DE1793657A1 - Process for the production of oxirane compounds - Google Patents

Description

PATENT LAWYERS DR. I. MAAS

DT W. PFEIFFtR DR F-VOiTHZNLElT ^ Fr

5 - ΪΗ. S2C2-G-.

Case 725 Ρ / 2

Halcon International, Inc., New York, N.Y., V.St.A.

Process for the production of oxirane compounds Addition to patent 14 68 025

Epoxy compounds are valuable commercial products of technical importance. It is "known for epoxidation numerous olefinic compounds, e.g. propylene, to use highly active substances such as peracids. However, the use of these peracids was in view of the high effort and the less selective implementation is unsatisfactory. The aim of the invention is therefore a improved process for the epoxidation of olefinically unsaturated * organic compounds using a organic hydroperoxide and a metal catalyst.

The invention relates to a further embodiment of the process for the preparation of oxirane compounds by means of Oxidation of an olefinically unsaturated compound with an organic hydroperoxide in the presence of catalysts according to patent 14 68 025, and is characterized by that a Ti- »Gr-, Nb-, Zr, Te, Ta, Re or V catalyst used.

1098B3 / 18U

Temperatures that can be used according to the invention can vary within wide limits depending on the reactivity and other properties of the particular system. One can temperatures ranging from about -20 to 200 ⁰ C, suitably from O to 150%, and preferably from 50 to 120 ⁰ G apply. The reaction is carried out under pressure conditions sufficient to maintain a liquid phase. Although pressures lower than £ atmospheric can be used, pressures are common

ranging from about normal pressure to about 70 atmospheres (1000 psig) most expedient.

The hydroperoxides used for the purposes of the invention are those with the formula ROOH, in which R is a substituted or unsubstituted alkyl, cycloalkyl or aralkyl radical with about 3 to 20 carbon atoms means. R can also mean a heterocyclic or similar radical.

Exemplary and preferred hydroperoxides are cumene hydroperoxide, A'thylbenzolhydroperoxyd, tert-butyl hydroperoxide ψ peroxide, Cyclohexanonperoxyd, Tetrahydronaphthalonhydroperoxyd, Methyläthylketonperoxyd and Methyleyclohexanhydroperoxyd. An organic hydroperoxide compound which can be used for the process according to the invention is the peroxide product which is formed by the oxidation of cyclohexanol with molecular oxygen in the liquid phase.

The epoxidation catalysts include Ter ~ bonds of the following elements: Ti, Gr, Zr, Fb, Te, Ta, Re, TJ. These can be called peracid or

1098B3 / 18U
BATHROOM OBlOINAL

Identify hydroxylation catalysts. By far the most preferred catalysts are compounds of Ti.

The one used as a catalyst in the epoxidation process The amount of metal in solution can vary within wide limits. As a rule, however, it is expedient to use at least 0.00001 mol and preferably 0.002 to 0.03 mol per mol of the hydroperoxide present. It appears that Amounts above about 0.1 mole have no advantage over smaller ones Amounts, although amounts up to 1 mole or more per mole of hydroperoxide can be employed. the Catalysts remain dissolved in the reaction mixture during the process and can after removal of the reaction products can be used again in the implementation.

You can use the catalytic components in the epoxidation reaction in the form of a compound or mixture which is initially soluble in the reaction medium, apply. The solubility depends to a certain extent on the particular reaction medium used, however belong to the substances with suitable solubility for the purposes of the invention, for example, organometallic compounds soluble in hydrocarbons with a Solubility of at least 0.1 g per liter in methanol at room temperature. Exemplary soluble forms of the catalytic substances are the naphthenates, stearates, octoates or carbonyls. Numerous chelates, addition compounds, and enol salts, e.g., acetoaeetonate, can can also be used. For the method according to the invention Particularly suitable catalytic compounds of this type are the naphthenates and carbonyls of titanium, Rhenium, tantalum and niobium. Azoxy compounds such as tetrabutyl titanate and tetraalkyl titanates are also very suitable.

109853/1814

To the olefinically unsaturated substances used as starting material, which are epoxidized according to the invention, include substituted and unsubstituted aliphatic and alicyclic olefins, for example Hydrocarbons, esters, alcohols, ketones or ethers can be. Preferred are compounds with about 2 to 30 carbon atoms, expediently with at least 3 carbon atoms. Examples of such olefins are ethylene,

Propylene, n-butylene, isobutylene, the pentenes, the methylpentenes, diene-hexenes, the octenes, the dodecenes, cyclohexene, methylcyclohexene, butadiene, styrene, methylstyrene, vinyltoluene, vinylcyclohexane and phenylcyclohexene. It is possible to use olefins which have, for example, halogen-, oxygen- or sulfur-containing substituents. Examples of such substituted olefins are allyl alcohol, methallyl alcohol, cyclohexanol, diallyl ether, methyl methacrylate, methyl oleate, methyl vinyl ketone and allyl chloride. In general, you can all olefinic materials which can be epoxidized by known processes, by the ^novel: epoxidizing method.

This also includes olefinically unsaturated Pdlyme'i'e.

The lower olefins with about 3 or 4 carbon atoms in an aliphatic chain can be epoxidized particularly advantageously by the process according to the invention.

The usual-as. alpha olefins or primary olefins designated class of olefins can be in a particularly effective manner by the process according to the invention epoxidize. It is known that these primary olefins, for example propylene, butene-1, decene-1 or Hexadecene_1, with the exception of ethylene, is much more difficult to epoxidize than other forms of olefins. Other olefins that epoxidize much more easily

10 9853 / 18U

* are substituted olefins, in the middle unsaturated alkenes, cycloalkenes and the like.

