JP2003034664A - Method for producing carbonate ester having ether group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an economical method for producing a high purity carbonic ester having an ether group useful as a component of an electrolyte solvent for a capacitor. SOLUTION: The method for producing a symmetric or asymmetric carbonic ester having the ether group by transesterification between a raw material carbonic ester and a hydroxyl compound having the ether group is characterized by recycling to the transesterification system the components separated from the product carbonic ester having the ether group by distillation of the reaction product.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a carbonic acid ester having an ether group, which is useful as a component of an electrolytic solution solvent of a capacitor.

[0002]

2. Description of the Related Art As a method for producing carbonic acid ester, a method of reacting phosgene or chlorocarbonic acid ester with a hydroxy compound, a method of transesterification of carbonic acid ester, and the like are known. As a method for producing a carbonic acid ester having an ether group, a method of reacting a trichloroacetic acid ester with a hydroxy compound (German Patent 2036026) or a method by a transesterification reaction of a carbonic acid ester and an alkoxy alcohol (WO9113)
No. 052) is known.

Furthermore, JP-A-63-233954, JP-A-6-166660 and JP-A-7-10.
No. 811 discloses a method of shifting the equilibrium by removing a hydroxy compound, which is a by-product of the transesterification reaction, to the outside of the system, and a method of distilling the transesterification reaction liquid to obtain the target carbonic acid ester, and then removing the remaining components. The method used for the transesterification reaction is described.

[0004]

The carbonic acid ester having an ether group used as a component of an electrolytic solution solvent is required to have high quality. However, carbonic acid ester produced from phosgene, trichloroacetic acid, chlorocarbonic acid ester, etc. contains organic chlorine compounds and inorganic chlorine compounds as impurities, and other organic compounds,
Further, there is a problem that an acid generated from the remaining raw material is present in the product.

Further, in the production method by the transesterification reaction, it is necessary to use an excessive amount of the hydroxy compound in order to shift the reaction equilibrium toward the intended direction. Although the raw materials such as carbonic acid ester and excess hydroxy compounds are recycled, they are not economically satisfactory. The present invention provides a method for economically producing a carbonic acid ester having an ether group.

[0006]

Means for Solving the Problems As a result of intensive investigations in view of such circumstances, the present inventors have found that one molecule of a hydroxy compound having an ether group is exchanged from one molecule of a starting ester carbonate to one molecule of an asymmetric carbonic acid. Of the ester and the symmetric carbonic acid ester having two molecules exchanged, the carbonic acid ester having the target ether group is separated by distillation, and the raw material carbonic acid ester contained in the remaining components, the hydroxy compound having the ether group, and the ether group other than the target It has been found that the carbonic acid ester having a can be economically produced by recycling it to a transesterification reaction system.

That is, the present invention provides a method for producing a symmetrical or asymmetric carbonic acid ester having an ether group by a transesterification reaction between a starting carbonic acid ester and a hydroxy compound having an ether group. The present invention provides a method for producing a carbonic acid ester having, and then recycling the remaining components to a transesterification reaction system.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
Any material can be used as the raw material carbonic acid ester.
Specifically, dimethyl carbonate, diethyl carbonate, di-n carbonate
Examples thereof include dialkyl carbonate such as propyl, di-n-butyl carbonate, di-n-pentyl carbonate and di-n-hexyl carbonate, and diphenyl carbonate. Of these, dimethyl carbonate or diethyl carbonate is preferable, and dimethyl carbonate is particularly preferable.

