WO2005028101A1 - Process for production of titanium-containing silicon oxide catalysts, such catalysts, and process for production of oxiranes with the same - Google Patents

Abstract

A process for the production of catalysts characterized by subjecting a titanium-containing silicon oxide prepared in a liquid phase in the absence of water by nonhydrolytic condensation represented by the reaction formula (I) to silylation; and a process for the production of oxiranes by reacting an olefinic compound with a hydroperoxide in the presence of a catalyst produced by the above process: (I) L1L2L3M-X+L4L5L6M-OR → L1L2L3M-O-ML4L5L6+RX wherein M is Si or Ti; X is halogeno or carboxy; R is hydrogen or hydrocarbyl; and L1 to L6 are each independently alkoxy, halogeno, carboxy, hydrogen, or hydrocarbyl.

Description

 TECHNICAL FIELD The present invention relates to a method for producing a titanium-containing silicon oxide catalyst, a method for producing the catalyst and an oxirane compound using the catalyst.

 The present invention relates to a method for producing an oxysilane compound. More specifically, the present invention relates to a propylene oxide in which an olefin compound such as propylene is reacted with a hydroperoxide using a titanium-containing silicon oxide catalyst prepared by a non-hydrolytic condensation reaction in the absence of water. The present invention relates to a method for producing an oxysilane compound such as a side. Background art

 There is known a method for reacting an olefin compound such as propylene with a hydroperoxide in the presence of a catalyst to obtain an oxysilane compound such as propylene oxide. As the catalyst used here, for example, US Pat. No. 4,367,342 discloses a specific titanium-containing silicon oxide catalyst, but it is insufficient from the viewpoint of the yield of the target product. On the other hand, Journal of Mo 1 ecu 1 ar Catalysis A: Chemica 1 182-183 (2002) 81 1-88 uses a catalyst prepared by a non-hydrolytic condensation reaction in the liquid phase. Although epoxidation of hexene is disclosed, there is no description about epoxidation of other olefin-type compounds, and from the viewpoint that it can exhibit high activity and selectivity as an epoxidation catalyst. It was not enough. Disclosure of the invention

An object of the present invention is to provide an olefin-type compound and a hydroperoxide using a catalyst obtained by subjecting a titanium-containing silicon oxide prepared by a non-hydrolytic condensation reaction to a silylation treatment in a liquid phase in the absence of water. Oxilla with high yield It is an object of the present invention to provide a method for producing an oxysilane compound capable of obtaining a halogenated compound.

 That is, the present invention provides a method of performing a silylation treatment on a titanium-containing silicon oxide prepared by a non-hydrolytic condensation reaction represented by the following formula (I) in a liquid phase in the absence of water. The present invention relates to a method for producing a titanium-containing silicon oxide catalyst, and a method for producing an oxysilane compound characterized by reacting an olefin compound with hydroperoxide in the presence of the catalyst.

L _X L ₂ L ₃ MX + L ₄ L ₅ L ₆ M-OR

→ L ₁ L ₂ L ₃ M-0-ML ₄ L ₅ L ₆ + RX (I)

(Where M is S i or T i, X is a halogeno group or a carboxy group and R is a hydrogen or hydrocarbon group, and 1 ^ to ₆ are each independently an alkoxy group, a halogeno group, a carpoxy group, Represents a hydrogen or hydrocarbon group.)

 Further, another object of the present invention is to react propylene with a peroxide at a port opening using a titanium-containing silicon oxide catalyst prepared by a non-hydrolytic condensation reaction in a liquid phase in the absence of water. An object of the present invention is to provide a method for producing propylene oxide, which can obtain propylene oxide with a high yield.

 That is, the present invention provides propylene and hydroperoxide in the liquid phase in the absence of water in the presence of a titanium-containing silicon oxide catalyst prepared by a non-hydrolytic condensation reaction represented by the following formula (I). Provided is a method for producing propylene oxide by reacting oxide.

→ L ₁ L ₂ L ₃ M-0-ML ₄ L ₅ L ₆ + RX (I)

(Where M is S i or T i, X is a halogeno group or a carboxy group and R is a hydrogen or hydrocarbon group, and 1 ^ to L ₆ are each independently an alkoxy group, a halogeno group, a carboxy group. Represents a hydrogen or hydrocarbon group.) Best Mode for Carrying Out the Invention In the present invention, the catalyst is obtained by subjecting a titanium-containing silicon oxide prepared by a non-hydrolytic condensation reaction represented by the following formula (I) to a silylation treatment in a liquid phase in the absence of water. can get.

