CS209269B1 - Manufacturing method of saturated and/or unsaturated aliphatic epoxide compounds having 20up to 80 carbon atoms - Google Patents

Description

(54) A method for producing saturated or unsaturated aliphatic epoxy compounds having 20 to 80 carbon atoms

The invention relates to a process for the production of saturated β or unsaturated aliphatic epoxy compounds having from 20 to 80 carbon atoms from available petrochemical raw materials prepared by oligomerization, polyolysis, polyol. by measurement or copolymerization, in particular of the alkenes and dienes, while achieving a relatively high epoxidation rate and selectivity to alkyloxiranes or alkenyloxiranes.

It is well known that epoxidation of alkenes can be accomplished by chlorohydrinating followed by dehydrochlorination, followed by organic peroxy acids: lines prepared in advance [Priležajev N.A .: Ber.

^! 42, 4811 (1909); V. Brit. pat. 990 883; SUI. pat.

481 089; Karanika VN et al .: Kinetics i kataliz 18, 1612 (1977)] or formed "in situ" from hydrogen peroxide, carbonic acid or its anhydride by the action of acid catalysts, e.g. cation exchanger [NSR Pat. 1,210,850; Šapilov OD et al .: Ž. Ex. chim. 45, 1578 (1972)], followed by cooxidation of the alkenes and aldehydes with oxygen, respectively. air to form alkene oxides and aldehydes of the corresponding acids [BljumbergE. A., Filip's TV: Nephtechimija 6, 863 (1966); Andrianov AA, Čemjak BI: Nephtechimija 8, 22 (1969); Tavadin LA et al., Neftechimija 18,667 (1978); Austral. pat. 405 028 and French. pat. 1,410,985]. The disadvantage, as in the case of epoxidation by peracids, is the high corrosion of the device and, in the latter case, also the low selectivity. Direct oxidation with air, resp. while it can only be applied with high selectivity to epoxidize ethylene to ethylene oxide. Although several processes are known for the preparation of propylene oxide by direct oxidation of propylene, none has yet found its application in the manufacture due to too low selectivity [NSR Pat. 896 941; V. Brit. pat. 724 207; Mis (r. JE: Petrochemistry 19, 43 (1979)) Thus, the epoxidation of olefins with organic hydroperoxides is currently the most industrially significant (belg. Pat. 644 090; french pat. 1 459 796 and 1 460 575; Krjuk SI, Farber MJ Neftechimija 11, 224 (1971), Sheng N.N, Zajacek JG: J. Org. Chem. 35, 1839 (1970)], in particular tert-butyl hydroperoxide, ethylbenzene hydroperoxide and cumene hydroperoxide, under the catalytic action of transition metals and their compounds, in particular the most important catalysts are based on molybdenum [Ševčíková I., Mistrík JE: Petrochemistry 18,186 (1978)]. however, it applies to the epoxidation of alkenes up to C ₁₈ at the most. However, the disadvantage is that both the reaction water and the epoxidation reaction medium, in particular alcohol resulting from organic hydroperoxides, mainly after their convection for epoxidation of alkenes (e.g. tert-butyl hydroperoxide) tert-butyl alcohol, ethylbenzene hydroperoxide (1-phenylethanol, and cumene hydroperoxide cumyl alcohol), respectively, is inhibited, respectively. retarding by epoxidation [Farber, Stozkova, Bondarenko, Glusker: Neftechimija 10, 218 (1970); Howe, Hiatt, J. Org. Chem. 36,2493 (1971); Ind., Brill: J. Org. Chem. 30, 2074 (1965); Boeva, Tanieljan, Ivanov: Nephtechimija 18, 768 (1978)]. The reason lies in the formation of competing complexes of alcohols and possibly of water with an epoxidation catalyst. These and other drawbacks are overcome and the known advantages of epoxidation of alkenes with hydroperoxides and peracids are analogously applied to the production of high molecular weight epoxy compounds by the method of the present invention.

