JP2001114719A - Preparation of glyceryl ether - Google Patents

Abstract

(57) Abstract: A method for producing glyceryl ether (3) by reacting glycidyl ether (1) with carbon dioxide to form glyceryl ether carbonate (2), followed by hydrolysis. Embedded image [R represents a C ₄ -C ₂₀ alkyl group which may be partially or entirely substituted with a fluorine atom, or an alkylene oxide adduct thereof. [Effect] Glyceryl ether can be produced simply and efficiently without using a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a simple and efficient method for producing glyceryl ether.

[0002]

2. Description of the Related Art Glyceryl ether is an emulsifier, a dispersant,
It is an excellent nonionic surfactant as a cleaning agent and the like, and its use is diversified.

As a method for producing glyceryl ether, a method is generally known in which glycidyl ether is synthesized from alcohol and epichlorohydrin using various catalysts by hydrolysis.

[0004] As a method of this hydrolysis, for example,
(1) a method of hydrolyzing glycidyl ether in the presence of an acid catalyst or an alkali catalyst; A method of decomposing, (3) a method of reacting glycidyl ether with a carbonyl compound to produce a 1,3-dioxolane compound and hydrolyzing it, (4) a method of reacting glycidyl ether with a lower fatty acid or acid anhydride to obtain glyceryl. There is known a method of forming an ester and hydrolyzing the ester.

However, for example, in the method (1), it is difficult to avoid side reactions such as polymerization between glycidyl ethers due to the inhomogeneity of glycidyl ether and water.
In the method (1), it is necessary to consider the problem of the side reaction of the solvent or the catalyst of the carbonyl compound and the recovery of the carbonyl compound.In the method (4), the lower fatty acid or the acid anhydride is used to prevent the glycidyl ether from being opened by glyceryl ether. There is a problem that it is necessary to use an excessive amount of the substance and to treat a large amount of a fatty acid salt after the reaction.

[0006]

As described above, glyceryl ether is excellent as a nonionic surfactant, and is expected to be used in many cases, but in many cases is subject to restrictions on the production method. A method for producing glyceryl ether has been desired.

[0007]

The present invention is represented by the following reaction formula.

[0008]

Embedded image

[In the formula, R represents a linear or branched alkyl group having 4 to 20 carbon atoms which may be partially or entirely substituted with a fluorine atom, or an alkylene oxide adduct thereof. ]

That is, the present invention provides a method of reacting glycidyl ether represented by the general formula (1) with carbon dioxide
An object of the present invention is to provide a method for producing a glyceryl ether represented by the general formula (3) by subjecting the glyceryl ether carbonate represented by the formula (2) to hydrolysis.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the glycidyl ether used as a raw material in the present invention, a linear or branched alkyl group having 4 to 20 carbon atoms represented by R in the general formula (1) is a butyl group or a pentyl group. Group, hexyl group, heptyl group,
Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, 2-ethylhexyl, 3,5,5- Examples thereof include trimethylhexyl groups and the like and alkylene oxide (ethylene oxide, propylene oxide, etc.) adducts thereof. Among them, those having a total carbon number of 5 to 16 are preferable. When the alkyl group is substituted by a fluorine atom, the degree of fluorine substitution and the substitution position are not particularly limited, and all can be preferably used.

Although the temperature and pressure of carbon dioxide used in the present invention are not particularly limited, the temperature is from room temperature to 150 ° C.
Range, the pressure is preferably from normal pressure to 30 MPa,
It is particularly preferable to use the fluid in a supercritical state (31.0 ° C. or higher and 7.4 MPa or higher).

In the reaction of glycidyl ether (1) with carbon dioxide, a solid base catalyst such as an oxide of an alkali metal or an alkaline earth metal and a composite thereof with silicon dioxide, a rare earth oxide, an ion It is preferable to use exchanged zeolite or the like, and particularly preferable are hydrotalcites which are known to catalyze the reaction of inserting carbon dioxide into α-olefin epoxide. The amount of use of these catalysts is not particularly limited, but is preferably 50% by weight or less based on glycidyl ether (1). The reaction temperature is preferably from 0 to 200C, particularly preferably from 0 to 160C. By converting glycidyl ether (1) to glyceryl ether carbonate (2), it becomes easy to mix with water, which contributes to suppression of side reactions in the next hydrolysis. Therefore, the conversion of glycidyl ether (1) to glyceryl ether carbonate (2) is preferably performed completely, but if the resulting crude glycidyl ether carbonate and water are almost uniformly mixed and melted, the glycidyl ether (1) is slightly converted. ) May remain.

