JP2000034249A - Production of ether compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for inexpensively and easily producing an ether compound with high purity suitable for e.g. cosmetic, detergent composition or lubricant oil. SOLUTION: This method is to produce an ether compound by reacting a hydroxy compound with a carbonyl compound in the atmosphere of hydrogen in the presence of a catalyst, wherein the reaction is carried out by setting the ratio of the total molar amount of the carbonyl compound to that of the hydroxy compound in the range of 1 to 5 and by keeping the ratio of the molar amount of the carbonyl compound to that of the hydroxy compound in the reaction system more than 5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a simple and inexpensive method for producing a high-purity ether compound.

[0002]

2. Description of the Related Art As a method for producing an ether compound, there is known a method of synthesizing a hydroxy compound and a carbonyl compound in a hydrogen atmosphere using a catalyst (JP-A-9-202743). issue). This method comprises a by-product ether compound (A) in which two molecules of a hydroxy compound are ether-bonded, a by-product hydroxy compound (B) in which a carbonyl compound is hydrogenated, or a by-product in which a carbonyl compound is reacted with the by-product hydroxy compound (B). To produce by-products such as raw ether compound (C),
When trying to obtain a high-purity ether compound that can be used in cosmetics, detergent compositions, lubricating oils, etc., there is a problem that special purification is required, and that effective purification is difficult, A highly selective reaction technique has been desired.

Accordingly, an object of the present invention is to provide a high-purity ether compound suitable for cosmetics, detergent compositions, lubricating oils and the like,
An object of the present invention is to provide a manufacturing method that can be supplied easily and at low cost.

[0004]

The present invention relates to a method for producing an ether compound by reacting a hydroxy compound and a carbonyl compound in a hydrogen atmosphere using a catalyst. And the ratio of the molar amount of the carbonyl compound to the molar amount of the hydroxy compound in the reaction system is 5
This is a method for producing an ether compound which is maintained and reacted as described above.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION As an example of the hydroxy compound used in the present invention, a compound represented by the general formula (1) is given.

R ^1- (OA) _n -OH (1) wherein R ¹ is a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 40 carbon atoms, and a cycloalkyl having 3 to 12 carbon atoms. An alkyl group or a fluorine substituent in which at least one hydrogen atom of these groups is substituted with a fluorine atom. A represents an alkylene group having 2 to 12 carbon atoms, and n
May be the same or different. n shows the number of 0-500. Among the hydroxy compounds represented by the general formula (1), aliphatic alcohols having 1 to 22 carbon atoms, particularly 6 to 22 carbon atoms, methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, Isopropyl carbitol, butyl carbitol, or an ethylene oxide or / and propylene oxide adduct of an aliphatic alcohol having 1 to 22 carbon atoms, particularly 6 to 22 carbon atoms (average addition mole number: 0.1 to 200);
General formula (2) having a cycloalkanol of 8; a diol having 2 to 10 carbon atoms; a fluorine substituent; Rf ¹ (CH ₂ ) _p OH (2) wherein Rf ¹ is a linear or It represents a branched-chain fluorine-containing alkyl, and p represents a number of 1 to 10. Fluorine-containing alcohols represented by
Diols such as aliphatic alcohols, cyclohexanol, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,9-nonanediol, and fluorine-containing alcohols represented by the general formula (2) are preferable. .

Another example of the hydroxy compound used in the present invention is a compound represented by the general formula (3).

R ² -XY- (OA) _m -OH (3) wherein R ² represents a linear or branched alkyl group having 6 to 24 carbon atoms, and X represents -COO-, -OCO- , -CO-, -CONR ³ -or -N
R ³ CO— (R ³ is a hydrogen atom or a methyl group), Y is a linear or branched alkylene group having 1 to 6 carbon atoms, A is as defined above, and m is 0 to 20 Indicates a number. As specific examples of the hydroxy compound represented by the general formula (3), monoethanolamide of a monofatty acid of an alkylene glycol having 4 to 6 carbon atoms (7 to 25 carbon atoms of an acyl group) or an alkylene oxide adduct thereof, alkyl Glycolic amides of amines (alkyl groups having 6 to 24 carbon atoms) or alkylene oxide adducts thereof,
And glycolic acid esters of 24 aliphatic alcohols or alkylene oxide adducts thereof. These hydroxy compounds can be used alone or as a mixture of two or more.

