JP4495272B2 - Method for producing oxirane compound - Google Patents

Description

＊１：細孔分布の最小値は窒素吸着法による測定限界値
【００４１】
表１のＥＢＨＰを用いたエポキシ化反応において、本発明による触媒は活性、選択性ともに明らかに高い性能を示していることがわかる。
【００４２】
【発明の効果】
以上説明したとおり、本発明により、チタン含有珪素酸化物触媒の存在下、高収率及び高選択率下に、オレフィン型化合物とエチルベンゼンハイドロパーオキサイドを反応させるオキシラン化合物の製造方法を提供することができた。
【図面の簡単な説明】
【図１】実施例１の触媒のＸ線回折チャートである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an oxirane compound. More specifically, the present invention relates to a method for producing an oxirane compound in which an olefin type compound and ethylbenzene hydroperoxide are reacted in the presence of a titanium-containing silicon oxide catalyst with high yield and high selectivity.
[0002]
[Prior art]
It is known that propylene oxide can be produced by reacting olefin type compound propylene with ethylbenzene hydroperoxide. For example, US Pat. No. 4,367,342 discloses a method using a titanium-supported silica catalyst. However, the conventional method is not necessarily sufficient from the viewpoint of obtaining an oxirane compound with a high yield and a high selectivity.
[0003]
[Problems to be solved by the invention]
Under such circumstances, the problem to be solved by the present invention is a method for producing an oxirane compound in which an olefin type compound and ethylbenzene hydroperoxide are reacted in the presence of a titanium-containing silicon oxide catalyst with high yield and high selectivity. The point is to provide.
[0004]
[Means for Solving the Problems]
That is, the present invention relates to a method for producing an oxirane compound in which an olefin type compound and ethylbenzene hydroperoxide are reacted in the presence of a catalyst comprising a titanium-containing silicon oxide that satisfies all the following conditions (1) to (5). Is.
(1): The average pore diameter is 10 mm or more (2): 90% or more of the total pore volume has a pore diameter of 5 to 200 mm (3): The specific pore volume is 0.2 cm ³ / g (4): It is obtained by using a quaternary ammonium ion represented by the following general formula (I) as a mold (template) and then removing the mold by a solvent extraction operation. [NR ¹ R ² R ³ R ⁴ ] ⁺ (I)
(In the formula, R ¹ represents a linear or branched hydrocarbon group having ² to 36 carbon atoms, and R ^{2 to} R ⁴ represent an alkyl group having 1 to 6 carbon atoms.)
(5): In X-ray diffraction, there is no peak indicating the surface separation d.
DETAILED DESCRIPTION OF THE INVENTION
The catalyst of the present invention is a catalyst comprising a titanium-containing silicon oxide that satisfies all the following conditions (1) to (5). By using such a catalyst, the problem of producing an oxirane compound from an olefin type compound and ethylbenzene hydroperoxide can be achieved at a high level with high yield and high selectivity.
[0006]
The condition (1) is that the average pore diameter is 10 mm or more.
[0007]
Condition (2) is that 90% or more of the total pore volume has a pore diameter of 5 to 200 mm.
[0008]
The condition (3) is that the specific pore volume is 0.2 cm ³ / g or more. Here, the specific pore volume means the pore volume per 1 g of catalyst.
[0009]
The measurement about said conditions (1)-(3) can be measured by a normal method using the physical adsorption method of gas, such as nitrogen and argon.
[0010]
Condition (4) is obtained by using a quaternary ammonium ion represented by the following general formula (I) as a mold, and then removing the mold by a solvent extraction operation.
[NR ¹ R ² R ³ R ⁴ ] ⁺ (I)
(In the formula, R ¹ represents a linear or branched hydrocarbon group having ² to 36 carbon atoms, and R ^{2 to} R ⁴ represent an alkyl group having 1 to 6 carbon atoms.)
The condition (4) will be described in detail in the catalyst production method.
