JPH023790B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing olefin oxide,
Specifically, the present invention is a method characterized by using an antimony compound as a catalyst in epoxidizing an olefin with hydrogen peroxide. Olefin oxides are used in a variety of applications in the chemical industry, including as intermediate raw materials for urethanes, glycol solvents, coating compositions, molding materials, surfactants, plasticizers, and many other products. It has been used and manufactured by various methods. The following three methods are conventionally well known for producing olefin oxide by epoxidizing olefin. One of them is called the chlorohydrin method, in which olefin is reacted with chlorine or sodium hypochlorite in an alkaline medium to produce chlorohydrin, and epoxide is obtained by dehydrochlorination of the chlorohydrin. Another method is to air oxidize hydrocarbons to obtain hydroperoxides, which then epoxidize olefins in the presence of a catalyst. This method has the disadvantage that a large amount of alcohol produced from hydroperoxide is produced as a by-product. Another method is to oxidize acetaldehyde in air to obtain peracetic acid, thereby epoxidizing the olefin. This method has the disadvantage that a large amount of by-product acetic acid must be recovered. In recent years, a method for epoxidizing olefins using hydrogen peroxide has been proposed, and many reports have been published on methods for producing olefin oxides by reacting olefins with hydrogen peroxide in an organic solvent in the presence of various epoxidation catalysts. being done. The epoxidation catalysts used in these reports are mainly molybdenum- and tundaste-based catalysts. Although these catalysts have high activity, they have the disadvantage of being very easy to decompose hydrogen peroxide. Boron and arsenic catalysts have also been proposed as catalysts that have the ability to epoxidize hydrogen peroxide without significantly decomposing it. However, boron-based catalysts have low activity and
Although arsenic-based catalysts have relatively high activity, they have the problem of strong toxicity, and are not yet suitable for industrialization. Furthermore, a method of epoxidation using a catalyst consisting of an antimony compound and molybdenum or tungsten has also been proposed. However, in this case, although the catalytic activity is relatively high, the selectivity and hydrogen peroxide reaction efficiency are poor. In view of the above points, the present inventors have conducted various studies on the epoxidation of olefins, and as a result, have discovered a highly active and highly selective catalyst, and have accomplished the present invention. The present invention provides a method for producing olefin oxide, in which olefin and hydrogen peroxide are contacted in a liquid phase in the presence of an antimony compound catalyst, and olefin is directly epoxidized with hydrogen peroxide. An object of the present invention is to provide a novel catalyst that has high catalytic activity and can efficiently epoxidize olefins with high selectivity. Further objects and advantages will become apparent from the description below. In the present invention, the catalyst that has high catalytic activity and efficiently produces olefin oxide with high selectivity is an antimony compound described below. The antimony compound used as a catalyst in the present invention is substantially free of molybdenum, tungsten, or other metals such as vanadium. According to the present invention, the olefin that can be epoxidized is an olefinic unsaturated hydrocarbon compound, and is a substituted or unsubstituted linear or cyclic olefin. The olefin usually contains 2 to 20 carbon atoms and has one or more double bonds. The olefin can be represented by the following formula. That is, (In the formula, R ₁ and R ₂ are hydrogen or a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms) (In the formula, R ₁ and R ₂ are the same as defined above, n
is 0 or 1 to 10) Also, (In the formula, R ₁ and R ₂ are alkyl groups having 1 to 4 carbon atoms, and R ₃ and R ₄ are each hydrogen or a substituted or unsubstituted linear or branched chain having 1 to 10 carbon atoms. The cyclic olefin has up to 10 carbon atoms and one unsaturated bond, and the cyclic olefin has 1 to 10 carbon atoms.
is a compound substituted with one or two alkyl groups having carbon atoms. In addition, R ₁ R ₂ C=CR ₃ R ₄ (wherein R ₁ and R ₃ are linear or branched alkyl groups having 1 to 10 carbon atoms, R ₂ and R ₄ are hydrogen or
Same as R ₁ and R ₃ ) Furthermore,