L ₁ L ₂ L ₃ MX + L ₄ L ₅ L ₆ M-OR

→ L ₁ L ₂ L ₃ M-0-ML ₄ L ₅ L ₆ + RX (I)

(Where M is S i or T i, X is a halogeno group or a carboxy group and R is a hydrogen or hydrocarbon group, and 1 ^ to 1 ^ ₆ are each independently an alkoxy group, a halogeno group, a carboxy group. Represents a group, hydrogen or a hydrocarbon group.)

 An example of the method for preparing the catalyst of the present invention is shown below.

 First, a silica source and a titanium source are gelled by a non-hydrolytic condensation reaction represented by the above formula (I) in a liquid phase to obtain a wet gel of a titanium-containing silicon oxide.

 As the silica source used here, a silicon compound represented by the following formula (1) can be preferably mentioned.

S i ( ¹ ), (OR ¹ ) _m (R ² ) _n (1)

(Where X ¹ represents a halogeno group or a carpoxy group, R ¹ and R ² each independently represent a hydrogen or a hydrocarbon group, and 1, m, and n are integers of 0 to 4 and 1 + m + n = 4 and 1 or m is 1 or more.

Fluorine examples of X ^1, chlorine, bromine, and a carboxy group such as a halogeno group Ya Asetokishi group iodine are exemplified, and among them, chlorine is preferred.

Examples of R ¹ include hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, and petyl (which may contain heteroatoms such as oxygen and nitrogen). An isopropyl group is preferred from the viewpoint of the conversion rate.

Examples of R ² include hydrocarbon groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, phenyl group and benzyl group (which may contain hetero atoms such as oxygen and nitrogen). Can be.

Specific examples of the silicon compound include silicon tetrachloride, tetraisopropoxysilane, methyltrichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane. Among the above silicon compounds, it is preferable to prepare a gel containing tetrahalogenosilane and / or tetraalkoxysilane as a main component from the viewpoint of strengthening the gel structure and stabilizing the structure.

 On the other hand, as the titanium source used here, a titanium compound represented by the following formula (2) can be preferably mentioned.

T i (X ² ). (OR ³ ) _p (OR ⁴ ) _q (2)

(Where X ² represents a halogeno group, R ³ and R ⁴ each independently represent a hydrocarbon group, and o, p, and Q are integers of 0 to 4 and o + p + qL = 4.)

Fluorine examples of X ^2, chlorine, bromine, although halogeno groups iodine and the like, and among them, chlorine is preferred.

Examples of R ³ and R ⁴ include a hydrocarbon group having 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a phenyl group (a heteroatom such as oxygen and nitrogen). May be included).

 Specific titanium compounds include halogeno-titanium such as titanium tetrachloride, titanium ethoxide, titanium isopropoxide, titanium isobutoxide, titanium mono-butoxide and the like titanium alkoxide, titanium diisopropoxide (bis-2 , 4-pennionate) and the like.

 For the gel preparation, the above-mentioned silica source and titanium source are mixed and used. One or more of the silica source and the titanium source may be used, respectively.

 In the non-hydrolytic condensation reaction, a non-aqueous solvent may or may not be used. It is important that the non-aqueous solvent does not substantially contain water, and specific examples include alcohols, ethers, hydrocarbons, and halogenated hydrocarbons. They can also be used as a mixture. The added non-aqueous solvent may react with the above-mentioned silicon source and titanium source.

 When preparing the gel, a structure-directing agent such as a primary to tertiary amine / quaternary ammonium ion or a surfactant may or may not be used.

The amount of the titanium source to be used relative to the Si force source is usually 10 ⁵ to 1, and preferably 0.000 to 0.4 in a molar ratio. More preferably, it is 0.01 to 0.1. The gelation temperature is usually −30 to 200 ° C., but the heating promotes the gelation. In the case of heating, it is preferable that the heating is performed by transferring to a pressure-resistant container and sealing in order to avoid vaporization of the silica source, the titanium source and the non-aqueous solvent.

