JPS5892673A - Preparation of olefine oxide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing olefin oxide, and more specifically, the present invention relates to a method for epoxidizing an olefin with hydrogen peroxide, which is characterized by using an organotin compound as a catalyst. It is.

Olefin oxides are used in a variety of applications in the chemical industry, including as intermediate raw materials for urethanes, Glyfur 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 as methods for producing olefin oxides by epoxidizing olefins. The method is called the chlorohydrin method.
This is a method in which chlorohydrin is produced by reacting an olefin with chlorine or sodium hypochlorite in an alkaline medium, and epoxide is obtained by dehydrochlorination of this chlorohydrin. Another method involves air oxidation of olefin to obtain hydroperoxide, which has the disadvantage of producing olefin as a by-product in the presence of a catalyst. 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 numerous reports have been published on methods for producing olefin oxides by reacting olefins with hydrogen peroxide in organic solvents in the presence of various epoxidation catalysts. being done.

The epoxidation catalysts used in these reports are mainly molybdenum and tungsten based catalysts. Although these catalysts have high activity, they have the drawback 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 arsenic-based catalysts have relatively high activity but are highly toxic. Alternatively, a method of epoxidizing using a catalyst consisting of 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 conducted various studies on the epoxidation of olefins, and as a result, discovered a highly active and highly selective catalyst.

This has led to the present invention.

The present invention provides a method for producing olefin oxide, in which an olefin and hydrogen peroxide are contacted in a liquid phase in the presence of a tin compound catalyst to directly epoxidize the olefin 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 excellent 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 organic tin compound described below.1 The organic tin compound used as a catalyst in the present invention consists essentially of molybdenum, tungsten, , or do not contain other metals such as vanadium.

According to the invention, the olefins that can be epoxidized are olefinically unsaturated hydrocarbon compounds, which are substituted or unsubstituted linear or cyclic solenoids. The olefin usually contains 2-20 carbon atoms and has - or more double bonds. The olefin can be represented by the following formula. That is, L C=CH (wherein R1 and R1 are hydrogen or a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms).

(In the formula, Rs and R1 are the same as defined above, n is 0 or 1 to 10), and (In the formula, R+ and the button are a furkyl group having 1 to 4 carbon atoms, and Rs s R4 is each hydrogen or a substituted or unsubstituted linear or branched furkyl group having 1 to 10 carbon atoms) The cyclic olefin has 1 to 10 carbon atoms in its cyclic portion.
up to 1 carbon atoms and 1 dissolvable bond, 1 to 1
It is a compound substituted with one or two furkyl groups having o carbon atoms.

In addition, fL t R* C= CRs R4 (wherein, B1 and Rs are linear or branched alkyl groups having 1 to 1 o carbon atoms, R2 and R4 are hydrogen or R1 and R
1) Furthermore, (wherein, R is a monovalent alkenyl group having 2 to 1 carbon atoms, and Br is a divalent alkenyl group having 2 to 5 carbon atoms).

Typical specific examples of the olefin represented by the above formula include aliphatic olefins such as propylene, butene, inbutene, and hexene; cyclopentene; cycloolefins such as cyclohexene and cyclooctene;
Alkyl and alkenylcycloolefins such as methylcyclohexene, methylcyclopentene, vinylcyclohexene; alkenyl aromatic hydrocarbons such as styrene, vinyltoluene, methylstyrene; 1,5-cyclooctadiene, 1,5,9-cyclosigma decatrie/, 1.4-
Conjugated or unconjugated diolefins such as cyclohexadiene and butadiene; Olefinic alcohols such as allyl alcohol, methylvinyl carbinol, and cyclohexenol; Halogenated olefins such as allyl chloride and allyl bromide; acrylic acid, methacrylic acid, and croton. Examples include oleic acid, allyl acetate, unsaturated fatty acids such as soybean oil, linseed oil, and esters thereof.

The organotin compound catalyst in the present invention has the general formula
R85XYZ, R8n (=0) hydroxyl group, alkoxy group,
Acy-oxy group, -S n R'R"R"', -os
na/a'I n1rl, -Na'r.

-08i R'R'R", -8-(R', R#, IL'
# is an alkyl group, an aralkyl group, or an aryl group)].

Specific examples of the above organic tin compounds include (CaHi)a8ws, (Cans)a8a, CH
18nCjs, C4Hs8n04m, (Ca H*)
*8a Cj m, (CsHs)18nCjs,
(C4Hs)sSnCj.

(CsHs)s8nci, (CaHe)t8n (O
CCHs ) *, 1 (C * Hm ) s 8 n OCCH@, (Cs
Hs ) s 8 a H.