The glyceryl ether carbonate (2) thus obtained is not only useful as a synthetic intermediate for glyceryl ether (3), but also has properties as a nonionic surfactant itself. Among them, perfluoroalkyl glyceryl ether carbonate has excellent properties and is particularly useful.

The above glyceryl ether carbonate (2)
Glyceryl ether
(3) is obtained, and this hydrolysis can be carried out according to a conventional method, for example, by heating in water in the presence of an acid catalyst or an alkali catalyst as a catalyst. The reaction temperature is preferably from 50 to 200 ° C, particularly preferably from 100 to 160 ° C.

The glyceryl ether (3) obtained as described above can be isolated and purified by known separation and purification means, specifically, distillation, washing, recrystallization, column chromatography and the like.

[0017]

EXAMPLE 1 Octyl glycidyl ether 200 was added to a 1 L autoclave.
g (1.08 mol) and 20 g of synthetic hydrotalcite (Alkamac L, manufactured by Kyowa Chemical Industry Co., Ltd.), and the pressure was increased to 5 MPa with carbon dioxide. Gradually raise the temperature to 50 ° C,
The reaction was performed for 2 hours. After completion of the reaction, the pressure was returned to normal pressure, and the catalyst was removed by filtration to obtain 220 g of octyl glyceryl ether carbonate. 220 g of the obtained octyl glyceryl ether carbonate, 200 g of water and 5 g of sodium hydroxide
g was placed in a 1 L four-necked flask and stirred at 90 ° C. for 8 hours. After the reaction is completed, the layers are separated at 80 ° C., and further added with 200 ml of water.
After washing twice, 175 g of octyl glyceryl ether was obtained. The yield is 85% and the purity is 99% according to GC analysis.
Met.

Example 2 3,3,4,4,5,5,6,6,7,7,8,8,8,8-tridecafluorooctyl [hereinafter referred to as "perfluorooctyl"] glycidyl in a 1 L autoclave 218 g (0.5 mol) of ether and 20 g of synthetic hydrotalcite (Alkamac L, manufactured by Kyowa Chemical Industry Co., Ltd.) were charged, and the pressure was increased to 5 MPa with carbon dioxide. The temperature was gradually raised to 50 ° C. and reacted for 12 hours. After completion of the reaction, the pressure was returned to normal pressure, and the catalyst was removed by filtration.
240 g of perfluorooctyl glyceryl ether carbonate were obtained. 240 g of the obtained perfluorooctyl glyceryl ether carbonate, 250 g of water and 5 g of sodium hydroxide were placed in a 1 L four-necked flask, and stirred at 90 ° C. for 8 hours. After the reaction is completed, separate the layers at 80 ° C, and add 200 ml
Was washed twice with water to obtain 197 g of perfluorooctyl glyceryl ether. The yield was 85% and the purity was 98% according to GC analysis.

Example 3 The same operation as in Example 1 was carried out except that a supercritical fluid of 10 MPa was used as carbon dioxide to obtain 170 g of octylglyceryl ether. The yield is 83% and the GC
Analysis showed a purity of 99%.

[0020]

According to the present invention, glyceryl ether can be produced more simply and efficiently without using a solvent.

Continued on the front page F term (reference) 4C048 AA01 BB09 CC01 UU03 XX10 4H006 AA02 AC41 AC48 BA69 BC11 BE41 BE60 GP01 GP10 4H039 CA42 CH10

Claims (3)

[Claims] [Claim 1] General formula (1) [In the formula, R represents a linear or branched alkyl group having 4 to 20 carbon atoms which may be partially or entirely substituted with a fluorine atom, or an alkylene oxide adduct thereof. After reacting glycidyl ether represented by) with carbon dioxide to form glyceryl ether carbonate,
By hydrolysis, the compound of the general formula (3) [Wherein, R has the same meaning as described above. ] The method for producing glyceryl ether represented by the formula: 2. The method for producing glyceryl ether according to claim 1, wherein carbon dioxide in a supercritical state is used. 3. The reaction of glycidyl ether (1) with carbon dioxide in the presence of a solid base catalyst.
A method for producing the glyceryl ether described.