As the hydroxy compound having an ether group, any compound can be used. Specifically, the following compounds can be mentioned. (1) Hydroxy compound having one ether group in the molecule 2-methoxyethanol, 2-methoxypropanol,
3-methoxypropanol, 1-methyl-2-methoxyethanol, 2-methoxybutanol, 3-methoxybutanol, 4-methoxybutanol, 1- (methoxymethyl) propanol, 1-methyl-2-methoxypropanol, 2-ethoxyethanol , 2-ethoxypropanol, 3-ethoxypropanol, 1-methyl-2-
Ethoxyethanol, 2-ethoxybutanol, 3-ethoxybutanol, 4-ethoxybutanol, 1- (ethoxymethyl) propanol, 1-methyl-2-ethoxypropanol, 2-butoxyethanol, 2-butoxypropanol, 3-butoxypropanol, 1-methyl-2-butoxyethanol, 2-butoxybutanol, 3-butoxybutanol, 4-butoxybutanol, 1- (butoxymethyl) propanol, 1-methyl-2-butoxypropanol, tetrahydrofurfuryl alcohol, tetrahydropyranylmethyl alcohol,
o-methoxyphenol, m-methoxyphenol, p
-Methoxyphenol. (2) Hydroxy compound having two ether groups in the molecule 2- (2-methoxyethoxy) ethanol, 2- (2-
Ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, 2- (2-methoxyethoxy) propanol, 2- (2-ethoxyethoxy) propanol, 2- (2-butoxyethoxy) propanol, 3-
(2-methoxyethoxy) propanol, 3- (2-ethoxyethoxy) propanol, 3- (2-butoxyethoxy) propanol, 4- (2-methoxyethoxy)
Butanol, 4- (2-ethoxyethoxy) butanol, 4- (2-butoxyethoxy) butanol, 2-
(2-methoxybutoxy) ethanol, 2- (2-ethoxybutoxy) ethanol, 2- (2-butoxybutoxy) ethanol, 2- (2-methoxybutoxy) propanol, 2- (2-ethoxybutoxy) propanol,
2- (2-butoxybutoxy) propanol, 3- (2
-Methoxybutoxy) propanol, 3- (2-ethoxybutoxy) propanol, 3- (2-butoxybutoxy) propanol, 4- (2-methoxybutoxy) butanol, 4- (2-ethoxybutoxy) butanol, 4
-(2-Butoxybutoxy) butanol. (3) Hydroxy compound 2- (2- (2-methoxyethoxy) ethoxy) ethanol, 2- (2- (2-ethoxyethoxy) ethoxy) having three ether groups in the molecule
Ethanol, 2- (2- (2-butoxyethoxy) ethoxy) ethanol. (4) Hydroxy compound 2- (2- (2- (2-methoxyethoxy) ethoxy) having 4 ether groups in the molecule
Ethoxy) ethanol, 2- (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) ethanol, 2-
(2- (2- (2-butoxyethoxy) ethoxy) ethoxy) ethanol. (5) Hydroxy compound 2- (2- (2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy) ethanol, 2- (2-) having 5 ether groups in the molecule
(2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) ethoxy) ethanol.

Of these, a hydroxy compound having one ether group in the molecule is preferable, and 2-methoxyethanol, 3-methoxypropanol, 4-methoxybutanol, 2-ethoxyethanol, 3-ethoxypropanol, 4-ethoxy. Particularly preferred are alkoxy alcohols such as butanol, 2-butoxyethanol, 3-butoxypropanol and 4-butoxybutanol, and alcohols having a cyclic ether group such as tetrahydrofurfuryl alcohol and tetrahydropyranylmethyl alcohol.

Since the equilibrium of the transesterification reaction depends on the molar ratio of the raw material carbonic acid ester and the hydroxy compound having an ether group, the molar ratio of the raw material carbonic acid ester and the hydroxy compound having an ether group (raw material carbonic acid ester /
A hydroxy compound having an ether group) is usually added to 0.1
.About.50, preferably 0.25 to 4, more preferably 0.
The range is from 4 to 2.5.

A catalyst is usually used in the transesterification reaction. A known transesterification catalyst can be used as the catalyst. For example, as a homogeneous catalyst, a tertiary aliphatic amine, an alkali metal compound, an alkaline earth metal compound, a thallium compound, a tin compound, a quaternary phosphonium salt, a titanium compound; as a heterogeneous catalyst, silica-titania solid acid Examples thereof include a catalyst, a basic ion exchange resin, an acidic ion exchange resin, and a Group III element oxide. Of these, alkali metal compounds are preferable, and sodium methoxide, sodium ethoxide, sodium carbonate, and potassium carbonate are particularly preferable.

In the homogeneous catalyst, the lower limit of the molar ratio (catalyst / raw material carbonate ester) to the raw material carbonate ester is 1000.
1/00, preferably 1/10000, upper limit is 5
It is used in the range of 1/100, preferably 1/100.
The heterogeneous catalyst has a lower limit of 0.1% by weight, preferably 0.5% by weight, and an upper limit of 40% by weight, preferably 30% by weight, based on the raw material carbonate ester in the batch reaction; (LHSV), the lower limit is 0.05 / h
r, preferably 0.1 / hr, and the upper limit value is 50 / hr, preferably 20 / hr.

The transesterification reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen, and the reaction temperature is usually -5.
It is 0 ° C to 200 ° C, preferably 0 to 150 ° C. The reaction pressure is usually 1 to 10 atm, preferably 1 to 2 atm.
Atmospheric pressure. Under such conditions, it is preferable to react for 5 minutes to 5 days, particularly 10 minutes to 10 hours. In the transesterification reaction, the hydroxy compound derived from the raw material carbonic acid ester, which is a by-product, can be removed from the reaction system to shift the reaction equilibrium in a desired direction. As a method for removing the hydroxy compound, a method of discharging a gas phase containing the hydroxy compound to the outside of the system, a method of blowing an inert gas such as nitrogen gas into the system, and entraining the hydroxy compound in the gas and discharging it to the outside of the system And so on. When the gas phase containing a hydroxy compound is discharged to the outside of the system, it is preferable to use an azeotropic agent such as an aliphatic hydrocarbon, an aromatic hydrocarbon, an ether or a ketone in order to accelerate the evaporation of the hydroxy compound. For example, in order to promote the evaporation of methanol generated from dimethyl carbonate, hexane, cyclohexane, benzene, etc. may be present in the reaction system.