[0011]
Condition (5) is that there is no peak indicating the interplanar spacing d in X-ray diffraction (XRD). The peak indicating the interplanar spacing d here refers to a peak derived from the crystallinity / regularity of the solid, and a broad peak derived from an amorphous portion may exist.
[0012]
The catalyst of the present invention preferably has an absorption peak in the region of 960 ± 5 cm ⁻¹ in the infrared absorption spectrum. This peak is considered to correspond to titanium introduced into the silica skeleton.
[0013]
The catalyst of the present invention can be optimally produced by a production method having the following steps.
First step: A step of obtaining a solid containing a catalyst component and a mold agent by mixing and stirring a silica source, a titanium source and a quaternary ammonium ion as a mold agent in a liquid state. Second step: obtained in the first step A step of obtaining a catalyst by removing a mold agent by subjecting a solid to a calcination operation.
The first step is a step of obtaining a solid containing a catalyst component and a mold agent by mixing and stirring a silica source, a titanium source and a quaternary ammonium ion as a mold agent in a liquid state. When the reagent to be used is solid, it may be used as a solution dissolved in a solvent.
[0015]
Examples of the silica source include amorphous silica and alkoxysilanes such as tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate and the like.
[0016]
Titanium alkoxides such as tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, tetra-2-ethylhexyl titanate, tetra titanate Examples include octadecyl, titanium (IV) oxyacetylacetonate, titanium (IV) diipropoxybisacetylacetonate, and titanium halides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide.
[0017]
As the mold agent, a quaternary ammonium ion represented by the following general formula (I) is used.
[NR ¹ R ² R ³ R ⁴ ] ⁺ (I)
(In the formula, R1 represents a linear or branched hydrocarbon group having 2 to 36 carbon atoms, and R2 to R4 each represents an alkyl group having 1 to 6 carbon atoms.)
R ¹ is a linear or branched hydrocarbon group having 2 to 36 carbon atoms, preferably 10 to 18 carbon atoms. R ^{2 to} R ⁴ are each an alkyl group having 1 to 6 carbon atoms, and all of R ^{2 to} R ⁴ are preferably methyl groups.
Specific examples of the quaternary ammonium ion represented by the general formula (I) include cations such as hexadecyltrimethylammonium, dodecyltrimethylammonium, and benzyltrimethylammonium .
[0018]
Examples of solvents include water and alcohols such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, sec-butanol, t-butanol, vinyl alcohol, allyl alcohol, cyclohexanol, benzyl alcohol, and the like, diols, Moreover, those mixtures etc. can be mention | raise | lifted.
[0019]
The amount of titanium source used relative to the silica source is ^10-5 to 1, preferably 0.00008 to 0.4, in molar ratio. Moreover, it is preferable that the usage-amount of the quaternary ammonium ion with respect to the total amount of these silica sources and titanium sources shall be 10 ^<-2 > ^-2 by molar ratio.
[0020]
Moreover, in order to accelerate | stimulate reaction of a silica source and a titanium source, it is preferable to provide alkalinity or acidity to a mixed solution. The alkali source is preferably quaternary ammonium hydroxide, and examples thereof include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and the like. Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as formic acid, acetic acid and propionic acid.
[0021]
As a method for preparing a catalyst that does not have a peak indicating an interplanar spacing d in XRD, a method of diluting with an excess solvent when mixing a quaternary ammonium ion as a silica source, a titanium source and a mold (template). Can be used. The optimum solvent and the mixing ratio vary depending on the type of silica source used. For example, when alkoxysilane is used, the number of moles of silica is determined by using an alcohol having the same or similar properties as the ligand alkoxide. By diluting at a ratio equal to or higher than that, it is possible to obtain a catalyst that does not have a peak indicating the interplanar spacing d in XRD.
[0022]
The mixing / stirring temperature is usually -30 to 100 ° C. A solid is produced by mixing and stirring, and this may be aged in order to further grow the solid. The aging time is usually 180 hours or less, and the aging temperature is usually 0 to 200 ° C. When heating is required at the time of aging, it is preferably carried out by transferring to a pressure vessel and sealing in order to avoid vaporization of the solvent.
