DE1518999A1 - Process for the production of oxirane compounds - Google Patents

Description

Process for the production of oxirane compounds. Epoxy compounds are valuable commercial products of teoh nical importance It is known for epoxidation numerous <- rich olefinic compounds, such as propylene, highly active substances, such as Peracids, to use. However, the use of these peracids was considered unsatisfactory because of the high cost and the less selective implementation The aim of the invention is therefore an improved process for olefinic epoxidation unsaturated organic compounds using an organic hydroperoxide and a metal catalyst. Another object of the invention is an improved one Process for obtaining oxirane compounds from the epoxidation reaction mixture while avoiding decomposition of components of the mixture ..

According to the invention, olefinically unsaturated organic compounds links into corresponding oxirane compounds by reaction with an organic hydroperoxide in the presence of a metal catalyst and also in the presence of a basic one Substance, for example sodium naphthenate, converts. In the practical implementation of the process according to the invention are considerable improvements in the selective Utilization of the organic hydroperoxide achieved in the epoxydi eration reaction. Further, by using the basic substance, the recovery processes The counterpart of the basic substance during the distillation improves to a considerable extent of the reaction mixture stabilizes the unreacted hydroperoxide and prevents it decomposition of this hydroperoxide and loss of its carbon configuration.

Temperatures that can be used according to the invention can be depending on the reactivity and other properties of the respective system within wide limit fluctuations. The temperatures can be in the range of about 20 to 200 ° C. appropriate from 0 to 15000 and preferably from 50 to 1200C apply.

The reaction is carried out under pressure conditions necessary to maintain a liquid phase suffice, although lower than atmospheric pressures can be used are usually prints in the range of e.tw normal pressure until about 70 at (1000 psig) ani is most practical.

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

Exemplary and preferred hydroperoxides are cumene hydro peroxide, Ethylbenzene hydroperoxide r tert-butyl hydroperoxide.

Cyclohexanone peroxide, tetrahydronaphthalone hydroperoxide, methyl ethyl ketone peroxide and methylcyclohexane hydroperoxide. A useful one for the process according to the invention organic hydroperoxide compound is the peroxide product produced by oxidation of Cyclohexanol is formed with molecular oxygen in the liquid phase.

The epoxidation catalysts include compounds of the following Elements: Ti. V, Cr Cb, Se Zr, Nb, Mo, Te, Ta, W, Re, U. These can be classified as peracid forming or Hydroxy @ierungskatalysatoren. By far the most preferred catalysts are compounds of V, W, Mo, Ti and Se.

The amount of ala K @@@ ysater used in the epoxidation process @@@@@ @@ Solution can vary within wide limits Usually is However, it is expedient to use at least 0.00001 mol and preferably 0.002 to 0.03 mol. apply per mole of hydroperoxide present. It seems that quantities liber about 0.1 mole gives no advantage over smaller amounts, although amounts up to to 1 mole or more per mole of hydroperoxide can be used. The catalysts stay during de. Procedure. dissolved in the reaction mixture and can after removal the reaction products can be used again in the conversion. To the molybdenum compounds include the organic molybdenum salts, the oxides, such as Mo2 O3, MoO2, MoO3, molybdic acid, the molybdenum chlorides and oxychlorides, molybdenum fluoride, molybdenum phosphate or molybdenum sulfide and the same.

Molybdenum-containing heteropolyacids and their salts can be used will. Examples are phosphomolybdic acid and its sodium and potassium salts. Similar or analogous compounds of the other metals and mixtures listed from it can be used.

Min can use the catalytic components in the epoxidation reaction in the form of a compound or a mixture which at the beginning is soluble in the reaction medium is to apply. The solubility depends to a certain extent on each reaction medium used, but belong to the substances with suitable solubility for the invention Purposes for example in the hydrocarbon Soluble organometallic compounds with a solubility of at least 0.1 g per Liters in methanol at room temperature; Exemplary soluble forms of the catalytic Substances are the napthenates, stearates, octoates or carbonyls. Numerous chelates, Addition compounds and enol salts, e.g.

Acetoacetonates, can also be used. For the inventive Catalytic compounds of this type which are particularly suitable for processes are the naphthenates and carbonyls of molybdenum, vanadium, tungsten, titanium, rhenium, tantalum, niobium and selenium. Alkoxy compounds such as tetrabutyl titanate and tetraalkyl titanates are also possible very suitable.