When the starting material is oxidized, the ratio of substrate to organic peroxide compounds can vary within wide limits. In general, molar ratios of olefin groups in the substrates to hydroperoxide in the range from 0.5: 1 to 100: 1, advantageously from 1: 1 to 20: 1 and preferably from 2: 1 to 10: 1 are used the starting material mixture for the oxidation reaction is usually 1 % or more at the start of the reaction, although lower concentrations are effective and can be used *

The oxidation reaction of the starting material can be carried out in the presence of a solvent, and in general it is convenient to use a solvent. In most cases, aqueous solvents cannot be used. Suitable means are, for example Hydrocarbons, which can be aliphatic, aromatic or naphthenic hydrocarbons, and the oxygen derivatives of these hydrocarbons. Preferably, the solvent has the same carbon skeleton as that used hydroperoxide, causing solvent separation difficulties be reduced or avoided.

The following examples illustrate the invention without restricting it. Percentages relate to that Weight, unless otherwise stated.

10985 3/1% 1 V ^:

- 6 example!

A number of experiments have been carried out using alpha-phenylethylhydroxide düfchgifüftfI «in order to convert * Öyelöhexen to Öyclohexenoxyd to epöxydiefifi * iHsWä 5Ö g 35 fa-lges alpha-Phenyläthylhydrdperöxyd düfchgifftfI" fi-göyolöhexen to Öyclohexenoxyd to epöxydiefifi * iHsWä 5Ö g 35 fa-lges alpha-Phenyiäthylhydrope'rOxyd 'fi ihyoleföisblöxyd'ifihyiäthylhydrope'rOxyd'ifihyiäthylhydrope'rOxyd'ifihyiäthylhydrope'rOxyd'ifihyolexefi Iieäe mixture were treated with the following Kiialy satoreh satoreh * and each sample * wufcle ¹ # ifi§ SttiMdi iärtg "reacted at 70 ⁰ O * The conversion ΐιβ'ζί§Η4 Äiif Cl Hydroperoxydumwandlühg And Selekiiviiäl itif Hi

of the cyclohexene oxide formed, bezögän ä'iif zii change product converted

T a b e lie:

Try the catalyst Tetrabutyl titanate 0.02 ^ ählluiis OIL ELECTIVENESS Rhenium heptoxide 0 * 01 i; ■ ί 1 Niobium acetylacetonate 98 8Ö 2 Niobium naphthenate
(4.84 # Nb) 0.02 100 20th 3 Tantalum naphthenate
(£ 9.42 Ta) 0.02 51 95 4th 67 95 5 44 90

Example 2

About 3 g of freshly precipitated Nb ₂ Oc were mixed with 5 g of tert-butyl hydroperoxide and 10 g of tert-butanol * This mixture was ^{heated to 75 °} C. for 6 hours.

09853 /

The resulting mixture was filtered in order to remove solid NbpOc, and the piltrate, which contained a small amount of catalyst dissolved, was combined with an equal amount by weight of cyclohexene and ^{reacted at 80 °} C. for 3 hours. The hydroperoxide conversion was 43% and the selectivity of the conversion to cyclohexene oxide, based on the hydroperoxide, was 91%.

B e i s ρ 1 e 1 3

A number of attempts have been made to epoxidize propylene to propylene oxide. In each case, 20 g of a solution of 34.6 # alpha-Phenyläthylhydroperoxyd in ethylbenzene together with 20 g of Pro, pylene and the amount of catalyst indicated in a pressure reactor eingeführt.Die reaction was carried out for one hour at 110 ⁰ C. The results obtained are shown in the following table. Conversion and selectivity are as given in Table I.

Tabel Try the catalyst Conversion selectivity

Ti naphthenate (2.5 wt .- ^ Ti)

Ta-naphthenate (9.4 wt, - # Ta)

Nb-naphthenate (4.84 fo Nb)

0.2

0.2 0.2

54.0 25.0 22.0

55.3 22.8

20.0

10 9853 / reu

Example 4

Example 3 was repeated, using 20 g. a 27.5% strength cumene hydroperoxide solution in cumyl alcohol (dimethylphenyl carbinol) and 20 g propylene were used. When using 0.1 g Tetrabutyltitanatkatalysator at one-hour reaction at 110 ⁰ C the Hy droper oxy dumwand lung 23.8 "/>, the selectivity to propylene oxide was 62.3%.

When using 0.2 g of tetrabutyl titanate under the same conditions, the circulation was 44.6 tfo and the selectivity was 61.5 %.

The above results clearly illustrate the actual and significant improvement in effectiveness when using the hydroperoxide to form the corresponding oxirane compound, which by the invention Procedure is achieved »

The procedure can be intermittent or intermittent or carried out continuously. In the case of the latter, one can see the oxidation reaction of the substrate in an elongated reaction zone, for example a pipe, a tower or a plurality of in series Perform switched reactors, and the hydroperoxide along spaced apart locations the path of the flowing solution.

In general, the epoxidation reaction mixtures are distilled to remove the oxirane compound as a product, but other separation methods are possible. Distillation temperatures in the range from about -40 to 200 ^° C. at the top and 20 to 250 plates at under normal or overpressure can be used in a suitable manner.

1098S3 / 16U

Claims (2)

Pat e η t a η a ρ r ü ο h e 1. Further training of the manufacturing process of oxirane compounds by oxidation of an olefinically unsaturated compound with an organic one Hydroperoxide in the presence of catalysts according to Patent 14 68 025, characterized in that as Catalyst a Ti-, Cr-, Nb-, Zr-, Te-, Ta-, Re- or V-catalystOT used. 2. The method according to claim 1, characterized in that a Ti, Ta, Nb or Re catalyst is used used. 109853/1814