[0023]
Next, the second step is a step of obtaining a catalyst by removing the mold by subjecting the solid obtained in the first step to a solvent extraction operation with a solvent. A technique for extracting a template with a solvent has been reported by Whitehurst et al. (See US Pat. No. 5,143,879). The solvent used for the extraction is not particularly limited as long as it can dissolve the compound used in the mold, and oxa- and / or oxo-substituted hydrocarbons that are liquid at normal temperature having 1 to about 12 carbon atoms can be used. Suitable solvents of this type can include alcohols, ketones, ethers (acyclic and cyclic) and esters such as methanol, ethanol, ethylene glycol, propylene glycol, isopropanol, Hydroxy-substituted hydrocarbons such as n-butanol and octanol; oxo-substituted hydrocarbons such as acetone, diethyl ketone, methyl ethyl ketone and methyl isobutyl ketone; hydrocarbon ethers such as diisobutyl ether and tetrahydrofuran; and methyl acetate, ethyl acetate, acetic acid And hydrocarbon esters such as butyl and butyl propionate. The weight ratio of these solvents to the catalyst is usually 1-1000, preferably 10-300. Moreover, in order to improve the extraction effect, an acid or a salt thereof may be added to these solvents. Examples of the acid used include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and odorous acid, and organic acids such as formic acid, acetic acid, and propionic acid. Examples of such salts include alkali metal salts, alkaline earth metal salts, ammonium salts and the like. The concentration of the acid to be added or a salt thereof in the solvent is preferably 10 mol / l or less, more preferably 1 mol / l or less. If the concentration of the acid to be added or the salt thereof in the solvent is excessive, titanium present in the catalyst may be eluted and the catalytic activity may be lowered.
[0024]
As one of the methods for preparing a catalyst that does not have a peak indicating an interplanar spacing d in XRD, a solvent containing water can be used in a mold (template) extraction step with a solvent. Although it varies depending on the extraction temperature and the amount of acid contained, generally, when the ratio of the weight of water in the solvent to the weight of the catalyst is 0.8 or more, a catalyst which preferably has no peak indicating the interplanar spacing d in XRD Can be obtained.
[0025]
After thoroughly mixing the solvent and the catalyst, the liquid phase part is separated by a method such as filtration or decantation. This operation is repeated as many times as necessary. It is also possible to extract by a method in which a washing solvent is passed through the catalyst layer. The end of the cleaning can be known, for example, by analyzing the liquid phase part. The extraction temperature is preferably 0 to 200 ° C, more preferably 20 to 100 ° C.
[0026]
It is also possible to perform extraction using a supercritical fluid instead of using the organic extraction solvent. Carbon dioxide is preferred as the supercritical fluid. The critical temperature of carbon dioxide is about 31 ° C. or higher, and the extraction temperature is preferably 31 to 100 ° C., more preferably 35 to 60 ° C. The critical pressure is approximately 7.4 MPa, preferably 10-30 MPa. Preferably, 50 to 500 g of supercritical carbon dioxide per minute is used for extraction per liter of catalyst, and the extraction time is 4 to 20 hours.
[0027]
The solid obtained after the extraction treatment may be subjected to a drying treatment. That is, heating is preferably performed at 10 to 800 ° C. in an atmosphere of a non-reducing gas such as nitrogen, argon, carbon dioxide, or an oxygen-containing gas such as air. 50-300 degreeC is still more preferable.
[0028]
In producing the catalyst, it is preferable to use the following third step following the first step and the second step.
Third step: A step of obtaining a silylated catalyst by subjecting the catalyst obtained in the second step to a silylation treatment. In the silylation treatment, the catalyst obtained in the second step is brought into contact with a silylating agent. This is carried out by converting a hydroxyl group present on the surface of the substrate into a silyl group. Examples of silylating agents include organic silanes, organic silylamines, organic silylamides and derivatives thereof, and organic silazanes and other silylating agents.