The carbonyl compound used in the present invention is
In addition to compounds having a carbonyl group, compounds that easily become a compound having a carbonyl group by an acid or heating are also included.
Specific examples of the carbonyl compound include a compound represented by the general formula (4).

[0010]

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[Wherein R ⁴ and R ⁵ are a linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms, or a fluorine-substituted group in which at least one hydrogen atom of these groups is substituted with a fluorine atom. And R ⁴ and R ⁵ may be the same or different. Further, a cyclic structure in which R ⁴ and R ⁵ are bonded may be used. Among these carbonyl compounds, a chain ketone having 3 to 19 carbon atoms, a cyclic ketone having 5 to 8 carbon atoms, and a fluorine-containing chain ketone having 1 to 12 carbon atoms are preferable, and acetone, methyl ethyl ketone, methyl isobutyl ketone ( 4-methyl-2-
A chain ketone having 3 to 6 carbon atoms such as pentanone) and a cyclic ketone having 5 to 6 carbon atoms such as cyclohexanone are particularly desirable. These carbonyl compounds can be used alone or as a mixture of two or more.

In the present invention, for example, the above general formula (1)
Or a hydroxy compound represented by (3) and a general formula (4)
Is reacted to obtain the desired ether compound represented by the general formula (5).

[0013]

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Wherein R ⁶ is R ¹ or R ² -XY- (R ¹ , R ² , X
And Y have the above-mentioned meanings), and R ⁴ , R ⁵ , A and n
Has the above-mentioned meaning. At this time, when a large amount of the hydroxy compound is present in the reaction system, a by-product ether compound represented by the general formula (A) in which two molecules of the hydroxy compound are ether-bonded is generated.

R ^6- (OA) _n -O- (AO) _n -R ⁶ (A) (wherein R ⁶ , A and n have the same meanings as described above). When it is high, the carbonyl compound is hydrogenated to newly generate a by-product hydroxy compound represented by the general formula (B).

[0016]

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(Wherein R ⁴ and R ⁵ have the same meanings as described above.) Further, the by-product hydroxy compound (B) reacts with the carbonyl compound (4) to be represented by the general formula (C) Produces by-product ether compounds.

[0018]

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(In the formula, R ⁴ and R ⁵ have the same meanings as above.) The side reaction for producing the by-product ether compound (A) is suppressed by reacting the carbonyl compound with the hydroxy compound in a large excess. can do. However,
If the carbonyl compound is present in a large excess in the reaction system, the amount of by-produced hydroxy compound (B) produced by hydrogenation of the carbonyl compound described later increases, or the purification load is increased when removing the large excess carbonyl compound after the reaction. Undesirably increases.

In the present invention, the ratio of the total molar amount of the carbonyl compound to the total molar amount of the hydroxy compound is from 1 to 5, preferably from 1 to 4, and the molar ratio of the carbonyl compound to the molar amount of the hydroxy compound in the reaction system. Amount ratio of 5
By performing the reaction while maintaining the above, the by-product ether compound (A) can be suppressed from being produced without reacting the carbonyl compound in a large excess. Specifically, a method in which a carbonyl compound is charged in advance into a reaction vessel together with a catalyst, and then a hydroxy compound is dropped into the reaction vessel under a hydrogen atmosphere as the reaction proceeds. The molar ratio in the reaction system can be determined by measuring the hydroxy compound and the carbonyl compound in the reaction solution by gas chromatography.

