JPS62234550A - Catalyst and its usage - Google Patents

Abstract

PURPOSE:To obtain the title catalyst for producing epoxides from olefins and hydrogen peroxide with high conversion efficiency and selectivity by using a specified quaternary ammonium ion and the salts of group V elements of the periodic table and tungsten with heteropolyacid ions or their peroxides. CONSTITUTION:A quaternary ammonium compd. shown by the formula R4N<+>.X<-> (in the formula, at least one of the Rs are a 8-18C alkyl group. other Rs are a 1-18C alkyl or benzyl group, and X<-> is an anionic counter ion) or a nitrogen ring-contg. quaternary ammonium and the heteropolyacids such as phosphonotungstic acid are respectively dissolved in a solvent such as water, both solns. are then mixed, and the deposited salt is isolated to obtain a catalyst. The catalyst is further treated with hydrogen peroxide before the catalyst is tested for the reaction, and the catalytic activity can be enhanced. High conversion efficiency of olefins and high selectivity can be obtained with use of the catalyst while using easy-to-handle comparatively low-concn. hydrogen peroxide.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to olefins (in the present invention, olefins refers to olefins and olefin-based compounds).
The present invention relates to a catalyst useful in producing an epoxide from hydrogen peroxide and hydrogen peroxide, and a method for using the same.

<Prior Art and Problems> Generally, in an epoxide production reaction by reacting olefins with hydrogen peroxide, both the conversion rate of olefin and the selectivity to epoxide are low. The reason for the low conversion rate is that hydrogen peroxide remains unreacted in low-temperature reactions, decomposes at high temperatures to generate oxygen, and is not effectively consumed in the reaction.

Furthermore, the selectivity to epoxide is low because polyol is produced as a by-product due to water introduced into the reaction system together with hydrogen peroxide and water generated by the reaction.

Conventionally, a method using a specific catalyst has been proposed in order to solve the above-mentioned problems in producing the corresponding ebosigide by the reaction of olefins and hydrogen peroxide. For example, there is a method (Japanese Unexamined Patent Publication No. 156475/1983) that uses a derivative of a specific element and a phase transfer catalyst in combination. However, this method has the drawback that the conversion rate of olefin is inevitably low because a large excess of olefin is subjected to the reaction. (50%) of hydrogen peroxide solution, it is difficult to handle, and the method is also disadvantageous in terms of equipment efficiency.

<Means for Solving the Problems> In view of the above-mentioned circumstances, it is an object of the present invention to be able to use a relatively low concentration hydrogen peroxide solution that is easy to handle, and to improve the conversion rate of olefins and the conversion to eboshikide. It is an object of the present invention to provide a catalyst for epoxidizing olefins, which has an unprecedentedly high selectivity, and a method for using the same.

That is, the present invention is based on the general formula % (1) [wherein at least one R is an alkyl group having 8 to 18 carbon atoms, and the other R is an alkyl group having 1 to 18 carbon atoms or a benzyl group] It is. X- is an anionic counterion. ] A salt of a quaternary ammonium ion derived from a quaternary ammonium compound or a nitrogen ring-containing quaternary ammonium compound with a heteropolyacid ion of an element of group II of the periodic table and tungsten, or a peroxide thereof and an epoxidation catalyst for olefins, characterized in that the olefins and hydrogen peroxide are reacted in a solvent at a temperature of 0 to 120°C using the above-mentioned catalyst. Concerning the use of chemical catalysts. The present invention will be explained in more detail below.

The catalyst of the present invention is a salt of a quaternary ammonium ion and a heteropolyacid ion of a Group I element of the periodic table and tungsten, and is a quaternary ammonium compound represented by the general formula (1) or a nitrogen ring-containing It can be obtained by dissolving a quaternary ammonium compound and the above-mentioned heteropolyacids in a solvent such as water, reacting them together, precipitating the desired salt that is insoluble in the solvent used, and then isolating and purifying it. can. From infrared absorption spectra and elemental analysis, it has been found that a salt obtained from cetylpyridinium imene and phosphonotungstate ion is represented by the following molecular formula.

