JPH1180144A - Selective epoxidation of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To control the ring opening of an epoxy ring without reducing a main reaction and to prevent the clogging of a catalyst channel caused by a by-product by using a specific cocatalyst in the epoxidation reaction of an olefin by a titanium atom-containing zeolite catalyst. SOLUTION: This selective epoxidation of an olefin comprises using a univalent thallium compound in reacting a 3-9C aliphatic olefin of the formula (R<1> to R<3> are each H or a 1-2C alkyl) with hydrogen peroxide or a compound to form hydrogen peroxide in the presence of a titanosilicate catalyst. A compound selected from thallium halide, thallium sulfate, thallium nitrate, thallium phosphate, thallium carbonate, thallium carboxylate and thallium hydroxide is used as the univalent thallium compound. Preferably a reaction phase is a liquid phase in the epoxidation and a solvent is water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for selective epoxidation of an aliphatic olefin having a chlorine-substituted allyl position. The epoxy compound obtained in the present invention is a highly reactive bifunctional compound comprising an allyl chlorine and an epoxy ring, and is a novel epoxy resin material, a resin modifier, and various synthetic intermediate materials such as agricultural and pharmaceutical products. Is a very useful compound.

[0002]

2. Description of the Related Art In order to produce an epoxy compound substituted with chlorine at allyl position, for example, epichlorohydrin, a direct epoxidation method using percarboxylic acid starting from allyl chloride, a chlorhydrin method via allyl chloride through chlorohydrin, and A direct epoxidation method using hydrogen peroxide and a certain titanium-containing synthetic zeolite catalyst is known. However, in the direct epoxidation method using a percarboxylic acid, a regeneration process of the oxidizing agent is required, and the oxidizing agent-organic system is explosive, which has problems in reaction operation and equipment. Further, the chlorhydrin method has a problem of treating by-product calcium chloride and a large amount of wastewater.

On the other hand, direct epoxidation using hydrogen peroxide and a certain kind of synthetic zeolite catalyst containing a titanium atom is disclosed in, for example, Japanese Patent Publication No. 4-5028 and US Pat. No. 4,833,260. Although the selectivity with respect to is generally high, when the epoxidation reaction is carried out in a protic solvent containing water and alcohol, the oligomerization or polymerization reaction of the starting olefin is caused by the catalytic action of the acidic hydroxyl groups present on the synthetic zeolite skeleton described above. Then, a ring-opening reaction of the formed epoxy ring and an etherification reaction by condensation of the ring-opened product with a solvent alcohol occur simultaneously with the epoxidation reaction. As a result,
In the above-mentioned titanium atom-containing synthetic zeolite catalyst, a by-product having a large molecular shape generated by these side reactions is
This obstructs the passage of reaction substrates and products called "channels" leading to the active site of the catalyst, causing a problem that the epoxidation activity is reduced and deactivated in a short time.

US Pat. No. 4,824,976 discloses a solution to the above problem by treating a synthetic zeolite catalyst containing a titanium atom with a suitable acid neutralizing agent before or during the reaction. It is described that an acidic hydroxyl group existing on a skeleton is neutralized, thereby improving the selectivity of an epoxy product. According to this method, for example, in the case of the epoxidation reaction of allyl chloride, the selectivity is improved, but the reactivity of the epoxidation is reduced by the pretreatment of the acid neutralizing agent, and the titanium atom which is not subjected to the pretreatment is treated. The production rate of epichlorohydrin is remarkably reduced as compared with the case where the contained zeolite catalyst is used.

Japanese Patent Application Laid-Open No. 8-225556 discloses a method for suppressing the ring-opening reaction of an epoxy ring by treating a catalyst with a non-basic salt to form an acidic hydroxyl group existing on the synthetic zeolite skeleton. To neutralize, thereby increasing the selectivity of the epoxy product. However, even with this method, the same selectivity improvement as described above is observed, but the reactivity of epoxidation is reduced, and the production rate of olefin oxide is significantly reduced as compared with the case where a catalyst without pretreatment is used. That is inevitable.