The transesterification reaction liquid is prepared by removing the catalyst by a conventional method and then distilled to obtain each of the starting carbonic acid ester, the hydroxy compound having an ether group, the asymmetric carbonic acid ester having an ether group and the symmetrical carbonic acid ester having an ether group. The components are separated to obtain a target ester carbonate having an ether group. Next, the remaining raw material carbonic acid ester, the hydroxy compound having an ether group, and each component of the carbonic acid ester having an ether group other than the target are recycled to the transesterification reaction system. It should be noted that some of these components can be removed from recycling if desired. Further, it is desirable to obtain the total amount of the target carbonic acid ester having an ether group as a pure product as much as possible, but usually, a part thereof is contained in other components and recycled to the transesterification system.

Upon recycling, the amount of the carbonic acid ester having an ether group other than the intended amount is 0.05 to 5 mol times, particularly 0. 5 times, the amount of the ether group-containing hydroxy compound supplied to the reaction system. It is preferable to set the molar ratio to be 1 to 1 times. Examples of the ester carbonate having an ether group, which is produced from the starting ester carbonate and the hydroxy compound having an ether group by the production method of the present invention, include the following. (1) Carbonic acid ester having one ether group in the molecule Carbonic acid (methyl) 2-methoxyethyl, Carbonic acid (methyl) 2
-Methoxypropyl, carbonic acid (methyl) 3-methoxypropyl, carbonic acid (methyl) 1-methyl-2-methoxyethyl, carbonic acid (methyl) 2-methoxybutyl, carbonic acid (methyl) 3-methoxybutyl, carbonic acid (methyl) 4- Methoxybutyl, carbonic acid (methyl) 1-methyl-2-methoxypropyl, carbonic acid (methyl) 2-ethoxyethyl, carbonic acid (methyl) 2-ethoxypropyl, carbonic acid (methyl) 3-ethoxypropyl, carbonic acid (methyl) 1-methyl -2-ethoxyethyl, carbonic acid (methyl) 2-ethoxybutyl, carbonic acid (methyl) 3-ethoxybutyl, carbonic acid (methyl) 4-ethoxybutyl, carbonic acid (methyl) 1-methyl-2-ethoxypropyl, carbonic acid (methyl) 2-butoxyethyl, carbonic acid (methyl) 2-butoxypropyl, carbonic acid (methyl) 3-butoxypropyl, carbonic acid ( 1-methyl-2-butoxyethyl carbonate, (methyl) 2-butoxybutyl carbonate, (methyl) 3-butoxybutyl carbonate, (methyl) -4-butoxybutyl carbonate, (methyl) 1-methyl-2-butoxypropyl carbonate , (Methyl) tetrahydrofurfuryl carbonate,
Carbonic acid (methyl) tetrahydropyranyl methyl, carbonic acid (ethyl) 2-methoxyethyl, carbonic acid (ethyl) 2-methoxypropyl, carbonic acid (ethyl) 3-methoxypropyl, carbonic acid (ethyl) 1-methyl-2-methoxyethyl, carbonic acid (Ethyl) 2-methoxybutyl, carbonic acid (ethyl) 3-methoxybutyl, carbonic acid (ethyl) 4-methoxybutyl, carbonic acid (ethyl) 1- (methoxymethyl) propyl, carbonic acid (ethyl) 1-methyl-2-methoxypropyl , Carbonic acid (ethyl) 2-ethoxyethyl, carbonic acid (ethyl) 2-ethoxypropyl, carbonic acid (ethyl) 3-ethoxypropyl, carbonic acid (ethyl) 1-methyl-2-ethoxyethyl,
Carbonic acid (ethyl) 2-ethoxybutyl, carbonic acid (ethyl) 3
-Ethoxybutyl, carbonic acid (ethyl) 4-ethoxybutyl, carbonic acid (ethyl) 1- (ethoxymethyl) propyl,
Carbonic acid (ethyl) 1-methyl-2-ethoxypropyl, carbonic acid (ethyl) 2-butoxyethyl, carbonic acid (ethyl) 2-
Butoxypropyl, carbonic acid (ethyl) 3-butoxypropyl, carbonic acid (ethyl) 1-methyl-2-butoxyethyl,
Carbonic acid (ethyl) 2-butoxybutyl, carbonic acid (ethyl) 3
-Butoxybutyl, carbonic acid (ethyl) 4-butoxybutyl, carbonic acid (ethyl) 1- (butoxymethyl) propyl,
Carbonic acid (ethyl) 1-methyl-2-butoxypropyl, carbonic acid (ethyl) tetrahydrofurfuryl, carbonic acid (ethyl)
Tetrahydropyranylmethyl, carbonic acid (butyl) 2-methoxyethyl, carbonic acid (butyl) 2-methoxypropyl, carbonic acid (butyl) 3-methoxypropyl, carbonic acid (butyl) 1
-Methyl-2-methoxyethyl, carbonic acid (butyl) 2-methoxybutyl, carbonic acid (butyl) 3-methoxybutyl, carbonic acid (butyl) 4-methoxybutyl, carbonic acid (butyl) 1-
(Methoxymethyl) propyl, carbonic acid (butyl) 1-methyl-2-methoxypropyl, carbonic acid (butyl) 2-ethoxyethyl, carbonic acid (butyl) 2-ethoxypropyl, carbonic acid (butyl) 3-ethoxypropyl, carbonic acid (butyl) 1-
Methyl-2-ethoxyethyl, carbonic acid (butyl) 2-ethoxybutyl, carbonic acid (butyl) 3-ethoxybutyl, carbonic acid (butyl) 4-ethoxybutyl, carbonic acid (butyl) 1-
(Ethoxymethyl) propyl, (butyl) 1-methyl-2-ethoxypropyl carbonate, (butyl) 2-butoxyethyl carbonate, (butyl) 2-butoxypropyl carbonate, (butyl) 3-butoxypropyl carbonate, carbonic acid (butyl) 1-
Methyl-2-butoxyethyl, carbonate (butyl) 2-butoxybutyl, carbonate (butyl) 3-butoxybutyl, carbonate (butyl) 4-butoxybutyl, carbonate (butyl) 1-
(Butoxymethyl) propyl, carbonic acid (butyl) 1-methyl-2-butoxypropyl, carbonic acid (butyl) tetrahydrofurfuryl, carbonic acid (butyl) tetrahydropyranylmethyl, carbonic acid (hexyl) 2-methoxyethyl, carbonic acid (hexyl) 2 -Methoxypropyl, carbonic acid (hexyl) 3-
Methoxypropyl, carbonic acid (hexyl) 1-methyl-2-
Methoxyethyl, carbonic acid (hexyl) 2-methoxybutyl, carbonic acid (hexyl) 3-methoxybutyl, carbonic acid (hexyl) 4-methoxybutyl, carbonic acid (hexyl) 1- (methoxymethyl) propyl, carbonic acid (hexyl) 1-methyl- 2-methoxypropyl, carbonic acid (hexyl) 2-ethoxyethyl, carbonic acid (hexyl) 2-ethoxypropyl, carbonic acid (hexyl) 3-ethoxypropyl, carbonic acid (hexyl) 1-methyl-2-ethoxyethyl, carbonic acid (hexyl) 2 -Ethoxybutyl, carbonic acid (hexyl) 3-ethoxybutyl, carbonic acid (hexyl) 4-ethoxybutyl, carbonic acid (hexyl) 1- (ethoxymethyl) propyl, carbonic acid (hexyl) 1-methyl-2-ethoxypropyl, carbonic acid (hexyl) ) 2-Butoxyethyl, carbonic acid (hexyl) 2
