JP2007186467A - Method for producing epoxide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an excellent method for producing an epoxide by reacting an organic hydroperoxide with an olefin, wherein the yield of the objective epoxide is high. <P>SOLUTION: The method for producing an epoxide comprises reacting an organic hydroperoxide with an olefin in the presence of a solid catalyst, wherein the solid catalyst is obtained by following steps. The steps are a impregnation step: a step for contacting a liquid titanium compound with a solid silica to obtain an impregnated solid without using a solvent, and a drying step: a step for drying the impregnated solid obtained in the impregnation step to obtain the solid catalyst. The sold silica is a comparatively high density and tight packing type porous synthetic silica comprising amorphous silica particles obtained by coagulation or mutual boning, and an example thereof is a silica gel. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing an epoxide. More specifically, the present invention relates to a method for producing an epoxide by reacting an organic hydroperoxide and an olefin, which has an excellent feature that the yield of the target epoxide is high.

  A method for obtaining an epoxide by reacting an organic hydroperoxide and an olefin in the presence of a heterogeneous catalyst containing titanium chemically bonded to a silicon compound selected from the group consisting of solid silica and inorganic silicate is known.

  Heterogeneous catalysts containing titanium chemically bonded to silica and / or inorganic silicates can be made in a variety of ways. For example, Patent Document 1 discloses a method for producing a catalyst composition by impregnating a solution in which titanium halide is dissolved in silica and / or inorganic silicate, and then firing the impregnated solid. Impregnated silica and / or inorganic silicate with a substantially anhydrous solvent of titanium halide or titanium alcoholate in hydroxyl or oxo substituted hydrocarbons of 1 to 8 carbon atoms as solvent, and then removed the solvent from the impregnated solid A method for producing a catalyst to be calcined later is provided, and Patent Document 3 provides a method for producing a catalyst by impregnating solid titanium and / or inorganic silicate with gaseous titanium tetrachloride, followed by calcining and hydrolysis. ing.

  However, in the production of epoxides using the catalyst synthesized by the above method, there is a problem that the yield of epoxides is low because the activity of the catalyst is not sufficient.

Special table 2002-514218 gazette Japanese Patent Publication No.54-40525 Japanese Examined Patent Publication No. 2-42072

  In view of the current situation, the problem to be solved by the present invention is a production method for obtaining an epoxide by reacting an organic hydroperoxide and an olefin, and has an excellent feature that the yield of the target epoxide is high. It is in providing a method for producing an epoxide.

That is, the present invention relates to a method for obtaining an epoxide by reacting an organic hydroperoxide and an olefin in the presence of a solid catalyst, wherein the solid catalyst has the following steps.
Impregnation step: A step in which a liquid titanium compound is brought into contact with solid silica without using a solvent to obtain an impregnated solid. A drying step: A step in which the solid impregnated in the impregnation step is dried to obtain a solid catalyst.

  According to the present invention, in a method for obtaining an epoxide by reacting an olefin and an organic hydroperoxide in the presence of a solid catalyst, it is possible to provide a method for producing an epoxide having an excellent feature that the yield of epoxide is higher than that of a known method. .

Solid silica is a relatively high-density, close-packed porous synthetic silica composed of coagulated or mutually bonded amorphous silica particles, and examples thereof include silica gel. Among the commercially available silica gels, silica gel having a specific surface area of 25 to 700 m ² / g and a silica content of 99% by weight or more is preferable.

Another example of solid silica is a synthetic silica powder made of amorphous silica that is produced by coagulation, has an open pack structure, is easy to disintegrate, and is loosely bonded. Examples thereof include calcined silica (fumed pyrogenic silica) obtained by performing a combustion operation of hydrogen and oxygen with silicon tetrachloride or silicon tetrafluoride. This type of silica is manufactured and sold by various vendors, such as those sold by Cabot Corporation (Cab-O-Zill) and Degussa (Aerosil) (the above-mentioned “Cab-O-Zyl” and “Aerosil”). Is a registered trademark). Among these calcined silicas, calcined silica having a specific surface area of 50 to 500 m ² / g and a silica content of 99% or more is preferable.