Further, in these conventional techniques, alcohols such as methanol or organic solvents such as acetone are preferable as reaction solvents, and when these are not added, the epoxidation reactivity is remarkably reduced. Have been. Further, for example, when methanol is used as a solvent, when the starting olefin is a lower olefin having 3 to 9 carbon atoms, in most cases, the starting olefin and / or
Since the produced epoxide, methanol, and water form an azeotropic composition, it is particularly difficult to recover the product, which is a major problem in putting this catalytic process into practical use.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an epoxidation reaction of an olefin with a titanium atom-containing zeolite catalyst (titanosilicate catalyst) without reducing the activity of the epoxidation reaction which is the main reaction. It is an object of the present invention to provide a method for suppressing ring opening and suppressing blockage of a catalyst “channel” by a by-product.

[0008]

The present invention relates to an aliphatic olefin having 3 to 9 carbon atoms represented by the following general formula (1) and hydrogen peroxide, or a compound which forms hydrogen peroxide in a reaction system. And c. In the presence of a titanosilicate catalyst, wherein a monovalent thallium compound is used as a co-catalyst.

[0009]

Embedded image (Wherein R ¹ , R ² and R ³ represent a hydrogen atom or C
₁ -C shows _two alkyl groups, or different an each identical. )

The aliphatic olefin represented by the general formula (1) used in the present invention includes allyl chloride, methallyl chloride, 1-chloro-2-butene, 1-chloro-
Examples thereof include 3-methyl-2-butene and 1-chloro-2-pentene. Industrially, allyl chloride or methallyl chloride, which produces epichlorohydrin by an epoxidation reaction, is useful. In addition, hydrogen peroxide is usually used as a hydrogen peroxide solution, and as a compound that generates hydrogen peroxide, for example, a hydrogen peroxide addition compound of urea,
Alternatively, t-butyl hydroperoxide and the like can be mentioned.

The titanosilicate catalyst used in the present invention has a general formula: xTiO ₂ · (1-x) SiO ₂ (where x is 0.002 to 0.20)
In the case of the composition of a titanium atom-containing synthetic zeolite catalyst (referred to as TS-1) having the composition represented by the following formula, the effect is particularly large, but the effect of the monovalent thallium compound as a cocatalyst is limited to this range. In general, a titanosilicate catalyst having epoxidation activity can exhibit the same cocatalyst effect.

The titanosilicate catalyst used in the present invention has a crystal structure of MFI, MEL or BE.
A generally exhibits a high epoxidation activity in the case of A. Therefore, in the case of titanosilicate catalysts having these crystal structures, the effect of adding a monovalent thallium compound as a cocatalyst is particularly remarkably exhibited. However, the crystal structure of the titanosilicate catalyst to which the present invention can be applied is not limited to these,
A titanosilicate catalyst having a large pore skeleton called mesopore can exhibit the same cocatalyst effect regardless of whether it is crystalline or amorphous.

The monovalent thallium compound used as a co-catalyst in the present invention may be a monovalent thallium salt such as a thallium halide, sulfate, nitrate, phosphate, carbonate, carboxylate or the like. Thallium hydroxide, and the counter anion is not particularly limited. As monovalent thallium salts, halides and nitrates exhibit excellent addition effects, and among these, thallium fluoride (monovalent) is the most excellent.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In preparing a titanosilicate (a synthetic zeolite containing a titanium atom) used in the present invention, a reaction mixture comprising silicon oxide, titanium oxide, a nitrogen-containing organic base and water is prepared. The silicon oxide source may be a tetraalkyl orthosilicate, preferably tetraethyl orthosilicate or simply colloidal silica. The titanium oxide source may be a compound selected from tetraalkoxytitanium, preferably tetraethoxytitanium, tetraisopropoxytitanium, or tetrabutoxytitanium, or an inorganic compound such as titanium tetrachloride or titanium oxychloride. The organic base is a compound selected from tetraalkylammonium hydroxide or tetraalkylammonium bromide, particularly preferably tetra-n-propylammonium hydroxide. The mixture of each reagent was stirred, the solvent was removed from the obtained precipitate, and then transferred to an autoclave.
Hydrothermal treatment is performed under conditions of 1 to 30 days until crystals of the titanosilicate precursor are formed. Next, these crystals are separated from the mother liquor, carefully washed with water and dried, and then calcined at 500 to 800 ° C. in air to obtain the desired titanosilicate catalyst.