(0NL(CI+2)15 Cl1s)3 (PJ
2040) 31 Another feature of the present invention is
A method of increasing the catalytic activity by pre-treating the catalyst salt with hydrogen peroxide before a reaction test is, for example, dispersing and stirring the catalyst salt prepared as described above in a 35% hydrogen peroxide solution (for 1 hour). It can be easily obtained by isolation and purification after co-treatment.Also, by mixing and stirring a hydrogen peroxide aqueous solution of a quaternary ammonium compound and a hydrogen peroxide aqueous solution of a tungsten heteropolyacid, - It is also possible to obtain the desired catalyst salt and at the same time increase its catalytic activity.

The reason why the catalytic activity is increased by pre-treating the catalyst with hydrogen peroxide is probably that the peroxide (hydroperoxy This is thought to be due to the formation of peroxotype or peroxotype on the catalyst.

Specific examples of the quaternary ammonium compound represented by the general formula (1) include trioctylmethylammonium chloride, dilauryldimethylammonium chloride, lauryltrimethylammonium bromide, stearyltrimethylammonium chloride, lauryldimethylbenzylammonium hydroxide, stearyldimethyl Ammonium bromide, etc.

Examples of nitrogen ring-containing quaternary ammonium compounds include quaternary ammonium compounds in which the nitrogen ring is composed of a pyridine ring, a picoline ring, a quinoline ring, an imidacilline ring, a morpholine ring, etc. Quaternary ammonium compounds are preferred. Specific examples of the nitrogen ring-containing quaternary ammonium compound include the following.

Alkylpyridinium salt [alkyl group has 8 to 2 carbon atoms]
0 (hereinafter, the alkyl group in this section indicates the same thing), such as N-cetylpyridinium chloride (hereinafter, the counteranion in this section indicates the same thing)], alkylpicolinium salt (N-laurylpicolinium salt) alkylquinolinium and alkylisoquinolinium salts, alkylhydroxylethylimidacyline salts, alkylhydroxyethylmorpholine salts, etc.

Examples of the heteropolyacids of Group V elements of the periodic table and tungsten include phosphonotungstic acid (phosphotungstic acid, 12-tungstophosphoric acid), arsenotungstic acid, and their sodium salts. Among them, phosphonotungstic acid is particularly preferred.

The olefins in the present invention can be expressed by the following general formula (where R1', R2', R3' and R4' are monovalent hydrocarbon groups which may have a double bond, and R1'
and R2' or R3' and R4' together represent a divalent hydrocarbon group optionally having a double bond; or R1' and R3' or R2' and R
4' together represent a divalent hydrocarbon group which may have a double bond).

In the general formula (2), R1', R2', R3' and R4' are monovalent hydrocarbon groups which may have a double bond, and examples of the hydrocarbon groups include aliphatic hydrocarbon groups such as Straight or branched alkyl or alkenyl groups having 1 to 30 carbon atoms; alicyclic hydrocarbon groups, such as 3 to 30 carbon atoms;
12 optionally branched cycloalkyl, cycloalkenyl, or polycycloalkyl groups; and aromatic hydrocarbon groups such as aryol, alkaryl, and aralkyl groups. R1' and R2' or R3
The divalent hydrocarbon group in which ' and R4' together may have a double bond is a group having 3 to 11 carbon atoms (
alkylene group, alkenylene group, etc.). Also R1' and R'3' or R2' and R4'
Examples of the divalent hydrocarbon group which may be taken together and have a double bond include a group having 1 to 10 carbon atoms (alkylene group,
alkenylene group, etc.). Examples of the olefins represented by the general formula (2) include the following compounds.

1. Aliphatic olefinic unsaturated hydrocarbons (11 alkenes ethylene, propylene, butene, pentene, ■-hexene, 3-hexene, 1-heptene, 1-octene, 1-
Nonene, 1-undecene, ■-dodecene, 1-1-lysocene, ■-tetradecene, 1-pentadecene, ■-hexadecene, ■-heptadecene, l-octadecene, 1-
Nonadecene, 1-icosene, diisobutylene, propylene trimer or tetramer, etc.

(2) Polyene Chain terpenes such as myrcene; polybutadiene, etc.