-Butoxypropyl, carbonic acid (hexyl) 3-butoxypropyl, carbonic acid (hexyl) 1-methyl-2-butoxyethyl, carbonic acid (hexyl) 2-butoxybutyl, carbonic acid (hexyl) 3-butoxybutyl, carbonic acid (hexyl) 4- Butoxybutyl, (hexyl) 1-methyl-2-butoxypropyl carbonate, (hexyl) tetrahydrofurfuryl carbonate, (hexyl) tetrahydropyranyl methyl carbonate. (2) Carbonic acid ester having 2 ether groups in the molecule Bis (2-methoxyethyl) carbonate, Bis (2-methoxypropyl) carbonate, Bis (3-methoxypropyl) carbonate,
Bis (1-methyl-2-methoxyethyl) carbonate, Bis (2-methoxybutyl) carbonate, Bis (3-methoxybutyl) carbonate, Bis (4-methoxybutyl) carbonate, Bis (1- (methoxymethyl) propyl carbonate ), Biscarbonate (1-
Methyl-2-methoxypropyl), bis (2-ethoxyethyl) carbonate, bis (2-ethoxypropyl) carbonate, bis (3-ethoxypropyl) carbonate, bis (1-methyl-2-ethoxyethyl) carbonate, biscarbonate (2-ethoxybutyl), bis (3-ethoxybutyl) carbonate, bis (4-ethoxybutyl) carbonate, bis (1- (ethoxymethyl) propyl) carbonate, bis (1-methyl-2-ethoxypropyl) carbonate, Bis (2-butoxyethyl) carbonate, bis (2-butoxypropyl) carbonate, bis (3-butoxypropyl) carbonate, bis (1-methyl-2-butoxyethyl) carbonate, bis (tetrahydrofurfuryl) carbonate, biscarbonate Symmetrical carbonic acid ester such as (tetrahydropyranylmethyl); carbonic acid (methyl) 2- (2-methoxyethoxy) ethyl, carbonic acid (methyl 2- (2-ethoxyethoxy) ethyl carbonate (methyl) 2- (2-butoxyethoxy) ethyl carbonate (methyl) 2- (2-methoxyethoxy) propyl carbonate (methyl) 2- (2-ethoxyethoxy)
Propyl, carbonic acid (methyl) 2- (2-butoxyethoxy) propyl, carbonic acid (methyl) 3- (2-methoxyethoxy) propyl, carbonic acid (methyl) 3- (2-ethoxyethoxy) propyl, carbonic acid (methyl) 3- (2-butoxyethoxy) propyl, (methyl) 4- (2-methoxyethoxy) butyl carbonate, (methyl) 4- (2-ethoxyethoxy) butyl carbonate, (methyl) 4- (2-butoxyethoxy) butyl carbonate, Carbonate (methyl) 2- (2-methoxybutoxy) ethyl, carbonate (methyl) 2- (2-ethoxybutoxy) ethyl, carbonate (methyl) 2- (2-butoxybutoxy) ethyl, carbonate (methyl) 2- (2 -Methoxybutoxy) propyl, carbonic acid (methyl) 2- (2-ethoxybutoxy) propyl, carbonic acid (methyl) 2- (2-butoxybutoxy) propyl Pills, carbonate (methyl) 3- (2-
Methoxybutoxy) propyl, carbonic acid (methyl) 3- (2
-Ethoxybutoxy) propyl, carbonic acid (methyl) 3-
(2-butoxybutoxy) propyl, carbonic acid (methyl) 4
-(2-Methoxybutoxy) butyl, carbonic acid (methyl) 4
-(2-Ethoxybutoxy) butyl, carbonic acid (methyl) 4
-(2-butoxybutoxy) butyl, carbonic acid (ethyl) 2
-(2-Methoxyethoxy) ethyl, carbonic acid (ethyl) 2
-(2-Ethoxyethoxy) ethyl, carbonic acid (ethyl) 2
-(2-Butoxyethoxy) ethyl, carbonic acid (ethyl) 2
-(2-Methoxyethoxy) propyl, carbonic acid (ethyl)
2- (2-ethoxyethoxy) propyl, carbonic acid (ethyl) 2- (2-butoxyethoxy) propyl, carbonic acid (ethyl) 3- (2-methoxyethoxy) propyl, carbonic acid (ethyl) 3- (2-ethoxyethoxy) Propyl, carbonic acid (ethyl) 3- (2-butoxyethoxy) propyl,
Carbonic acid (ethyl) 4- (2-methoxyethoxy) butyl,
Carbonic acid (ethyl) 4- (2-ethoxyethoxy) butyl,
Carbonic acid (ethyl) 4- (2-butoxyethoxy) butyl,
Carbonic acid (ethyl) 2- (2-methoxybutoxy) ethyl,
Carbonic acid (ethyl) 2- (2-ethoxybutoxy) ethyl,
Carbonic acid (ethyl) 2- (2-butoxybutoxy) ethyl,
Carbonic acid (ethyl) 2- (2-methoxybutoxy) propyl, carbonic acid (ethyl) 2- (2-ethoxybutoxy) propyl, carbonic acid (ethyl) 2- (2-butoxybutoxy) propyl, carbonic acid (ethyl) 3- (2 -Methoxybutoxy)
Propyl, carbonic acid (ethyl) 3- (2-ethoxybutoxy) propyl, carbonic acid (ethyl) 3- (2-butoxybutoxy) propyl, carbonic acid (ethyl) 4- (2-methoxybutoxy) butyl, carbonic acid (ethyl) 4- (2-ethoxybutoxy) butyl, (ethyl) carbonate 4- (2-butoxybutoxy) butyl, (butyl) 2- (2-methoxyethoxy) ethyl carbonate, (butyl) 2- (2-ethoxyethoxy) ethyl carbonate, Carbonate (butyl) 2- (2-butoxyethoxy) ethyl, carbonate (butyl) 2- (2-methoxyethoxy) propyl, carbonate (butyl) 2- (2-ethoxyethoxy) propyl, carbonate (butyl) 2- (2 -Butoxyethoxy) propyl, carbonic acid (butyl) 3- (2-methoxyethoxy) propyl, carbonic acid (butyl) 3- (2-ethoxyethoxy) propyl Pills, carbonate (butyl) 3- (2-
Butoxyethoxy) propyl, carbonic acid (butyl) 4- (2
-Methoxyethoxy) butyl, carbonic acid (butyl) 4- (2
-Ethoxyethoxy) butyl, carbonic acid (butyl) 4- (2
-Butoxyethoxy) butyl, carbonic acid (butyl) 2- (2
-Methoxybutoxy) ethyl, carbonic acid (butyl) 2- (2
-Ethoxybutoxy) ethyl, carbonic acid (butyl) 2- (2
-Butoxybutoxy) ethyl, carbonic acid (butyl) 2- (2
-Methoxybutoxy) propyl, carbonic acid (butyl) 2-
(2-ethoxybutoxy) propyl, carbonic acid (butyl) 3
-(2-Methoxybutoxy) propyl, carbonic acid (butyl)
3- (2-ethoxybutoxy) propyl, carbonic acid (hexyl) 2- (2-methoxyethoxy) ethyl, carbonic acid (hexyl) 2- (2-ethoxyethoxy) ethyl, carbonic acid (hexyl) 2- (2-butoxyethoxy) Ethyl, (hexyl) carbonate 2- (2-methoxyethoxy) propyl,
Carbonic acid (hexyl) 2- (2-ethoxyethoxy) propyl, carbonic acid (hexyl) 3- (2-methoxyethoxy) propyl, carbonic acid (hexyl) 3- (2-ethoxyethoxy) propyl, carbonic acid (hexyl) 4- (2 -Methoxyethoxy) butyl, (hexyl) 4- (2-ethoxyethoxy) butyl carbonate, (hexyl) 2- (2-methoxybutoxy) ethyl carbonate, (hexyl) 2- (2-ethoxybutoxy) ethyl carbonate, carbonic acid ( Hexyl) 2- (2-methoxybutoxy) propyl, carbonic acid (hexyl) 3- (2
-Asymmetric carbonic acid esters such as methoxybutoxy) propyl. (3) Carbonate ester having 3 ether groups in the molecule Carbonate (methyl) 2- (2- (2-methoxyethoxy) ethoxy) ethyl, Carbonate (methyl) 2- (2- (2-ethoxyethoxy) ethoxy) Ethyl, carbonic acid (methyl) 2-