The preferred concentration of the titanosilicate catalyst with respect to the olefin represented by the general formula (1) is 0.1.
The epoxidation selectivity based on olefin and the yield are 5 to 20% by weight, and the highest is 2 to 15% by weight. The preferred concentration of hydrogen peroxide in the aqueous solution used is from 1 to
Although it is 60% by weight, it is 10 to 40 in terms of storability and operability.
% By weight is preferred. The charged amount of the monovalent thallium compound serving as a cocatalyst with respect to the titanosilicate catalyst is 0.1 to
It is 20% by weight, preferably 0.5 to 10% by weight. In the treatment method using a thallium compound, a thallium compound is dissolved in an appropriate solvent, for example, water or alcohol, and a titanosilicate catalyst is added to prepare a slurry solution.The slurry solution is stirred to form a slurry in the pores of the titanosilicate. Then, the thallium compound is taken in, and then the catalyst can be separated by filtration or centrifugation and decantation, and, if necessary, washed and dried to be introduced into the reaction system. Needless to say, the thallium compound may be directly introduced into the reaction system separately from the titanosilicate catalyst to cause the reaction.

The epoxidation reaction can be performed in the presence of a suitable solvent. Suitable solvents include water, lower alcohols such as methanol and isopropyl alcohol, organic solvents such as acetone, and mixtures thereof. In the present invention, the method of using water as a single solvent as described later is particularly advantageous depending on the type of the starting olefin. In this case, the water contained in the hydrogen peroxide solution can be used as it is.

The reaction temperature of the epoxidation reaction of the present invention is 0.
The reaction can be carried out at a temperature of up to 150 ° C, preferably at a temperature of 10 to 80 ° C. However, in the conventional method in which a thallium compound is not used as a co-catalyst, in parallel with the epoxidation reaction, the epoxy ring opening involving the acid sites on the catalyst, which becomes predominant at a high temperature, is involved in secondary reactions such as oligomerization and polymerization of the starting olefin. Since the reaction occurs, when the reaction temperature is 40 ° C. or higher, the epoxy selectivity is significantly reduced. On the other hand, when a thallium compound is used as a co-catalyst, the acid sites serving as side reaction sites in the catalyst are selectively and effectively blocked, and the ring-opening reaction of the epoxy ring involving these acid sites is performed. Since the oligomerization or polymerization reaction of the starting olefin is almost completely suppressed, the epoxidation reaction can be completed in a short time without substantially lowering the epoxy selectivity even at a reaction temperature of 60 ° C. The reaction pressure of the epoxidation reaction can be performed in a wide pressure range from atmospheric pressure to 20 atm. The reaction method may be any of a continuous flow method and a batch method.

After completion of the epoxidation reaction, the titanosilicate catalyst or the titanosilicate catalyst treated with a monovalent thallium compound is separated from the epoxidation reaction mixture by a method such as filtration or centrifugation, and then the recovered titanosilicate catalyst is recovered. The nosilicate catalyst can be effectively used in the next epoxidation reaction. The reaction solution after the catalyst separation is separated into two layers, an aqueous layer and an organic layer, and 99% of the raw materials and products are separated.
The above is the organic layer. Since the water content is 0.1 to 0.8% by weight, it is possible to directly recover the raw material and purify the product by distillation, after the separation, as it is, or after removing a trace amount of the remaining catalyst by microfiltration. .