[Formula] or

[Formula] (wherein R is a monovalent alkenyl group having 2 to 10 carbon atoms, and R' is a divalent alkenyl group having 2 to 5 carbon atoms). Typical specific examples of olefins represented by the above formula include propylene, butene,
Aliphatic olefins such as isobutene and hexene;
Cycloolefins such as cyclopentene, cyclohexene, cyclooctene; alkyl and alkenylcycloolefins such as methylcyclohexene, methylcyclopentene, vinylcyclohexene; alkenyl aromatic hydrocarbons such as styrene, vinyltoluene, methylstyrene; 1,5-cyclooctadiene, Conjugated or non-conjugated diolefins such as 1,5,9-cyclodecatriene, 1,4-cyclohexadiene, butadiene; Olefin alcohols such as allyl alcohol, methylvinylcarbinol, cyclohexenol; allyl chloride, allyl bromide halogenated olefins such as;
Examples include acrylic acid, methacrylic acid, crotonic acid, oleic acid, allyl acetate, and unsaturated fatty acids and esters thereof such as soybean oil and linseed oil. The antimony compound catalyst in the present invention is an inorganic antimony compound, an organic antimony compound, or a mixture thereof. The inorganic antimony compounds include antimony oxides, oxyacids, salts of oxyacids, or esters, halides, oxyhalides, and sulfides. Specific examples of these include, for example:
Sb ₂ O ₃ , Sb ₂ O ₄ , Sb ₂ O ₅ , Sb(OH) ₃ , H[Sb
(OH) ₆ ], NaSbO ₂ , KSbO ₂ , K ₃ SbO ₄ , SbC ₃ ,
Examples include SbBr ₃ , Sb ₄ O ₅ C, SbOC, Sb ₂ S ₃ and Sb ₂ O ₅ . When the valence of antimony is +3, the organic antimony compound is a compound represented by the general formula RSbXY. (wherein, R is an alkyl group, an aralkyl group, an aryl group, X or Y
is hydrogen, alkyl group, aralkyl group, aryl group, halogen, hydroxyl group, alkoxy group,
Acyloxy group, −SbR′R″, −OSbR′R″, −NR′R″,
−PO(OR′) ₂ , −OSiR′R″R, −S, and (R′,
R'', R is an alkyl group, an aralkyl group, or an aryl group)) In addition, the formula (RSb=O)n (wherein R is the same as above, n indicates the number of repeating units in the polymer structure) Stibonic acid anhydride, represented by the formula

Mention heterocyclic derivatives such as stiborane represented by the formula [formula] (wherein R is the same as above) or antimono derivatives represented by the formula (RSb=) ₂ (wherein R is the same as above) Can be done. Also, if the valence of antimony is +5,
General formula R′R″RSbXY, R′R″Sb (=O)X, R
Examples include compounds represented by Sb(=O)XY.
₍ In the _formula , R', R _{' '} , _R , ，
( _CH3 ) _{2SbC ,} ( _CH3 ) _4SbC , ( _C6H5 ) _{2SbC2 ,}
(C ₂ H ₅ ) ₂ SbOCH ₃ , (C ₆ H ₅ ) ₄ SbOH, (C ₆ H ₅ ) ₃ Sb
(OH) ₂ , (C ₆ H ₅ ) ₂ Sb(OCH ₃ ) ₂ ,

【formula】

[Formula] (CH ₃ ) ₂ Sb-Sb (CH ₃ ) ₂ , (C ₆ H ₅ ) ₂ Sb-O-Sb (C ₆ H ₅ ) ₂ ,

[Formula] (CH ₃ ) ₂ Sb・N (CH ₃ ) ₂ ,

【formula】

[Formula] (CH ₃ ) ₂ Sb・OSi (CH ₃ ) ₂ ,

[Formula] CH ₃ Sb (SC ₆ H ₅ ) ₂ , (C ₆ H ₅ ) ₃ Sb=S, (C ₆ H ₅ ) ₃ Sb=O,

【formula】

【formula】

【formula】

[Formula] C ₆ H ₅ SbO ₃ H ₂ ,

【formula】

【formula】

【formula】

【formula】

【formula】

Examples include antimony derivatives such as (C ₆ H ₅ ) ₃ Sb, (C ₆ H ₅ ·Sb)n, and (C ₆ H ₅ Sb=O)n. Among the above antimony compounds, preferred are
A compound represented by R′R″Sb(=O)X, RSb(=O)XY, particularly preferably R′R″Sb(=
O) OH, R Sb (=O) (OH) ₂ Organic stibonic acid, organic stibic acid. Specifically, for example, methylstivonic acid

