JP5833363B2 - Method for producing epoxy compound adduct - Google Patents

Description

  The present invention relates to a method for producing an epoxy compound adduct.

Adducts resulting from the addition reaction of a polyhydric alcohol compound and an epoxy compound are used in the fields of cosmetics, pharmaceuticals and the like as detergents, solubilizers, emulsifiers, dispersants and foaming agents.
When the above adduct is used in a cleaning agent, a 1: 1 adduct in which one molecule of an epoxy compound is added to one molecule of a polyhydric alcohol exhibits excellent cleaning performance, and a compound in which an epoxy compound is excessively added. It is known that the cleaning performance and cloud point are reduced.

An addition reaction of an epoxy compound to a polyhydric alcohol compound is generally performed using a basic catalyst (Patent Document 1). However, since active hydrogen derived from an epoxy compound is newly generated in the reaction product, the reaction product contains Furthermore, there was a problem that an excessive epoxy compound was added.
In order to overcome such problems, studies have been conducted from the viewpoint of a catalyst. For example, Patent Document 2 describes that excessive epoxy compound addition is suppressed by reacting using a calcined magnesium-aluminum composite oxide as a catalyst.
Patent Document 3 describes that, in the addition reaction between a hydroxy compound and an epoxy compound, an excessive addition reaction of glycidyl ether to the resulting hydroxy ether compound can be suppressed by using an acidic or basic solid catalyst. Has been.
However, the inhibitory effect by a catalyst is limited, and the yield of the 1: 1 addition product of a polyhydric alcohol compound and an epoxy compound was not sufficient. Moreover, although an aprotic solvent is illustrated as a solvent, it is an illustration of only a solvent having a boiling point lower than the reaction temperature, and a practical use mode and effect of the solvent are not illustrated.

  Patent Document 4 describes a polyglycerin alkyl ether obtained by reacting in the presence of an aprotic solvent having an ether bond. However, there is no mention of the addition of excess epoxy compound to the reactants and the selectivity of the 1: 1 adduct.

U.S. Pat. No. 4,086,279 Japanese Patent Laid-Open No. 11-315043 Japanese Patent No. 4346382 JP 2010-100531 A

  The present invention provides a method for producing a polyhydric alcohol compound and an epoxy compound, wherein the use amount of the polyhydric alcohol compound is reduced and the formation of by-products is suppressed, and an addition product of the polyhydric alcohol compound and the epoxy compound, Preferably, it is an object to provide a method for producing a 1: 1 adduct of a polyhydric alcohol compound and an epoxy compound in a high yield.

The present invention provides an epoxy compound adduct in which a polyhydric alcohol compound and an epoxy compound are reacted using a solid catalyst in the presence of an ether solvent having no active hydrogen represented by the following general formula (4) as a means for solving the problem. A manufacturing method is provided.
R ² -O - _{[(PO) m / (EO)} n ] -R ³ (4)
[Wherein R ² and R ³ are alkyl groups having 1 to 8 carbon atoms, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, and m and n indicate the added mole number of PO or EO. , 0 to 10 respectively, and the sum of m and n is 2 to 20. The order of addition of PO and EO does not matter. “/” Means that the addition form of PO and EO may be block or random. ]

  The epoxy compound adduct obtained by the production method of the present invention is a 1: 1 adduct (monoalkyl ether) in which one molecule of an epoxy compound is added to one molecule of a polyhydric alcohol (hereinafter referred to as “1: 1 adduct”). Is included.

In the production method of the present invention, an excessive addition reaction of an epoxy compound, which is a sequential reaction, is suppressed in a reaction between a polyhydric alcohol compound and an epoxy compound by reacting with an ether solvent having no active hydrogen and a solid catalyst. can do. This gives a 1: 1 adduct with high productivity and high purity.
In addition, the epoxy compound adduct obtained by this method can be used as a cleaning agent, a solubilizer, an emulsifier, a dispersant or a foaming agent in the field of cosmetics, pharmaceuticals, and the like. The 1: 1 adduct has a high cloud point and can exhibit high cleaning performance.

<Polyhydric alcohol>
The polyhydric alcohol compound used as a reaction raw material in the present invention is a polyol, acetal or ketal having 2 to 30 carbon atoms and 2 to 30 hydroxyl groups from the viewpoint of detergency when an epoxy compound adduct is used as a cleaning agent. And polyoxyalkylene alkyl ethers are preferred.
More preferred are polyols having 2 to 18 carbon atoms and 2 to 18 hydroxyl groups, and acetals and ketals thereof, and more preferred are ethylene glycol, propanediol, glycerin, pentaerythritol, polyglycerin, sorbitol, glucose, sucrose and glycerin. Ketals, more preferably glycerin and / or polyglycerin, particularly preferably polyglycerin.

