JP2005087905A - Production method for titanium-containing silicon oxide catalyst and production method for oxirane compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method for a titanium-containing silicon oxide catalyst usable for a reaction of producing an oxirane compound from an olefin type compound and a hydroperoxide at a high yield, and an efficient production method for the oxirane compound using the catalyst. <P>SOLUTION: In the absence of water, silylation of a titanium-containing silicon oxide produced by non-hydrolytic condensation reaction defined by the formula (I) is carried out in liquid phase: L<SB>1</SB>L<SB>2</SB>L<SB>3</SB>M-X+L<SB>4</SB>L<SB>5</SB>L<SB>6</SB>M-OR →L<SB>1</SB>L<SB>2</SB>L<SB>3</SB>M-O-ML<SB>4</SB>L<SB>5</SB>L<SB>6</SB>+RX (I) (M is Si or Ti; X is a halogeno or carboxy group; R is hydrogen or a hydrocarbon group; L1 to L6 are each independently an alkoxy, a halogeno, carboxy group, hydrogen, or a hydrocarbon group). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a titanium-containing silicon oxide catalyst and a method for producing an oxirane compound. More specifically, the present invention reacts an olefinic compound and hydroperoxide using a catalyst obtained by subjecting a titanium-containing silicon oxide prepared by a nonhydrolytic condensation reaction to a silylation treatment in the absence of water. The present invention relates to a method for producing an oxirane compound.

  A method of obtaining an oxirane compound by reacting an olefin type compound and hydroperoxide in the presence of a catalyst is known. As a catalyst used here, for example, Patent Document 1 discloses a specific titanium-containing silicon oxide catalyst, which is insufficient from the viewpoint of yield to the target product. On the other hand, Non-Patent Document 2 epoxidizes cyclohexene using a catalyst prepared by a non-hydrolytic condensation reaction in a liquid phase, but there is no description regarding epoxidation of other olefin type compounds. From the viewpoint of being able to exhibit high activity and selectivity as an epoxidation catalyst, it was not sufficient.

US Pat. No. 4,367,342 Journal of Molecular Catalysis A: Chemical 182-183 (2002) 81-88

  Under such circumstances, the problem to be solved by the present invention is that an olefin is produced using a catalyst obtained by subjecting a titanium-containing silicon oxide prepared by a non-hydrolytic condensation reaction in the absence of water to a liquid phase in a liquid phase. The present invention resides in providing a method for producing an oxirane compound capable of reacting a mold compound with hydroperoxide to obtain an oxirane compound with high yield.

That is, the present invention is characterized by subjecting a titanium-containing silicon oxide prepared by a nonhydrolytic condensation reaction represented by the following formula (I) to silylation in the 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 oxirane compound in which an olefin type compound and a hydroperoxide are reacted in the presence of the catalyst catalyst.
L ₁ L ₂ L ₃ M-X + L ₄ L ₅ L ₆ M-OR
_{→ L 1 L 2 L 3 M} -O-ML 4 L 5 L 6 + RX (I)
(Wherein M is Si or Ti, X is a halogeno group or carboxy group, R is hydrogen or a hydrocarbon group, L _{1 to} L ₆ are any of an alkoxy group, a halogeno group, a carboxy group, hydrogen or a hydrocarbon group. Represents.)

  As described above, according to the present invention, a method for producing a titanium-containing silicon oxide catalyst that can be used in a reaction for obtaining an oxirane compound from an olefin type compound and a hydroperoxide and can exhibit a high yield, and the catalyst are used. An efficient method for producing an oxirane compound could be provided.

The catalyst of the present invention is obtained by subjecting a titanium-containing silicon oxide prepared by a nonhydrolytic condensation reaction represented by the following formula (I) to silylation in the liquid phase in the absence of water. .
L ₁ L ₂ L ₃ M-X + L ₄ L ₅ L ₆ M-OR
_{→ L 1 L 2 L 3 M} -O-ML 4 L 5 L 6 + RX (I)
(Wherein M is Si or Ti, X is a halogeno group or carboxy group, R is hydrogen or a hydrocarbon group, L _{1 to} L ₆ are any of an alkoxy group, a halogeno group, a carboxy group, hydrogen or a hydrocarbon group. Represents.)