[Formula] Hue Nilstivonic acid

[Formula] (o, m, and p-)methylphenylstibonic acid

[Formula] (o, m, and p-)methoxyphenylstibonic acid

[Formula] (o, m, and p -)carboxyphenylstibonic acid

[Formula] (o, m, and p -)chlorophenylstibonic acid

[Formula] (o, m, and p-)nitrophenylstibonic acid

[Formula] Dimethylstibic acid (

[Formula] Diethylstivic acid (

[Formula] Diphenylstibic acid

Examples include [Formula]. The antimony compound used as a catalyst in the present invention is preferably soluble or partially soluble. From this point of view, organic antimony compounds are preferable among the above antimony compounds. However, poorly soluble or insoluble ones can also be used. Also, conventional techniques are used to effect sufficient contact of the reactants with the catalyst. In the present invention, it is preferable to carry out the reaction using a reaction catalyst, and the reaction solvent used is one that can maintain the reaction system in a liquid phase and is inert to the reactants and the catalyst. Generally, the reaction solvent can be arbitrarily selected from alcohols, esters, ethers, saturated hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, organic carboxylic acids, and the like.
These solvents include, for example, n-propanol,
iso-propanol, n-butanol, iso-butanol, t-butanol, aluminum alcohol, cyclohexanol, ethylene glycol, propylene glycol, ethyl ether, isopropyl ether, dioxane, tetrahydrofuran, ethylene oxide, methyl acetate, ethyl acetate, enyl acetate, cyclohexyl acetate, n-pentane, cyclohexane, cyclohexene, dichloromethane, dichloroethane,
Examples include dichloropropane, tetrachloroethane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, acetic acid, propionic acid, butyric acid, isobutyric acid, and benzoic acid. Among these, particularly preferred are organic carboxylic acids or mixtures of organic carboxylic acids and other solvents. For example, to name a few specific examples, acetic acid, propionic acid, butyric acid, isobutyric acid, acetic acid-benzene, acetic acid-dichloromethane, acetic acid-dichloroethane, acetic acid-dichloropropane, propionic acid-benzene, propionic acid-cyclohexane, propionic acid -dichloromethane, propionic acid-dichloroethane, propionic acid-dichloropropane, propionic acid-
t-Butanol, propionic acid-methyl acetate, propionic acid-dioxane, m-chlorobenzoic acid-
Dioxane etc. Whether the solvent used is an organic carboxylic acid alone, a mixture of an organic carboxylic acid and another solvent, or the mixing ratio of the solvents depends on the type of olefin used in the reaction, the type of epoxide produced, Furthermore, it can be determined as appropriate in consideration of operational convenience and economic efficiency. For example, if the produced epoxidized product is easily ring-opened by an organic carboxylic acid, the ring-opening reaction can be avoided by lowering the proportion of the organic carboxylic acid in the solvent. When an organic carboxylic acid is used as a solvent, the amount of the organic carboxylic acid used is preferably 1% or more, preferably 5% or more of the total liquid in the reaction system. In the present invention, the concentration of hydrogen peroxide used in the reaction is preferably such that the reactants, excluding the catalyst, remain as homogeneous as possible under the reaction conditions.
Therefore, usually about 30 to 90% (by weight) is used. However, since some target olefins are susceptible to ring opening due to moisture in the reaction system, a higher concentration of hydrogen peroxide may be required. In such cases, during the reaction, water may be removed from the reaction system by azeotropy with the reaction solvent, or nitrogen, argon,
A method in which an inert gas such as helium is continuously introduced into the reactor and the reaction is carried out while removing moisture from the system, or a method in which a dehydrating agent such as anhydrous sodium sulfate or anhydrous magnesium sulfate is added to remove moisture. is also a desirable method. The reaction temperature is selected over a wide range depending on the activity of the catalyst, the reactivity of the target olefin, the ease of ring opening of the epoxy compound to be produced, and the type of solvent selected, but is generally about 0°C to about 0°C. The temperature is in the range of 150°C, preferably in the range of 40 to 120°C. Furthermore, the reaction can be carried out under conditions that allow the reaction system to maintain a liquid phase, either below atmospheric pressure or under elevated pressure. Usually 1~
A pressure of 150 atmospheres is desirable. The catalyst concentration used in the present invention can be selected over a fairly wide range, and the range depends on the type of antimony compound used as a catalyst, the type of target olefin, reactivity, etc. to achieve a preferable catalytic activity. The concentration is selected as appropriate. Therefore, the amount of catalyst used is the amount necessary for catalytic activation, and is generally 1/2000 to 1/2 mole, preferably 1/400 mole per mole of hydrogen peroxide.
~1/5 mole. There is also no particular limit to the concentration of olefin in the reaction system, but generally the molar ratio to hydrogen peroxide in the reaction system is 1/30 to 30/