Specifically, the polyglycerin is preferably a compound of the following general formula (1).
HO- (Gly-O) _r -H (1)
[In formula, Gly shows the residue remove | excluding two hydroxyl groups from glycerol, r shows the number of 1.01-10 in average addition mole number. ]
In general formula (1), from the viewpoint of detergency when an epoxy compound adduct is used as a cleaning agent, r is preferably 1.1 to 5, and more preferably 2 to 4.

<Epoxy compound>
The epoxy compound used as a reaction raw material in the present invention is preferably an epoxy compound represented by the following general formula (2).

(In the formula, A is a linear or branched alkyl group having 2 to 36 carbon atoms, alkenyl group, alkoxyl group or alkenyloxyl group, aryl group or aryloxyl group having 5 to 36 carbon atoms, or general formula (3).
R ⁴ —O—CH ₂ — (3)
(Wherein R ⁴ is a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms, or an aryl group having 5 to 22 carbon atoms)
It is group represented by these. )

In general formula (2), from the viewpoint of detergency when an epoxy compound adduct is used as a cleaning agent, A is a straight chain having 2 to 36 carbon atoms, preferably 5 to 22 carbon atoms, more preferably 8 to 18 carbon atoms. A branched alkyl group, an alkenyl group, an alkoxyl group or an alkenyloxyl group, an aryl group or an aryloxyl group having 5 to 36 carbon atoms, preferably 5 to 22 carbon atoms, more preferably 8 to 18 carbon atoms, or a general formula (3) Those groups that are preferred are preferred.
In the general formula (2), A represents an alkoxyl group, an alkenyloxyl group, an aryloxyl group, or the general formula (3) from the viewpoint of detergency when an epoxy compound adduct is used as a cleaning agent. The group represented by General formula (3) is more preferable. More specific examples of the epoxy compound include glycidyl ether.

In general formula (3), from the viewpoint of detergency when an epoxy compound adduct is used as a cleaning agent, R ⁴ is a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms, or carbon number. An aryl group having 5 to 22 carbon atoms, more preferably a linear or branched alkyl group, alkenyl group or aryl group having 8 to 18 carbon atoms, and a linear or branched alkyl group or alkenyl having 10 to 16 carbon atoms Group or aryl group is more preferable, and a linear or branched alkyl group, alkenyl group or aryl group having 12 to 14 carbon atoms is particularly preferable. R ⁴ is preferably a linear or branched alkyl group, alkenyl group, or aryl group from the viewpoint of detergency when an epoxy compound adduct is used as a cleaning agent, and a linear or branched alkyl group or An alkenyl group is more preferable, a linear or branched alkyl group is further preferable, and a linear alkyl group is particularly preferable.
For example, as described in Japanese Patent No. 3544134, such an epoxy compound is obtained by reacting an alcohol with α-epihalohydrin in the presence of an acid catalyst and then ring-closing the resulting halohydrin ether by alkali treatment. Can be obtained.

<Ether solvent without active hydrogen>
The ether solvent without active hydrogen used in the present invention can increase the selectivity and yield of the 1: 1 adduct.
The reason why the selectivity of the 1: 1 adduct is not necessarily clear, but is considered to be due to the improvement of the compatibility of the reaction raw materials other than the catalyst and the solvation phenomenon of the addition product.

  The ether solvent having no active hydrogen is preferably one having a dielectric constant of 4 or more, more preferably a dielectric constant of 4 to 40, and still more preferably a dielectric constant of 5 from the viewpoint of increasing the selectivity and yield of the 1: 1 adduct. .About.20, particularly preferred are those having a dielectric constant of 6-10.