[0019]

The epoxidation reaction will be discussed below. When a monovalent thallium compound is used as a cocatalyst, the acid sites are blocked and the epoxy ring is opened without reducing the reactivity of the olefin, as compared with the case where an alkali metal or alkaline earth metal is used as a cocatalyst. Was found to be almost completely suppressed. This is because the charge of monovalent thallium is +1
And this +1 charge is shielded by the thick outer electrons due to heavy elements, resulting in "Si-O (δ-) Tl (
δ +) ", the electric field gradient due to the bond polarization is located at a lower period than that of the thallium atom, and the shielding of outer electrons is less alkaline metal (Na, K) or alkaline earth metal (Mg,
Ca, Sr, Ba), which is presumed to be due to a decrease in the hydrophobicity near the active site in the channel in the zeolite leading to the active site. Furthermore, when the acid site is blocked with monovalent thallium, the gradient becomes smaller than the electric field gradient due to the bond polarization in the bond of “Si—O (−) H (+)” when the acid site is not blocked. Contrary to the case where no treatment with thallium is used, a double effect is obtained in combination with the acid site block, in which the hydrophobicity is increased and the activity is improved.

In the epoxidation reaction of the present invention, when the solvent in the liquid phase is water only, the olefin having an allyl chloride skeleton in the reaction liquid phase has at least one methyl group substituted on the double bond carbon. Particularly high epoxidation activity is obtained when it is an olefin. This is because in the case of allyl chloride where R ¹ , R ² and R ³ in the general formula (1) are all hydrogen, the electron donating property of the double bond is reduced due to the effect of the chlorine atom substituted at the allyl position. As a result, the reaction rate of epoxidation, which proceeds due to electrophilic attack on the double bond of oxygen in hydrogen peroxide, decreases, while one or more of R ¹ , R ² and R ³ are methyl. In the case of a group, it is presumed that this is to restore the electrophilicity of the double bond due to the electron donating effect of the substituted methyl group on the double bond. For example, in β-methylallyl chloride (methallyl chloride), no methanol solvent is added,
Since the epoxidation reaction can be carried out most efficiently in a simpler reaction liquid phase, the unreacted olefin and the epoxy product can be easily separated to a high purity by distillation.

When methallyl chloride or the like is used as the olefin shown above, the rate of the epoxidation reaction is reduced by the addition of a solvent such as methanol, but the effect of the thallium compound as a cocatalyst, that is, The effect of almost completely suppressing the ring opening reaction and the oligomerization or polymerization reaction of the starting olefin is not affected. Therefore, depending on the purpose, for example, methanol or the like may be used to make the reaction liquid phase a single phase. Can be added.

[0022]

The present invention will be specifically described below with reference to examples and comparative examples. In the examples, the composition percentages are all weight percentages. Catalyst Preparation Example 1 Cogel solution preparation: 2-propanol was placed in a 1 L-separable flask equipped with a Dimroth, thermometer and dropping funnel.
100 g of (IPA) was added, and 93 g of tetraethyl orthosilicate (> 99.999% manufactured by Aldrich) was added thereto at room temperature under stirring. On the other hand, IPA 70.4gr, 0.05N hydrochloric acid aqueous solution 17.5
gr was added, and this was put into a dropping funnel and added dropwise at room temperature under stirring to obtain a colorless transparent solution. Next, to IPA 49.0gr,
5.44 gr of tetrabutyl titanate (manufactured by Aldrich) was added, and the mixture was placed in a dropping funnel and added dropwise at room temperature with stirring. Upon addition, the solution became a pale yellow clear solution. Further, Aldrich 20% -tetrapropyl ammonium hydroxide (hereinafter referred to as `` TPAOH '') 23.
5 gr was put into a dropping funnel, and this aqueous solution was added dropwise at room temperature under stirring to obtain 318 g of an agar-like precipitate.

Concentration of the precipitate to dryness:
The mixture was transferred to an eggplant flask, and the solvent was distilled off with a rotary evaporator at 80 ° C. under a reduced pressure of a water pump. Further, the precipitate was dried on an oil bath at 110 ° C. for 2 hours to recover 35.1 gr of a white precipitate. This white precipitate was pulverized with an automatic mortar made of alumina.