 Since the wet gel obtained by the above method contains RX and / or a non-aqueous solvent described in the above formula (I), it is removed by drying to obtain a titanium-containing silicon oxide. Drying is performed at 0 to 200 ° C. under reduced pressure or under a flow of gas such as nitrogen.

 Wet gels obtained by the hydrolytic condensation of alkoxides in the presence of water have the disadvantage that when dried, they contract due to strong capillary forces of water, reducing the surface area and pore volume. To overcome this, drying with supercritical carbon dioxide is performed, but it has the disadvantage that high-pressure equipment is required.

 On the other hand, the wet gel obtained by non-hydrolytic condensation has only a small capillary force during drying, and only the RX and / or non-aqueous solvent described in the above formula (I) is removed. A titanium-containing silicon oxide having a large pore volume is obtained.

In the case of using the resulting titanium-containing silicon oxide as a catalyst, the specific surface area is preferably not less than 2 0 O mV g, 4 0 0 m 2 / g or more is more preferable. The specific pore volume is preferably 0.2 m 1 / g or more.

 By reacting propylene with hydroperoxide using the titanium-containing silicon oxide obtained by the above method as a catalyst, propylene oxide can be obtained in high yield.

From the viewpoint of further enhancing the performance as a catalyst for producing an oxysilane compound by the reaction of a olefin compound such as propylene with a hydroperoxide. Preferably, a treatment is applied. The silylation treatment is performed by bringing the titanium-containing silicon oxide obtained by the non-hydrolytic condensation reaction into contact with a silylating agent and converting the halogeno group ノ alkoxy group remaining on the catalyst surface into a silyl group. Examples of the silylating agent include organic halogenosilanes, organic silylamines, organic silylamides and derivatives thereof, and organic silazanes. Specific examples include chlorotrimethylsilane, methoxytrimethylsilane, and hexamethyldisilazane. The silylation treatment may be performed in the gas phase, It may be performed in the liquid phase. A solvent may or may not be used. The treatment temperature is not particularly limited, but is preferably in the range of 0 ° C to 200 ° C. Although the contact time is not particularly limited, it is preferably 10 minutes to 10 hours.

 The silylation treatment may be performed after the wet gel is dried, or may be performed before the drying or simultaneously with the gel preparation.

 The catalyst obtained by the above method can be optimally used particularly for a method for producing an oxysilane compound by reacting an olefin compound with a hydroperoxide. The olefin type compound may be an acyclic, monocyclic or polycyclic olefin compound, and may be a monoolefin type, a diolefin type or a polyolefin type having three or more double bonds. When there are two or more olefin bonds, these may be a conjugate bond or a non-conjugate 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 monoolefin hydrocarbons include ethylene, propylene, 1-butene, isobutylene, 1-hexene, 2-hexene, 3-hexene, 1-octene, 1-decene, styrene, cyclohexene, etc. Can be Examples of suitable diolefin type compounds include butadiene and isoprene. When it has a substituent, examples thereof include a halogen atom, and further, various substituents containing an oxygen, sulfur, or nitrogen atom together with a hydrogen and / or a carbon atom may be used. Particularly preferred substituted olefinic compounds are olefinic unsaturated alcohols, and olefinic unsaturated hydrocarbons substituted with octogen, examples of which include aryl alcohol, crotyl alcohol, and aryl chloride. . Particularly preferred as olefin-type compounds are those having 3 to 40 carbon atoms, which may be substituted by hydroxyl groups or halogen atoms.

Hydroperoxides used for converting an olefin type compound to an oxysilane compound include organic hydroperoxides and hydrogen peroxide, and organic hydroperoxides are preferred. Examples of the organic hydroperoxide include cumene hydroperoxide, ethylbenzene hydroperoxide, and tributyl octyl peroxide. Most preferred is cumene hydroperoxide. The organic hydroperoxides and hydrogen peroxide used may be dilute or rich purified or unpurified products.

 The reaction can be carried out in the liquid phase in the presence or absence of a solvent. Preferably, the solvent is liquid at the temperature and pressure during the reaction and is substantially inert to the reactants and products. The solvent may consist of substances present in the hydroperoxide solution used. For example, when cumene hydroperoxide is a mixture of cumene hydroperoxide and its raw material, cumene, it can be used in place of a solvent without adding a solvent. It is.