C4Hs8n(0)OH-(CsHs), 5nOC*H
s.

(04H meeting), SnO, (C@us)sSn8n(Ca
Hi)s, (C@Hs), Sn, (Cabs)s8n
0-8n(C@Hs>5-(CHi)s8n N(
C, Ha)*, (CaHe)s8n 0-8 Todoroki (Ca
Examples include organic tin derivatives such as He)m and ((CaHe)m8n)*8.

Among the above organic tin compounds, preferred ones are R8n (=
It is a compound represented by 0 ) Specifically, for example, -methylstannonic acid (CHs8n), \OH ethylstannonic acid (Cm Hs8n"0), O butylstannonic acid (04""O)l), octylstannonic acid (Cm H2t 8<u), phenylstannonic acid<Q-an?:H).

I rioo phenylstanone ra <'Q-sn? :
H>, etc.

The organotin compound used as a catalyst in the present invention is preferably soluble or partially soluble. However, those that are releasable or insoluble can also be used later. 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 solvent, which can maintain the reaction system in a liquid phase and is inert to the reactants and the catalyst. Generally, the reaction solution m can be arbitrarily selected from alcohols, esters, ethers, saturated hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, organic carboxylic acids, and the like. These solvents include even 4f, n-furopanol, k@o-furo t<7i, o-butanol, 1io-butanol, t-butanol, amyl alcohol, cyclohexanol, ethyl acetate,
Propylene glyconyl, ethyl ether, isopropyl ether, dioxane, tetrahydrofuran, ethylene oxide, methyl acetate, ethyl acetate, phenyl 7-acetate, cyclohexyl acetate, aL' monopentane, cyclohexane, cyclohexene.

Examples include dichloromethane, dichloroethane, dichloropropane, detracoolethane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, acetic acid, propio/acid, butyric acid, inbutyric acid, benzoic acid, and the like. Particularly preferred among these are organic carboxylic acids or mixtures of organic carboxylic acids and other solvents, for example, acetic acid, propionic acid, butyric acid, isobutyric acid, acetic acid-benzene, acetic acid-benzene, and acetic acid-benzene. dichloromethane,
Acetic acid-dichloroethane, acetic acid-dichloropropane, propionic acid-benzene, propionic acid-cyclohexane,
Propionic acid-dichloromethane, propionic acid-dichloroethane, propionic acid-dichloromethane, propionic acid-1-butano-7, propionic acid-methyl acetate, propionic acid-dioxane, m-chlorobenzoic acid-
It is dioxane. Whether the solvent used is an organic carboxylic acid alone or 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 and the type of epoxidized proboscis formed. In addition, laws will be enacted as appropriate in consideration of operational convenience and economic efficiency. For example, if the generated epoxy compound is likely to be 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 in combination as a solvent, the amount of the organic carboxylic acid used is preferably 1% or more, particularly preferably 5% or more, of the total liquid phase of 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 5
About 0 to 90% (by weight) is used. but,
Depending on the target olefin, some may be easily ring-opened by moisture in the reaction system, so a more concentrated 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 an inert gas such as nitrogen, argon, or helium may be continuously introduced into the reactor. It is also desirable to carry out the reaction while removing moisture from the system, or to remove moisture by adding a dehydrating agent such as anhydrous sodium sulfate or anhydrous magnesium sulfate.

The reaction temperature can be selected over a wide range depending on the activity of the catalyst, the reactivity of the target olefin, the ease with which the epoxy compound is formed, and the type of solvent selected, but it is generally about 150'C to about 150'C. range, preferably 4o to 1
The reaction temperature is in the range of 20"C. The reaction can be carried out under conditions where the reaction system can maintain a liquid phase, either below atmospheric pressure or under elevated pressure. Usually, a pressure of 1 to 150 atmospheres is desirable.

The concentration of the catalyst used in the present invention can be selected within a fairly wide range, and the range will vary depending on the type of organotin compound used as the catalyst, the type 1 reactivity of the target olefin, etc. The water concentration is selected appropriately. Therefore, the amount of catalyst used is the amount necessary for catalytically active action, and is generally per mole of hydrogen peroxide. . . ~4 mol, preferably '/a
oo ~ 115 moles. In addition, the concentration of olefin in the reaction system is also a special number [although there is no limit, generally the molar ratio to the hydrogen peroxide concentration in the reaction system is 14 to 50y,
is within the range of

Note that raw material hydrogen peroxide is a relatively unstable substance, and if it is contaminated with heavy metals, it decomposes and disappears during the reaction, which tends to lead to a decrease in yield, so it is desirable to add a stabilizer such as a chelating agent. be.