To the olefinically unsaturated substances used as starting material, which are epoxidized according to the invention include substituted and unsubstituted aliphatic and alicyclic olefins, such as hydrocarbons, esters, Alcohols, ketones or ethers can be. Connections with around 2 up to 30 carbon atoms, expediently with at least 3 carbon atoms. Examples for such olefins are ethylene, propylene butylene, iso-butylene, the pentenes, the Methylpentene, diene-hexene, octene, dodecene, cyclohexene, methylcyclohexene, Butadiene, styrene methylstyrene, vinyltoluene, vinylcyclohexane and the phenylcyclo hexen, You can use olefins, for example halogen, oxygen or have 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, all olefinic substances that are known according to Process can be epoxidized, epoxidize according to the inventive method.

This also includes olefinically unsaturated polymers.

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

Commonly referred to as alpha olefins or primary olefins Class of olefins can be according to the fiction, contemporary process in particular Epoxidize effectively It is known that these primary olefins, for example Propylene, butene-1, decene-1 or hexadecene-1, with the exception of ethylene, are considerably more difficult are epoxidized than other forms of olefins. Other olefins that are essential are more easily epoxidized, are substituted olefins, in the middle are unsaturated Alkenes, cycloalkenes and the like. For example, it has been found that cyclohexene with all in the description Exercise specified metals easily It is epoxidized as shown in Table I ip. However, it was found that # three of the specified catalysts are particularly useful in epoxidation of primary olefins, for example propylene. These three catalysts are moybden, titanium and tungsten. It was found that # their effectiveness for the Epoxidation of the primary olefins is surprisingly high and a high selectivity from propylene to propylene oxide. These high selectivities are at one high degree of conversion of hydroperoxide, namely 50% or higher, achieved. These The degree of conversion is extraordinary for the technical usefulness of this process important.

When the starting material is oxidized, the ratio of substrate to organic peroxide compounds vary within wide limits. Generally applies one molar ratios of olefin groups in the substrates to hydroperoxide in the range from 0.5? 1 to 100: 1. expediently from 1: 1 to 20: 1 and preferably from 2: 1 up to 10: 1. The hydroperoxide concentration in the starting material mixture for the oxidation reaction is usually 1% or more at the start of the reaction whether lower concentrations are effective and can be used.

The oxidation reaction of the starting material can in the presence of a Solvent can be carried out, and in general the use of a Solvent expedient.

In most cases, aqueous solvents are out of the question. Suitable agents are, for example, hydrocarbons, the aliphatic, aromatic or sewage hydrocarbons, and the oxygen derivatives of these hydrocarbons. The solvent preferably has the same carbon skeleton as that used Hydroperoxide, which reduces or prevents solvent separation difficulties will.

The basic substances used in the method according to the invention are alkali or alkaline earth compounds.

The compounds of sodium, potassium, lithium, Calciiim, Magnesium, Rubidium? Oesium, strontium, and barium will be most useful Compounds applied which are soluble in the reaction medium but can also insoluble forms are used and are effective when in the reaction medium Can be dispersed Compounds of organic acids, æ. BO acetates, naphthenates, Use stearate, octoate or butyl rate of metals. You can also use inorganic Salts, for example sodium carbonate, magnesium carbonate or trisodium phosphate use The particularly preferred metal salts include, for example Sodium naphthenate, potassium stearate and magnesium carbonate. One can also use hydroxides and oxides of alkali and alkaline earth metals, for example NaOH, MgO, CaO, Ca (OH) 2, and KO, alkoxides, e.g.

Na-ethylate, K-cumylate or Na-phenolate, amides, for example Na NH2 and use quaternary ammonium salts. In general, any compound of Alkali or alkaline earth metals which give a basic reaction in water are useful.