  Furthermore, crystalline porous silica is also suitable as an example of solid silica. Examples of the crystalline porous silica include high silica zeolite (zeolite containing a small amount of other metals such as aluminum). As an example of high silica zeolite, silicalite, which is a pentasil zeolite, is known (R.W. Grose and EM Flaigen, US 4,061,724). Moreover, although it is not crystalline, it has MCM-41 (JS Beck, et al., J. Am. Chem. Soc., 114, 10834 (1992)) and SBA-15 having a regular pore structure. (G. D. Stacky et al., J. Am. Chem. Soc., 120, 6024 (1998)) can also be used as a carrier.

  Liquid titanium compounds are liquid titanium salts and titanates. Examples of liquid titanium compounds include tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, titanium tetrachloride, titanium tetrabromide, and titanium (IV) diisopropoxide bisacetyl. You can give acetonate. Among these, titanium tetrachloride is preferable because high activity of the solid catalyst can be obtained.

  The impregnation step is a step of obtaining an impregnated solid by bringing a liquid titanium compound into contact with solid silica without using a solvent.

  In the impregnation step, it is necessary to bring the liquid titanium compound into contact with the solid silica without using a solvent.

  When a liquid titanium compound is brought into contact with solid silica using a solvent, a catalyst having high activity cannot be obtained, which is disadvantageous because the yield of epoxide is reduced.

  The impregnation step is usually performed at 0 to 150 ° C. for 0.1 to 10 hours.

  A drying process is a process of drying the impregnation solid obtained at the impregnation process, and obtaining a solid catalyst.

  In the drying step, excess liquid titanium compound is separated from the impregnated solid.

  As a method for drying the impregnated solid, distillation is preferable because excess liquid titanium compound can be effectively removed from the impregnated solid.

  A drying process is normally performed at 150-300 degreeC for 1 to 24 hours.

  The obtained solid catalyst is preferably converted into a calcined solid catalyst by performing a calcining step. The calcining step is a step of calcining the solid catalyst obtained in the drying step to obtain a calcined solid catalyst. The firing step is preferably performed in an inert gas atmosphere, for example, an atmosphere of nitrogen, argon, or carbon dioxide. The firing temperature is usually 300 to 900 ° C., and the heating time is 0.1 to 10 hours. When the firing step is not performed, the activity may not be high.

  The obtained solid catalyst or calcined solid catalyst is preferably converted into a hydrated solid catalyst by performing a hydration step. The hydration step is a step of obtaining the hydrated solid catalyst by heating the solid catalyst obtained in the drying step or the calcined solid catalyst obtained in the calcination step in the presence of water. The hydration step can be performed in the presence of liquid water or water vapor. The hydration temperature is usually 50 to 500 ° C., and the hydration time is preferably 0.1 to 6 hours. If the hydration step is not performed, the selectivity may not be high.

  The obtained solid catalyst, calcined solid catalyst or hydrated solid catalyst is preferably a solid catalyst silylated by a silylation step. The silylation process is the silylation by treating the solid catalyst obtained in the drying process, the calcined solid catalyst obtained in the calcination process, or the hydrated solid catalyst obtained in the hydration process with a silylating agent. In this step, a solid catalyst is obtained. The silylation step can be performed by contacting the catalyst and the silylating agent in a gas phase or a liquid phase. The silylation step is usually performed at 0 to 200 ° C. for 0.1 to 10 hours. If the silylation step is not performed, the activity may not be high.