Hydrothermal synthesis reaction: 31.098 gr of the crushed precipitate was placed in a 500 ml-SUS autoclave containing an inner tube made of Teflon (trade name), and 34.8 gr of 20% -TPAOH was added thereto. Without stirring, the temperature was raised to 30 to 170 ° C in 2 hours, and the reaction was carried out at 170 ° C for 24 hours. The pressure at 170 ° C. was about 17 kg / cm ² . After the reaction, the precipitate was filtered, and deionized water was added to the precipitate for washing. The washing was repeated with an N / 10-AgNO ₃ aqueous solution until the washing solution was not clouded, and the precipitate was filtered and dried in a constant-temperature oven at 120 ° C. for 4 hours.

Firing: The dried precipitate was placed in a magnetic crucible and fired in a muffle furnace at 550 ° C. for 3 hours in an air atmosphere to obtain a pure white fired product. This titanosilicate catalyst had SiO ₂ / TiO ₂ = 28.4 (formula ratio) on a charged basis.

Comparative Example 1 A catalyst prepared in Catalyst Preparation Example 1 (hereinafter simply referred to as titanosilicate catalyst (A)) was placed in a 300 ml glass autoclave.
1.001 g was added, and thereto, methanol (22.42 g) and 35% -hydrogen peroxide (36.61 g) were added, and methallyl chloride 6 was further added.
After adding 1.80 g, it was sealed with a plug screw with a pressure gauge. The mixture was reacted for 2 hours in a water bath at 40 ° C. with stirring by a stirrer. After the reaction,
After cooling the glass autoclave with ice, the catalyst was separated, and the reaction product was analyzed and quantified by gas chromatography and the remaining hydrogen peroxide by iodometry. This analysis method was similarly performed in each of the following examples. The reaction results are shown in Table 1 together with the following examples.

Comparative Example 2 A 100 ml glass autoclave was used to prepare 2.003 g of titanosilicate catalyst (A), 10.7 g of 35% hydrogen peroxide solution and 16.5 g of methallyl chloride, except that methanol was not added.
An epoxidation reaction was performed in the same manner as in Comparative Example 1.

Catalyst Preparation Example 2 (Thallium Fluoride Treated Catalyst) A titanosilicate catalyst (A) was placed in a 100 ml glass autoclave.
5 g was added thereto, and 18.5 g of a 2% -TlF aqueous solution was added thereto and sealed. The mixture was treated in a water bath at 40 ° C. for 2 hours with stirring. After adding 40.2 g of methanol to the mixture and stirring well, the catalyst was centrifuged (6000 rpm, 30 minutes), and the supernatant was removed by decantation to obtain 2.6 g of a precipitate. 53.3 g of deionized water in this precipitate
Was added and washed by stirring with a magnetic stirrer at room temperature for 30 minutes. After washing, the slurry was centrifuged (6000
rpm, 45 minutes) to obtain 2.4 g of a wet precipitate, which was air-dried for 17 hours to obtain 1.511 g of a TIF-treated catalyst.

Example 1 In a 50 ml glass autoclave, 1.511 g of the above-mentioned thallium fluoride treatment catalyst was added, 8.5 g of 35% hydrogen peroxide solution was added thereto, and further 12.5 g of methallyl chloride was added. The epoxidation reaction was carried out in a water bath at 40 ° C. for 2 hours with stirring.

Example 2 In a 50 ml glass autoclave, 1.004 g of titanosilicate catalyst (A) was added, and 5.4 g of 35% hydrogen peroxide solution and 1.381 g of 2% -TlF aqueous solution were added thereto, followed by stirring for 2 minutes. did. After adding 8.6 g of methallyl chloride to the slurry, the slurry was sealed and subjected to an epoxidation reaction in a 40 ° C. water bath with stirring for 2 hours.

Example 3 Titanosilicate catalyst (A) 1.00 was added to a 50 ml glass autoclave.
Using 1 g, 5.7 g of 35% -hydrogen peroxide solution, 1.473 g of 2% -TlF aqueous solution, and 8.7 g of methallyl chloride, the epoxy was reacted in the same manner as in Example 2 except that the reaction was carried out in a 60 ° C. water bath for 30 minutes. The reaction was carried out.