It is within the range of 1. In addition, raw material hydrogen peroxide is a relatively unstable substance, and if heavy metals etc. are mixed in, it decomposes and disappears during the reaction.
It is desirable to add a stabilizer such as a chelating agent since this tends to lead to a decrease in yield. Examples of the chelating agent include ethylenediaminetetraacetic acid, diethylenetetraminepentaacetic acid, cyclohexanediaminetetraacetic acid, aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1
- diphosphonic acid (e.g. trade name Dequest
2010, manufactured by Monsanto), ethylenediaminetetramethylenephosphonic acid (e.g., trade name,
Examples include Dequest 2041 (manufactured by Monsanto). As described above, the method of the present invention is a method that can epoxidize olefins with hydrogen peroxide in high yield and high selectivity by using an antimony compound as a catalyst, and is extremely advantageous industrially. It's a method. Example 1 In a SUS316 autoclave with an internal volume of 300 c.c., 25 ml of dichloromethane and t-butanol were added as solvents.
10 ml, propionic acid 5 ml, p-methoxyphenylstibonic acid 0.5 g as a catalyst were added, and then 90% hydrogen peroxide 0.113 mol and propylene were added.
0.40 mol was added and reacted at 70°C for 60 minutes. The amount of unreacted hydrogen peroxide was 0.025 mol, and the amount of propylene oxide produced was 0.074 mol when analyzed by gas chromatography. This had a selectivity of 84% and a conversion rate of 77% based on hydrogen peroxide. Example 2 Dioxane 15 was added as a solvent to a four-bottle flask with an internal volume of 100 c.c. equipped with a water separator and a reflux condenser.
ml, acetic acid 10ml, phenylstibonic acid as catalyst
Add 0.5 g, then 40 ml of cyclohexene and reflux. 60% hydrogen peroxide with stirring
0.104 mol was added dropwise over 30 minutes. After dripping
The reaction was carried out under reflux for 30 minutes. Unreacted hydrogen peroxide is
It was 0.011 mole. Further, when the produced cyclohexene oxide was analyzed by gas chromatography, it was found to be 0.086 mol. This has a selectivity of 92% and a conversion rate of 89% based on hydrogen peroxide.
It was hot. Example 3 In a SUS316 autoclave with an internal volume of 300 c.c., 25 ml of benzene, 15 ml of t-butanol, and
p-chlorophenylstibonic acid as catalyst 0.5
Next, 0.112 mol of 90% hydrogen peroxide and 0.40 mol of propylene were added, and the mixture was reacted at 70°C for 60 minutes. The amount of unreacted hydrogen peroxide was 0.088 mol, and the amount of propylene oxide produced was 0.021 mol when analyzed by gas chromatography. This has a selectivity of 87% and a conversion rate of 21% based on hydrogen peroxide.
It was %. Example 4 20 ml of propionic acid as a solvent, 20 ml of dichloromethane as a solvent, and 1.0 g of phenylstibonic acid as a catalyst were added to a 200 c.c. glass autoclave.
Next, add 20ml of allyl chloride, stabilizer (Dequest
2041 (manufactured by Monsanto) and 0.098 mol of 90% hydrogen peroxide were added and reacted at 110° C. for 60 minutes with stirring. Unreacted hydrogen peroxide in the reaction solution is
It was 0.007 mol. Further, when the product in the reaction solution was analyzed by gas chromatography, it was found that 0.076 mol of epichlorohydrin was produced. This has a selectivity of 84% and a conversion rate of 93% based on hydrogen peroxide.
It was hot. Example 5 45 ml of propionic acid as a solvent and antimony trichloride as a catalyst in a four-necked flask with a reflux condenser.
0.5 g was added, and then 20 ml of allyl chloride was added and the mixture was refluxed with stirring. There 60% hydrogen peroxide
0.100 mol was added and the reaction was further carried out under reflux for 120 minutes. The amount of unreacted hydrogen peroxide was 0.022 mol, and the amount of epichlorohydrin produced was 0.060 mol when analyzed by gas chromatography. This has a selectivity of 76% and a conversion rate based on hydrogen peroxide.
It was 78%. Example 6 90% hydrogen peroxide 0.105 under the same conditions as Example 5
Using moles, epichlorohydrin selectivity was 75% and conversion was 94% based on hydrogen peroxide.
It was hot. Example 7 Under the same conditions as Example 5, using 0.5 g of triphenylantimony and 0.104 mol of 90% hydrogen peroxide as a catalyst, the selectivity of epichlorohydrin was 84% and the conversion rate was 88% based on hydrogen peroxide.
It was hot. Example 8 Propionic acid was added as a solvent to a 4-neck flask with an internal volume of 100 c.c. equipped with a water separator and a reflux condenser.
ml, 20 ml of dichloroethane, 1.0 g of diphenylstibic acid as a catalyst, and then allyl chloride.
30 ml was added and refluxed. While stirring, 0.103 mol of 60% hydrogen peroxide was added dropwise over 30 minutes. After dropping, the reaction was carried out for 120 minutes. During the reaction, water in the reaction system was removed by refluxing the reaction solution. The amount of unreacted hydrogen peroxide was 0.008 mol, and the amount of epirohydrin produced was 0.088 mol. This had a selectivity of 93% and a conversion rate of 92% based on hydrogen peroxide.