Further, in the present invention, the hydrogen partial pressure is adjusted so that the conversion of the hydroxy compound is 0 to 50%, preferably 0.5 M
Pa or less, more preferably 0.3 MPa or less, after the conversion exceeds 50%, preferably 0.3 MPa or less, more preferably
By performing the reaction while maintaining the pressure at 0.2 MPa or less, the formation of the by-product hydroxy compound (B) and the by-product ether compound (C) can be suppressed, which is preferable.

That is, the by-product hydroxy compound (B) is produced by hydrogenating a carbonyl compound in a hydrogen atmosphere in the presence of a catalyst. This hydrogenation reaction is carried out as the hydrogen partial pressure in the reaction system increases. The higher the concentration of the carbonyl compound, the easier the process proceeds, and the pressure is remarkable when it exceeds 1 MPa. On the other hand, if the reaction of the present invention is carried out while removing water in the reaction system, even if the hydrogen partial pressure is low (for example, 0.01%).
The reaction proceeds rapidly. Therefore, it is preferable to control the hydrogen partial pressure as described above. Specific methods for controlling the hydrogen partial pressure include a method in which a pressure control valve is provided in the gas phase of the reactor to control the reaction pressure (total pressure), and a method in which each component in the reactor is controlled by controlling the reaction temperature. For example, a method of changing the vapor pressure of water.

Examples of the catalyst used in the present invention include palladium catalysts; palladium compounds such as palladium hydroxide and palladium oxide; ruthenium, rhodium and platinum catalysts; ruthenium oxide, rhodium oxide and platinum oxide. Further, a catalyst such as iridium, osmium, rhenium or the like can be used. These catalysts may be supported on a carrier such as carbon, alumina, silica-alumina, silica and zeolite. Among these catalysts,
Preferably, it is a palladium catalyst, more preferably a palladium catalyst supported on carbon, alumina, silica alumina, silica or zeolite, palladium hydroxide or palladium oxide, and particularly preferably a palladium catalyst supported on carbon. The catalyst is usually used while being supported at a ratio of 2 to 10% by weight based on a carrier such as carbon and alumina, but may be used as it is without being supported on the carrier. Further, it may be a water-containing product of about 20 to 60% by weight. The catalyst is preferably used in an amount of 0.1 to 10% by weight with respect to the hydroxy compound, and it is economical and has few by-products, and more preferably 0.5 to 5% by weight.

In the present invention, the reaction temperature is preferably from 10 to 200 ° C, particularly preferably from 30 to 180 ° C. The reaction time may be appropriately selected depending on the reaction temperature, hydrogen pressure, amount of catalyst, and the like,
Usually, it is 1 to 24 hours, preferably 1 to 12 hours.

In the present invention, an equimolar amount of water is produced together with the desired ether compound. It is preferable to carry out the reaction while removing the produced water, since the reaction is accelerated.
Specific methods for removing water include a method of removing water by performing a reaction in the presence of a dehydrating agent, a method of removing water while passing a gas such as hydrogen, and a method of removing water by azeotropic dehydration. And the like. Among these methods, a method of removing water by performing a reaction in the presence of a dehydrating agent, or a method of removing water while flowing hydrogen is preferable, and particularly, a method of flowing hydrogen using a reactor equipped with a dehydrating unit. A preferred method is to remove water produced as a by-product of the reaction out of the system while performing the reaction, and to separate unreacted raw materials that have gone out of the reaction system together with the water into the reaction system.

In the present invention, the reaction may be carried out using a solvent which does not affect the reaction at all. Examples of the solvent include hydrocarbon solvents such as hexane, heptane, and octane. The amount of solvent used depends on the reaction solution.
0.5 to 2 times capacity is desirable.

