Method for producing epoxyalkane, and solid oxidation catalyst

Abstract

The present invention provides: a method for producing an epoxyalkane capable of obtaining an epoxide in a high yield while attaining a high olefin conversion rate and a high selectivity for epoxides even when an olefin includes a long carbon chain, and a solid oxidation catalyst used in the method. The method for producing an epoxyalkane of the present invention comprises reacting an olefin with an oxidant in the presence of a solid oxidation catalyst, wherein the solid oxidation catalyst comprises a transition metal and a carrier that supports the transition metal, and the carrier is a metal oxide having a silyl group represented by the following general formula (1):
R.sup.1R.sup.2R.sup.3Si(1) wherein R.sup.1, R.sup.2, and R.sup.3 are each independently a single bond, a hydrocarbon group, a halogenated hydrocarbon group, an alkoxy group, or a halogen, and at least one of R.sup.1, R.sup.2, and R.sup.3 is a hydrocarbon group having 3 or more carbon atoms or a halogenated hydrocarbon group having 3 or more carbon atoms.

Claims

1. A method for producing an epoxyalkane, which method comprises reacting an olefin with an oxidant in the presence of a solid oxidation catalyst, wherein the solid oxidation catalyst comprises a transition metal and a carrier that supports the transition metal, and the carrier is a metal oxide having a silyl group represented by the following general formula (1):
R.sup.1R.sup.2R.sup.3Si(1) wherein R.sup.1, R.sup.2, and R.sup.3 are each independently a single bond, a hydrocarbon group, a halogenated hydrocarbon group, an alkoxy group, or a halogen, and at least one of R.sup.1, R.sup.2, and R.sup.3 is a hydrocarbon group having 3 or more carbon atoms or a halogenated hydrocarbon group having 6 or more carbon atoms.

2. The method for producing an epoxyalkane according to claim 1, wherein at least one of R.sup.1, R.sup.2, and R.sup.3 in the general formula (1) is a hydrocarbon group having 6 or more carbon atoms or a halogenated hydrocarbon group having 6 or more carbon atoms.

3. The method for producing an epoxyalkane according to claim 1, wherein the transition metal is W.

4. The method for producing an epoxyalkane according to claim 1, wherein the metal oxide contains Al and/or phosphoric acid.

5. The method for producing an epoxyalkane according to claim 1, wherein the metal oxide is AlPO.sub.4.

6. The method for producing an epoxyalkane according to claim 1, wherein the olefin has 8 or more carbon atoms.

7. The method for producing an epoxyalkane according to claim 1, wherein the temperature at the time of the reaction is 40? C. or higher and 90? C. or lower.

8. The method for producing an epoxyalkane according to claim 1, wherein the oxidant is a peroxide.

9. The method for producing an epoxyalkane according to claim 1, wherein the oxidant is hydrogen peroxide.

10. A solid oxidation catalyst that is used in a method for producing an epoxyalkane by reacting an olefin with an oxidant, wherein the solid oxidation catalyst comprises a transition metal and a carrier that supports the transition metal, and the carrier is a metal oxide having a silyl group represented by the following general formula (1):
R.sup.1R.sup.2R.sup.3Si(1) wherein R.sup.1, R.sup.2, and R.sup.3 are each independently a single bond, a hydrocarbon group, a halogenated hydrocarbon group, an alkoxy group, or a halogen, and at least one of R.sup.1, R.sup.2, and R.sup.3 is a hydrocarbon group having 3 or more carbon atoms or a halogenated hydrocarbon group having 6 or more carbon atoms.

11. The solid oxidation catalyst according to claim 10, wherein at least one of R.sup.1, R.sup.2, and R.sup.3 in the general formula (1) is a hydrocarbon group having 6 or more carbon atoms or a halogenated hydrocarbon group having 6 or more carbon atoms.

12. The solid oxidation catalyst according to claim 10, wherein the transition metal is W.

13. The solid oxidation catalyst according to claim 10, wherein the metal oxide contains Al and/or phosphoric acid.

14. The solid oxidation catalyst according to claim 10, wherein the metal oxide is AlPO.sub.4.

15. The method for producing an epoxyalkane according to claim 2, wherein the transition metal is W.

16. The method for producing an epoxyalkane according to claim 2, wherein the metal oxide contains Al and/or phosphoric acid.

