JP2001031611A - Production of hydroxyether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily obtain a hydroxyether compound useful as a lubricant or the like without using an organohalide and generating salt or the like as by- product by reacting a specific alcohol with a carbonyl compound in a hydrogen atmosphere having a specific hydrogen pressure in the presence of a specific catalyst at a specific temperature, and thereafter, conducting hydrogenolysis of the thus obtained product. SOLUTION: This compound such as 1,3-dihexyl glyceryl ether is obtained by reacting (A) a polyhydric alcohol (except monohydric and dihydric alcohols) such as glycerol with (B) a carbonyl compound such as hexylaldehyde (C) in a hydrogen atmosphere having a hydrogen pressure of ordinary pressure to 2 Mpa, (D) in the presence of a palladium-based catalyst such as Pd-C, at 10-200 deg.C, and thereafter, conducting hydrogenolysis of the thus obtained product. In the above reaction, when the component B is added through dripping from the beginning, it is desirable to allow the component C to flow into the system and the reaction temperature is pref. 100-200 deg.C and reaction time pref. 2-25 h, and furthermore it is desirable that the dripping amount of the component B is 2-4 molar times the component A when it is a trihydric alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an industrial method for producing hydroxy ether useful as a detergent, an oil agent, a solvent, an emulsifier and the like.

[0002]

2. Description of the Related Art Hydroxyethers are known to have an emulsifying action. Those having a long alkyl chain or those having more ether bonds than the number of hydroxyl groups have high lipophilicity, and are expected to be used as oils, detergents, emulsifiers in the fields of cosmetics and the like. As a method for producing such a hydroxy ether, for example, epichlorohydrin and an alcohol are reacted in the presence of an alkali,
A method of reacting the obtained alkyl glycidyl ether with an alcoholate (a method of producing dialkyl glyceryl ether) and the like are known.

[0003]

However, the above technique has a problem that an organic halide is used and a large amount of salt is produced as a by-product. Therefore, there is no need to use an organic halide, and a method for producing a hydroxyether in a high yield with a simple operation without generating a large amount of salts and the like, especially a hydroxyether having more ether bonds than a hydroxyl group. There has been a demand for a method of manufacturing.

[0004]

Means for Solving the Problems The present inventors prepared a polyhydric alcohol having a valence of 3 or more and a carbonyl compound at 10 to 200 ° C. in a hydrogen atmosphere having a hydrogen pressure of from normal pressure to 2 MPa in the presence of a palladium catalyst. It was found that hydroxyether can be easily obtained by hydrogenolysis (late reaction) after the reaction (first reaction). In addition, the method does not require isolation and purification of the intermediate, and can perform the first-stage reaction and the second-stage reaction continuously, so that the operation is simple and the yield is high, and there is no need to use an organic halide. It has also been found that no salt or the like is produced as a by-product.

That is, in the present invention, a polyhydric alcohol having a valency of 3 or more and a carbonyl compound are reacted with a carbonyl compound under a hydrogen atmosphere at a hydrogen pressure of from normal pressure to 2 MPa in the presence of a palladium catalyst.
The present invention provides a method for producing a hydroxy ether, which comprises reacting at a temperature of ° C. followed by hydrogenolysis.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The alcohol used in the present invention is preferably a polyhydric alcohol having three or more hydroxyl groups, more preferably one having three or five hydroxyl groups, and glycerin, trimethylolpropane. , Trimethylolethane, xylitol and arabit are particularly preferred.

In the present invention, the carbonyl compound is preferably a linear, branched or cyclic compound having 1 to 20 carbon atoms having one carbonyl group, and an aliphatic aldehyde having 1 to 19 carbon atoms having one carbonyl group; A straight-chain or branched-chain ketone having 3 to 19 carbon atoms, or a cyclic ketone having 5 to 8 carbon atoms is more preferable, and an aliphatic aldehyde having 1 to 12 carbon atoms having one carbonyl group and a straight-chain having 3 to 6 carbon atoms are preferable. Particularly preferred are chain or branched chain ketones or cyclic ketones having 5 to 6 carbon atoms. Of these, propylaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, hexylaldehyde, heptylaldehyde, octylaldehyde, isononylaldehyde, dodecylaldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are most preferred. In the present invention, one or more of such carbonyl compounds can be used.