[0029]
Examples of organosilanes include chlorotrimethylsilane, dichlorodimethylsilane, chlorobromodimethylsilane, nitrotrimethylsilane, chlorotriethylsilane, iododimethylbutylsilane, chlorodimethylphenylsilane, dichlorodimethylsilane, dimethyl n-propylchlorosilane, dimethylisopropyl Chlorosilane, t-butyldimethylchlorosilane, tripropylchlorosilane, dimethyloctylchlorosilane, tributylchlorosilane, trihexylchlorosilane, dimethylethylchlorosilane, dimethyloctadecylchlorosilane, n-butyldimethylchlorosilane, bromomethyldimethylchlorosilane, chloromethyldimethylchlorosilane, 3-chloro Propyldimethylchlorosilane, dimethoxymethylchlorosilane, dimethyl Examples include phenylchlorosilane, triethoxychlorosilane, dimethylphenylchlorosilane, methylphenylvinylchlorosilane, benzyldimethylchlorosilane, diphenyldichlorosilane, diphenylmethylchlorosilane, diphenylvinylchlorosilane, tribenzylchlorosilane, and 3-cyanopropyldimethylchlorosilane.
[0030]
Examples of organic silylamines include N-trimethylsilylimidazole, Nt-butyldimethylsilylimidazole, N-dimethylethylsilylimidazole, N-dimethyln-propylsilylimidazole, N-dimethylisopropylsilylimidazole, N-trimethylsilyldimethylamine, Examples thereof include N-trimethylsilyldiethylamine, N-trimethylsilylpyrrole, N-trimethylsilylpyrrolidine, N-trimethylsilylpiperidine, 1-cyanoethyl (diethylamino) dimethylsilane, and pentafluorophenyldimethylsilylamine.
[0031]
Examples of organic silylamides and derivatives include N, O-bistrimethylsilylacetamide, N, O-bistrimethylsilyltrifluoroacetamide, N-trimethylsilylacetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoro Examples include acetamide, N-methyl-N-trimethylsilylheptafluorobutyramide, N- (t-butyldimethylsilyl) -N-trifluoroacetamide, N, O-bis (diethylhydrosilyl) trifluoroacetamide.
[0032]
Examples of organic silazanes include hexamethyldisilazane, heptamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,3-bis (chloromethyl) tetramethyldisilazane, 1,3-divinyl- Examples include 1,1,3,3-tetramethyldisilazane and 1,3-diphenyltetramethyldisilazane.
[0033]
Other silylating agents include N-methoxy-N, O-bistrimethylsilyl trifluoroacetamide, N-methoxy-N, O-bistrimethylsilyl carbamate, N, O-bistrimethylsilylsulfamate, trimethylsilyl trifluoromethanesulfonate, N, N′-bistrimethylsilylurea is exemplified. A preferred silylating agent is hexamethyldisilazane.
[0034]
The catalyst of the present invention can be used in any physical form such as powders, flakes, spherical particles, pellets.
[0035]
The catalyst of the present invention can be optimally used in a method for producing an oxirane compound in which an olefin type compound and ethylbenzene hydroperoxide are reacted. The olefinic compound may be an acyclic, monocyclic, bicyclic or polycyclic compound, and may be of monoolefin type, diolefin type or polyolefin type. If there are two or more olefinic bonds, this may be a conjugated bond or a non-conjugated bond. Olefin type compounds having 2 to 60 carbon atoms are generally preferred. Although it may have a substituent, the substituent is preferably a relatively stable group. Examples of such hydrocarbons include ethylene, propylene, butene-1, isobutylene, hexene-1, hexene-2, hexene-3, octene-1, decene-1, styrene and cyclohexene. Examples of suitable diolefin type hydrocarbons include butadiene and isoprene. Substituents may be present, examples include halogen atoms, and various substituents containing oxygen, sulfur, and nitrogen atoms together with hydrogen and / or carbon atoms may also be present. Examples of such olefin type compounds include olefin type unsaturated alcohols and olefin type unsaturated hydrocarbons substituted with halogen. Examples thereof include allyl alcohol, crotyl alcohol, and allyl chloride. Particularly preferred are alkenes having 3 to 40 carbon atoms, which may be substituted with hydroxyl groups or halogen atoms. The hydroxyl compound obtained as a result of the reaction of ethylbenzene hydroperoxide is 1-phenylethanol, which can be converted to styrene by a dehydration reaction. Styrene is an industrially useful substance. The ethylbenzene hydroperoxide used as the raw material may be a diluted or concentrated purified product or non-purified product.