 The reaction temperature is generally between 0 and 200 ° C, preferably between 25 and 200 ° C. The pressure may be sufficient to keep the reaction mixture in a liquid state. In general, it is advantageous for the pressure to be between 100 and 1000 kPa.

 The amount of the olefin-type compound (mole number) relative to the hydroperoxide (mole number) in the reaction is not limited, but is usually 1 or more, preferably 1 to 50 times by mol, in a molar ratio.

 The process of the invention can be carried out in the form of a slurry, fixed bed. This reaction can be carried out by a batch method, a semi-continuous method or a continuous method. Example

 Hereinafter, the present invention will be described specifically with reference to examples.

Example 1

 Preparation of catalyst

Under an inert gas atmosphere, titanium isopropoxide, tetrisopropoxysilane and silicon tetrachloride were added to a pressure-resistant ampoule at a molar ratio of 1.0: 4.5: 5.5, mixed and sealed. The content weight was 17.6 g. The mixture was heated in an oven at 110 ° C. for 4 days to gel. After opening the wet gel under vacuum at 150 ° C for 4 hours Drying for 6. lg of dried gel was obtained. The resulting red-brown dried gel was ground using a mortar to obtain a titanium-containing silicon oxide (powder). This was used as a catalyst.

 Synthesis of propylene oxide

 The catalyst obtained as described above was reacted with a cumene solution having a concentration of 25% by weight of cumene hydride (CHPO) and propylene in a reactor (autoclave) to synthesize and evaluate propylene oxide. The autoclave was charged with 30 g of a solution of lg, CHPO in cumene of CHPO, and 17 g of propylene, and reacted under autogenous pressure at a reaction temperature of 85 ° (with a reaction time of 1.5 hours (including a heating time). The results are shown in Table 1. Example 2

 Preparation of catalyst

 3 g of the powder obtained in the preparation of the catalyst of Example 1 was placed in a flask, 2 g of hexamethyldisilazane and 30 g of toluene were mixed, and heated at 110 for 1.5 hours. The powder was collected by filtration, and dried under reduced pressure at 110 T: 1 OmmHg for 2 hours to obtain a silylated catalyst.

Synthesis of propylene oxide

 Using this catalyst, CHHPO and propylene were reacted in the same manner as in the synthesis of propylene oxide in Example 1 to synthesize propylene oxide.

The reaction results are shown in Table 1.

table 1

*: PO / C 3 'selectivity = mole of propylene oxide produced / mol of propylene reacted x 100 Example 3

 Preparation of catalyst

 Under an inert gas atmosphere, add titanium isopropoxide, tetrisopropoxysilane, silicon tetrachloride, and trimethylchlorosilane to a pressure-resistant ampoule in a molar ratio of 1.0: 8.0: 7.1: 7.5, and add a solvent. 12 ml of dichloromethane was mixed and closed. The content weight was 26.0 g. The mixture was heated in an oven at 110 ° C for 4 days to gel. After opening, the wet gel was dried under vacuum at 150 for 4 hours to obtain 5.1 dry gel. The obtained pale red dried gel was pulverized using a mortar to obtain a titanium-containing silicon oxide (powder). Synthesis of propylene oxide

 Using the powder obtained as described above as a catalyst, CHP〇 and propylene were reacted in a reactor (autoclave) to synthesize propylene oxide and evaluated. A catalyst 1 g, cumene drop peroxide concentration 25% by weight (30 g of 11〇-cumene solution, 17 g of propylene) were charged into an autoclave, and under autogenous pressure, a reaction temperature of 85 ° (: a reaction time of 1.5 The reaction was carried out for a time (including heating), and as a result, the CHPO conversion was 74.1% and the selectivity for PO / C 3 ′ was 92.8%.