17. The method for producing an epoxyalkane according to claim 2, wherein the metal oxide is AlPO.sub.4.

18. The method for producing an epoxyalkane according to claim 2, wherein the olefin has 8 or more carbon atoms.

19. The method for producing an epoxyalkane according to claim 2, wherein the temperature at the time of the reaction is 40? C. or higher and 90? C. or lower.

20. The method for producing an epoxyalkane according to claim 2, wherein the oxidant is a peroxide.

Description

EXAMPLES

(1) Hereinafter, the present invention will be specifically described based on Examples. Unless otherwise specified in the table, the content % of each component indicates % by mass. In addition, various measurement methods are as follows.

Calculation of Supported Amount of Tungsten

(2) The supported amount (% by mass) of tungsten in the solid oxidation catalyst was calculated from the charged amount of the raw materials.

Measurement of Olefin Conversion Rate

(3) After converting the reaction solution to TMS using a TMSI-H (GL Sciences Inc.), a column Ultra ALLOY-1HT (manufactured by Frontier Laboratories Ltd.: Capillary column 30.0 m?250 ?m?0.15 mm) was attached to a gas chromatograph analyzer GC6850 (manufactured by Agilent). Analysis was performed using a hydrogen flame ion detector (FID) under the conditions of an injection temperature of 300? C., a detector temperature of 350? C., and a He flow rate of 4.6 mL/min, and then the product was quantified. The olefin conversion rate was calculated by the following formula.
Olefin conversion rate (%)=[100?(Amount of olefin)]/[(Amount of olefin)+(Amount of epoxide)+(Total amount of by-products)]?100

Measurement of Selectivity for Epoxides

(4) The selectivity for epoxides was calculated by the following formula. For each amount in the formula, the value obtained from the gas chromatograph analysis of the olefin conversion rate measurement was used.
Selectivity for epoxides (%)=(Amount of epoxide)/[(Amount of olefin)+(Amount of epoxide)+(Total amount of by-products)]?100

Example 1

Preparation of Composite of Ethylphosphonic Acid with Aluminum Phosphate

(5) In a 2 L separable flask, 600 g of ion-exchange water, 7.4 g (0.07 mol) of ethylphosphonic acid, 20.7 g (0.18 mol) of 85% aqueous phosphoric acid solution, and a solution prepared by dissolving 84 g (0.2 mol) of Al(NO.sub.3).sub.3.9H.sub.2O in 150 g of ion-exchange water were charged, and then a stirrer, a pH electrode, a thermometer, and a dropping tube holder were attached to the flask. After stirring the mixture at 25? C. and 400 rpm for 10 minutes, a 10% aqueous NH.sub.3 solution was added dropwise at 25? C. using a dropping tube pump at a rate of 0.6 mL/min over the period of 3 hours until the pH reached 5. After completion of the dropping, the mixture was aged for 1 hour with stirring. Thereafter, a white cake collected by filtration under reduced pressure was washed five times with 1.5 L of ion-exchange water until the electric conductivity reached 40 mS/m (each stirring was performed at 700 rpm for 1 hour). Then, the obtained cake was dried at 120? C. overnight (about 15 hours), pulverized in a coffee mill, and further calcined at 350? C. for 3 hours to obtain a composite (EtPOO.sub.2Al PO.sub.4) of ethylphosphonic acid with aluminum phosphate.

Preparation of W-Supported Composite

(6) In a 300 mL four-necked flask, 200 g of ion-exchange water and 1.0 g of tungstic acid (H.sub.2WO.sub.4) were charged, and a 28% aqueous NH.sub.3 solution was added little by little until the pH reached 7 while stirring, thereby to obtain an aqueous ammonium tungstate solution. The prepared aqueous ammonium tungstate solution (200 g) was added to a 1 L round-bottom flask charged with 20 g of the composite, and the flask was immersed in an oil bath set at 63? C. and stirred for 0.5 hours. Next, water was removed from the flask by an evaporator to collect a solid. The obtained solid was dried at 120? C. overnight (about 15 hours), pulverized by a coffee mill, and calcined at 350? C. for 3 hours to obtain a W-supported composite (W/EtPOO.sub.2AlPO.sub.4) having tungsten supported on a composite.