[0027]

EXAMPLE 1 In a 1 L autoclave equipped with a hydrogen gas inlet tube, a hexadecyl alcohol dripping device and a stirring device, 90.75 g (0.375 mol) of hexadecyl alcohol, 300 g (3.0 mol) of 4-methyl-2-pentanone, 7.26 g of 5% Pd-C as catalyst
, And the pressure was increased to 0.25 MPa by introducing hydrogen.
The hydrogen partial pressure at the start of the reaction was 0.12 MPa. Thereafter, while flowing hydrogen at 15 NL / hr, the temperature was raised to 130 ° C. to start the reaction. The reaction was carried out at a reaction temperature of 130 ° C., and the reaction was carried out while separating 4-methyl-2-pentanone entrained by hydrogen from water and returning to the reaction system. 90.75 g (0.375 mol) of hexadecyl alcohol, which had been heated and dissolved in advance, was added dropwise over 1 hour using a pump together with the start of the reaction.
After aging for 7 hours after the completion of the dropwise addition, the reaction was terminated (the conversion of hexadecyl alcohol was 99.4%). The hydrogen partial pressure at the end of the reaction was 0.16 MPa. The ratio of the total molar amount of 4-methyl-2-pentanone to the total molar amount of hexadecyl alcohol is 4, and the ratio of the molar amount of 4-methyl-2-pentanone to the molar amount of hexadecyl alcohol in the reaction system. Was a minimum value of 5.8 at the third hour of the reaction.

After the completion of the reaction, the catalyst was removed by filtration, and at a temperature of 100 ° C. and a pressure of 5.33 kPa, an excess of 4-methyl-2-pentanone and 4-methyl-2-pent (by-product hydroxy compound (B)) were obtained. -Remove pentanol and remove
Products containing 1,3-dimethylbutylhexadecyl ether
246.3 g were obtained. Gas chromatographic analysis of this product showed that the composition of dihexadecyl ether, a by-product ether compound (A), was 0.4%, and bis (1,3-dimethylbutyl) ether, a by-product ether compound (C), Was 0.15%.

Example 2 The same reactor as in Example 1 was charged with 150 g (1.5 mol) of 4-methyl-2-pentanone and 7.26 g of 5% Pd-C as a catalyst, and hydrogen was introduced to raise the pressure to 0.6 MPa. did. afterwards,
The temperature was raised while flowing hydrogen at 15 NL / hr. After the temperature reached 150 ° C., 181.5 g (0.75 mol) of hexadecyl alcohol, which had been heated and dissolved in advance, was added dropwise over 4 hours, and 4-methyl-2-pentanone accompanying hydrogen was separated from water. The reaction was performed while returning to the reaction system. The hydrogen partial pressure at the start of the reaction was 0.36 MPa. Reaction pressure (total pressure) after 3 hours of reaction
Was reduced to 0.2 MPa, and the reaction was continued. At this time, the conversion of hexadecyl alcohol was 48.5%. After aging for 3 hours after completion of the dropwise addition, the reaction was terminated (conversion rate of hexadecyl alcohol 99.1%). Hydrogen partial pressure at the end of the reaction is 0.08
MPa. The ratio of the total molar amount of 4-methyl-2-pentanone to the total molar amount of hexadecyl alcohol is 2, and the ratio of the molar amount of 4-methyl-2-pentanone to the molar amount of hexadecyl alcohol in the reaction system. Was a minimum of 6.2 at the 4th hour of the reaction.

After the completion of the reaction, the same operation as in Example 1 was carried out to obtain 249.5 g of a product containing 1,3-dimethylbutylhexadecyl ether. Gas chromatographic analysis of this product showed that the by-product ether compound
The composition of dihexadecyl ether (A) is 0.38%,
The composition of bis (1,3-dimethylbutyl) ether, which is a by-product ether compound (C), was 0.01%.