2. Aromatic olefinic hydrocarbons styrene, α-methylstyrene, divinylbenzene, stilbene, etc.

3. Alicyclic olefinic hydrocarbon cycloalkenes or cyclopolyenes such as cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclopentadiene, cyclooctadiene, cyclododecatriene, etc.; dicycloalkapolyenes such as dicyclopentadiene, tetrahydro indene, etc.; alkylenecycloalkanes such as methylenecyclopropane, methylenecyclopenkune, methylenecyclohexene, etc.; vinylcycloalkenes such as vinylcyclohexene; cyclic terpenes such as α-
Limonene, pinene, camphene, etc. Norbornene compounds such as norbornene, methylnorbornene, ethylnorbornene, vinylnorbornene, ethylidenenorbornene, etc.

The above olefins can also be used as a mixture of two or more.

The hydrogen peroxide used in the present invention may be any conventional hydrogen peroxide, and an aqueous solution having a concentration of 3 to 70% by weight can be used, but it is preferable to use a hydrogen peroxide with a concentration of 20 to 35% because it is easy to handle. preferable. In reacting olefins and hydrogen peroxide, the ratio of the olefins and hydrogen peroxide may be equimolar, but the molar amount of one of the raw materials may be too small or too large. For example, typically 0.1 to 5 moles of hydrogen peroxide can be used per mole of olefin, preferably 0.7 to 2 moles.

The lower limit of the amount of catalyst used per mol of olefin is usually 0,000 mol or more, preferably 0.0001 mol or more, most preferably 0.0005 mol or more,
The upper limit is usually 0.5 mol or less, preferably 0.1 mol or less.

The solvent used is one that is as inert as possible to the reactants (olefins, hydrogen peroxide) and the epoxidized product produced. For example, alcohol (primary alcohol with 1 to 6 carbon atoms)
．． 2. Tertiary monohydric alcohols (such as methanol, ethanol, n- or isopropanol, tertiary butanol, amyl alcohol, cyclohexanol, etc.), polyhydric alcohols (ethylene glycol, propylene glycol, glycerin, etc.), polyhydric alcohols Derivatives (e.g., oligomers of ethylene oxide, propylene oxide, such as diethylene glycol, triethylene glycol, dipropylene glycol; ethers of these oligomers, such as dimethoxyethylene glycol, jetoxyethylene glycol, dimethoxydiethylene glycol, etc.)
, ether (ethyl ether, isopropyl ether,
dioxane, tetrahydrofuran, etc.), esters (alcohols, formic or acetate esters of polyhydric alcohols, such as ethyl acetate), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl propyl ketone, cyclohexanone, acetylacetone, etc.), nitrogen compounds (dimethylformamide, nitromethane, etc.), phosphorus compounds (phosphate esters, such as triethyl-, trioctyl-, diethylhexyl-esters, etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride, ethylene dichloride, etc.), aliphatic carbonization Hydrogen (n-hexane, etc.), aromatic hydrocarbons (hensen, 1-luene, xylene, etc.), alicyclic hydrocarbons (cyclohexane, etc.), and the like can be used. Among these, preferred solvents are non-hydrophilic solvents such as halogenated hydrocarbons, aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons, and particularly preferred solvents are halogenated hydrocarbons.

The reaction can be carried out by charging an olefin, a solvent, and a catalyst, raising the temperature, dropping hydrogen peroxide solution at the reaction temperature, and allowing the reaction and aging to proceed. The reaction temperature is usually 0 to 120°C, preferably 20 to 80°C. When the reaction temperature is higher than 120°C, self-decomposition of hydrogen peroxide is significant, and when the reaction temperature is lower than 0°C, the reaction is extremely slow. The reaction time can be varied depending on the catalyst, solvent, and olefin used, but is usually from several minutes to 50 hours. After the reaction, extraction or/
Then, the catalyst, water, and solvent are removed by distillation or the like to obtain the desired olefin epoxide.

The olefin epoxide obtained by the present invention is useful as a raw material for epoxy resins and as an intermediate for organic chemicals, medicines, agricultural chemicals, and the like.

<Example> Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to this.

Example 1 (Preparation of catalyst salt) 70 ml of an aqueous solution containing 5.31 mmol of cetylpyridinium chloride was placed in a flask with a volume of 200 ml, and then approximately 1.7 mmol of phosphotungstic acid dissolved in 10 ml of water was added to give 50 ml of aqueous solution. After stirring and reacting at ℃ for 2 hours, a milky white solid gradually formed. The aqueous solution was centrifuged, washed with water, and purified by vacuum drying to obtain a white solid in a yield of 70%.