Preparation of Solid Oxidation Catalyst

(7) A 300 mL round-bottom flask was charged with 10 g of a W-supported composite (W/EtPOO.sub.2AlPO.sub.4), 157 g of toluene, and 1.0 g of trimethoxyoctenylsilane ((CH.sub.3O).sub.3Si(CH.sub.2).sub.6CH?CH.sub.2) as a silylating agent and was equipped with a stirrer and a thermometer. Then, the mixture was refluxed and stirred at 300 rpm for 7 hours. After allowing to stand for cooling, the mixture was filtered under reduced pressure to collect a solid, which was washed with 150 ml of ion-exchange water three times. After that, the solid was dried at 120? C. overnight (about 15 hours) to obtain a solid oxidation catalyst (W/EtPOO.sub.2AlPO.sub.4Si(CH.sub.2).sub.6CH?CH.sub.2).

Synthesis of Epoxyalkane

(8) In a 100 mL four-neck flask, 2 g of the prepared solid oxidation catalyst (W/EtPOO.sub.2AlPO.sub.4Si(CH.sub.2).sub.6CH?CH.sub.2) and 40 g (0.18 mol) of 1-hexadecene were charged. The flask was equipped with a stirrer, a thermometer, and an N.sub.2 flow, and 12 g (0.21 mol, 1.2 equivalents/1 equivalent of olefin) of 60% aqueous hydrogen peroxide was added in the flask. Thereafter, the flask was immersed in an oil bath set at 80? C. and the reaction was performed for 8 hours to synthesize epoxyhexadecane. The stirring was stopped on the way and sampling was performed every 0.5 to 2 hours to determine the olefin conversion rate and the selectivity for epoxides by the method described above. Table 1 shows the olefin conversion rate and the selectivity for epoxides at the reaction times shown in Table 1.

Example 2

(9) A solid oxidation catalyst (W/EtPOO.sub.2AlPO.sub.4SiC.sub.8H.sub.17) was obtained in the same manner as in Example 1 except that 0.2 g of trimethoxyoctylsilane was used as the silylating agent in the preparation of the solid oxidation catalyst.

(10) Then, using the solid oxidation catalyst (W/EtPOO.sub.2AlPO.sub.4SiC.sub.8H.sub.17), epoxyhexadecane was synthesized by the same method as in Example 1 except that the reaction time was changed to that shown in Table 1. Then, an olefin conversion rate and a selectivity for epoxides were determined and the results were described in Table 1.

Example 3

(11) A solid oxidation catalyst (W/EtPOO.sub.2AlPO.sub.4SiC.sub.8H.sub.17) was obtained in the same manner as in Example 1 except that 1.0 g of trimethoxyoctylsilane was used as the silylating agent in the preparation of the solid oxidation catalyst.

(12) Then, using the solid oxidation catalyst (W/EtPOO.sub.2AlPO.sub.4SiC.sub.8H.sub.17), epoxyhexadecane was synthesized by the same method as in Example 1 except that the reaction time was changed to that shown in Table 1. Then, an olefin conversion rate and a selectivity for epoxides were determined and the results were described in Table 1.

Examples 4 to 11 and Comparative Example 2

Preparation of Aluminum Phosphate

(13) In a 2 L separable flask, 600 g of ion-exchange water, 25.8 g (0.22 mol) of an 85% aqueous phosphoric acid solution, and a solution in which 84 g (0.2 mol) of Al(NO.sub.3).sub.3.9H.sub.2O was dissolved in 150 g of ion-exchange water were charged, and a stirrer, a pH electrode, a thermometer, and a dropping tube holder were attached to the flask. After stirring the mixture at 25? C. and 400 rpm for 10 minutes, a 10% aqueous NH.sub.3 solution was added dropwise at 25? C. using a dropping tube pump at a rate of 0.6 mL/min over 3 hours until the pH reached 5. After completion of the dropwise addition, the mixture was aged for 1 hour with stirring. Thereafter, a white cake collected by filtration under reduced pressure was washed five times with 1.5 L of ion-exchange water until the electric conductivity reached 40 mS/m (each stirring was performed at 700 rpm for 1 hour). Then, the obtained cake was dried at 120? C. overnight (about 15 hours), pulverized by a coffee mill, and further calcined at 350? C. for 3 hours to obtain aluminum phosphate (AlPO.sub.4).