  Examples of silylating agents include organic silanes, organic silylamines, organic silylamides and derivatives thereof, and organic silazanes and other silylating agents. Examples of organic silanes include chlorotrimethylsilane, dichlorodimethylsilane, chlorobromodimethylsilane, nitrotrimethylsilane, chlorotriethylsilane, iododimethylbutylsilane, chlorodimethylphenylsilane, chlorodimethylsilane, dimethyl n-propylchlorosilane, dimethylisopropyl Chlorosilane, t-butyldimethylchlorosilane, tripropylchlorosilane, dimethyloctylchlorosilane, tributylchlorosilane, trihexylchlorosilane, dimethylethylchlorosilane, dimethyloctadecylchlorosilane, n-butyldimethylchlorosilane, bromomethyldimethylchlorosilane, chloromethyldimethylchlorosilane, 3-chloro Propyldimethylchlorosilane, dimethoxymethylchlorosilane, Chill phenyl chlorosilane, triethoxy chlorosilane, dimethyl phenyl chlorosilane, methyl phenyl vinyl chlorosilane, benzyl dimethyl chlorosilane, diphenyl chlorosilane, diphenylmethylchlorosilane, diphenyl vinyl chlorosilane, tribenzyl chlorosilane, 3-cyanopropyl dimethylchlorosilane and the like.

  Examples of organic silylamines include N-trimethylsilylimidazole, Nt-butyldimethylimidazole, N-dimethylsilylimidazole, N-dimethylsilyl n-propylimidazole, N-dimethylisopropylsilylimidazole, N-trimethylsilyldimethylamine, N- Examples include trimethylsilyldiethylamine, N-trimethylsilylpyrrole, N-trimethylsilylpyrrolidine, N-trimethylsilylpiperidine, pentafluorophenyldimethylsilylamine, and 1-cyanoethyl (diethylamino) dimethylsilane.

  Examples of organic silylamides and their derivatives include N, O-bistrimethylsilyl trifluoroacetamide, N-trimethylsilylacetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyl trifluoroacetamide, N-methyl-N -Trimethylsilyl heptafluorobutyramide, N- (t-butyldimethylsilyl) -N-trifluoroacetamide, N, O-bis (diethylhydrosilyl) trifluoroacetamide.

  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.

  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.

  The solid silica is preferably made into dry solid silica by performing a silica drying step before the impregnation step. The silica drying step is a step of obtaining dry solid silica by heating and drying solid silica. The silica drying step can be performed in an air atmosphere or an inert gas atmosphere such as nitrogen, argon, or carbon dioxide. The silica drying step is preferably performed at 200 to 900 ° C. and 0.01 to 200 kPa for 0.1 to 24 hours.

  The catalyst can be used in any physical form such as powder, flakes, spherical particles, pellets.

  Epoxides are produced by an epoxidation reaction between an organic hydroperoxide and an olefin in the presence of the solid catalyst prepared by the above-described method.

  The organic hydroperoxide is a compound having the general formula R—OOH (where R is a hydrocarbon group), and preferably R is a hydrocarbon group having 3 to 20 carbon atoms. More preferably, it is a hydrocarbon group having 3 to 10 carbon atoms, particularly a second or third alkyl group or an aryl group-substituted alkyl group.

Examples of the second alkyl group include a cyclopentyl group and a cyclohexyl group, and examples of the third alkyl group include a third butyl group and a third pentyl group.
Examples of the aryl group-substituted alkyl group include a 1-phenyl-1-ethyl group and a 2-phenyl-2-propyl group.

  The organic hydroperoxide may be a diluted or concentrated purified product or non-purified product.

  An organic hydroperoxide (general formula R—OOH) reacts with an olefin to produce a hydroxyl compound (general formula R—OH). When ethylbenzene hydroperoxide is used as the organic hydroperoxide, the resulting hydroxyl compound is 1-phenylethanol, which can be converted to styrene by a dehydration reaction. When cumene hydroperoxide is used, the resulting hydroxyl compound is 2-phenyl-2-propanol, which can be converted to α-methylstyrene by a dehydration reaction. Both styrene and α-methylstyrene are industrially useful materials.

  The third amylene obtained by the dehydration reaction of the third pentyl alcohol obtained when the third pentyl hydroperoxide is used is a substance useful as a precursor of isoprene. Further, tertiary butyl alcohol obtained when tertiary butyl hydroperoxide is used is a substance useful as a precursor of methyl tertiary butyl ether which is an octane number improver.