(2- (2-butoxyethoxy) ethoxy) ethyl, carbonic acid (ethyl) 2- (2- (2-methoxyethoxy) ethoxy) ethyl, carbonic acid (ethyl) 2- (2- (2-ethoxyethoxy) ethoxy) ethyl , Carbonic acid (ethyl) 2-
(2- (2-butoxyethoxy) ethoxy) ethyl, (hexyl) carbonate 2- (2- (2-methoxyethoxy) ethoxy) ethyl, (hexyl) 2- (2- (2-ethoxyethoxy) ethoxy) ethyl carbonate , Carbonic acid (2-methoxyethyl) 2- (2-methoxyethoxy) ethyl, carbonic acid (2-methoxyethyl) 2- (2-ethoxyethoxy)
Ethyl carbonate (2-methoxyethyl) 2- (2-butoxyethoxy) ethyl carbonate (2-methoxyethyl) 2-
(2-methoxyethoxy) propyl, carbonic acid (2-methoxyethyl) 2- (2-ethoxyethoxy) propyl, carbonic acid (2-methoxyethyl) 2- (2-butoxyethoxy) propyl, carbonic acid (2-methoxyethyl) 3 -(2-
Methoxyethoxy) propyl, carbonic acid (2-methoxyethyl) 3- (2-ethoxyethoxy) propyl, carbonic acid (2
-Methoxyethyl) 3- (2-butoxyethoxy) propyl, carbonic acid (2-methoxyethyl) 4- (2-methoxyethoxy) butyl, carbonic acid (2-methoxyethyl) 4-
(2-ethoxyethoxy) butyl, carbonic acid (2-methoxyethyl) 4- (2-butoxyethoxy) butyl, carbonic acid (2-methoxyethyl) 2- (2-methoxybutoxy)
Ethyl carbonate (2-methoxyethyl) 2- (2-ethoxybutoxy) ethyl carbonate (2-methoxyethyl) 2-
(2-Butoxybutoxy) ethyl, carbonic acid (2-methoxyethyl) 2- (2-methoxybutoxy) propyl, carbonic acid (2-methoxyethyl) 2- (2-ethoxybutoxy)
Propyl, carbonic acid (2-methoxyethyl) 2- (2-butoxybutoxy) propyl, carbonic acid (2-methoxyethyl)
3- (2-methoxybutoxy) propyl, carbonic acid (2-methoxyethyl) 3- (2-ethoxybutoxy) propyl, carbonic acid (2-methoxyethyl) 3- (2-butoxybutoxy) propyl, carbonic acid (2-methoxyethyl) ) 4-
(2-methoxybutoxy) butyl, carbonic acid (2-methoxyethyl) 4- (2-ethoxybutoxy) butyl, carbonic acid (2-ethoxyethyl) 2- (2-methoxyethoxy)
Ethyl carbonate (2-ethoxyethyl) 2- (2-ethoxyethoxy) ethyl, carbonic acid (2-ethoxyethyl) 2-
(2-Butoxyethoxy) ethyl, carbonic acid (2-ethoxyethyl) 2- (2-methoxyethoxy) propyl, carbonic acid (2-ethoxyethyl) 2- (2-ethoxyethoxy)
Propyl, carbonic acid (2-ethoxyethyl) 2- (2-butoxyethoxy) propyl, carbonic acid (2-ethoxyethyl)
3- (2-methoxyethoxy) propyl, carbonic acid (2-ethoxyethyl) 3- (2-ethoxyethoxy) propyl, carbonic acid (2-ethoxyethyl) 3- (2-butoxyethoxy) propyl, carbonic acid (2-ethoxyethyl) ) 4-
(2-methoxyethoxy) butyl, carbonic acid (2-ethoxyethyl) 4- (2-ethoxyethoxy) butyl, carbonic acid (2-ethoxyethyl) 4- (2-butoxyethoxy)
Butyl, carbonic acid (2-ethoxyethyl) 2- (2-methoxybutoxy) ethyl, carbonic acid (2-ethoxyethyl) 2-
(2-Ethoxybutoxy) ethyl, carbonic acid (2-ethoxyethyl) 2- (2-butoxybutoxy) ethyl, carbonic acid (2-ethoxyethyl) 2- (2-methoxybutoxy)
Propyl, carbonic acid (2-ethoxyethyl) 2- (2-ethoxybutoxy) propyl, carbonic acid (2-ethoxyethyl)
3- (2-methoxybutoxy) propyl, carbonic acid (2-ethoxyethyl) 3- (2-ethoxybutoxy) propyl, carbonic acid (2-ethoxyethyl) 4- (2-methoxybutoxy) butyl, carbonic acid (2-ethoxyethyl) ) 4- (2
-Ethoxybutoxy) butyl, (tetrahydrofurfuryl) 2- (2-methoxyethoxy) ethyl carbonate. (4) Carbonic acid ester having 4 ether groups in the molecule Bis (2- (2-methoxyethoxy) ethyl) carbonate, Bis (2- (2-ethoxyethoxy) ethyl) carbonate, Bis (2- (2- (2- Propoxyethoxy) ethyl), carbonic acid (2-methoxyethyl) 2- (2- (2-methoxyethoxy) ethoxy) ethyl, carbonic acid (2-ethoxyethyl)
2- (2- (2-methoxyethoxy) ethoxy) ethyl, carbonic acid (2-butoxyethyl) 2- (2- (2-methoxyethoxy) ethoxy) ethyl, carbonic acid (2-methoxyethyl) 2- (2- ( 2-ethoxyethoxy) ethoxy) ethyl, carbonic acid (2-methoxyethyl) 2- (2-
(2-butoxyethoxy) ethoxy) ethyl, carbonic acid (2
-Ethoxyethyl) 2- (2- (2-butoxyethoxy) ethoxy) ethyl, carbonic acid (2-butoxyethyl) 2
-(2- (2-ethoxyethoxy) ethoxy) ethyl,
Carbonic acid (methyl) 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethyl, carbonic acid (ethyl) 2-
(2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethyl, carbonic acid (butyl) 2- (2- (2- (2-
Methoxyethoxy) ethoxy) ethoxy) ethyl, carbonic acid (butyl) 2- (2- (2- (2-ethoxyethoxy))
Ethoxy) ethoxy) ethyl, carbonic acid (methyl) 2- (2
-(2- (2-Ethoxyethoxy) ethoxy) ethoxy) ethyl, carbonic acid (methyl) 2- (2- (2- (2-butoxyethoxy) ethoxy) ethoxy) ethyl, carbonic acid (ethyl) 2- (2- ( 2- (2-butoxyethoxy)
Ethoxy) ethoxy) ethyl. (5) Carbonate ester having 5 ether groups in the molecule Carbonate (methyl) 2- (2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy) ethyl, Carbonate (methyl) 2- ( 2- (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) ethoxy) ethyl, carbonic acid (ethyl) 2- (2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy) ethyl , Carbonic acid (ethyl) 2- (2- (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) ethoxy) ethyl, carbonic acid (2-methoxyethyl) 2- (2- (2- (2-methoxyethoxy) ) Ethoxy) ethoxy) ethyl, carbonic acid (2-
Methoxyethyl) 2- (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) ethyl, carbonic acid (2-ethoxyethyl) 2- (2- (2- (2-ethoxyethoxy))
Ethoxy) ethoxy) ethyl, carbonic acid (2- (2-methoxyethoxy) ethyl) 2- (2- (2-methoxyethoxy) ethoxy) ethyl, carbonic acid (2- (2-ethoxyethoxy) ethyl) 2- (2- (2-Methoxyethoxy) ethoxy) ethyl, carbonic acid (2- (2-methoxyethoxy))
Ethyl) 2- (2- (2-ethoxyethoxy) ethoxy) ethyl, carbonic acid (2- (2-ethoxyethoxy) ethyl) 2- (2- (2-ethoxyethoxy) ethoxy) ethyl. (6) Carbonic acid ester carbonate having 6 ether groups in the molecule bis (2- (2- (2-methoxyethoxy) ethoxy) ethyl) carbonate, bis (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) ethyl carbonate ), Biscarbonate (2- (2-
(2-propoxyethoxy) ethoxy) ethyl).