Comparative Example 1 181.5 g (0.75 mol) of hexadecyl alcohol was placed in a 1 L autoclave equipped with a hydrogen gas inlet tube and a stirring device.
112.5 g (1.125 mol) of -methyl-2-pentanone, 3.63 g of 5% Pd-C as a catalyst, and 25.2 g (0.21 mol) of anhydrous magnesium sulfate as a dehydrating agent were introduced, and hydrogen was introduced thereinto to give a pressure of 7%.
Pressurized to MPa. Then do not circulate hydrogen, 1
The temperature was raised to 50 ° C. to start the reaction. The hydrogen partial pressure at the start of the reaction was 6.8 MPa. The reaction temperature was 150 ° C., and the reaction was completed in 4 hours. The hydrogen partial pressure at the end of the reaction was 6.92 MPa. 4- based on the total molar amount of hexadecyl alcohol
The ratio of the total molar amount of methyl-2-pentanone is 1.5,
The ratio of the molar amount of 4-methyl-2-pentanone to the molar amount of hexadecyl alcohol in the reaction system was 1.5 at the beginning of the reaction.

After completion of the reaction, the catalyst and magnesium sulfate were removed by filtration, and an excess of 4-methyl-2-pentanone and 4- by-product hydroxy compound (B) were removed at a temperature of 100 ° C. and a pressure of 5.33 kPa. The methyl-2-pentanol was removed to obtain 251.4 g of the desired product containing 1,3-dimethylbutylhexadecyl ether. The product was analyzed by gas chromatography to find that the composition of dihexadecyl ether, a by-product ether compound (A), was 1.2%.
%, And the composition of bis (1,3-dimethylbutyl) ether as a by-product ether compound (C) was 5.8%.

Comparative Example 2 Hexadecyl alcohol 18 was added to the same reactor as in Example 1.
1.5 g (0.75 mol), 225 g of 4-methyl-2-pentanone
(2.25 mol) and 5.26 g of 5% Pd—C as a catalyst were charged, and hydrogen was introduced to raise the reaction pressure (total pressure) to 0.25 MPa.
Thereafter, the temperature was raised to 150 ° C. while flowing hydrogen at 15 NL / hr. The hydrogen partial pressure at the start of the reaction was 0.07 MPa. The reaction was carried out while separating 4-methyl-2-pentanone entrained by hydrogen from the water and returning to the reaction system, and the reaction was completed in 7 hours. The hydrogen partial pressure at the end of the reaction was 0.13 MPa. 4-methyl-2 based on the total molar amount of hexadecyl alcohol
The ratio of the total molar amount of pentanone is 3, and the ratio of 4-methyl- to the molar amount of hexadecyl alcohol in the reaction system is
The ratio of the molar amount of 2-pentanone was a minimum value of 3 at the start of the reaction.

After the completion of the reaction, the same operation as in Example 1 was carried out to obtain 242.7 g of the desired product containing 1,3-dimethylbutylhexadecyl ether. The product was analyzed by gas chromatography to find that the composition of dihexadecyl ether, a by-product ether compound (A), was 2.2%,
The composition of bis (1,3-dimethylbutyl) ether, which is a by-product ether compound (C), was 0.16%.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasuyuki Fujii 1334 Minato 1334, Minato, Wakayama, Wakayama, Japan (72) Inventor Hisaka Kogaki 1334 Minato, Wakayama City, Wakayama Reference) 4H006 AA02 AC43 BC11 BC31 BC40 BE20 GN23 GP01 4H039 CA61 CD10 CD40

Claims (2)

[Claims] In producing an ether compound by reacting a hydroxy compound and a carbonyl compound in a hydrogen atmosphere using a catalyst, the ratio of the total molar amount of the carbonyl compound to the total molar amount of the hydroxy compound is 1 to 5. hand,
A process for producing an ether compound, wherein the reaction is carried out while maintaining the ratio of the molar amount of the carbonyl compound to the molar amount of the hydroxy compound in the reaction system at 5 or more. 2. The reaction wherein the hydrogen partial pressure in the reaction system is maintained at 0.5 MPa or less when the conversion of the hydroxy compound is 0 to 50% and 0.3 MPa or less when the conversion exceeds 50%. 1
Production method as described.