  An olefin is a compound having at least one carbon-carbon double bond. The olefin may be an acyclic, monocyclic, bicyclic or polycyclic compound and may have one or more carbon-carbon double bonds. Olefins having 2 to 60 carbon atoms are generally preferred. Examples of such olefins include ethylene, propylene, 1-butene, isobutylene, 1-hexene, 2-hexene, 3-hexene, 1-octene, 1-decene, styrene, cyclohexene, butadiene and isoprene.

  In addition, the olefin may be a compound having a substituent. Examples of the substituent include halogen atoms and substituents containing oxygen, sulfur, and nitrogen atoms together with hydrogen and / or carbon atoms. Examples of the halogen atom include a fluoro atom, a chloro atom, a bromo atom, and an iodo atom. Examples of the substituent containing an oxygen, sulfur, or nitrogen atom together with a hydrogen and / or carbon atom include a hydroxyl group, a formyl group, and a mercapto group. Group, sulfinyl group, sulfonyl group, amino group, monoalkylamino group, dialkylamino group and imino group. Examples of the olefin having such a substituent include allyl alcohol, crotyl alcohol, and allyl chloride.

  The amount of olefin used is preferably 1 to 20 mol (per mol of organic hydroperoxide).

  The epoxidation reaction can be carried out in the liquid phase using a solvent and / or diluent. Solvents and diluents 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 organic hydroperoxide solution used. For example, when cumene hydroperoxide (CMHP) is a mixture of CMHP and its raw material cumene, it can be used as a substitute for the solvent without adding any solvent.

  A second solvent can be further used as the diluent, and examples of the solvent useful as the diluent include aromatic monocyclic compounds and alkanes. Examples of aromatic monocyclic compounds include benzene, toluene, chlorobenzene, bromobenzene, and orthodichlorobenzene, and examples of alkanes include hexane, heptane, octane, decane, and dodecane. It is also possible to use an excess amount of olefin as a solvent. That is, an excess amount of olefin can be used as the solvent together with the solvent supplied together with the organic hydroperoxide. The total amount of the solvent used is preferably 20 mol or less (per mol of organic hydroperoxide).

  The epoxidation reaction temperature is usually 25 to 200 ° C, preferably 25 to 150 ° C. The pressure may be sufficient to keep the reaction mixture in a liquid state, and is preferably 100 to 10,000 kPa.

  At the end of the epoxidation reaction, the liquid mixture containing the desired product can be easily separated from the solid catalyst. The liquid mixture can then be purified by a suitable method. Examples of the purification method include fractional distillation and selective extraction. The solvent, catalyst, unreacted olefin and unreacted organic hydroperoxide can be recycled and reused. The process of the present invention can be carried out with a slurry or a fixed bed. For large scale industrial operations, it is preferred to use a fixed bed. The process according to the invention can be carried out by batch, semi-continuous or continuous processes. When the liquid containing the organic hydroperoxide and the olefin is passed through the fixed bed, the liquid mixture exiting the reaction zone contains no or substantially no catalyst.

  Epoxides are useful industrial chemicals. Propylene oxide obtained by epoxidizing propylene is industrially important as a raw material for propylene glycol or polypropylene glycol. Epichlorohydrin obtained by epoxidizing allyl chloride is industrially important as a raw material for glycidyl ether or glycerin. Epoxides obtained by epoxidizing allyl alcohol are also important as raw materials for glycerin.

The following examples illustrate the invention.
Example 1
Impregnation step: In a 100 mL 2-necked eggplant flask equipped with a cooler and a nitrogen inlet under a nitrogen atmosphere, 3.00 g of silica (manufactured by Fuji Silysia, trade name G-10) is placed, and titanium tetrachloride (Wako Pure) 12.42 g of medicinal product, first grade) was added. This eggplant flask was immersed in an oil bath and heated for 2 hours so that the temperature of the oil bath was 140 ° C., and then the eggplant flask was raised from the oil bath and cooled to obtain an impregnated solid.

  Drying step: A distillation apparatus was attached to the eggplant flask containing the impregnated solid, immersed in an oil bath, heated so that the temperature of the oil bath was 155 ° C., and excess liquid was distilled off by distillation. Thereafter, the temperature of the oil bath was raised to 200 ° C. and dried at that temperature for 2 hours to obtain 3.34 g of a solid catalyst.