The ether solvent having no active hydrogen used in the present invention is a compound of the following general formula (4).
R ² -O - _{[(PO) m / (EO)} n ] -R ³ (4)
[Wherein R ² and R ³ are alkyl groups having 1 to 8 carbon atoms, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, and m and n indicate the added mole number of PO or EO. , 0 to 10 respectively, and the sum of m and n is 2 to 20. The order of addition of PO and EO does not matter. “/” Means that the addition form of PO and EO may be block or random. ]

The number of carbon atoms of R ² and R ³ is preferably independently 1 to 8, more preferably 1 to 3, and still more preferably 1 from the viewpoint of increasing the selectivity and yield of the 1: 1 adduct. is there.
The total of m and n is preferably 2 to 20, more preferably 2 to 10, more preferably 3 to 5, particularly preferably from the viewpoint of increasing the selectivity and yield of the 1: 1 adduct. Is 3-4.
If the sum of m and n is within the above range, m is preferably 0 from the viewpoint of increasing the selectivity and yield of the 1: 1 adduct.
Specific examples include diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, pentaethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol diethyl ether, tetraethylene glycol diethyl ether, or pentaethylene glycol diethyl ether. : 1 From the viewpoint of increasing the selectivity and yield of the adduct, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, or pentaethylene glycol dimethyl ether is preferable, and triethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether is more preferable. There.

The boiling point of the ether solvent having no active hydrogen is preferably equal to or higher than the reaction temperature in the present invention from the viewpoint of increasing the selectivity and yield of the 1: 1 adduct. The boiling point represents a standard boiling point, that is, a temperature at which the saturated vapor pressure becomes equal to 101.25 hPa (1 atm). When the boiling point is equal to or higher than the reaction temperature, it is not necessary to raise the reaction pressure to a normal pressure or higher, and the equipment load does not increase.
Specifically, the boiling point of the ether solvent having no active hydrogen is preferably 100 ° C. to 500 ° C., more preferably 150 ° C. to 400 ° C., and further preferably 160 ° C. to 350 ° C. from the viewpoint of equipment load. Especially preferably, it is 180 to 300 ° C.

<Solid catalyst>
The solid catalyst used in the present invention is preferably a solid catalyst containing aluminum, magnesium or zinc from the viewpoint of increasing the selectivity of the 1: 1 adduct. Other elements may be contained for the purpose of improving selectivity, reaction rate, and other catalyst performance.

Examples of the solid catalyst used in the present invention include single or composite metal oxides, metal sulfates, and metal phosphates composed of the above elements. From the viewpoint of increasing the selectivity of the 1: 1 adduct, single or mixed metal oxides are preferable.
As the single or composite metal oxide, aluminum oxide, magnesium oxide, zinc oxide or a composite oxide of aluminum and magnesium is preferable from the viewpoint of enhancing the selectivity of a 1: 1 adduct of a polyhydric alcohol compound and an epoxy compound.
In addition, oxides of other elements may be included for the purpose of improving selectivity, reaction rate, and other catalyst performance.

  The manufacturing method of the catalyst used by this invention is not specifically limited, It can prepare by a well-known method. For example, the precipitate obtained by adding a precipitant to a mixed aqueous solution or aqueous dispersion containing a compound such as chloride, hydroxide, oxide, nitrate, sulfate, carbonate, etc. of each element is washed, dried, It can be prepared by a coprecipitation method for calcination or an impregnation method in which a compound that can be a catalyst component other than the carrier component is impregnated and supported on a poorly water-soluble powder carrier in the form of an aqueous solution or aqueous dispersion, and then dried and calcined. When prepared by a coprecipitation method or an impregnation method, any compound can be used if it is water-soluble or water-dispersible.

<Production method: reaction method of polyhydric alcohol and epoxy compound>
The production method of the present invention may be any method that allows a polyhydric alcohol compound and an epoxy compound to react with each other using a solid catalyst in the presence of an ether solvent having no active hydrogen. Two methods can be mentioned.
Method 1: A method in which a polyhydric alcohol compound, an epoxy compound, an ether solvent having no active hydrogen, and a catalyst are placed in a reaction vessel and reacted.
Method 2: A method in which a polyhydric alcohol compound, an ether solvent having no active hydrogen, and a solid catalyst are placed in a reaction vessel, mixed, dehydrated, and then added with an epoxy compound for reaction.

As in Method 2, adding a dehydration step so that no water is present at the beginning of the reaction makes it possible to suppress competition of the hydrolysis reaction of the epoxy compound. Since yield and selectivity can be improved, it is preferable from the viewpoint of productivity improvement.
The dehydration method is not particularly limited, and for example, the dehydration operation can be performed at a predetermined temperature and pressure after putting the reaction raw material, the solvent and the catalyst into the reaction apparatus. Further, it can be dehydrated and dried by a conventional method such as using a desiccant such as a metal hydride.

  The ratio of the polyhydric alcohol compound and the epoxy compound (the number of moles of the epoxy compound / the number of moles of the polyhydric alcohol compound) as the raw material for production is preferably 0.3 to 1, and preferably 0.5 to 1 from the viewpoint of improving productivity. Is more preferable, and 0.7 to 0.9 is still more preferable.