Preparation of W-Supported Aluminum Phosphate

(14) In a 300 mL four-necked flask, 200 g of ion-exchange water and 1.0 g of tungstic acid (H.sub.2WO.sub.4) were charged, and a 28% aqueous NH.sub.3 solution was added little by little until the pH reached 7 while stirring, thereby to obtain an aqueous ammonium tungstate solution. The prepared aqueous ammonium tungstate solution (200 g) was added to a 1 L round-bottom flask charged with 20 g of the prepared aluminum phosphate, and the flask was immersed in an oil bath set at 63? C. and stirred for 0.5 hours. Next, water was removed from the flask by an evaporator to collect a solid. The obtained solid was dried at 120? C. overnight (about 15 hours), pulverized by a coffee mill, and calcined at 350? C. for 3 hours to obtain a W-supported aluminum phosphate (W/AlPO.sub.4) having tungsten supported on aluminum phosphate.

Preparation of Solid Oxidation Catalyst

(15) Each solid oxidation catalyst (W/AlPO.sub.4SiR) shown in Table 1 was obtained in the same manner as in Example 1 except that the silylating agent and the blending amount shown in Table 1 were used.

Synthesis of Epoxyalkane

(16) Epoxyhexadecane was synthesized in the same manner as in Example 1 except that each solid oxidation catalyst (W/AlPO.sub.4SiR) shown in Table 1 was used and the reaction time was changed to that shown in Table 1. Then, an olefin conversion rate and a selectivity for epoxides were determined and the results were shown in Table 1. It should be noted that in Example 9, 200 parts by mass of t-butyl alcohol was used with respect to 100 parts by mass of 1-hexadecene.

Comparative Example 1

Synthesis of Epoxyalkane

(17) Epoxyhexadecane was synthesized in the same manner as in Example 1 except that the prepared W-supported aluminum phosphate (W/AlPO.sub.4) was used and the reaction time was changed to that shown in Table 1. Then, an olefin conversion rate and a selectivity for epoxides were determined and the results were shown in Table 1.

Comparative Example 3

Preparation of Catalyst

(18) A round bottom flask having a capacity of 30 cm.sup.3 was charged with 0.387 g (3 mmol) of quinoline, 0.596 g (3 mmol) of chloropropyltrimethoxysilane and 5 cm.sup.3 of petroleum ether, and the mixture was vigorously stirred in a hot water bath at 70? C. under a nitrogen atmosphere for 5 hours. After completion of the stirring, 5 cm.sup.3 of dry ethanol and 3 g of silica gel were added thereto, and the mixture was vigorously stirred at the same temperature for another 1 hour. After completion of the stirring, the reaction solution was cooled to room temperature. Then, 2.88 g (1 mmol) of 12-tungstophosphoric acid dissolved in 5 cm.sup.3 of dry ethanol was added, and the mixture was vigorously stirred at room temperature for 5 hours under a nitrogen atmosphere. After the stirring was completed, the solvent was distilled off at 50? C. under reduced pressure (133 Pa). Then, the residue was dried for 5 hours under reduced pressure (133 Pa) under a nitrogen atmosphere to prepare a catalyst.

Synthesis of Epoxyalkane

(19) Epoxyhexadecane was synthesized in the same manner as in Example 1 except that the prepared catalyst was used and the reaction time was changed to that shown in Table 1. Then, an olefin conversion rate and a selectivity for epoxides were determined and the results were shown in Table 1.