As described above, the method of the present invention is a method that can perform epoxidation of olefins with hydrogen peroxide in high yield and high selectivity by using an organic tin compound as a catalyst, and is extremely industrially advantageous. This is a great method.

Example 1 15 d1 of t-butanol was added as a solvent to a 4-100-volume internal volume flask equipped with a water separator and a reflux condenser.
Propionic acid 5d, butyl stannonic acid as catalyst
Add 0.5 g, then add cyclohexene 5011j and reflux.

While stirring, add 0.105 mol of 90% hydrogen peroxide to 10
It took several minutes to drip. After the dropwise addition, the mixture was reacted under reflux for 30 minutes. Water produced during the reaction was removed using a water dispenser. Unreacted hydrogen peroxide was 0.006 mol. Further, when the produced cyclohexene oxide was analyzed by gas chromatography, it was found to be 0.0.84 mol. This has a conversion rate of 94% and a selectivity of 8 based on hydrogen peroxide.
It was 7%.

Example 2 Under the same conditions as Example 1, t-butanol 2 was used as the solvent.
When the reaction was carried out for 120 minutes using 0@l, a conversion rate of 47% and a selectivity of cyclohexene oxide of 40% were obtained based on hydrogen peroxide.

Example 3 In a 100 CC 4-bottle flask, propionic acid was used as a solvent and phenyl stannonic acid was used as a 45-1 catalyst.
Add 0.5 g, then add allyl chloride 20- and reflux. While stirring, 0.101 mol of 90% hydrogen peroxide was added dropwise over 10 minutes. After the dropwise addition, the mixture was reacted under reflux for 110 minutes. Unreacted hydrogen peroxide was 0.018 mol. In addition, when the produced epichlorohydrin was analyzed by gas chromatography, it was found to be (1,077 mol).This is a conversion rate of 8 based on hydrogen peroxide.
2%, and the selectivity was 93%.

Example 4 When diphenyltin oxide was used as a catalyst under the same conditions as in Example 3, the conversion rate was 80% based on hydrogen peroxide, and the selectivity of epichlorohydrin was 9.
It was 4%.

Example 5 To a 2DDcc glass autoclave were added 20 m of propion ill as a solvent, 0.5 g of octylstannonic acid as a dichloroethane 20-1 catalyst, and then allyl chloride 20-1 stabilizer (Dequest 20).
41) (manufactured by Monsanto) and 0.101 mol of 90% hydrogen peroxide were added and heated to 100°C with stirring.
Analysis by anti-gas chromatography for 60 minutes revealed that 0.082 mol of shrimp coolhydrin had been produced.

This is a conversion rate of 90% and a selectivity of 90% based on hydrogen peroxide.
%Met.

Example 6 In a 5us316 autoclave with an internal volume of 300Ce,
Dichloromethane 25d% monobutanol as solvent
1011j, propionic acid 51, and 0.5II of butylstaninic acid as a catalyst were added, and then 0.102 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 0.029 mol, and the amount of propylene oxide produced was 0.063 mol when analyzed by gas chromatography. This is the conversion rate based on hydrogen peroxide.72
%, selectivity was 86%.

Patent applicant Sanyu Gas Chemical Co., Ltd. Representative Kazuyoshi Nagano :1

Claims (1)

[Claims] +11 A method for producing olefin oxide characterized by reacting an olefin and hydrogen perfluoride in a liquid phase in the presence of an organotin compound catalyst (2) The reaction is carried out in the presence of an organic solvent. The method (3) according to claim 1, 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 2, wherein the organic solvent is an organic carboxylic acid (5) The method according to claim 2, wherein the organic tin compound catalyst is group, aryl group, X, Y
or 2 is hydrogen, alkyl group, 7ralkyl group, 7lyl group, halogen, hydroxyl group, alkoxy group, 7siloxy group, -8nR'R'R", -O8n R'R'R-
, -NR'R'', -O8i R'R'R-1-8- (R'R''R# is a furkyl group, an aralkyl group, or an aryl group)), Ran(=0)X. The method according to claim 1, 2 or 3, which is at least one compound selected from the compounds represented by RR'8a (wherein R, R' and (6) The organotin compound catalyst is 2R8n(=O)X(
1 of the compound n, where R and X are the same as above)
The method (7) according to claim 1, 2 or 3, wherein the organotin compound catalyst has the formula Ran(0)OH(R
The organic tin compound catalyst (8) according to claim 1, 2 or 3 is one of the compounds represented by
The method according to claim 1 or 2, in which the molar ratio of olefin to hydrogen peroxide is ζ. How to describe