  The amount of the ether solvent that does not have active hydrogen is preferably 1 to 500 parts by mass, more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the polyhydric alcohol compound, from the viewpoint of increasing the selectivity of the 1: 1 adduct. 200 parts by mass, more preferably 40 to 150 parts by mass, particularly preferably 50 to 130 parts by mass.

  The amount of the catalyst used is preferably 0.05 to 20 parts by mass, more preferably 1 to 10 parts by mass, with respect to 100 parts by mass of the polyhydric alcohol compound, from the viewpoint of the selectivity of the 1: 1 adduct. 7 parts by mass is more preferable.

  The reaction temperature is preferably 100 ° C. or higher, more preferably 150 ° C. or higher, even more preferably 160 ° C. or higher, from the viewpoint of productivity to improve the yield and selectivity of the 1: 1 adduct. Preferably, it is 180 ° C or higher, and from the viewpoint of coloring and / or odor of the adduct, it is preferably 250 ° C or lower, more preferably 220 ° C or lower, still more preferably 210 ° C, and particularly preferably 200 ° C. It is as follows.

The reaction pressure is not particularly limited, but is preferably equal to or higher than the vapor pressure of the reaction raw material and the solvent. From the viewpoint of equipment load, it is preferably 2000 hPa or less, more preferably 1500 hPa or less, and still more preferably 1100 hPa or less.
In addition, this reaction is preferably performed in an inert gas atmosphere, and more preferably in an argon gas or nitrogen gas atmosphere, from the viewpoint of coloring and / or odor of the adduct.

  The reaction method may be either a continuous method in which raw materials are charged into the reaction vessel and a product is withdrawn from the reaction vessel in the middle of the reaction, or a batch method in which the product is withdrawn from the reaction vessel after completion of the reaction. A reaction method (such as a dropping method) can also be employed.

As a continuous type, a fixed bed reaction method in which a catalyst is packed and fixed, and a polyalcohol compound, an epoxy compound and a solvent are passed therethrough to advance the reaction, or a solid catalyst is supplied to a reactor together with raw materials, etc. Is mentioned. From the viewpoint of separation of the catalyst after the reaction, a fixed bed reaction method is preferable.
In the case of a batch type, either a batch type in which a polyhydric alcohol compound, an epoxy compound, a solvent and a catalyst are charged into the reaction vessel before the start of the reaction, or a raw material in a reaction vessel in which other raw materials have already been charged. Any of the dropping methods may be used.
When adopting a dropping method as another reaction method, it is preferable to add an epoxy compound dropwise to the reaction system from the viewpoint of increasing the selectivity of the 1: 1 adduct.
From the viewpoint of shortening the reaction time, the batch method is preferable.

  The method for separating the catalyst after the reaction is not particularly limited, and a method for separating the product after the reaction whose viscosity has been lowered by heating can be applied. It is also possible to add a variety of solvents (water, lower monohydric alcohol, etc.) and filter aids (diatomaceous earth, cellulosic aids, activated clay, etc.) to lower the viscosity and filter the catalyst. it can.

According to the production method of the present invention, an epoxy compound adduct containing a 1: 1 adduct (a mixture containing a 1: 1 adduct) is obtained. Here, the 1: 1 adduct refers to a compound in which one molecule of an epoxy compound is added to one molecule of a polyhydric alcohol compound.
The obtained epoxy compound adduct is a cosmetic product as a cleansing agent, a solubilizer, an emulsifier, a dispersant or a foaming agent as a mixture as it is or as a product obtained by further increasing the purity of the 1: 1 adduct by a purification operation. It can be used in fields such as pharmaceuticals.

<Measurement method>
The composition of each compound contained in the mixture after completion of the reaction in the examples and comparative examples shown in Table 1 is obtained by adding tetradecane as an internal standard to the sample and adding a trimethylsilylating agent (manufactured by GL Sciences, TMSI-H). After mixing, the solid content was filtered off, and quantitative analysis was performed by gas chromatography under the following conditions. The selectivity of monoalkyl ether (1: 1 adduct) was calculated from the following formula.
Monoalkyl ether selectivity = monoalkyl ether concentration (mass%) in reaction product / (monoalkyl ether concentration (mass%) in reaction product + dialkyl ether concentration (mass%) in reaction product) × 100