(20) TABLE-US-00001 TABLE 1 EXAMPLE EXAMPLE EXAMPLE EXAMPLE UNIT 1 2 3 4 CARRIER EtPOO.sub.2AlPO.sub.4 AlPO.sub.4 SOLID OXIDATION CATALYST W/EtPOO.sub.2AlPO.sub.4SiR W/AlPO.sub.4SiR R GROUP OF SILYLATING Octeny Octyl Octyl Propyl AGENT (MeO).sub.3SiR CARBON NUMBER OF R IN C8 C8 C8 C3 SILYLATING AGENT (MeO).sub.3SiR NON-IONIC/IONIC NON- NON- NON- NON- IONIC IONIC IONIC IONIC AMOUNT OF SILYLATING AGENT % BY 10 2 10 10 (VS W-SUPPORTED CATALYST AMOUNT) MASS W-SUPPORTED AMOUNT % BY 3.5 3.5 3.5 3.5 MASS REACTION TEMPERATURE ? C. 80 80 80 80 REACTION TIME hr 4 6.25 2 2 OLEFIN CONVERSION RATE % 18 15 18 17 SELECTIVITY FOR EPDXIDES % 60 65 59 55 PREPATION OF AMOUNT OF CARRIER ETHYLPHOS g 7.4 7.4 7.4 PHONIC ACID MOLE OF mol 0.07 0.07 0.07 ETHYLPHOS PHONIC ACID AMOUNT OF g 20.7 20.7 20.7 25.8 85% PHOSPHORIC ACID MOLE OF mol 0.18 0.18 0.18 0.22 PHOSPHORIC ACID AMOUNT OF g 600 600 600 600 ION- EXCHANGE WATER AMOUNT OF g 84 84 84 84 ALUMINUM NITRATE MOLE OF mol 0.2 0.2 0.2 0.2 ALUMINUM NITRATE AMOUNT OF g 150 150 150 150 ION- EXCHANGE WATER (FOR DISSOLVING ALUMINUM NITRATE) PREPARATION PREPARATION AMOUNT OF g 1.0 1.0 1.0 1.0 OF W- OF H.sub.2WO.sub.4 SUPPORTED IMPREGNATION CATALYST SOLUTION AMOUNT OF g 200 200 200 200 ION- EXCHANGE WATER IMPREGNATION AMOUNT OF g 20 20 20 20 OF W CARRIER H.sub.2WO.sub.4 + NH.sub.3 g 200 200 200 200 AQ. SOLUTION SILYLATION AMOUNT OF g 10 10 10 10 TREATMENT W-SUPPORTED CATALYST AMOUNT OF g 1.0 0.2 1.0 1.0 SILYLATING AGENT (VS AMOUNT OF SUPPORTED CATALYST) AMOUNT OF g 157 157 157 157 TOLUEN (15.7 TIMES THE AMOUNT OF W-SUPPORTED CATALYST) EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE 5 6 7 8 9 CARRIER AlPO.sub.4 SOLID OXIDATION CATALYST W/AlPO.sub.4SiR R GROUP OF SILYLATING Hexyl Dodecyl Dodecyl Dodecyl Dodecyl AGENT (MeO).sub.3SiR CARBON NUMBER OF R IN C6 C12 C12 C12 C12 SILYLATING AGENT (MeO).sub.3SiR NON-IONIC/IONIC NON- NON- NON- NON- NON- IONIC IONIC IONIC IONIC IONIC AMOUNT OF SILYLATING AGENT 10 2 5 10 10 (VS W-SUPPORTED CATALYST AMOUNT) W-SUPPORTED AMOUNT 3.5 3.5 3.5 3.5 3.5 REACTION TEMPERATURE 80 80 80 80 80 REACTION TIME 2 2 4 2 2 OLEFIN CONVERSION RATE 14 16 18 15 20 SELECTIVITY FOR EPDXIDES 62 62 57 63 57 PREPATION OF AMOUNT OF CARRIER ETHYLPHOS PHONIC ACID MOLE OF ETHYLPHOS PHONIC ACID AMOUNT OF 25.8 25.8 25.8 25.8 25.8 85% PHOSPHORIC ACID MOLE OF 0.22 0.22 0.22 0.22 0.22 PHOSPHORIC ACID AMOUNT OF 600 600 600 600 600 ION- EXCHANGE WATER AMOUNT OF 84 