Of these, asymmetric carbonic acid esters are preferable, and asymmetric carbonic acid esters having one ether group in the molecule are particularly preferable. ,

[0018]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The analysis of the reaction solution was carried out by gas chromatography (GC14B, manufactured by Shimadzu; column TC5H).
T, manufactured by GL Sciences; held at 40 ° C. for 5 minutes, heated to 250 ° C. at 10 ° C./minute and held for 3 minutes; injection,
An internal standard substance (n-decane) was used by a detector (FID) at 250 ° C.) to quantify with a calibration curve.
Fractions from the distillation were analyzed using area percentage. Comparative Example 1 In a 500 mL four-necked flask equipped with a distillation column having five plates, 144 g (1.6 mol) of dimethyl carbonate, 122 g (1.6 mol) of 2-methoxyethanol, and 8.6 mg (0.16) of sodium methoxide. Mmol) and 143 g of hexane were charged, and the mixture was heated at 66 to 101 ° C. for 5.5 hours while distilling an azeotropic mixture of hexane and methanol from the top of the column. The reaction solution was cooled to room temperature and passed through a column filled with 4.0 mL of a strongly acidic ion exchange resin (manufactured by Mitsubishi Chemical, Diaion SK1B; Diaion is a registered trademark of the same company) to remove the catalyst. When the obtained solution was analyzed by gas chromatography, the conversion rate of dimethyl carbonate was 7
9%, the conversion rate of 2-methoxyethanol was 94%, the yield of methyl carbonate (2-methoxyethyl) based on 2-methoxyethanol was 42%, and the yield of bis (2-methoxyethyl) carbonate was 25%. %Met.