According to the present invention, a process for the production of saturated or unsaturated aliphatic epoxy compounds having 20 to 80 carbon atoms and the corresponding oxygenated compounds, respectively, by epoxidation with organic hydroperoxides such as tert-butyl hydroperoxide, ethylbenzene solution of ethylbenzene hydroperoxide and first cumene solution and a Vl.a subgroup of the Periodic Table of the Elements at a temperature of 30 to 160 ° C, or hydrogen peroxide in association with organic or inorganic acids and catalysts based on cationic ion exchangers or at least one of boron, molybdenum, tungsten, mercury, bismuth, antimony and arsenic compounds; preferably heterogeneous or heterogeneous catalysts, at a temperature of 20 to 120 ° C, in the presence of inert solvents which are not subject to oxidative changes under the conditions of epoxidation, in particular cyclohexane, of saturated, aromatic or aliphatic-aromatic hydrocarbons, is carried out by epoxidizing a copolymer or homopolymer of C2 -C5 alkenes, the components in the mixture being in a ratio of 0.1: 1 to 1: 0.1 wt. parts or conjugated dienes of 4 to 5 carbon atoms containing on average 1 to 4 double bonds in a macromolecule, at a total pressure of 0.1 to 200 kPa and a total molar ratio of organic hydroperoxide or hydrogen peroxide to epoxidized homopolymer or copolymer of 1 to 5: 1, wherein the released alcohol or water is discharged alone or as an azeotrope, typically with an organic solvent, wherein the epoxidation catalyst is removed from the crude product and preferably recovered.

The advantages of the process according to the invention are the easy technical availability of the starting materials, the possibility of production in non-pressurized or low-pressure plants, higher yields of epoxy compounds, and the fact that the heat of evaporation of distilled alcohol or water, respectively. The azeotropes of alcohols and hydrocarbon water are technically undemanding and efficient to remove the heat of reaction, while at the same time carrying out another technological operation, separating the by-products.

By controlling the pressure, it is further possible to maintain an optimum epoxidation temperature. In doing so, valuable products and intermediates for further organic synthesis and production are obtained from available but not yet technically upgraded starting petrochemical raw materials. Thus, in the production of ethene oligomers, resp. production of 1-alkenes by oligomerization of ethene; The process of production of linear primary higher fatty alcohols eliminates relatively large quantities of alkenes above _C20 , which generally lack more attractive use.

In addition, oligomers or relatively low molecular weight polymers and copolymers can be produced only from 1'ahko refined, but also practical technical olefins C ₂ to C _s conjugated diene and C ₄ and C _5, individual and mixtures of olefins and diene, also mixed with other saturated and optionally unsaturated hydrocarbons using cheap cationic, anionic or complex catalysts, free radical initiators and the like.

Of the organic hydroperoxides, tertiary butyl hydroperoxide, tertiary amyl hydroperoxide, ethylbenzene hydroperoxide, cumene hydroperoxide are particularly suitable, the more molecular hydroperoxides are less suitable, because the corresponding alcohols formed therefrom

ROOH-I-R'CH = CHR '- > ROH + R'CH CHR

it is not possible to continuously remove the reaction medium from the reaction medium in a technically simple manner in the said pressure range and at an approximate optimum epoxidation temperature. The need for substantial amounts of solvent additives to form an azeotrope with the released alcohol also substantially reduces the process preference. It is possible to use known epoxidation catalysts based on elements and compounds of elements V.a and Vl.a of a subgroup of the periodic system, but mainly of rpolybdenum, vanadium, tungsten and chromium. Compounds are, on the one hand, oil-soluble forms of said elements, e.g. in the form of salts of organic acids (molybdenum phthenate, molybdenum stearate, etc.), which, however, are quite difficult to remove from the reaction products, regenerate the capsules, either in the form of oxides, sulfides, either alone or supported on carriers. Of particular interest are forms of heterogenized epoxidation catalysts, such as e.g. molybdenum compounds deposited on polymer matrices [Tanieljan S. K. et al., Neftechimija 18, 760 (1978)]. Such heterogeneous or heterogenized epoxidation catalysts, especially if they have a sufficient specific surface area, are particularly important because they are easy to regenerate and do not contaminate the product.