The compounds are during the epoxidation reaction in a Amount from 0.05 to 10 moles per mole of epoxidation catalyst, advantageously from 0.25 to 3.0 and preferably from 0.50 to 1.50 mol. It has been found that one remarkable as a result of the presence of the basic compound in the reaction system improved efficiencies in the utilization of organic hydroperoxides in the Epoxidation achieved This means that when using the basic compound a higher yield of oxirane compound, based on consumed hydroperoxide, receives. In the process according to the invention, the used hydroperoxide is also used instead of other undesirable products, a larger amount is reduced to alcohol Further by using the basic compound it becomes possible to obtain lower ratios from unsaturated compound to hydroperoxide to apply and thereby the conversion to improve the unsaturated compound while satisfactorily high reaction selectivities remain.

Another significant advantage of the method according to the invention lies in the higher stability of the reaction mixture leaving the epoxidation zone obtained due to the presence of the basic compound. The decomposition of not converted hydroperoxide to compounds with a different carbon configuration during the subsequent extraction process is conspicuously suppressed.

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

Example 1 65 g of a liquid feed consisting of 12.9% by weight Cumene hydroperoxide, 18.5% cumene, 33.7% cumene alcohol, 34.5% propylene and 0.4% molybdenum naphthenate (5% molybdenum content) was introduced into a reactor. In the feed it also contained 0.285 g sodium naphthenate with a sodium content of 0.84%, so that # 50 mol% sodium, based on the molybdenum, was present. The response time was 3 hours, the reaction temperature 90 ° C. The conversion of non cumyl hydroperoxide was 94.9% and the selectivity to propylene oxide 91 * (based on hydroperoxide).

For comparison, the experiment with a response time of one Repeated hour at 90 ° C with the exception that no sodium naphthenate was added became. 94.4% of the oumol hydroperoxide settled with a selectivity of 2.5 % to propylene oxide.

In the above experiments, the product mixtures were used for epoxidation distilled to separate propylene oxide as a product. When trying without sodium naphthenate all cumene hydroperoxide in the mixture was at a temperature in the Distillation still from 13000 to Oumyl alcohol and also to Acetophenone and Phenol decomposed. The latter decomposition is particularly undesirable because it involves the C9 configuration is lost and therefore the material cannot be reused. Furthermore, was a high percentage of that in the mix. contained cumyl alcohol alpha methyl styrene dehydrated what at that time. point because of Polymer formation is undesirable when attempting to use sodium naphthenate at the same temperature in the still only 30 des were not reacted cumene hydroperoxide decomposed. There was also virtually no dehydration of cumyl alcohol Example 2 The procedure of Example 1 was carried out in a series of experiments repeated, each using a feed mixture, the 12.9% cumene hydroperoxide, 18.4% cumene, 33.8% cumyl alcohol, 34.5% propylene and 0.4% molybdenum naphthenate (5% molybdenum content). The trials were different amounts of sodium naphtenate were used in each case. All experiments were carried out carried out at 90 ° C.

The results obtained are given in the table below.

Table I. Trial mol% * time cumene selectivity No. Sodium (hour) hydroperoxide for propylene oxide as conversion%% Naphtenant 1 0 1 92.3 70.6 2 25 1 82.9 81.2 3 50 2 89.6 100s0 4 100 2 18.8 93.2 * Based on Mo ** Based on converted hydro peroxide Example 3 The procedure of Example 1 was repeated in a series of experiments, each using a feed mixture containing 46.4% cumene oxydate with 42.2% cumene hydroperoxide, 26.2% cumyl alcohol, 27% propylene and 0.4% molybdenum naphthenate contained. Various alkali and alkaline earth metal naphthenates were used in the individual experiments. Experiments 5 to 9 were carried out at 90 ° C. and experiments 10 to 22 at 100 ° C. The results obtained are listed in the following table.