[0036]
The epoxidation reaction can be performed by bringing an olefin type compound and ethylbenzene hydroperoxide into contact with a catalyst. This reaction can be carried out in a liquid phase using a solvent and / or a diluent. The solvent and diluent must be liquid under the temperature and pressure during the reaction and be substantially inert to the reactants and products. The solvent may consist of substances present in the hydroperoxide solution used. For example, when ethylbenzene hydroperoxide (EBHP) is a mixture of EBHP and its raw material ethylbenzene, it can be used as a substitute for the solvent without adding a solvent. The epoxidation reaction temperature is generally 0 to 200 ° C, but a temperature of 25 to 200 ° C is preferable. The pressure may be sufficient to keep the reaction mixture in a liquid state. In general, the pressure is advantageously between 100 and 10000 kPa. After completion of the epoxidation reaction, the liquid mixture containing the desired product can be easily separated from the catalyst composition. The liquid mixture is then purified by an appropriate method to obtain the desired oxirane compound. Purification includes fractional distillation, selective extraction, filtration, washing and the like. The solvent, catalyst, unreacted olefin and unreacted hydroperoxide can be recycled and reused. The process according to the invention can advantageously be carried out using a catalyst in the form of a slurry or a fixed bed. For large scale industrial operations, it is preferred to use a fixed bed. The process of the present invention can be carried out by a batch process, a semi-continuous process or a continuous process. When the liquid containing the reaction raw material is passed through the fixed bed, the liquid mixture discharged from the reaction zone contains no or substantially no catalyst.
[0037]
Oxirane compounds are useful industrial chemicals. Propylene oxide can be converted to useful polymer products by polymerization or copolymerization reactions. Epichlorohydrin obtained from allyl chloride is also industrially important. Epichlorohydrin can be converted to glycerin. It is also possible to produce glycerin from an oxirane compound obtained from allyl alcohol.
[0038]
【Example】
The following examples illustrate the invention.
Example 1
Catalyst preparation (according to the invention)
27 g of cetyltrimethylammonium bromide and 47 g of 25% tetramethylammonium hydroxide aqueous solution were mixed with 175 g of water, and 105 g of tetraethylorthosilicate, 4.8 g of 75% titanium (IV) diisopropoxybisacetylacetonate, isopropyl alcohol at room temperature. 60 g of the mixed solution was added. After stirring for 1 hour, the resulting precipitate was filtered off and washed with water. Washing with water was performed until the washing solution became neutral. The obtained precipitate catalyst was put into a flask and stirred and mixed with 500 ml of a sulfuric acid / ethanol mixed solution (0.05 mol / l of sulfuric acid) per 10 g of the catalyst. While stirring, the mixture was continuously heated at the reflux temperature for 1 hour, allowed to cool to 40 ° C. or lower, and then the solvent was removed by filtration. The same operation was repeated once again, and the finally filtered white solid was transferred to a tubular furnace and dried at 150 ° C. for 6 hours in a nitrogen stream.