Claims (1)

[Claims] 1. A method for producing olefin oxide, which comprises reacting olefin and hydrogen peroxide in a liquid phase in the presence of an antimony compound catalyst. 2. The method according to claim 1, wherein the reaction is carried out in the presence of an organic solvent. 3. The method according to claim 1 or 2, wherein the organic solvent is at least one selected from alcohols, esters, ethers, saturated hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, and organic carboxylic acids. . 4. The method according to claim 1 or 2, wherein the organic solvent is an organic carboxylic acid. 5. Claim 1, wherein the antimony compound catalyst is at least one selected from antimony oxides, oxyacids, oxyacid salts, oxyacid esters, halides, oxyhalides, and sulfides; The method described in paragraph 2 or 3. 6 The antimony compound catalyst has the formula RSbXY [wherein R is an alkyl group, an aralkyl group, an aryl group, and X or Y is hydrogen, an alkyl group, an aralkyl group, an aryl group, a halogen, a hydroxyl group, an alkoxy group, an acyloxy group, - SbR′R″,−
OSbR′R″, −NR′R″, −PO(OR′) ₂ , −OSiR′R″R
, -S, (R′, R″, R is an alkyl group,
aralkyl group or aryl group)], R′R″R−
SbXY, R′R″Sb(=O)X, RSb(=O)XY
[In the formula, R', R'', R and XY are the same as above], (RSbO)n (R is the same as above, n
is at least one type selected from the number of repeating units in the polymer structure,
The method described in paragraph 2 or 3. 7 The antimony compound catalyst has the formula R′R″R
SbXY, R′R″RSb(O)X, RSb(O)XY
(wherein R′, R″, R and XY are the same as above) The method according to claim 1, 2 or 3, wherein the antimony compound catalyst is at least one selected from Formula R′R″Sb(O)
OH or RSb(O)(OH) ₂ (R', R'', R are the same as above) according to claim 1, 2 or 3, which is one of the compounds represented by Method. 9. The method according to claim 1 or 2, wherein the antimony compound catalyst is used in an amount of 1/2000 to 1/2 mol per 1 mol of hydrogen peroxide. 10. The molar ratio of olefin to hydrogen peroxide is 1. /30
30/1. The method according to claim 1 or 2, wherein