Particularly suitable as inert solvents are those which form azeotropes from the organic hydroperoxide released by the alcohol. Thus, in the case of cumene hydroperoxide with released cumyl alcohol, a suitable azeotrope produces cumene, which at the same time is also a diluent of cumene hydroperoxide, in the case of ethylbenzene hydroperoxide ethylbenzene, in the case of hydrogen peroxide water and the like.

The total epoxidation pressure usually depends on the type of epoxidizing agent as well as on the epoxidation temperature. In the case of tertiary butyl hydroperoxide, it is possible to work at atmospheric pressure, respectively. slightly elevated since the boiling point of tertiary butyl alcohol at a pressure of about 101 kPa (and slightly higher in the epoxidizing environment) is almost identical to the optimal for catalyzed epoxidation with organic hydroperoxides. For ethylbenzene hydroperoxide, respectively. cumene hydroperoxide is desirable to operate under reduced pressure and typically with the addition of solvents needed to form an azeotrope boiling in the optimum temperature range of 70 to 120 ° C, in an epoxidation system of acids with a hydrogen peroxide of 40 to 100 ° C. Pre-prepared organic and inorganic peracids, such as peroxyacetic acid, peroxy formic acid, peroxyisobutyric acid, peroxiboric acid and the like can also be used for epoxidation.

Further details of the production method of the present invention are apparent from the examples.

Example 1

A three-necked flask having a volume of 500 cm ³ equipped with a sealed stirrer, thermometer and reflux condenser was weighed 200 g of polypropylene oil on the average of the molecular weight of 495 J (brómovéčíslo = 57.05 gBr2 / 100 g; cl / ¹ = 846 kg. M ^{- 3} ; per macromolecule, there is an average of 1.77 double bonds; nD = 1.4700; viscosity at 20 ° C = 504 mPas; temperature = -1.5 to 42 ° C) and heated to 90 ° C with stirring . Then 1.5 g of molybdenum oxide powder and 120 g of tert-butyl alcohol solution of tertiary butyl hydroperoxide with conc. 61% wt. (mole ratio of polypropylene oil to tertiary butyl hydroperoxide is 1: 2). While stirring and refluxing, the reaction mixture is maintained for an additional 4 h, then cooled, the suspended molybdenum catalyst is filtered off and the tertiary butyl alcohol as well as the unconverted tertiary butyl hydroperoxide are shaken with water and separated. The epoxidized and unconverted polypropylene oil is further purified on a rotary evaporator. The bromine number of the product was 40 g Br _2/100 g, so that the conversion of polypropylene is 29% oil, respectively. 52.8% when calculating the epoxidability of one double bond in the macromolecule of polypropylene oil, conversion of tertiary butyl hydroperoxide 62.1% and selectivity to epoxidized polypropylene oil 29.0%, yield of epoxidized polypropylene oil (calculated for epoxidation of 1 double bond) is 20.5 %.

However, under otherwise similar conditions, but with the addition of tertiary butyl hydroperoxide by dropwise addition to the reaction medium during 1h, simultaneously distilling off the tertiary butyl alcohol at a total pressure of 101.3 kPa (both added together with tertiary butyl hydroperoxide with its distillation for a further hour at a temperature of 90 ± 0.5 ° C, the obtained mixture of epoxidized and starting polypropylene oil has a bromine number of 27.1 g Br ₂ / 100g and an epoxy group content of 2.4%. The conversion of polypropylene oil is 52.5%, respectively. 92.8% (if the epoxidability of 1 double bond is calculated) and the conversion of tertiary butyl hydroperoxide 87.1%. The selectivity for epoxidized polypropylene oil is

58.9%.

Example 2

The procedure is similar to that of Example 1, except that 0.5 g of molybdenum naphthenate, containing 2.9% by weight, is applied per experiment instead of 1.5 g of suspended molybdenum trioxide catalyst. molybdenum. Further, from the epoxidation product the catalyst is not regenerated and the total reaction time instead of 5 h is 6 h. The bromine number of the product without distillation of tertiary butyl alcohol is 27.2 and with distillation

21.7 g Br ₂ / 100g. The conversion of tertiary butyl alcohol in the first case is 95 and 92.3%, respectively. The conversion of the polypropylene oil without distilling off the tertiary butyl alcohol was 58.3, respectively.