84 84 84 84 ALUMINUM NITRATE MOLE OF 0.2 0.2 0.2 0.2 0.2 ALUMINUM NITRATE AMOUNT OF 150 150 150 150 150 ION- EXCHANGE WATER (FOR DISSOLVING ALUMINUM NITRATE) PREPARATION PREPARATION AMOUNT OF 1.0 1.0 1.0 1.0 1.0 OF W- OF H.sub.2WO.sub.4 SUPPORTED IMPREGNATION CATALYST SOLUTION AMOUNT OF 200 200 200 200 200 ION- EXCHANGE WATER IMPREGNATION AMOUNT OF 20 20 20 20 20 OF W CARRIER H.sub.2WO.sub.4 + NH.sub.3 200 200 200 200 200 AQ. SOLUTION SILYLATION AMOUNT OF 10 10 10 10 10 TREATMENT W-SUPPORTED CATALYST AMOUNT OF 1.0 0.2 0.5 1.0 1.0 SILYLATING AGENT (VS AMOUNT OF SUPPORTED CATALYST) AMOUNT OF 157 157 157 157 157 TOLUEN (15.7 TIMES THE AMOUNT OF W-SUPPORTED CATALYST) COMPARATIVE COMPARATIVE COMPARATIVE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE 10 11 1 2 3 CARRIER AlPO.sub.4 AlPO.sub.4 SOLID OXIDATION CATALYST W/AlPO.sub.4SiR W/AlPO.sub.4 W/AlPO.sub.4SiR R GROUP OF SILYLATING Octadcyl CH.sub.2CH.sub.2 Ethyl Chloropropyl AGENT (MeO).sub.3SiR (CF.sub.2).sub.7CF.sub.3 CARBON NUMBER OF R IN C18 C10 C2 C3 SILYLATING AGENT (MeO).sub.3SiR NON-IONIC/IONIC NON- NON- NON- NON- IONIC IONIC IONIC IONIC IONIC AMOUNT OF SILYLATING AGENT 2 2 0 10 10 (VS W-SUPPORTED CATALYST AMOUNT) W-SUPPORTED AMOUNT 3.5 3.5 3.5 3.5 37.5 REACTION TEMPERATURE 80 80 80 80 80 REACTION TIME 2 8 8 2 8 OLEFIN CONVERSION RATE 15 13 0 16 0 SELECTIVITY FOR EPDXIDES 64 65 0 43 0 PREPATION OF AMOUNT OF CARRIER ETHYLPHOS PHONIC ACID MOLE OF ETHYLPHOS PHONIC ACID AMOUNT OF 25.8 25.8 25.8 25.8 85% PHOSPHORIC ACID MOLE OF 0.22 0.22 0.22 0.22 PHOSPHORIC ACID AMOUNT OF 600 600 600 600 ION- EXCHANGE WATER AMOUNT OF 84 84 84 84 ALUMINUM NITRATE MOLE OF 0.2 0.2 0.2 0.2 ALUMINUM NITRATE AMOUNT OF 150 150 150 150 ION- EXCHANGE WATER (FOR DISSOLVING ALUMINUM NITRATE) PREPARATION PREPARATION AMOUNT OF 1.0 1.0 1.0 1.0 OF W- OF H.sub.2WO.sub.4 SUPPORTED IMPREGNATION CATALYST SOLUTION AMOUNT OF 200 200 200 200 ION- EXCHANGE WATER IMPREGNATION AMOUNT OF 20 20 20 20 OF W CARRIER H.sub.2WO.sub.4 + NH.sub.3 200 200 200 200 AQ. SOLUTION SILYLATION AMOUNT OF 10 10 10 TREATMENT W-SUPPORTED CATALYST AMOUNT OF 0.2 0.2 1.0 SILYLATING AGENT (VS AMOUNT OF SUPPORTED CATALYST) AMOUNT OF 157 157 157 TOLUEN (15.7 TIMES THE AMOUNT OF W-SUPPORTED CATALYST)

INDUSTRIAL APPLICABILITY

(21) The method for producing an epoxyalkane and the solid oxidation catalyst according to the present invention are useful for producing an epoxyalkane for a variety of uses.