Table II Trial Mol% Metal Time Cumene Selectivity for No. as Naphthenate (hours) hydroperoxide propylene oxide% based on mole conversion% 5 0 2 72.0 43.6 6 50-Li 2 85.8 59.3 7 50-K 2 74.3 60.2 8 50-Mg 2 73.2 51.3 9 50-Ca 2 71.6 57.7 10 0 2.5 94.9 42.8 11 100-Li 2.5 97.8 66.6 12 100-Na 2.5 89.9 79.6 13 100-K 2.5 88.0 89.7 14 100-Mg 2.5 90.0 52.9 15 100-Ca 2.5 85.9 61.8 16 0 2.5 95.6 58.6 17 50-Li 2.5 97.8 45.8 18 50-Na 2.5 86.8 65.5 19 50-K 2.5 89.6 67.2 20 50-Mg 2.5 90.7 51.7 21 150-Ca 2.5 91.3 52.3 22 150-Li, 2.5 93.7 70.3 example 4 The procedure of Example 1 was repeated where. with a loading off 50 g of a mixture of 141% ethyl benzene hydroperoxide in ethyl benzene, 10i5 g propylene and 0.2 g of 5% molybdenum naphthenate was used. The response time was one hour at 900C0 There were about 0.27 g of potassium naphthenate in cumene with a Content of 1.5% potassium applied so that 100 mole% potassium as naphthenate. based on molybdenum, present The conversion of hydro peroxide was 91.5% with 89.8% Selectivity to propylene oxide, without the potassium naphthenate the hydroperoxide was conversion 92.4% with a selectivity of 78.6% to propylene oxide. Example 5 Die The procedure of Example 7 was repeated using a charge of 20 g of 40% cumene hydroperoxide in cumene, 12.3 g cyclohexene and 0.1 g 3.4% vanadium naphthenate The reaction time was one hour, the reaction temperature 90 ° C When using 100 mol% sodium as naphthenate - based on vanadium - was the hydroperoxide conversion 97.2% with a selectivity of 98.6% to cyclohexene epoxide without the sodium naphthenate, 98.1 @ with a S @ strength of 93.3 to cycl ohe @ enexyd example 6 The procedure of Example 1 was repeated using a charge from 10 g of tert-butyl hydroperoxide, 10 g of tert-butyl alcohol, 10 g of butene-1 and 0.2 g of 5% strength Molybdenum naphthenate was used. The reaction time was 8 hours, the reaction temperature 130 ° C. When using 100 mol% potassium as naphthenate, based on molybdenum, the hydroperoxide conversion was 98.4% with a selectivity of 78.9% to butene epoxide, without the potassium naphthenate 99.3%, with a selectivity of 49.6% to the epoxy.

Example 7 The procedure of Example 1 was repeated, wherein a charge of 31.2 ffi cumene oxidate with a content of 42.2% cumene hydroperoxide, Made from 33.8% dumyl alcohol, 34.6% propylene and 0.4% 5% molybdenum naphthenate became.

A number of tests were carried out at 1100C using additives carried out from pulsed MgCO3. The following table shows the results obtained.

Table III Attempt mol% Mg CO3 time cumene hydro selectivity for No. based on (hours) peroxide Conversion of propylene oxide% Mo% 23 0 0.5 99.6 53.4 24 100 1.5 99f7 79.8 25 1000 1.5 99.8 67.2 Example 8 A series of experiments were carried out using alpha @ phenylethyl hydroperoxide to epoxidize cyclohexene to cyclohexene oxide. About 50 g of 35 --iges alpha-phenylethylhydrop.'oroxide in ethylbenzene were mixed with 100 g of cyclohexene. The following catalysts were added to 5 g samples of this mixture, and each sample was reacted for one hour at 70 ° C. The conversion relates to the hydroperoxide conversion and selectivity to the amount of cyclohexene oxide formed, based on the hydroperoxide converted to another product. Table IV Attempt catalyst conversion selectivity j Mo naphthenate (5 wt% Mo) 0.02 100 95 2 V-naphthenate (3.4 wt% V) 0s02 97 95 5 tetrabutylititanate 0.02 98 4 rhenium beptoxide 0.01 100 20 5 tungsten carbonyl 0.005 98 95 6 Niobium acetylacetonate 5 @ 95 7 niobium naphthenate (4.84% Nb) 0.02 67 95 8 tantalum naphthenate (9.42% Ta) 0.02 44 90 Example 9 About 3 g of commercially available MoO3 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.

The resulting mixture was filtered to remove solids and the filtrate, which contained a small amount of catalyst dissolved, with an equal Amount by weight of cyclonexene combined and reacted at 800C for 3 hours. the Hydroperoxide conversion was 82, the selectivity of conversion to cyclohexene oxide, based on hydroperoxide, 93%.

The above experiment was repeated, with 3 g of freshly precipitated Nb205 were used instead of 3 g MoO3. The hydroperoxide conversion was 43%, the selectivity to cyclohexene oxide based on hydroperoxide 91%.