  The method for preparing the catalyst of the present invention is shown below. First, a silica source and a titanium source are gelled in the liquid phase by a nonhydrolytic condensation reaction represented by the above formula (I) to obtain a wet gel of titanium-containing silicon oxide.

Examples of the silica source used here include a silicon compound represented by the following formula (1).
Si (X) _l (OR ¹ ) _m (R ² ) _n (1)
(Where X is a halogeno group or a carboxy group, R ¹ and R ² are each independently hydrogen or a hydrocarbon group, l, m, and n are integers of 0 to 4, l + m + n = 4, and l or m is 1) That's it.)

  Examples of X include halogeno groups such as fluorine, chlorine, bromine and iodine, and carboxy groups such as acetoxy group, among which chlorine is preferred.

Examples of R ¹ include hydrocarbon groups such as methyl group, ethyl group, propyl group, isopropyl group, and butyl group (which may include heteroatoms such as oxygen and nitrogen). From the viewpoint, an isopropyl group is preferable.

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 heteroatoms such as oxygen and nitrogen). .

  Specific examples of the silicon compound include silicon tetrachloride, tetraisopropoxysilane, methyltrichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane.

  Among the above silicon compounds, it is preferable to adjust the gel with tetrahalogenosilane and / or tetraalkoxysilane as the main component from the viewpoint of strengthening the gel structure and stabilizing the structure.

On the other hand, examples of the titanium source used here include a titanium compound represented by the following formula (2).
Ti (X) _o (OR ³ ) _p (OR ⁴ ) _q (2)
(Here, X represents a halogeno group, R ³ and R ⁴ each independently represents a hydrocarbon group, and o, p, and q are integers of 0 to 4 and o + p + q = 4.)

  Examples of X include halogeno groups such as fluorine, chlorine, bromine and iodine, with chlorine being preferred.

Examples of R ³ and R ⁴ include hydrocarbon groups having 1 to 18 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, and phenyl group (may contain heteroatoms such as oxygen and nitrogen). ).

  Specific examples of the titanium compound include titanium tetrachloride, titanium isopropoxide, titanium diisopropoxide (bis-2,4-pentandionate), and the like.

  For the gel preparation, a mixture of the above silica source and several titanium sources is used.

  In this nonhydrolytic condensation reaction, a solvent may or may not be used. It is important that the solvent is substantially free of water, and specific examples include alcohols, ethers, hydrocarbons, halogenated hydrocarbons and the like. They can also be used as a mixture. The added solvent may react with the silica source and the titanium source.

  At the time of gel preparation, a structure-directing agent (molding agent) such as 1 to 3 amines, quaternary ammonium ions, and surfactants may or may not be used.

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. More preferably, it is 0.01-0.1.

  The gelation temperature is usually −30 to 200 ° C., but the gelation is promoted by heating. In the case of heating, it is preferable to transfer to a pressure vessel and seal in order to avoid vaporization of the silica source, titanium source and solvent.

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

  The wet gel obtained by hydrolytic condensation of alkoxide in the presence of water has the disadvantage that the surface area and pore volume decrease due to shrinkage due to strong capillary force of water during drying. In order to overcome this, drying with supercritical carbon dioxide is performed, but it has a disadvantage that a high-pressure facility is required.

  On the other hand, the wet gel obtained by the non-hydrolytic condensation of the present invention only removes the RX and / or the solvent described in the above formula (I), which has a weak capillary force when dried, and therefore has a high surface area in a normal drying facility. A large pore volume titanium-containing silicon oxide is obtained.

When the obtained titanium-containing silicon oxide is used as a catalyst, the specific surface area is preferably 200 m ² / g or more, and more preferably 400 m ² / g or more. The specific pore volume is preferably 0.2 ml / g or more.