The palladium-based catalyst used in the first reaction includes carbon, alumina, silica-alumina or a palladium catalyst supported or not supported on silica,
Palladium hydroxide or palladium oxide is preferred, and a palladium catalyst supported on carbon is particularly preferred. The catalyst may be any of an anhydride and a water content having a water content of 20 to 60% by weight. When supported on a carrier, the supported amount of the catalyst is 2 to 2.
10% by weight is preferred. The amount of the catalyst used is, for example, in the case of 5% by weight supported on a carrier, from 0.1 to 10% by weight based on the alcohol having three or more odd-numbered hydroxyl groups from the viewpoint of promoting the reaction and economy. , Especially 0.5 to
8% by weight is preferred. The catalyst used in the present invention has a pH of 2 g dispersed in 30 g of ion-exchanged water.
Is preferably 8 or less.

The reaction between the trihydric or higher polyhydric alcohol and the carbonyl compound (pre-reaction) must be carried out at 10 to 200 ° C., and the temperature can be controlled according to the method of adding the carbonyl compound. preferable. When the carbonyl compound is added dropwise from the beginning, it is preferably added under a hydrogen atmosphere, preferably while flowing hydrogen through the system.
The reaction is carried out at a temperature of 100C or higher, particularly preferably 100 to 200C. In the case of a trihydric alcohol, the amount of the carbonyl compound added is preferably 2 to 5 times, especially 2 to 4 times the mole of the alcohol. The reaction time is 2 to 30 hours, especially 2 to 30 hours.
25 hours is preferred. The amount of the carbonyl compound dropped in the case of a pentahydric alcohol is twice that in the case of a trihydric alcohol. When the carbonyl compound is charged together with the alcohol without first being added dropwise, it is preferably 10 to 100 ° C., particularly preferably 20 to 70 ° C., and preferably 0.1 to 100 ° C. in a hydrogen atmosphere (which may or may not be passed). 5-10 hours,
Particularly preferably, the mixture is stirred for 0.5 to 5 hours. In the case of a trihydric alcohol, the amount of the carbonyl compound to be charged is preferably 1 to 1.5 times, particularly preferably 1 to 1.2 times, the mole of the alcohol. In the case of a pentahydric alcohol, the amount is preferably twice that in the case of a trihydric alcohol. Thereafter, hydrogen is preferably passed through the system, and the reaction temperature is preferably raised to 70 ° C. or higher, particularly preferably 100 to 200 ° C., to convert the carbonyl compound into a trihydric alcohol,
The amount is preferably 1 to 3 moles, more preferably 1 to 2 moles, added dropwise to the alcohol. The reaction time is preferably 2 to 20 hours, particularly preferably 2 to 15 hours.

The hydrogen pressure needs to be from normal pressure to 2 MPa, preferably from normal pressure to 1 MPa. Hydrogen may be present in the system, but in the case of dropping a carbonyl compound, it is particularly preferable to pass hydrogen. The flow rate of hydrogen can be appropriately selected according to the reaction scale. For example, in the case of a 70 mL scale, 0.7 to 2100 mL /
min is preferable, and 0.7 to 700 mL / min is particularly preferable. Here, the scale is the capacity of the reaction vessel.
The flow of hydrogen may be continuous or intermittent, but is preferably performed continuously to make the reaction proceed smoothly. The hydrogen that has flowed into the reaction system may be released to the atmosphere as it is. Preferred from a viewpoint.

The dropping rate of the carbonyl compound is 0.2 to 360 g / hr, particularly 1.2 to 120 g on a 1 L scale.
/ Hr is preferred. 0.2-360g / L scale
If it is hr, ether acetal can be produced in high yield. The dropping time is preferably 0.5 to 20 hours, more preferably 0.5 to 12 hours, and particularly preferably 1 to 10 hours. The dropping method may be continuous or intermittent. It is preferable to continue stirring for 1 to 5 hours after the completion of the dropping.

Next, hydrogenolysis (late reaction) is performed. The hydrocracking can be performed in a closed system or a hydrogen circulation system in the presence of the catalyst. Preferably, it is a closed system. The hydrogenolysis produces a hydroxyl group and an ether linkage. When performing in a closed system, the hydrogen pressure is normal pressure to 30M
Pa is preferable, and 5 to 25 MPa is particularly preferable. The time of the hydrocracking is not particularly limited, but is preferably, for example, 1 to 20 hours. The temperature of the hydrocracking is not particularly limited in both cases, but is preferably 100 to 300 ° C, particularly preferably 120 to 250 ° C.

After the completion of the hydrogenolysis, the hydroxy ether can be obtained by removing the carbonyl compound, the catalyst and the like, and purifying as appropriate.