This material (5 g), hexamethyldisilazane (3.4 g), and toluene (50 g) were mixed and heated to reflux for 1 hour with stirring. The liquid was distilled off from the mixture by filtration. The catalyst was obtained by washing with toluene (100 g) and vacuum drying (120 ° C., 10 mmHg, 3 hours). The catalyst thus synthesized had a specific surface area of 1015 m ² / g, an average pore diameter of 31 kg, a pore volume of 0.8 cc / g, and a pore distribution range of 5 to 140 kg.
Synthesis of cyclohexene oxide (CHO) 0.30 g of the catalyst thus synthesized, 33 g of an ethylbenzene solution containing 19% ethylbenzene hydroperoxide (EBHP) and 23 g of cyclohexene were charged into a 150 cc SUS autoclave, and the reaction temperature was Epoxidation reaction was performed by batch reaction at 80 ° C. and reaction time of 90 minutes. The reaction results are shown in Table 1.
[0039]
Comparative Example 1
Preparation of titanium-supporting silica catalyst Under a nitrogen stream, acetylacetone (3.2 g) was slowly added dropwise to a solution of tetraisopropyl titanate (4.4 g) in isopropanol (20 ml) and stirred for 30 minutes at room temperature. . The above solution was added dropwise to a mixture of commercially available silica gel (10 to 20 mesh, surface area 326 m ² / g, average pore diameter 100 mm) (50 g) and isopropanol (230 ml), and the mixture was filtered after stirring at room temperature for 1 hour. The solid portion was washed 3 times with isopropanol (total 250 ml). The solid part was dried at 150 ° C. for 2 hours in an air atmosphere. Further, it was calcined at 600 ° C. for 4 hours in an air atmosphere. This material (10 g), hexamethyldisilazane (4 g), and toluene (50 g) were mixed and heated to reflux for 1 hour with stirring. The liquid was distilled off from the mixture by filtration. The catalyst was obtained by washing with toluene (100 g) and vacuum drying (120 ° C., 10 mmHg, 3 hours).
The catalyst synthesized as described above had a specific surface area of 244 m ² / g, an average pore diameter of 148 kg, a pore volume of 0.9 cc / g, and a pore distribution range of 5 to 200 kg.
Reaction evaluation was performed in the same manner as in Example 1 except that the amount of catalyst was 0.76 g. The epoxidation reaction results are shown in Table 1.
[0040]
[Table 1]

* 1: The minimum value of the pore distribution is the measurement limit value by the nitrogen adsorption method.
In the epoxidation reaction using EBHP in Table 1, it can be seen that the catalyst according to the present invention clearly shows high performance in both activity and selectivity.
[0042]
【The invention's effect】
As described above, according to the present invention, it is possible to provide a method for producing an oxirane compound in which an olefin type compound and ethylbenzene hydroperoxide are reacted in the presence of a titanium-containing silicon oxide catalyst with high yield and high selectivity. did it.
[Brief description of the drawings]
1 is an X-ray diffraction chart of a catalyst of Example 1. FIG.

Claims (2)

A method for producing an oxirane compound in which an olefin type compound and ethylbenzene hydroperoxide are reacted, wherein the reaction is performed in the presence of a catalyst comprising a titanium-containing silicon oxide that satisfies all of the following conditions (1) to (5): A method for producing an oxirane compound.
(1): The average pore diameter is 10 mm or more (2): 90% or more of the total pore volume has a pore diameter of 5 to 200 mm (3): The specific pore volume is 0.2 cm ³ / g (4): It is obtained by using a quaternary ammonium ion represented by the following general formula (I) as a mold (template) and then removing the mold by a solvent extraction operation. [NR ¹ R ² R ³ R ⁴ ] ⁺ (I)
(In the formula, R ¹ represents a linear or branched hydrocarbon group having ² to 36 carbon atoms, and R ^{2 to} R ⁴ represent an alkyl group having 1 to 6 carbon atoms.)
(5): In X-ray diffraction, there is no peak indicating the surface separation d. The production method according to claim ¹ , wherein the catalyst has an absorption peak in a region of 960 ± 5 cm ^{−1 in} an infrared absorption spectrum.

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