  In the present invention, silylation treatment is performed on the titanium-containing silicon oxide from the viewpoint of improving the performance of the catalyst.

  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 or alkoxy group remaining on the catalyst surface into a silyl group. Examples of silylating agents include organic halogenosilanes, organic silylamines, organic silylamides and derivatives thereof, and organic silazanes. Specific examples include chlorotrimethylsilane, methoxytrimethylsilane, hexamethyldisilazane and the like. The silylation treatment may be performed in the gas phase or in the liquid phase. A solvent may or may not be used.

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

  Thus, the catalyst used in the present invention can be obtained.

  In particular, the catalyst can be optimally used in a method for producing an oxirane compound in which an olefin type compound and a 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, cyclohexene and the like. Examples of suitable diolefin type compounds are 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. Particularly preferred olefin type compounds are 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.

  Examples of the hydroperoxides used for the reaction with the olefin type compound include organic hydroperoxides and hydrogen peroxide, with organic hydroperoxides being preferred.

  Examples of the organic hydroperoxide include cumene hydroperoxide, ethylbenzene hydroperoxide, t-butyl hydroperoxide, and the like.

The organic hydroperoxide and hydrogen peroxide used as raw materials may be a diluted or concentrated purified product or non-purified product.
This reaction can be carried out in the liquid phase in the presence or absence of a solvent. The solvent is preferably a liquid at the temperature and pressure during the reaction and 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 cumene, which is a raw material thereof, it can be used as a substitute for a solvent without particularly 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.

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

The following examples illustrate the invention.
Comparative Example 1 (according to Non-Patent Document 2)
Under an inert gas atmosphere, titanium isopropoxide, tetraisopropoxysilane and silicon tetrachloride were added to a pressure-resistant ampoule at a molar ratio of 1.0: 4.5: 5.5, and the mixture was sealed. The weight of the contents was 17.6 g. Gelation was carried out in an oven at 110 ° C. for 4 days. After opening, the wet gel was dried under vacuum at 150 ° C. for 4 hours to obtain 6.1 g of dry gel. The obtained reddish brown gel was pulverized using a mortar to obtain a titanium-containing silicon oxide (powder).

Example 1
3 g of the powder obtained as described above was put in a flask, 2 g of hexamethyldisilazane and 30 g of toluene were mixed and heated at 110 ° C. for 1.5 hours. The powder was collected by filtration and then dried under reduced pressure at 110 ° C. and 10 mmHg for 2 hours to obtain a silylated catalyst.

Synthesis of Propylene Oxide (PO) The catalyst obtained as described above was evaluated in a batch reactor (autoclave) using 25% cumene hydroperoxide (CHPO) and propylene (C3 ′). 1 g of catalyst, 30 g of CHPO, and 17 g of C3 ′ were charged into an autoclave, and reacted at an autogenous pressure at a reaction temperature of 85 ° C. and a reaction time of 1.5 hours (temperature increase). The reaction results are shown in Table 1.

*: PO / C3 ′ selectivity = generated PO mole / reaction C3 ′ mole × 100

Claims (3)

Titanium-containing silicon oxide characterized by subjecting titanium-containing silicon oxide prepared by a nonhydrolytic condensation reaction represented by the following formula (I) in the liquid phase in the absence of water to silylation treatment A method for producing a catalyst.
L ₁ L ₂ L ₃ M-X + L ₄ L ₅ L ₆ M-OR
_{→ L 1 L 2 L 3 M} -O-ML 4 L 5 L 6 + RX (I)
(Wherein M is Si or Ti, X is a halogeno group or carboxy group, R is hydrogen or a hydrocarbon group, L _{1 to} L ₆ are any of an alkoxy group, a halogeno group, a carboxy group, hydrogen or a hydrocarbon group. Represents.) The manufacturing method of the oxirane compound which makes an olefin type compound and a hydroperoxide react in presence of the titanium containing silicon oxide catalyst of Claim 1. The manufacturing method of the propylene oxide whose olefin type compound of Claim 2 is a propylene.