92.5% and by distilling62, resp. 109.5%, when calculating the epoxidation of 1 double bond (from an average of 1.77) in the macromolecule of polypropylene oil. The content of epoxy groups in the first case is 2.19% and in the second case 3.5. The yield of epoxidized polypropylene oil in the case of epoxidation without distilling off tertiary butyl alcohol is

49.1% and with distillation 79.8%. The remainder to 100% are mainly diols of polypropylene oil and unidentified oxygenated organic compounds.

Example 3

100 g of the polypropylene oil specified in Example 1 and 1.5 g of molybdenum oxide powder are weighed into a three-necked reaction vessel specified in Example 1, equipped with a water condenser and a separator attached to an oil pump instead of a bad condenser. The contents of the flask are then heated to 90 ° C with stirring, the pump is switched on and 92.2 g of cumene hydroperoxide solution with conc. 50 wt. (mole ratio of polypropylene oil to cumene hydroperoxide is thus 1: 1.5). At the same time, at a total pressure of 1.6 kPa, the azeotrope of cumene with cumyl alcohol distills off. At this pressure, the reaction mixture is maintained at a temperature of 100 to 110 ° C for a further 6 h. Distilling off

81.3 g of a mixture of cumene (46 g) with cumyl alcohol (29 g) and cumene hydroperoxide (6.3 g); 10.9 g are collected in the pump protective equipment. Any residual cumene hydroperoxide and cumyl alcohol may be washed with water saturated with butanol.

The bromine number of the product was 28.06 g Br _2/100 g and the amount of epoxy groups 2.51%. The conversion of cumene hydroperoxide reached 69.3% and polypropylene oil reached 50.8%, respectively. 89.8% and the yield of epoxidized polypropylene oil (calculated for epoxidation of 1 double bond) is 57%. Under otherwise similar conditions, but without distilling off the cumyl alcohol, the conversion of the polypropylene oil is only 28.8%, respectively. 50.9%.

and

Example 4

An podobjíů that in Example 1, except that instead of 200 g of polypropylene is used oil, 100 g of polybutene prepared cationic _{(polymerization,} respectively. EXAMPLE copolymerization of olefinically unsaturated hydrocarbon pyrolysis almost pdbutadienizovanej C ₄ -fractions (izobutón = _43.58%: wt 1-butene = 33.50% by weight: 1,3-butadiene = 1.53% by weight; cis-2-butene = 2.39% by weight; trans-2-butene = 6.8% by weight; propen = 0.15% (w / w; isobutane = 2.2% w / w; n-butane = 8.49%, w / w) at 60 ° C on the basis of the Czech Certificate No. 193 855. Average mol. weight polybutenes. after purification was 590, and 71.21 g bromine ^number? _Br2 / 100 g. in one macromolecule event of default as a measure 2,63 double bond. when epoxidation at. 90 ° C and the tertiary butyl hydroperoxide as the epoxidizing agent and a molybdenum oxide powder j at distilling off t-butylal-, alcohols are obtained the (ID = prámové and 23.79 g _Br2 / 100 g) conversion of the polybutene enes, respectively. 66.6% copolymer, and distilling off free (bromine number = kr ₂ 30.3 g / 100 g) 57.5%.

This means that, on average, 1 macromolecule of ¹ scored-1.75 double bond in the distillation experiments and 1.51 double bond without distillation of tertiary butyl alcohol is based on 1 macromolecule. and

Example 5

A mixture of homopolymers and copolymers prepared at 70 ° C from a crude hydrocarbon mixture (containing, in addition to saturated hydrocarbons, 34.26% by weight of 1,3-butadiene; 25.57% by weight of isobutene; 35% by weight of 1-butene, 3.42% by weight of cis-2-butene, 4.6% by weight of trans-2-butene, 0.36% by weight of methylacetylene and 0.2% by weight of propene), and odbutadienized (Specified in Example 4) pyrolysis C ₄ -fraction according to MS. aut. Certificate No. 193 855. Average mol. the weight of the refined mixture is 433; bromine number = 102.47 g _Br2 / 100 g; refractive index n _D ²⁰ = 1.478.