Calcination step: Put 3.34 g of the obtained solid catalyst in a quartz tube, set the internal temperature to be about 600 ° C. in an electric furnace, and introduce 2 at a flow rate of 0.83 cm ³ / s. Heated for a time to obtain a calcined solid catalyst.

Hydration step: Put the obtained calcined solid catalyst in a quartz tube, set the internal temperature to about 400 ° C. in an electric furnace, and introduce nitrogen saturated with water vapor at a flow rate of 0.83 cm ³ / s The mixture was heated for 2 hours to obtain 2.97 g of a hydrated solid catalyst.

Silylation step: Under a nitrogen atmosphere, 2.97 g of a hydrated solid catalyst, 29.7 g of toluene, and 2.0 g of hexamethyldisilazane were added to a 100 mL 2-neck eggplant flask provided with a condenser and a nitrogen inlet. Then, it was immersed in an oil bath, the temperature of the oil bath was set to 110 ° C., and heated for 1.5 hours. After completion of the heating, the eggplant flask was raised from the oil bath and cooled, and then the solid and the liquid were separated by decantation. The solid was dried at 110 ° C. and 1.33 × 10 ³ Pa for 1.5 hours to obtain 3.12 g of a silylated solid catalyst.

Synthesis of octene oxide (OO) by epoxidation using 1-octene cumene hydroperoxide (CMHP): synthesized silylated solid catalyst (0.3 g), cumene containing 25% by weight of cumene hydroperoxide (15 g) and 1-octene (22.1 g) were charged into an autoclave equipped with a magnetic stirrer and reacted at 105 ° C. for 1.5 hours. The epoxidation reaction results are shown in Table 1. here,
CMHP conversion rate = consumed CMHP (mol) / prepared CMHP (mol) × 100
OO yield = produced OO (mol) / consumed CMHP (mol)
OO selectivity = product OO (mol) / (product OO (mol) + product octene glycol (mol)) × 100
It is expressed.

Comparative Example 1
Example 1 except that 30 g of heptane (made by Wako Pure Chemicals, special grade) was used as a solvent in addition to silica and titanium tetrachloride in the impregnation step, and that the oil bath was heated to 115 ° C. Similarly, a catalyst was produced and octene oxide was synthesized. The results are shown in Table 1.

  From Table 1, it is clear that a catalyst having a higher epoxide yield can be obtained by impregnation without using a solvent and then drying, compared to when impregnation with a solvent and then drying. is there.

Claims (6)

A process for producing an epoxide by reacting an organic hydroperoxide and an olefin in the presence of a solid catalyst, wherein the solid catalyst has the following steps.
Impregnation step: A step in which a liquid titanium compound is brought into contact with solid silica without using a solvent to obtain an impregnated solid. A drying step: A step in which the solid impregnated in the impregnation step is dried to obtain a solid catalyst. The manufacturing method of the epoxide of Claim 1 which has the following baking process in addition to each process of Claim 1.
Calcination step: a step of calcination of the solid catalyst obtained in the drying step to obtain a calcination solid catalyst The method for producing an epoxide according to any one of claims 1 and 2, further comprising the following hydration step in addition to each step according to claims 1 and 2.
Hydration step: A step of obtaining a hydrated solid catalyst by heating the solid catalyst obtained in the drying step or the calcined solid catalyst obtained in the calcination step in the presence of water. The method for producing an epoxide according to one of claims 1 to 3, further comprising the following silylation step in addition to each step according to claims 1 to 3.
Silylation step: The solid catalyst obtained in the drying step, the calcined solid catalyst obtained in the calcining step, or the hydrated solid catalyst obtained in the hydration step was treated with a silylating agent to be silylated. Step of obtaining a solid catalyst The manufacturing method of the epoxide of Claim 1 which has the following silica drying process in addition to the process of Claim 1.
Silica drying step: a step of heating solid silica to obtain dry solid silica The method for producing an epoxide according to claim 1, wherein the titanium compound is titanium tetrachloride.