・ Device: HEWLETT PACKARD, HP6850Series GC System
Column: DB1-HT (manufactured by J & W, inner diameter 0.25 mm, length 15 m, film thickness 0.1 mm)
・ Carrier gas: He, 1.0 mL / min ・ Inlet temperature: 300 ℃
・ Detection: FID method, 300 ℃
Column temperature conditions: 60 ° C (2 minutes hold) → 10 ° C rise / minute → 350 ° C (5 minutes hold)

Example 1
Diglycerin (manufactured by Tokyo Chemical Industry Co., Ltd.) 25.1 g, catalyst 1.25 g, and solvent 27.8 g were mixed at 160 ° C. with stirring, and then subjected to dehydration treatment under reduced pressure of 1 mmHg for 1 hour.
After dehydration, the temperature was raised to 200 ° C. in a nitrogen gas atmosphere, and 29.3 g of lauryl glycidyl ether was mixed with stirring, followed by reaction for 4 hours. The diglycerin conversion was 66% and the selectivity for lauryl monoalkyl ether (1: 1 adduct) was 83%.

Comparative Example 1
After mixing 30.0 g of diglycerin (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.50 g of the catalyst with stirring at 160 ° C., dehydration treatment was performed for 1 hour under a reduced pressure of 1 mmHg.
After dehydration, the temperature was raised to 200 ° C. in a nitrogen gas atmosphere, and 35.0 g of lauryl glycidyl ether was mixed with stirring, followed by reaction for 2 hours. The diglycerin conversion was 66% and the monoalkyl ether selectivity was 74%.

Example 2
After 18.0 g of diglycerin (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.900 g of catalyst, 21.1 g of lauryl glycidyl ether and 20.0 g of solvent were mixed with stirring, the temperature was raised to 200 ° C. in a nitrogen gas atmosphere, and 4.5 hours Reaction was performed. Diglycerin conversion was 48% and monoalkyl ether selectivity was 81%.

Example 3
After 60.0 g of diglycerin (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.00 g of catalyst and 104 g of solvent were mixed with stirring, the temperature was raised to 200 ° C. in a nitrogen gas atmosphere, and lauryl glycidyl ether was added dropwise at 10.5 g / hour for 1 hour. did. Then, after aging at 200 ° C. and confirming the disappearance of lauryl glycidyl ether, lauryl glycidyl ether was added dropwise again at 10.5 g / hour for 1 hour to ripen. The diglycerin conversion was 28% and the monoalkyl ether selectivity was 96%.

Example 4
After 19.4 g of diglycerin (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.900 g of catalyst, 22.6 g of lauryl glycidyl ether and 17.1 g of solvent were mixed with stirring, the temperature was raised to 180 ° C. in a nitrogen gas atmosphere and the reaction was carried out for 10 hours. went. Diglycerin conversion was 48% and monoalkyl ether selectivity was 78%.

Example 5
After mixing 20.5 g of diglycerin (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.960 g of catalyst, 23.9 g of lauryl glycidyl ether, and 14.6 g of solvent, the temperature was raised to 180 ° C. in a nitrogen gas atmosphere and 7.2 hours. Reaction was performed. The diglycerin conversion was 49% and the monoalkyl ether selectivity was 77%.

Comparative Example 2
After mixing 25.8 g of diglycerin (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.30 g of catalyst and 30.1 g of lauryl glycidyl ether with stirring, the mixture was heated to 200 ° C. in a nitrogen gas atmosphere and reacted for 2.5 hours. Diglycerin conversion was 48% and monoalkyl ether selectivity was 72%.

Comparative Example 3
9.10 g of diglycerin (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.440 g of catalyst, 10.4 g of lauryl glycidyl ether, and 19.7 g of solvent were mixed with stirring, and the temperature was raised to 200 ° C. in a nitrogen gas atmosphere for 5.5 hours. Reaction was performed. Formation of a monoalkyl ether was not confirmed.

Comparative Example 4
After 60.0 g of diglycerin (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.00 g of catalyst were mixed with stirring, the temperature was raised to 200 ° C. under a nitrogen gas atmosphere, and lauryl glycidyl ether was added dropwise at 10.5 g / hour for 1 hour. Then, after aging at 200 ° C. and confirming the disappearance of lauryl glycidyl ether, lauryl glycidyl ether was added dropwise again at 10.5 g / hour for 1 hour, and aging was repeated twice. The diglycerin conversion was 30% and the monoalkyl ether selectivity was 85%.