The method of the present invention is suitable for the production of hydroxyethers having one more ether bond than the number of hydroxyl groups, more suitable for the production of dialkylhydroxyethers and trialkylhydroxyethers, especially 1,3 -Dihexyl glyceryl ether, 1,
3-dipentyl glyceryl ether, 1,3-bis (3
-Methylbutyl) glyceryl ether, 1,3-dioctylglycerylether, 1,3-bis (1,3-dimethylbutyl) glycerylether, trimethylolpropanedihexylether, trimethylolethanedihexylether, suitable for the production of xylitol trihexylether ing.

[0015]

Example 1 Production of 1,3-dihexyl glyceryl ether A 20 equipped with a hydrogen gas inlet tube, a stirrer and a reflux dehydration tube.
In a 0 mL autoclave, 36.8 g of glycerin was added.
(0.4 mol), 5% by weight based on carbon as catalyst
Supported palladium (5% Pd-C, pH 7.2)
After charging 2.2 g and continuously flowing hydrogen gas at 170 mL / min, the temperature was raised to 150 ° C., and 96 g (0.96 mol) of hexylaldehyde was added dropwise over 8 hours.
The mixture was further stirred for 2 hours. Then return to the closed system,
The mixture was stirred at a temperature of 190 ° C. and a hydrogen pressure of 20 MPa for 8 hours. After completion of the reaction, the catalyst was removed by filtration and the low-boiling components were removed under reduced pressure, and the desired 1,3-dihexylglyceryl ether 9
1.5 g (0.35 mol) were obtained as a colorless transparent liquid. The isolation yield was 88%. This method is easy to operate because there is no need to isolate and purify the intermediate product,
There was no need to use an organic halide, and there was no salt by-product.

Examples 2 to 8 Under the conditions shown in Tables 1 and 2, each hydroxy ether was produced according to the method of Example 1.

[0017]

[Table 1]

[0018]

[Table 2]

Comparative Example 1 Synthesis of 1,3-dioctylglyceryl ether by a method according to JP-A-56-163281 (1) Synthesis of octylglycidyl ether A reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas inlet tube In a 1 L flask equipped with a stirring device, sodium hydroxide 80
g and 87 g of water were charged to dissolve sodium hydroxide. After the temperature was raised to 50 ° C, octyl alcohol 130
g and tetrabutylammonium bromide 2 g were added, and the mixture was stirred at 50 ° C. for 1 hour. Next, 185 g of epichlorohydrin was added dropwise over 1 hour, and the mixture was aged for 3 hours. 150 g of water to dissolve the precipitated NaCl
In addition, two layers were separated. After the separated oil layer was washed twice with water, it was distilled under reduced pressure to obtain 158 g of octyl glycidyl ether. (2) Synthesis of 1,3-dioctylglyceryl ether 40 g of sodium hydroxide and 40 g of water were charged into a 500 mL flask equipped with a reflux condenser, a thermometer, a dropping funnel, a nitrogen gas inlet tube, and a stirrer. Dissolved. After the temperature was raised to 50 ° C., 65 g (0.5 mol) of octyl alcohol and 1 g of tetrabutylammonium bromide were added, and the mixture was stirred for 1 hour. Next, 84 g (0.45 mol) of octyl glycidyl ether was added dropwise over 1 hour, and the mixture was aged for 3 hours. NaC precipitated
To dissolve 1, 70 g of water was added and the layers were separated.
After the separated oil layer was washed twice with water, it was distilled under reduced pressure to give 1,
120 g of 3-dioctylglyceryl ether were obtained. In this method, since the reaction was performed in two stages as compared with Example 4, the operation was complicated, and the amount of salt by-product was large.

[0020]

According to the method of the present invention, it is not necessary to use an organic halide, and it is possible to produce a hydroxyether in a high yield by a simple operation without generating a salt or the like as a by-product.

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Claims (3)

[Claims] Claims 1. A polyhydric alcohol having a valency of 3 or more and a carbonyl compound are reacted at 10 to 200 ° C in the presence of a palladium-based catalyst in a hydrogen atmosphere having a hydrogen pressure of from normal pressure to 2 MPa. A process for producing a hydroxy ether. 2. The method according to claim 1, further comprising an operation of flowing hydrogen during the reaction.
A method for producing the hydroxy ether according to claim 1. 3. The process for producing a hydroxy ether according to claim 1, which comprises an operation of dropping a carbonyl compound during the reaction.