Claims (1)

SUBJECT A process for the production of saturated or unsaturated aliphatic epoxy compounds having 20 to 80 carbon atoms and, if appropriate, the corresponding oxygenated compounds by epoxidation with organic hydroperoxides such as tertiary butyl hydroperoxide, ethylbenzene solution of ethylbenzene hydroperoxide and cumene solution of cumene or first hydroperoxide compounds. and a subset of the periodic system of elements at a temperature of 30 to 160 ° C or hydrogen peroxide with the participation of organic or inorganic 150 g of said mixture of homopolymers and copolymers, 1.5 g of powdered molybdenum oxide and 182 g of tert-butyl alcohol solution of tertiary butyl hydroperoxide are added to the epoxidation on the apparatus specified in Example 1. 61% wt. The resulting molar ratio of homopolymers and copolymers to tertiary butyl alcohol is thus 1: 3.55. This is because one macromolecule has 2.78 double bonds. At a temperature of 90 ° C, a pressure of 101 kPa and a reaction time of 5 h by an otherwise similar procedure to that of Example 1, the conversion of tert-butyl hydroperoxide is achieved in an attempt to distill off tertiary butyl alcohol 68.6% (also a small portion of tertiary butyl hydroperoxide is distilled off) and without distillation 39.6%. The double bond conversion of the mixture of homopolymers and copolymers in the first case reaches 59.7% (bromine product number = 41.34) and in the second, without distillation of tertiary butyl alcohol, 42.1% (bromine number in product without tertiary butyl alcohol = 59.3 gBr ₂₎ / 100 g). This means that in the first case the macromolecule converted 1.63 and in the second 1.17 double bonds. Example 6 Three-necked flask of a volume of 100 ^cm3 equipped with magnetic stirrer, a special dropping funnel and water condenser, connected via a template for the vacuum pump, weigh 40 g of polypropylene oil specified in Example 1 and further 8 g ion exchanger in the H form (Ostion KS) and 0 4 g of boric acid. The pump is then started and the contents of the flask are heated to 70 ± 1 ° C with stirring. At this temperature and a pressure of 32 ± 1 kPa, 18.4 g of an aqueous solution of hydrogen peroxide with conc. 30% wt. (mole ratio of polypropylene oil to H ₂ O ₂ = 1: 2). All water is gradually distilled off from the reaction solution. After 3 h, the experiment was stopped. The conversion of double bonds of polypropylene oil is 45.2% and the yield of epoxidized polypropylene oil (calculated for epoxidation in double bond macromolecule 1) is 61.5%. OF THE INVENTION The acids and catalysts based on cationic ion exchangers or at least one of boron, molybdenum, tungsten, mercury, bismuth, antimony and arjene compounds, preferably heterogeneous or heterogenized catalysts, at a temperature of 20 to 120 ° C, optionally in the presence of other boron solvents conditions of epoxidation are not subject to oxidative changes, in particular cyclohexane, heptane, 1,2-dichloroethane, saturated aromatic or aliphatic-aromatic hydrocarbons, characterized in that the copolymer or homopolymer of C2-C5 alkenes is epoxidized, the individual components in the mixture being in the mixture ratio 0.1: 1 to 1: 0.1 wt. parts or conjugated dienes having 4 to 5 carbon atoms containing an average of 1 to 4 double bonds in a macromolecule, at a total pressure of 0.1 to 200 kPa and a total molar ratio of organic hydroperoxide or hydrogen peroxide to epoxidized upper polymer or copolymer of 1: 5: 1; wherein the released alcohol or water is discharged alone or as an azeotrope, typically with an organic solvent, wherein the epoxidation catalyst is removed from the crude product and preferably recovered.