This solution was added to a distillation column having 5 plates to obtain 12
By vacuum distillation at a pressure of mmHg, 79 g of 100% pure methyl carbonate (2-methoxyethyl) was obtained. As other fractions, 30 g of dimethyl carbonate, 6 g of 2-methoxyethanol and 13 g of a methyl carbonate (2-methoxyethyl) fraction containing impurities were obtained. In addition, 72 g of bis (2-methoxyethyl) carbonate was obtained as a bottom residue. Example 1 Dimethyl carbonate 3 obtained in Comparative Example 1 in the same apparatus as in Comparative Example 1.
0 g (0.3 mol), 2-methoxyethanol 6 g
(0.1 mol) and bis (2-methoxyethyl) carbonate 6
Charge 0 g (0.3 mol), dimethyl carbonate 159 g
(1.8 mol) and 2-methoxyethanol 128 g
(1.7 mol) was added. Then, 13 mg (0.24 mmol) of sodium methoxide and 96 g of cyclohexane were charged, and the mixture was distilled off at the top of the azeotropic mixture of cyclohexane and methanol at 75 to 106 ° C.
Heated for hours. The reaction solution was cooled to room temperature, and a strongly acidic ion exchange resin (Mitsubishi Chemical, Diaion SK1B) 6.0
The catalyst was removed by passing through a column filled with mL. When the obtained solution was analyzed by gas chromatography, the conversion rate of dimethyl carbonate was 69%, the conversion rate of 2-methoxyethanol was 89%, and methyl carbonate of 2-methoxyethanol standard (the sum of recycling and additional charging) ( The yield of 2-methoxyethyl) was 62%, and the yield of bis (2-methoxyethyl) carbonate was 59%.