Example 10 A series of experiments were carried out on propylene to epoxidize to propylene oxide. In each case 20 g of a 34.6% solution were used of alpha.Phenyläthylhydroperoxyd in ethylbenzene together with 20 g of propylene and introduced the specified amount of catalyst into a pressure reactor. The implementation was carried out at 110 ° C for one hour. In the following table are the obtained Results given. Conversion and selectivity are as given in Table IV.

Table V Attempt catalyst conversion selectivity g%% 11 Monaphthenate (5 wt% Mo) 0.2 97.2 70.8 12 Ti naphthenate (2.5 wt% Ti) 0.2 54s0 55.3 13 Ta naphthenate (9.4 wt% Ta) 0.2 25.0 22.8 14 Nb-naphthenate (4.84% Nb) 0.2 22.0 20.0 15 W naphthenate (5 wt% W) 0.4 83.0 65F0 Example 11 Example 10 was repeated using 20 g of a 27.5% strength cumene hydroperoxide solution in cumyl alcohol (dimethylphenyl carbinol) and 20 g of propylene. When 0.1 g of tetrabutyl titanate catalyst was used for a one-hour reaction at 11,000, the hydroperoxide conversion was 23.8% and the selectivity to propylene oxide was 62.3%.

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

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

The process can be batch or intermittent or continuous Way to be carried out. 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 carry out a plurality of reactors connected in series, and the hydroperoxide at spaced locations along the path of the flowing solution introduce.

In general, the epoxidation reaction mixtures are distilled, to separate the oxirane compound as a product, however, other separation methods are also available possible. Distillation temperatures in the range of about -40 to 2000C at the head and 20 to 250 soils at under-normal or overpressure can be applied in a suitable manner will

Claims (1)

P a t e n t a n s p r ü c h e 1. Process for the production of oxirane compounds, characterized in that there is an olefinically unsaturated compound in liquid Phase with an organic hydro peroxide in the presence of epoxidation conditions a catalytic amount of an epoxidation catalyst and in the presence of a to increase the efficiency of the epoxidation reaction suitable amount of a basic connection implements. 2. The method according to claim 1, characterized in that as Epoxidation catalyst a catalyst from the group of molybdenum, tungsten, vanadium or selenium is used. 3. The method according to claim 1, characterized in that as basic compound an alkali or alkaline earth compound used0 4. Method according to claim 1, characterized in that one is used as the unsaturated compound lower olefin having 2 to 4 carbon atoms is used So procedure according to claim 1, characterized in that the organic hydroperoxide is used used with the formula ROOH, in which R is an alkyl! Cycloalkyl or aralkyl radical having 3 to 20 carbon atoms means used 6. Method of preparation of oxirane compounds, characterized in that one olefinically unsaturated Combination in liquid phase with an organic hydroperoxide at one temperature in the range from -20 to 2000 C in the presence of a catalytic amount of an epoxidation catalyst from the group of molybdenum, tungsten, vanadium or selenium and in the presence of 0.05 to 10 moles of a basic compound per mole of epoxidation catalyst at a molar ratio from unsaturated compound to organic hydroperoxide in the range of about Of 5, : 1 to tOO: 1 implements. 7. The method according to claim 6, characterized in that as unsaturated compound propylene, as organic hydroperoxide cumene hydroperoxide and a molybdenum catalyst is used as the epoxidation catalyst @ 8. Process according to claim 6, characterized in that the unsaturated compound is propylene, as, organic hydro. peroxide ethylbenzene hydroperoxide and as an epoxidation catalyst. lyser uses a molybdenum catalyst. 9. A method for obtaining an oxirane compound from one of these and also a Zpoxydierungsgemiooh containing organic hydroperoxide, thereby characterized in that one does not incorporate a basic compound into the mixture, the mixture distilled and thereby separates the Oxi ranverbindungen. 10. A process for the preparation of oxirane compounds, characterized in that that one is an olefinically unsaturated compound lit an organic hydroperoxide in the presence of a catalyst from the group consisting of Ti, Cr, Nb, Zr, Te, Ta, Re or U implements. 11. The method according to claim 10, characterized in that as Catalyst uses a Ti, Ta, Nb, or Re catalyst,