Catalyst Preparation Example 3 (Thallium Nitrate Treatment Catalyst) 2.0 g of the titanosilicate catalyst (A) was placed in a 100 ml glass autoclave, and 32.2 g of a 2% -TlNO ₃ aqueous solution was added thereto, and the mixture was sealed. This was placed in a 60 ° C. water bath and treated with stirring for 2 hours. After the treatment, the glass autoclave was cooled with water and opened, and 41.0 g of methanol was added thereto, followed by stirring for several minutes. The slurry was centrifuged (6000 rpm, 30 minutes), the supernatant was removed by decantation, and 52.0 g of deionized water was added, followed by washing at room temperature. The washed catalyst is centrifuged (6000 rpm,
40 minutes), air-dry for 16 hours, and then use a gas circulation dryer at 70 ° C for 3 hours.
After drying for an hour, 2.05 g of thallium nitrate-treated catalyst was obtained.

EXAMPLE 4 1.08 g of the above thallium nitrate treatment catalyst, 35% hydrogen peroxide solution
An epoxidation reaction was carried out in the same manner as in Example 1 except that 5.5 g and 8.8 g of methallyl chloride were used.

Example 5 1.007 g of titanosilicate catalyst (A), 35% hydrogen peroxide solution
5.6 g, 2.678 g of 2% -TlNO ₃ aqueous solution, 8.6 g of methallyl chloride
Epoxidation reaction was carried out in the same manner as in Example 2 except that

Catalyst Preparation Example 4 (Thallium chloride treated catalyst) 2.1 g of titanosilicate catalyst (A) was placed in a 300 ml glass autoclave, and 113.6 g of a 0.49% -TlCl aqueous solution was added thereto.
Sealed. This was placed in a 60 ° C. water bath and treated for 2 hours with stirring. After the treatment, the slurry was centrifuged in the same manner as in Catalyst Preparation Example 3, washed with deionized water, and dried.
1.88 g of thallium chloride treated catalyst were obtained.

Example 6 1.004 g of the above thallium chloride-treated catalyst, 35% -hydrogen peroxide solution
An epoxidation reaction was carried out in the same manner as in Example 1 except that 6.3 g and 8.8 g of methallyl chloride were used.

Comparative Example 3 In a 100 ml glass autoclave, 2.006 g of the titanosilicate catalyst (A) was placed, and 11.4 g of 35% hydrogen peroxide solution was added thereto.
And 14 mg of LiF were added and stirred for 2 minutes. After adding 16.7 g of methallyl chloride to the slurry, the slurry was sealed and an epoxidation reaction was carried out in a water bath at 40 ° C. for 2 hours with stirring.

Catalyst Preparation Example 5 (Sodium hydroxide-treated catalyst) 1.504 g of the titanosilicate catalyst (A) was placed in a 100 ml-glass autoclave, and 3.4 g of a 2% -NaOH aqueous solution was added thereto, followed by sealing. This was placed in a 40 ° C. water bath and treated for 2 hours. After the treatment, this slurry was centrifuged in the same manner as in Catalyst Preparation Example 3, washed with deionized water, and air-dried to obtain 1.306 g of a sodium hydroxide-treated catalyst.

Comparative Example 4 An epoxidation reaction was carried out in the same manner as in Example 1 except that 1.306 g of the above sodium hydroxide-treated catalyst, 6.9 g of 35% hydrogen peroxide solution, and 10.9 g of methallyl chloride were used. .

Catalyst Preparation Example 6 (potassium carbonate treatment catalyst) 2.046 g of titanosilicate catalyst (A), 2% -K ₂ CO ₃ aqueous solution 7.
Except that 6 g was used, 1.848 g of a potassium carbonate-treated catalyst was obtained in the same manner as in Catalyst Preparation Example 5.

Comparative Example 5 1.848 g of the above potassium carbonate treatment catalyst, 35% -hydrogen peroxide solution
The epoxidation reaction was carried out in the same manner as in Example 1 except that 9.9 g and 15.4 g of methallyl chloride were used.