Comparative Example 5
After mixing 25.0 g of diglycerin (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.250 g of boron trifluoride diethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.), 29.3 g of lauryl glycidyl ether, and 27.8 g of solvent, nitrogen gas was mixed. The temperature was raised to 90 ° C. in the atmosphere, and the reaction was performed for 3 hours. As a result of analysis by gas chromatography, the diglycerin conversion was 26% and the selectivity of monoalkyl ether was 55%.

Comparative Example 6
After mixing 30.0 g of diglycerin (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.310 g of boron trifluoride diethyl ether (manufactured by Wako Pure Chemical Industries) and 35.1 g of lauryl glycidyl ether, the temperature was raised to 90 ° C. in a nitrogen gas atmosphere. And reacted for 3 hours. As a result of analysis by gas chromatography, the conversion of diglycerin was 25%, and the selectivity of monoalkyl ether was 57%.

From the results of Example 1 and Comparative Example 1, Example 2 and Comparative Examples 2 and 3, and Example 3 and Comparative Example 4, a solid catalyst was used in the presence of an ether solvent having no active hydrogen according to the present invention. Thus, it was found that the selectivity of the 1: 1 adduct was high when the polyhydric alcohol compound and the epoxy compound were reacted.
Further, from the results of Example 3 and Comparative Example 4, it can be confirmed that the selectivity of the 1: 1 adduct is high in the presence of an ether solvent having no active hydrogen even in the drop-type reaction advantageous in terms of selectivity. The usefulness of the present invention could be confirmed regardless of the reaction form.
From the results of Comparative Example 5 and Comparative Example 6, when the polyhydric alcohol compound and the epoxy compound were reacted using a homogeneous catalyst, even in the presence of an ether solvent having no active hydrogen according to the present invention, No improvement in the selectivity of the 1: 1 adduct was observed.

(1) Glycidyl ether: can be synthesized by a general production method. For example, as described in Japanese Patent No. 3544134, it can be obtained by reacting an alcohol with α-epihalohydrin and then ring-closing it by alkali treatment.
(2) γ-alumina: purchased from Mizusawa Chemical Co., Ltd. (3) KW2000: Kyoward 2000 (composition formula: Mg _0.7 Al _0.3 O _1.15 ), Kyowa Chemical Co., Ltd. (4) TEG-DME: tetraethylene glycol dimethyl ether (boiling point) 275 ° C), Wako Pure Chemical Industries, Ltd. (5) N-methylpyrrolidone: (boiling point 202 ° C), Wako Pure Chemical Industries, Ltd. (6) TrEG-DME: triethylene glycol dimethyl ether (boiling point 216 ° C), Wako Pure Chemicals Made by Kogyo

Claims (8)

Addition of an epoxy compound to react a polyhydric alcohol compound and an epoxy compound by heating using a solid catalyst containing aluminum, magnesium or zinc in the presence of an ether solvent having no active hydrogen of the following general formula (4) Manufacturing method.
R ² -O - _{[(PO) m / (EO)} n ] -R ³ (4)
[Wherein R ² and R ³ are alkyl groups having 1 to 8 carbon atoms, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, and m and n indicate the added mole number of PO or EO. , 0 to 10 respectively, and the sum of m and n is 2 to 20. The order of addition of PO and EO does not matter. “/” Means that the addition form of PO and EO may be block or random. ]   The epoxy compound addition according to claim 1, wherein the polyhydric alcohol compound, the ether solvent having no active hydrogen of the general formula (4) and the solid catalyst are mixed, dehydrated, added with an epoxy compound, and reacted by heating. Manufacturing method. The production method according to claim 1 or 2, wherein the polyhydric alcohol compound is glycerin and / or polyglycerin. The method for producing an adduct of an epoxy compound according to any one of claims 1 to 3 , wherein the epoxy compound is glycidyl ether. The method for producing an epoxy compound adduct according to any one of claims 1 to 4 , wherein the ether solvent having no active hydrogen of the general formula (4) has a boiling point of 100 ° C or higher. The method for producing an epoxy compound adduct according to any one of claims 1 to 5, wherein the reaction temperature is 100 ° C or higher and 250 ° C or lower. The method for producing an epoxy compound adduct according to any one of claims 1 to 6, wherein the solid catalyst is aluminum oxide, magnesium oxide, zinc oxide, a composite oxide of aluminum and magnesium, or γ-alumina. The usage-amount of the ether solvent which does not have active hydrogen of General formula (4) is 50-500 mass parts with respect to 100 mass parts of polyhydric alcohol compounds, The any one of Claims 1-7. Manufacturing method of epoxy compound adduct.