Based on infrared absorption spectrum and elemental analysis, this substance is tricetylpyridinium-12-kungestric acid C.
I).

(Produced by Activated Catalyst Salt 1!) In a flask with a volume of 100 ml, 5 g of tricetylpyridinium-12-tungstophosphoric acid prepared in Example 1 and 3
50 ml of 5% hydrogen peroxide solution was added, and the mixture was vigorously stirred at 50° C. for 5 hours. After the reaction, centrifugation, water washing, and vacuum drying yield a white solid activated catalyst, namely tricetylpyridinium-12-tungstophosphoric acid peroxide (II
)was gotten.

(Example of epoxidation reaction) (1) In a flask with a volume of 50 m1, 6.5 1-octene
mmol, chloroform 151 and (1) 0.0
After adding 26 mmol, 9.8 mmol of 35% hydrogen peroxide solution was gradually added while stirring, and the mixture was reacted at a temperature of 60° C. for a predetermined time. After the reaction, the aqueous layer was separated by centrifugation to obtain a chloroform layer. Further, remove the aqueous layer with 25 ml of chloroform.
The mixture was extracted and separated to obtain a chloroform layer.

After combining both of the obtained chloroform layers, this was analyzed by gas chromatography, and the 1-
The octene epoxidation rate (conversion rate x selectivity) was determined.

The results are shown in Figure 1.

(2) The experiment was carried out in the same manner as in (11) except that (If) was used instead of catalyst (1). The results are shown in FIG.

(3) As a comparative example, the experiment was carried out in the same manner as in (11) except that 0.026 mmol of tricetylpyridinium-12-molybdophosphoric acid (I[[) was used instead of 0.026 mmol of catalyst (+). The results are shown in Figure 1.

In addition, in FIG. 1, ◯, △, and X marks are as follows.

O: The results of epoxidation reaction example (2) [catalyst: activated tricetylpyridinium-12-tungstophosphoric acid ([)] are shown.

Δ: Shows the results of eboxidation reaction example (1) [catalyst nitricetylpyridinium-12-tungstophosphoric acid (I)].

×: Comparative example, shows the results of epoxy reaction example (3) (catalyst nitricetylpyridinium-12-molybdophosphoric acid (■)).

As is clear from FIG. 1, the reaction using the catalyst (1) of the present invention (Δ mark) has a higher epoxidation rate than the comparative example (x mark) using the molybdenum catalyst (III). It can also be seen that the reaction time is shortened.

In addition, the reaction (marked with ◯) using the catalyst (ff) of the present invention activated by hydrogen peroxide treatment has a higher epoxidation rate and a shorter reaction time.

Example 2 The experiment was conducted in the same manner as in Example 1 (1) except that dicyclopentadiene was used as the olefin. The reaction conditions (temperature, time) and the results obtained are shown in Table 1.

Table 1 As is clear from Table 1, the selectivity of the product to epoxide was 100% and no polyol was produced as a by-product.

Example 3 (Preparation of activated catalyst salt) 40 ml of a 35% aqueous hydrogen peroxide solution containing 3 mmol of cetylpyridinium chloride and 10 ml of a 35% aqueous hydrogen peroxide solution containing 1 mmol of phosphotungstic acid were prepared in advance, and the volumes were reduced. The mixture was gradually added to a 100 ml flask and reacted at 40°C for 2 hours, producing a white precipitate. A white solid was obtained in a yield of 80% by vacuum drying after removing the dissolved bone and excess hydrogen peroxide by suction filtration. 540 cm- and 57 in the infrared absorption spectrum
Since it showed a remarkable characteristic absorption near 0 cm-, it was found to be a peroxo-type peroxide (TV) of tricetylpyridinium-12-kungestric acid (Fig. 2, side 8).

(Example of epoxidation reaction) (1) In a flask with a volume of 50 m1: cyclohexene 6
5 mmol, 15 ml of chloroform and (IV)
After adding 0.026 mmol, 9.8 mmol of 35% hydrogen peroxide solution was gradually added under stirring for 11 minutes, and the mixture was reacted at a temperature of 60° C. for 5 hours. The epoxidation rate of cyclohexene obtained by performing the same post-treatment as in the experiment in Example 1 (1) was 95
%Met.

