidation catalyst, this solution same suitable for use in the production of compounds [...] as previously described.

Examples given below to [...] limiting is will further understand how the invention can be implemented.

Example 1. - Is introduced a solution formed by 2.5% by weight of glycerol, 72.5 by weight of alpha-phenylethanol and 25% by weight of a 12% solution of ethylbenzene hydroperoxide in ethylbenzene in a suitable container. Are added to 50 grams of this solution 0.75 gram of molybdenum metal finely pulverized. The resulting mixture is maintained at a temperature of about 85 °C, while stirring, for five hours. After this period of time, the resulting solution contains 0.1% molybdenum form of a compound which is soluble. The entire hydroperoxide is decomposed, mainly [...].

Is introduced 2 grams of the catalyst solution prepared as described above in a reactor, in conjunction with 16 grams of propylene, 74 grams ethylbenzene containing few percent of alpha-phenyl ethanol and 10 grams of ethylbenzene hydroperoxide. Is reacted mixture into the reactor for one hour at 120 °C, at a gauge pressure of about 35 kg/cm^2. There is that the reaction mixture contains 2.9 grams of propylene oxide.

The metals catalyst, used in elemental form or in the form of inorganic compounds or minerals, are [...] molybdenum, vanadium, tungsten, titanium, tantalum, the [...], the rhenium, selenium, chromium, zirconium, tellurium and uranium. These metals are used in the form of metal powder or inorganic compounds, including oxides, hydroxides, sulfides, chlorides, oxy-chlorides, fluorides, phosphates, andc. The preferred forms of compounds are oxides and acids these oxides by hydration.

The solution in which the catalyst is dissolved may comprise the following components:

The catalyst mixture is maintained as inorganic or elemental and containing the hydroperoxide solution at temperatures generally between 25 and 200 °C, [...] between 50 and 100 °C, and preferably between 75 and 90 °C, while stirring or circulating otherwise, over a period generally of thirty minutes to ten hours and preferably four to six hours. At the end of this period, a solution is obtained containing the catalyst in the form of a dissolved compound, the solution suitable ideal for the catalytic production of a compound by reacting a compound [...] unsaturated olefin with a hydroperoxide [...].

Aralkyl The hydroperoxides are derived from alpha-aralkyl preferably hydrocarbons of the general formula:

Hh

I I

A-c-c-r "

I I

wherein each of the substituents R ', R " and R^{w may be hydrogen or} an alkyl radical preferably having from one to twenty carbon atoms, and A is an aromatic ring. The aromatic ring A can be benzene, and it may be substituted by fluoro, chloro, bromo, nitro, alkoxyl, [...] or carboxy (or their esters). The core may have one or more side chains containing up to twelve carbon atoms each, these chains may be branched themselves. Hydroperoxides The alpha-aralkyl are of the formula:

O-h

I

Oh

I I

A-c-c-r "

I I

R ' r "

wherein R ', R ", R' " and A have the same meaning as previously. Exemplary, hydroperoxides include toluene, ethylbenzene, , cumene, of [...], of isobutylbenzene, tetralin, diisopropylbenzene, para- [...], ortho-xylene, meta-xylene, para- [...], of [...], andc. Preferred species are those derived from a cumene, i.e. the hydroxide of alpha- [...], and ethylbenzene, i.e. hydroxide [...].

Solubilizing agents are, preferably, used to prepare the catalyst solutions according to the invention. By way of suitable solubilizing agents, include highly polar compounds type [...], the diketones, alcohols such as glycerin, andc.

See patent mentioned above with respect to the complete description and reagents for epoxidation reaction conditions, as well as the percentage of catalyst, andc.

Materials to non-olefinic unsaturation are epoxidized which the defined according to the invention include aliphatic and alicyclic substituted and unsubstituted, which can be hydrocarbons, esters, alcohols, ketones, ethers, andc. As preferred compounds, include those containing from two to thirty carbon atoms approximately, and preferably at least three carbon atoms. Include, as [...], ethylene, propylene, normal butylene, isobutylene, pentenes, the Methylpentenes, the normal [...], octenes, the dodecenes, cyclohexene, methylcyclohexene the, [...] butadiene, styrene, methylstyrene, the [...], the [...], the [...], andc. Olefins may be used having substituents containing halogen, oxygen, sulfur, andc. As substituted olefins of this type, include [...] alcohol, methallyl alcohol, cyclohexanol, [...] ether, methyl methacrylate, methyl oleate, the [...], [...] chloride, etc Generally, all epoxidized olefin materials by the method pre-