Catalyst Preparation Example 7 (Calcium chloride-treated catalyst) 1.447 g of the titanosilicate catalyst (A) was placed in a 30 ml glass autoclave, and 8.8 g of a 2% -CaCl ₂ aqueous solution was added thereto, and the mixture was sealed. The following operation was carried out in the same manner as in Catalyst Preparation Example 5, to obtain 1.302 g of a calcium chloride-treated catalyst.

Comparative Example 6 Except that 1.302 g of the above-mentioned calcium chloride-treated catalyst, 7.0 g of 35% hydrogen peroxide solution, and 11.2 g of methallyl chloride were used,
An epoxidation reaction was performed in the same manner as in Example 1.

Catalyst Preparation Example 8 (Barium acetate-treated catalyst) Except that 1.526 g of titanosilicate catalyst (A) and 21.3 g of 2% -Ba (CH ₃ COO) ₂ aqueous solution were used, the same procedure as in Catalyst Preparation Example 5 was used. 1.920 g of a barium acetate-treated catalyst was obtained.

Comparative Example 7 1.920 g of the above-mentioned barium acetate-treated catalyst, 35% -hydrogen peroxide solution
Except using 10.2g and methallyl chloride 16.0g,
An epoxidation reaction was performed in the same manner as in Example 1.

Comparative Example 8 0.498 g of the titanosilicate catalyst (A) was placed in a 100 ml glass autoclave, and 19.9 g of 35% hydrogen peroxide solution was added thereto.
Was added, and further 26.4 g of allyl chloride (hereinafter referred to as AC) of a fraction having a boiling point of 45.0 to 45.5 ° C. distilled under normal pressure was added thereto, followed by a reaction in a 40 ° C. water bath with stirring for 2 hours. After the reaction, after cooling the glass autoclave with ice, the catalyst was separated,
The reaction product was analyzed and quantified by gas chromatography and the residual hydrogen peroxide was determined by iodometry. (Less than,
The reaction results are shown in Table 2 together with the following examples.

Comparative Example 9 0.498 g of titanosilicate catalyst (A), 11.1 g of methanol
An epoxidation reaction was carried out in the same manner as in Comparative Example 8, except that 18.1 g of 35% aqueous hydrogen peroxide and 26.0 g of AC were used.

Comparative Example 10 An epoxy resin was prepared in the same manner as in Comparative Example 8 except that a 50 ml glass autoclave was used, and 1.013 g of titanosilicate catalyst (A), 6.2 g of 35% hydrogen peroxide solution, and 9.1 g of AC were used. The reaction was carried out.

Example 7 Using a 50 ml glass autoclave, 1.003 g of titanosilicate catalyst (A), 6.3 g of 35% hydrogen peroxide solution, and methanol 4.
0 g, 1.154 g of 2% -TlF aqueous solution, except that AC 8.6 g was used,
An epoxidation reaction was performed in the same manner as in Comparative Example 8.

Comparative Example 11 Using a 50 ml glass autoclave, 1.018 g of titanosilicate catalyst (A), 6.3 g of 35% hydrogen peroxide solution and 8.8 g of AC, a reaction temperature of 60 ° C. and a reaction time of 1 An epoxidation reaction was performed in the same manner as in Comparative Example 8 except that the time was changed.

Example 8 Using a 50 ml glass autoclave, 1.013 g of titanosilicate catalyst (A), 6.2 g of 35% hydrogen peroxide solution, 2% aqueous solution of TlF
The epoxidation reaction was carried out in the same manner as in Comparative Example 8 except that 1.507 g and 8.9 g of AC were used, the reaction temperature was 60 ° C., and the reaction time was 1 hour.