(2) As a comparative example, a catalyst (TV > 0.026 mi°
Cetylpyridinium chloride 0.0 instead of rimole
The experiment was carried out in the same manner as in (1) except that a mixed catalyst (V) of 78 mmol and 026 mmol of phosphotungsten MO was used. The epoxidation rate after 5 hours of reaction was 12%, and even after 24 hours of reaction, the epoxidation rate was 15%.
I stayed there.

<Effects of the Invention> In the conventional reaction of producing epoxides from olefins using hydrogen peroxide, it is necessary to use highly concentrated hydrogen peroxide in order to reduce the amount of water introduced with hydrogen peroxide, making it difficult to handle. Met. In addition, the olefin conversion rate and epoxide selectivity were poor, and of course the epoxidation rate (conversion rate x selectivity) was also unsatisfactory.

However, when the catalyst of the present invention consisting of a salt of a quaternary ammonium ion and a tungsten heteropolyacid ion or a peroxide thereof is used in an olefin epoxidation reaction,
A relatively low concentration hydrogen peroxide solution that is easy to handle can be used. Moreover, there is no need to specifically remove water introduced together with hydrogen peroxide and water produced by the reaction, and the reaction can proceed as is. Furthermore, compared to the above-mentioned conventional methods, the present invention can considerably increase the conversion rate of olefins, the selectivity to eboxide, and the rate of epoxidation.

[Brief explanation of drawings]

FIG. 1 shows the results of Example 1. FIG. 2 is a diagram plotting the epoxidation rate (%, conversion rate x selector) of -octene against reaction time for each catalyst. FIG. 2 is an infrared absorption graph of peroxo type peroxide of tricetylpyridinium-12-tungstophosphoric acid.

Claims (1)

[Claims] 1. General formula R_4N^+・X^- (1) [In the formula, R
At least one of R is an alkyl group having 8 to 18 carbon atoms, and the other R is an alkyl group having 1 to 18 carbon atoms or a benzyl group. X^- is an anionic counterion. ] Salts of quaternary ammonium ions derived from quaternary ammonium compounds or nitrogen ring-containing quaternary ammonium compounds with heteropolyacid ions of Group V elements of the periodic table and tungsten, or their peroxides A catalyst for epoxidizing olefins, characterized by comprising: 2. The catalyst according to claim 1, wherein the quaternary ammonium ion is derived from a nitrogen ring-containing quaternary ammonium compound. 3. The catalyst according to claim 2, wherein the nitrogen ring is a pyridine ring. 4. The catalyst according to any one of claims 1 to 3, wherein the heteropolyacid ion is a phosphonotungstate ion. 5. The catalyst according to any one of claims 1 to 4, wherein the peroxide is of the hydroperoxy type or peroxo type. 6. General formula R^4N^+・X^-…………………………(1) [In the formula, R
At least one of R is an alkyl group having 8 to 18 carbon atoms, and the other R is an alkyl group having 1 to 18 carbon atoms or a benzyl group. X^- is an anionic counterion. ] Using a catalyst consisting of a salt of a quaternary ammonium ion derived from a quaternary ammonium compound or a nitrogen ring-containing quaternary ammonium compound and a heteropolyacid ion of a group V element of the periodic table and tungsten. A method for using a catalyst for epoxidizing olefins, which comprises reacting olefins and hydrogen peroxide at a temperature of 0 to 120 degrees in a solvent. 7.Olefins have general formulas▲Mathematical formulas, chemical formulas, tables, etc.▼……………………(2) (In the formulas, R_1', R_2', R_3' and R_4'
is a monovalent hydrocarbon group which may have a double bond; R_1' and R_2' or R_3' and R_4
' taken together represent a divalent hydrocarbon group which may have a double bond; or R_1' and R_3'
or R_2' and R_4' together represent a divalent hydrocarbon group which may have a double bond. 8. The method of use according to claim 6 or 7, wherein the catalyst is subjected to hydrogen peroxide treatment in advance and subjected to the reaction. 9. Claims 6 to 9, wherein the solvent is a non-hydrophilic solvent.
Use as described in any of Section 8. 10. The method according to claim 9, wherein the non-hydrophilic solvent is a halogenated hydrocarbon.