 Preparation of catalyst

 3 g of the powder obtained in the same manner as in the preparation of the catalyst of Example 3 was placed in a flask, 2 g of hexamethyldisilazane and 30 g of toluene were mixed, and the mixture was heated at 110 ° C for 1.5 hours. did. After the powder was collected by filtration, it was dried under reduced pressure at 110 ° C and 1 OmmHg for 2 hours to obtain a silylated catalyst. Synthesis of propylene oxide

Propylene oxide was produced in the same manner as in the synthesis of propylene oxide in Example 3, except that the catalyst obtained in the above catalyst preparation was used. As a result, the CHP〇 conversion was 89.0%, and the selectivity for PO / C 3 ′ was 99.2%. Example 5

 Preparation of catalyst

 In an inert gas atmosphere, titanium tetrachloride, silicon tetrachloride, trimethylchlorosilane, trimethylchlorosilane, and diisopropyl ether are added in a pressure-resistant ampoule in a molar ratio of 1.0: 6.0: 2.0: 2.0: 18.0. In addition, 15 ml of dichloromethane as a solvent was mixed and sealed. The content weight was 44.4 g. Heated in an oven at 110 to gel. After opening, the wet gel was dried under vacuum at 150 ° C. for 4 hours to obtain 5.9 g of a dry gel. The resulting yellow-brown dried gel was ground using a mortar to obtain a titanium-containing silicon oxide (powder).

 Synthesis of propylene oxide

 Propylene oxide was produced in the same manner as in the synthesis of propylene oxide in Example 3, except that the catalyst obtained above was used. As a result, the CHPO conversion was 43.6%, PO / C3, and the selectivity was 92.4%. Example 6

 Preparation of catalyst

 3.3 g of the powder obtained in the same manner as in the preparation of the catalyst of Example 5 was placed in a flask, 2.3 g of hexamethyldisilazane and 34 g of toluene were mixed, and the mixture was mixed at 110 ° (: 1.5 hours). After the powder was collected by filtration, it was dried under reduced pressure at 110 ° C. and 1 OmmHg for 2 hours to obtain a silylated catalyst.

 Synthesis of propylene oxide

 Propylene oxide was produced in the same manner as in the synthesis of propylene oxide in Example 3, except that the catalyst obtained above was used. As a result, the CHPO conversion was 72.8%, PO / C3, and the selectivity was 99.6%. Industrial applicability

As described above, according to the present invention, it can be used in a reaction for obtaining an oxysilane compound from a olefin compound such as propylene and a hydroperoxide. Accordingly, it is possible to provide a method for producing a titanium-containing silicon oxide catalyst capable of exhibiting a high yield, and an efficient method for producing an oxysilane compound using the catalyst.

Claims

The scope of the claims 1. In a liquid phase in the absence of water, a titanium-containing silicon oxide obtained by subjecting a titanium-containing silicon oxide prepared by a non-hydrolytic condensation reaction represented by the following formula (I) to a silylation treatment: A method for producing an oxide catalyst. Ι ^ ₂ Μ— X + L ₄ L ₅ L ₆ M-OR → L ₁ L ₂ L ₃ M-0-ML ₄ L ₅ L ₆ + RX (I) (Where M is S i or T i, X is a halogeno group or a hepoxy group, and R is a hydrogen or hydrocarbon group, and ι ^ to ί ₆ are each independently an alkoxy group, an octa-geno group, Represents a hydrogen or hydrocarbon group.)  2. A titanium-containing silicon oxide catalyst obtained by the method according to claim 1.  3. A method for producing an oxysilane compound, comprising reacting an olefin compound with hydroperoxide in the presence of the titanium-containing silicon oxide catalyst according to claim 2.  4. The method according to claim 3, wherein the olefin type compound is propylene. 5. The method according to claim 3, wherein the hydroperoxide is an organic hydroperoxide.  6. Reaction of propylene with hydroxide in the presence of a titanium-containing silicon oxide catalyst prepared by a non-hydrolytic condensation reaction represented by the following formula (I) in the liquid phase in the absence of water A method for producing propylene oxide. LiLaLgM-X + L ₄ L ₅ L ₆ M-OR → L ₁ L ₂ L ₃ M-0-ML ₄ L ₅ L ₆ + RX (I) (Where M is S i or T i, X is a halogeno group or a hepoxy group, and R is a hydrogen or hydrocarbon group, and 1 ^ to! ^ ₆ are each independently an alkoxy group, a no, a logeno group, Represents a carboxy group, hydrogen or a hydrocarbon group.)  7. The method according to claim 6, wherein the hydroperoxide is cumene hydroperoxide.