[0020]

Industrial Applicability According to the present invention, a carbonate having a high-purity ether group can be economically obtained.

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Claims (7)

[Claims] 1. A method for producing a symmetrical or asymmetric carbonic acid ester having an ether group by a transesterification reaction between a starting carbonic acid ester and a hydroxy compound having an ether group, wherein the carbonic acid ester having an intended ether group is prepared from a transesterification reaction solution. And then recycling the remaining components to the transesterification reaction system. 2. The production method according to claim 1, wherein the intended carbonic acid ester having an ether group is an asymmetric carbonic acid ester. 3. In a transesterification reaction, a tertiary aliphatic amine, an alkali metal compound, an alkaline earth metal compound, a thallium compound, a tin compound, a quaternary phosphonium salt, a titanium compound, a silica-titania solid acid catalyst, a base. The method according to claim 1 or 2, wherein a catalyst selected from the group consisting of a cationic ion exchange resin, an acidic ion exchange resin and a Group III element oxide is used. 4. The production method according to claim 1, wherein the starting carbonic acid ester is a dialkyl carbonate. 5. The hydroxy compound having an ether group is an alkoxy alcohol.
5. The manufacturing method according to any one of 4 to 4. 6. The carbonic acid ester having an ether group other than the intended purpose, which is 0.05 to 5 mol times, of the hydroxy compound having an ether group supplied to the transesterification reaction system is recycled. 6. The method according to any one of 5 to 5. 7. A method for producing (methyl) 2-methoxyethyl carbonate by a transesterification reaction between dimethyl carbonate and 2-methoxyethanol, wherein the transesterification reaction liquid is distilled to obtain (methyl) 2-methoxyethyl carbonate. However, the remaining dimethyl carbonate, 2-methoxyethanol and bis (2-methoxyethyl) carbonate are recycled to the transesterification reaction system.
Method for producing methoxyethyl.