[0052]

[Table 1]

[0053]

[Table 2]

The calculation method of the above numerical values is based on the following equation. (1) Reaction rate of MAC, AC (MAC added, moles of AC-MAC in product,
(Mol number of AC) × 100 / mol number of added MAC and AC (2) Hydrogen peroxide reaction rate (mol number of added hydrogen peroxide−mol number of hydrogen peroxide in product) × 100 / added Number of moles of hydrogen peroxide (3) Selectivity of MEP and EP Number of moles of MEP and EP in product × 100 / M reacted
AC, mole number of AC (4) diol selectivity mole number of diol in product × 100 / MA reacted
C, mole number of AC (5) Carbon balance (MAC in the product, mole number of AC + ME in the product
Number of moles of P, EP + number of moles of diol in product) × 1
00 / moles of added MAC and AC

As shown in the above Examples and Comparative Examples, the method of the present invention is excellent in selectivity, although the production rate of epoxide is not much different from the case where only a titanosilicate catalyst is used. In addition, the rate of epoxidation is increased as compared with the case where an alkali metal or an alkaline earth metal is used as a promoter. In the case of using only the titanosilicate catalyst, addition of methanol as a solvent has no effect on the epoxidation reaction of methallyl chloride, but rather decreases the selectivity (Comparative Example 1). On the other hand, in the epoxidation reaction of allyl chloride, the production rate of the epoxide is greatly promoted, but the selectivity is not sufficient (Comparative Example 9). In the method of the present invention, the reaction temperature is set at 60.
Even when the temperature is raised to ° C., the production rate is promoted while a sufficient selectivity is maintained (Examples 3 and 8).

[0056]

According to the present invention, in carrying out the epoxidation reaction of olefins with hydrogen peroxide, a monovalent thallium compound is used as a co-catalyst of a titanosilicate catalyst, so that the epoxidation activity is not reduced. ,
Not only the ring-opening reaction of the produced epoxy compound, but also the oligomerization and polymerization reaction of the starting olefin are almost completely suppressed, so the epoxy ring-opening product into the pores in the catalyst,
In addition, it is possible to prevent clogging due to accumulation of oligomers, polymers, and the like, and it is possible to increase the generation rate of the epoxidation reaction and the selectivity. In addition, long-term repeated use is possible without performing any treatment for regenerating the catalytic activity.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 303/08 C07D 303/08 // C07B 61/00 300 C07B 61/00 300

Claims (8)

[Claims] 1. A compound having 3 to 3 carbon atoms represented by the following general formula (1):
Wherein the aliphatic olefin of No. 9 is reacted with hydrogen peroxide or a compound that generates hydrogen peroxide in the reaction system in the presence of a titanosilicate catalyst, wherein a monovalent thallium compound is used as a promoter. Process for selective epoxidation of olefins. Embedded image (Wherein R ¹ , R ² and R ³ represent a hydrogen atom or C ₁ -C
_{And represents two} alkyl groups, which may be the same or different. ) 2. An aliphatic olefin represented by the general formula (1) is allyl chloride, methallyl chloride, 1-chloro-2-butene, 1-chloro-3-methyl-2-butene or 1-chloro-2-. The epoxidation method according to claim 1, which is pentene. 3. The titanosilicate catalyst has a general formula: xTiO ₂
· (1-x) epoxidation process of claim 1 (the x in the formula .002 to .20) SiO ₂ is a compound represented by. 4. A titanosilicate catalyst comprising MFI, MEL
4. The epoxidation method according to claim 3, which has a BEA crystal structure. 5. The epoxy according to claim 1, wherein the monovalent thallium compound is at least one selected from a thallium halide, a sulfate, a nitrate, a phosphate, a carbonate, a carboxylate and a hydroxide. Chemical method. 6. The epoxidation method according to claim 5, wherein the monovalent thallium halide is thallium fluoride or chloride. 7. The olefin epoxidation reaction according to claim 1, wherein a titanosilicate catalyst treated with a monovalent thallium compound is used, or a monovalent thallium compound and a titanosilicate catalyst are separately reacted. A method characterized by being introduced into a system. 8. The method according to claim 1, wherein the reaction phase is a liquid phase in conducting the epoxidation reaction of the olefin according to claim 1, and the solvent in the liquid phase is water.